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EP2001584A1 - Microparticules et microcapsules matricielles thermiquement stables pour additifs pour plastiques et leur procede de fabrication - Google Patents

Microparticules et microcapsules matricielles thermiquement stables pour additifs pour plastiques et leur procede de fabrication

Info

Publication number
EP2001584A1
EP2001584A1 EP07723640A EP07723640A EP2001584A1 EP 2001584 A1 EP2001584 A1 EP 2001584A1 EP 07723640 A EP07723640 A EP 07723640A EP 07723640 A EP07723640 A EP 07723640A EP 2001584 A1 EP2001584 A1 EP 2001584A1
Authority
EP
European Patent Office
Prior art keywords
thermally stable
matrix microparticles
microcapsules according
preparation
stable matrix
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.)
Withdrawn
Application number
EP07723640A
Other languages
German (de)
English (en)
Inventor
Jacqueline Lang
Geerald Rafler
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.)
Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV
Original Assignee
Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV
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 Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV filed Critical Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV
Publication of EP2001584A1 publication Critical patent/EP2001584A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • 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
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/08—Simple coacervation, i.e. addition of highly hydrophilic material
    • 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
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/20—After-treatment of capsule walls, e.g. hardening
    • B01J13/22—Coating
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • Y10T428/2998—Coated including synthetic resin or polymer

Definitions

  • the invention relates to polyimide matrix microparticles or microcapsules having a thermally stable polyimide wall or matrix and functional plastic additives as core materials, which can be incorporated into high-melting plastics by melt compounding.
  • the particle parameters as well as the thermal and mechanical stability of the matrix particles or microcapsules can be adjusted specifically via the polyamide structure and / or technological parameters of particle formation (shear, reaction conditions for wall formation).
  • Polyimides of polyimides and microencapsulated plastic additives with a simple or complex particle wall made of polyimides are especially for the production of specially equipped polyamides, polyesters and polyimides High performance plastics that require high temperatures for processing or that are used at high temperatures.
  • Thermoplastic and duromeric polymer materials are adapted in a variety of ways by inert fillers and / or functional additives specific usage requirements.
  • the optimizations sought by means of additive treatment frequently relate both to the mechanical material properties directly (tensile strength and flexural strength, toughness, modulus) and also to other useful properties of the materials, such as light and heat stability, flexibility or the burning behavior.
  • Dyes are often added to plastics.
  • plastics in the case of smart materials, recent developments also use plastics as matrices for thermo- or photochromic or sensory substances as well as for the absorption of heat storage materials.
  • Plastic additives have to meet a number of criteria which, in addition to the actual effect, have a decisive influence on the type and limits of their use.
  • microencapsulation With its microencapsulation, an efficient and versatile method is available, which is used for the coating of microparticulate solids, finely divided liquids or waxy substances.
  • Applications are known in agriculture and forestry, in products of the food, cosmetics, packaging, construction, paint and paint industries. They are used as dispersions, free-flowing powders or by direct incorporation into other materials, in particular in various thermoplastic, elastomeric and thermosetting polymer materials.
  • Microencapsulation with polymeric materials is well known and broadly described in the scientific and patent literature, such as in Encyclopedia of Polymer Science, J. Wiley & Sons, 1968, Vol. 8, p. 719; W. Sliwka, Angew. Chem. Boarding school. Edit. 14 (1975) 539; Acta Polymerica 40 (1989) 243; 40 (1989) 325; KONA 10 (1992) 65; Drugs Pharm. 73 (1996) Microencapsulation 1; RE Sparks, microencapsulation in Encyclopedia of Chemical Process ing, S. 162.
  • an active ingredient / polymer system is converted into a particulate form from preferably organic solution by dispersing, dripping or spraying processes or by processes based on the principle of liquid-liquid phase separation.
  • Dispersing, dripping and spraying methods include solvent evaporation;
  • phase separation processes are based on the principle of precipitation of the wall material, e.g. by adding an incompatible component to the polymer solution.
  • melamine-formaldehyde resins are very frequently used (DE 199 23 202, UK 2 301 117), but also isocyanate / amine systems are described (AZ 101 56 672).
  • Melamine-formaldehyde resins are broad and easy to use for the coating of hydrophobic core materials, and they can be applied for particle formation from the aqueous phase. Reaction processes require core materials that are inert to the wall-forming monomers or oligomers, i. that they do not react with other components involved.
  • the application-relevant microparticle parameters such as particle size and their distribution, shape and morphology of the particles and their surface are determined in a complex manner by the chemical structure of the polymer phase of particle wall or matrix and the reaction conditions of the particle formation.
  • Control parameters for particle geometry and particle morphology are, above all, the duration and intensity of the dispersion, the solubility and interfacial properties of wall and core material, and the structure of the wall or matrix-forming polymer material.
  • thermoplastic and thermosetting wall materials are limited as a result of meltability or lack of thermal stability in their applicability for the production of microencapsulated additives for engineering plastics with their high processing temperatures of 240 to 280 0 C. Due to their chemical structure, heat-resistant and temperature-stable plastics, such as polyaramides, polyether ketones, polysulfones or polyphenylene sulfide, are often insoluble in the customary organic solvents used for particle formation processes.
  • Solvents for these heat-resistant and thermostable polymers require complex encapsulation techniques, are difficult to remove from the particles due to high boiling points or limited miscibility with low-boiling extraction agents, or they dissolve or react with the core materials.
  • Heat-resistant wall materials made from linear-chain polymers having solubility in solvents customary for particle processes are only a few known. Particularly noteworthy are polyacrylonitrile and cellulose ethers. Although these polymers do not melt, their thermal capacity is also limited.
  • DE 10 231 706 describes a encapsulation process for plastic additives with polyacrylonitrile.
  • polyimides Apart from polybenzimidazoles and polyoxadiazoles, polyimides have the highest thermal and chemical stability of all organic polymer materials. Due to the known solubility problems that these polymer materials cause, they have not been used to microencapsulate drugs. It is an object of the invention to produce microcapsules or micromatrix particles of high mechanical and thermal stability for the plastic additive after an efficient and reliable in situ process.
  • the invention is solved for the matrix microcapsules or matrix microparticles of high mechanical and thermal stability by the features of claim 1 and for the method of their preparation by the features of claim 16. Uses of the method according to the invention are characterized by the features of claim 45.
  • the respective subclaims contain advantageous developments for the microcapsules or for the method.
  • the microcapsules or micromatrix particles of high mechanical and thermal stability consist of a polyimide which in one capsule is the particle wall and in the case of matrix particles the whole
  • further functional plastic additives may be incorporated into both the matrix microparticle and the microcapsule.
  • Flame retardants, color pigments, metal flake and / or powder, matting agents and phase change materials are preferably used as additives.
  • the polyimide particles according to the invention exhibit the following properties:
  • agglomeration a monomodal particle distribution at an average diameter of 1 and 50 microns, preferably between 2 and 40 microns, more preferably between 5 and 30 microns on. They show spherical geometry with slight structuring of the particle surface. Characteristic feature of poly- imide-based microcapsules and particles is their high thermal, thermo-oxidative and chemical stability, due to the chemical structure of Wandstanding. Matrix materials. Depending on the chemical structure of an appreciable mass loss, is caused by thermogravimetry ones by Thermolysereakti- observed in a range from 450 0 C to 530 0 C.
  • the polyimide-based matrix microparticles or microcapsules have the advantageous property, under inert conditions (nitrogen as inert gas) to 500 0 C and to be stable in air up to 350 0 C.
  • Preferred polyimides for matrix microparticle formation or microencapsulation are e.g. Poly (4,4'-diphenyl-oxide-pyromellithimide), poly (4,4'-diphenylmethanopyromellithimide), poly (4,4'-diphenyloxide-di-phthalimide), poly (m-phenylene-isopropylidene-di- phthalimide), poly (2,2-dimethyl-4,4'-diphenylmethanopyromellithimide), poly (2,2-bis (trifluoromethyl) -4,4'-diphenylmethane-oxy-diphthalimide and poly (4 , 4'-diphenyloxide-carbonyl-diphthalimide).
  • the polyimide particles can, under application-relevant aspects, also have a complex shell structure, depending on the profile of requirements for the microencapsulated additives or microparticulate fillers, wherein the second or also third shell can be produced both from the same material and from different materials.
  • shells made of linear-chain polymers or of low-molecular-weight organic or inorganic substances, such as waxes, fatty acid derivatives are used for structure-differing shell materials. Silicones, siloxanes or silicates are preferred.
  • Structurally different polymers which are particularly suitable for the coating of polyimide microparticles include, in particular, polyacrylates, polyethylene glycols and starch fatty acid esters and starch carbamates of long-chain isocyanates.
  • the polyimide particles with core-shell or matrix structure are prepared by a multistage process comprising the steps
  • the solution of the polyamidocarboxylic acid is adjusted to the desired concentration and optionally the plastic additive is added or dispersed in.
  • a plastic additive selected from the group consisting of flame retardants, color pigments, metal flakes and / or powder, matting agents and phase change materials.
  • An extractant is added to the emulsion to remove the solvent to form the microcapsule or matrix microparticles.
  • microcapsules or matrix microparticles are isolated by liquid-solid separation techniques.
  • any aliphatic, aromatic and / or aliphatic-aromatic diamine can be reacted with an aliphatic, aromatic and / or aliphatic-aromatic tetracarboxylic acid derivative.
  • Suitable carboxylic acid derivatives here are carboxylic anhydrides, free carboxylic acids, carboxylic esters and carboxylic acid chlorides.
  • polyamidocarboxylic acids can be dissolved in one of the solvents described below.
  • the monomers can be dissolved in solvents that are miscible with water.
  • the amide-type solvents known for this synthesis such as dimethylacetamide and N-methylpyrrolidone, are preferably used.
  • the solutions with the polyamidocarboxylic acids formed can be further processed directly into microparticles. It is also possible to store at temperatures below room temperature and exclude moisture. Under these conditions, the solutions are storage stable for several weeks. For further processing, dilution with the same solvent or with another, water-miscible solvent is possible.
  • the concentration of the polymer solution is determined by the chemical structure and molecular weight of the polyamidocarboxylic acid. Both determine the viscosity of the polymer solution, which in turn is responsible for the size and morphology of the microcapsules and matrix particles. More soluble polyamidocarboxylic acids and higher molecular weights are used at lower concentrations, less soluble and lower molecular weight require higher concentrations.
  • the concentration of the polymer solution is in a range between 1 and 50% by weight, preferably between 2 and 20% by weight.
  • all emulsifiers are suitable which have no or only limited miscibility with the solvent, do not react with the polyamidocarboxylic acid and do not represent a solvent for the polymeric wall or matrix material, nor for the plastic additive.
  • plant and mineral oils preferably silicone oils, are particularly suitable for producing an emulsion having the appropriate viscosity. or paraffin oil.
  • the polymer solution or additive suspension is finely dispersed in the solution of the polymer by intensive mixing. With respect to the dissolved polymer, the emulsifier is used in excess. It is advantageous if the excess is between two to ten times, preferably between three to five times, of the polymer.
  • the distribution of the additive-containing or additive-free polymer solution in the emulsifier is supported by the addition of further organosoluble emulsifiers in a concentration between 0.1 and 5 wt .-%, preferably between 0.5 and 2 wt .-%.
  • organosoluble emulsifiers also improve the stability of the emulsion and thus also support the formation of artefact-free microparticles.
  • Preferred emulsifiers are nonionic or anionic substances, such as SPAN 18 SS or TWEEN ® .
  • the extractant is added to the emulsion with stirring.
  • Singular particle distributions facilitate separation, processing and optionally redispersion of the particles.
  • water or aqueous inorganic or organic phases are preferably used as extractants. These extractants are unlimited with the polyamidocarboxylic acid solvent and immiscible with the emulsifier. At the same time, it must be ensured that the extractant for the polymer and the additive does not represent a solvent.
  • the ratio between emulsion and extractant should be adjusted so that the poly- solvent is completely extracted. After the formation of the microparticles by curing of the particle wall or the particle matrix, these are solidly isolated by conventional phase separation methods. Particularly suitable are centrifugation and
  • the isolated microcapsules or matrix particles in an air or inert gas or under vacuum 0.5 to 10 hours, preferably 2 to 5 hours to a temperature between 100 and 400 0 C, preferably heated between 100 and 300 0 C.
  • the obtained polyimide particles can be used in this form as microfine powders directly for the thermoplastic additive.
  • redispersion in aqueous or oily phases and application as a microfine suspension is also possible.
  • the cyclization of the polyamidocarboxylic acid matrix particles ie of microparticles having a relatively small particle size and monomodal particle size distribution by the thermal cyclization of the polyamidocarboxylic acid matrix particles or microcapsules, can also be carried out in suspension, using high-boiling media in which the polyamidocarboxylic acids are insoluble.
  • high-boiling hydrocarbons, fatty acid esters and silicone oils are suitable, which can then be used or separated directly as a suspension. It is also worth mentioning that this can be done at a temperature above the boiling point of water, but not much higher (100-150 0 C), in vacuo or with azeotropic distillation.
  • microparticles according to the invention having a core-shell or matrix structure are preferably used as particulate fillers for improving the material properties of plastics. Another application is in the incorporation of KunststoffStoffadditiven in polymeric materials.
  • the microparticles according to the invention can be introduced into thermoplastic or thermosetting polymer materials by means of twin-screw extruders or kneaders analogous to particulate fillers or additives, and the additized plastics can be further processed by conventional shaping processes, such as injection molding or extruding in thermoplastics and thermosetting in thermosets.
  • Example 2 Analogously to Example 1, the monomers listed in Table 1 are combined and the resulting polyamidocarboxylic acids are used for microencapsulation and matrix particle formation.
  • the mean particle size was determined by laser diffraction.
  • Example 2 Analogously to Example 8, 10% strength NMP solutions of the polyamidocarboxylic acids (Examples 2-7) compiled in Table 1 are processed into microparticles and worked up. The microparticles obtained are summarized in Table 2. Table 2
  • Example 17 - 18 micro-encapsulated substances prepared analogously to Example 20 - 25 heated in vacuum or forced-air drying cabinet for 5 h at 200 0 C.
  • the polyimide microcapsules produced in this way have the application-relevant material and particle parameters listed in Table 4.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacturing Of Micro-Capsules (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

L'invention concerne des microparticules ou microcapsules matricielles de polyimide munies d'une paroi ou d'une matrice en polyimide thermiquement stable et d'additifs fonctionnels pour plastiques en tant que noyau, pouvant être incorporée dans la masse fondue d'un plastique à haute température de fusion.
EP07723640A 2006-04-06 2007-03-27 Microparticules et microcapsules matricielles thermiquement stables pour additifs pour plastiques et leur procede de fabrication Withdrawn EP2001584A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102006016307A DE102006016307B4 (de) 2006-04-06 2006-04-06 Thermisch stabile Matrixmikropartikel und Mikrokapseln für die Kunststoffadditivierung und Verfahren zu ihrer Herstellung und ihre Verwendung
PCT/EP2007/002694 WO2007115683A1 (fr) 2006-04-06 2007-03-27 Microparticules et microcapsules matricielles thermiquement stables pour additifs pour plastiques et leur procede de fabrication

Publications (1)

Publication Number Publication Date
EP2001584A1 true EP2001584A1 (fr) 2008-12-17

Family

ID=38198288

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07723640A Withdrawn EP2001584A1 (fr) 2006-04-06 2007-03-27 Microparticules et microcapsules matricielles thermiquement stables pour additifs pour plastiques et leur procede de fabrication

Country Status (5)

Country Link
US (1) US20100311900A1 (fr)
EP (1) EP2001584A1 (fr)
DE (1) DE102006016307B4 (fr)
RU (1) RU2008137374A (fr)
WO (1) WO2007115683A1 (fr)

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DE102009038532A1 (de) * 2009-08-25 2011-03-10 Eads Deutschland Gmbh Hydrofobe Zähmodifizierung hydrofiler Harzsysteme
US8319299B2 (en) 2009-11-20 2012-11-27 Auman Brian C Thin film transistor compositions, and methods relating thereto
CN102712753B (zh) 2009-11-20 2015-08-26 E·I·内穆尔杜邦公司 热稳定的且尺寸稳定的聚酰亚胺薄膜及与其相关的方法
CN103726119A (zh) * 2013-12-27 2014-04-16 天津孚信达光电科技有限公司 一种光致变色线的制备方法
GB201503566D0 (en) * 2015-03-03 2015-04-15 Spheritech Ltd Microparticles
RU2635140C2 (ru) * 2016-04-07 2017-11-09 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Курский государственный университет" Способ получения микрокапсул пигмента
GB201615050D0 (en) 2016-09-05 2016-10-19 Spheritech Ltd Microparticles
US10253166B2 (en) 2017-09-07 2019-04-09 International Business Machines Corporation Flame-retardant microcapsule containing cyclic phosphazene
CN110079880B (zh) * 2019-04-08 2021-09-24 山东银鹰化纤有限公司 一种无机阻燃调温粘胶纤维及其制备方法
CN110862686A (zh) * 2019-11-20 2020-03-06 天津工业大学 一种高分子导热复合材料及其制备方法
CN111808286B (zh) * 2020-07-30 2022-05-03 浙江道明光电科技有限公司 一种分别盛装二胺和二酐的聚酰亚胺胶囊体的制备方法
CN112915936B (zh) * 2021-01-21 2022-07-22 清华大学 一种耐高温高分散有机壳微胶囊及其制备方法
CN114471391A (zh) * 2022-02-25 2022-05-13 明士新材料有限公司 一种自润滑pi微胶囊及其制备方法
CN115322569A (zh) * 2022-09-14 2022-11-11 明士新材料有限公司 一种含自润滑pi微胶囊的聚酰亚胺膜及制备方法

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Also Published As

Publication number Publication date
DE102006016307B4 (de) 2011-07-28
RU2008137374A (ru) 2010-05-20
US20100311900A1 (en) 2010-12-09
DE102006016307A1 (de) 2007-10-11
WO2007115683A1 (fr) 2007-10-18

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