EP2699628A2 - Polymérisats expansibles composés d'acétate-butyrate de cellulose et de polymérisat de styrène - Google Patents

Polymérisats expansibles composés d'acétate-butyrate de cellulose et de polymérisat de styrène

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Publication number
EP2699628A2
EP2699628A2 EP12721401.3A EP12721401A EP2699628A2 EP 2699628 A2 EP2699628 A2 EP 2699628A2 EP 12721401 A EP12721401 A EP 12721401A EP 2699628 A2 EP2699628 A2 EP 2699628A2
Authority
EP
European Patent Office
Prior art keywords
polymer
oxa
dihydro
dops
styrene
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Withdrawn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
EP12721401.3A
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German (de)
English (en)
Inventor
Roman Eberstaller
Gerhard Hintermeier
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.)
Sunpor Kunststoff GmbH
Original Assignee
Sunpor Kunststoff GmbH
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 Sunpor Kunststoff GmbH filed Critical Sunpor Kunststoff GmbH
Publication of EP2699628A2 publication Critical patent/EP2699628A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/141—Hydrocarbons
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0019—Use of organic additives halogenated
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066—Use of inorganic compounding ingredients
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • 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
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/08—Cellulose derivatives
    • C08J2301/14—Mixed esters
    • 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
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes

Definitions

  • the invention relates to expandable polymers or polymer granules of a polymer mixture comprising a cellulose acetate butyrate (CAB) and a styrene polymerate and corresponding polymer foams.
  • CAB cellulose acetate butyrate
  • Celluioacetate butyrate is a biopolymer based on cellulose. It is an ester of cellulose with aliphatic carboxylic acids. Whereas, for example, in the case of cellulose acetate the esterification takes place only by acetic acid, esterification with acetic acid and butyric acid takes place with cellulose acetate butyrate.
  • the celulose acetate butyrate polymer may be generally represented by the formula
  • Cellulose fermentate butyrate has a relatively low density as compared to cellulose acetate and cellulose propionate and has high strength, hardness and toughness. It is dimensionally stable in the temperature range of - 45 ° C to 1 15 ° C, has high temperature and UV resistance and is resistant to moisture and a variety of chemicals and environmental factors.
  • Celluioseacetatbutyrat As industrially manufactured plastic Celluioseacetatbutyrat is since 1946 in the trade. Celluioseacetatbutyrat is used for the production mainly as granules, which is suitable for both extrusion and injection molding.
  • Celluioseacetatbutyrat ranges from Griffbe Anlagenun- gene, such as handles of the Swiss Army Knives, Klarsichtkuppein, toys, cable conduits, coatings and paints, for example in the automotive and automotive industry, explosion-proof windows, vehicle lighting, automotive accessories, contact lenses and office equipment to films and packaging material or as part of nail varnishes, printing inks, known trade names are Cellidon®, Tenite® and Tenex®.
  • EPS Extra Polystyrene
  • the aim is to completely or partially replace fossil raw materials with renewable raw materials and to maintain the good mechanical, thermal and processing properties.
  • Biodegradability has great advantages for short-lived consumer goods, for durable goods such as thermal insulation panels in and on buildings - the use of polymer foam as thermal insulation has a long tradition and is well established - but this is an exclusion criterion.
  • Such expandable polymer granules should be reliable and easy to process foamed foam moldings with good welding, which have a Gietcherede cell structure with average Zelfrestn between 20 and 500 pm and a density of 8 to 250 kg / m 3 .
  • the polymer granules and the foam moldings produced therefrom should not show any biodegradability according to EN 13432: 2000 (requirements for the recycling of packaging due to composting and biodegradation).
  • expandable polymer granules should be processible in equipment such as is commonly used to process expandable particulate foams, e.g. of EPS, are used, in particular in commercially available pre-expanders and molding machines or block molds.
  • a further important criterion is the shelf life of the polymer granules during transport and during storage to processing and the processing parameters during the pre-expansion, intermediate storage and sintering, which should be as close as possible to those of EPS.
  • the foam parts produced from the granules described must meet the requirements of Formstabiitician, eg Nachblähen, shrinkage, cutability with hot wire and mechanical Schneideantagen. In the not yet published application A 2054/2009 the applicant is the
  • CAB as a raw material for the production of expandable polymers or polymer granules described.
  • the CAB materials produced in this way have certain disadvantages with regard to their processability and achievable product properties in comparison with fossil source-derived products.
  • polymer particles whose polymer matrix consists largely of CAB tend to collapse, i. a shrinkage of the prefoamed beads during or immediately after the VorMOum processes, at the usual for example EPS pentane content of 6 wt .-%.
  • EPS pentane content 6 wt .-%.
  • the polymers are formed from a polymer mixture comprising a cellulose acetate butyrate (CAB) and a styrene polymer.
  • expandable polymers or “expandable polymer granules” are to be understood as meaning expandable particulate particles comprising or consisting of CAB and polystyrene or CAB / PS particles of relatively small size, similar to commercially available EPS perienes Storage and transport normal conditions and froth by selecting the processing parameters to various densities and sizes, which are then sintered into moldings. These particles are thus easily expandable by increasing the temperature. It is both the production of open-cell and marunterenzelligen foams and all intermediates possible.
  • Advantageous embodiments or further developments of the invention are defined by the features of the dependent claims:
  • At least one further compatible polymer to be present in the polymer mixture when cellulose acetate butyrate (CAB) and styrene polymer together constitute more than 80% by weight, preferably more than 90% by weight, of the total mass of the polymer mixture.
  • CAB cellulose acetate butyrate
  • styrene polymer together constitute more than 80% by weight, preferably more than 90% by weight, of the total mass of the polymer mixture.
  • polyurethane, polylactide or other thermoplastic polymers are possible.
  • polystyrene polymers are obtained when the polymer mixture consists exclusively of a cellulose acetate butyrate (CAB) and a styrene polymer.
  • CAB cellulose acetate butyrate
  • CAB cellulose acetate butyrate
  • Particularly advantageous polymers are obtained when the cellulose acetate butyrate (s) used have a molecular weight average of Mn> 30,000 g / mol, in particular> 40,000 g / mol, in particular from 30,000 to 70,000 g / mol.
  • the method and the test conditions for determining the molar mass distribution and the molar mass Mn (number average) were chosen analogously to the standard DIN 55672-1, for tetrahydrofuran (THF) -soluble polymers by Geipermeationschromatographie (GPC). The calibration was done with commercially available, linear and polystyrene standards characterized according to independent absoluivery.
  • the molecular weight number center! or the number average molecular weight n is the weighted arithmetic mean of the moimasse of a polymer sample. Mn is identical to the mean value of the molecular weight distribution of the polymer.
  • the weight of hydroxyl groups on cellulose acetate butyrate determined according to ASTM D8 7-96 (2010) (Standard Test Methods of Testing Cellulose Acetate Propionate and Ceilulose Acetate Butyrate), about 0.5 to about 2.5 wt .-%, preferably about 0.8 to about 1, 8 wt .-% based on cellulose acetate butyrate, is.
  • the reference quantity for the data in% by weight is the cellulose acetate butyrate as such, and not the weight of the polymers.
  • Mn molecular weight or molecular weight average
  • homopolymers and copolymers of styrene preferably glass-clear polystyrene (GPPS), toughened polystyrene (HIPS), anionically polymerized polystyrene or toughened polystyrene (A-IPS), styrene-alpha-methylstyrene copolymers, acrylonitrile-butadiene-styrene polymers (ABS) are used as the polystyrene polymers.
  • GPPS glass-clear polystyrene
  • HIPS toughened polystyrene
  • A-IPS anionically polymerized polystyrene or toughened polystyrene
  • ABS acrylonitrile-butadiene-styrene polymers
  • SAN Styrene-acrylonitrile
  • ASA acrylonitrile-styrene-acrylic ester
  • MBS methylacrylate-butadiene-styrene
  • MABS methylmethacrylate-acrylonitrile-butadiene-styrene
  • PPE polyphenylene ether
  • EPS expandable styrene polymers
  • the propellant-free CAB / PS polymer mixture has a glass transition temperature Tg in the range from 90 ° C. to 145 ° C.
  • Tg glass transition temperature
  • a propellant-free polymer mixture is obtained, for example, by adding no propellants for comparison or that the propellants are completely outgassed by prolonged storage at elevated temperature.
  • At least one blowing agent is contained in the particles themselves or as part of the particle, in particular pentane or vanillin, preferably in a concentration of 3 to 10 wt .-%, based on the total weight of the polymer.
  • the CAB / PS particles are thereby ready to be processed and can be readily and easily expanded at any time by increasing the temperature.
  • the flameproofing agent is a halogenated organic compound, for example a bromine compound, preferably with a halogen content of at least 50 wt .-%.
  • a thermal Radikaibildner such as dicumyl peroxide, di-tert-butyl peroxide or dicumyl may be included as a synergist.
  • a halogenated or non-halogenated organic phosphorus compound for example 9,10-dihydro-9-oxa-10-phospha-phenanthrene-10-oxide (DOPO) or 9, 10-dihydro-9-oxa-10-phospha- phenanthrene-0-sulfide (DOPS) and derivatives thereof, for example, 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-OH), (10-hydroxy-9,10-dihydro -9-oxa-10-phosphaphenanthrene-10-oxide ammonium salt (DOPO-ONH), triphenyl phosphate (TPP), etc., or one or more further anti-fouling agents may be added from the list of claim 10.
  • Advantageous amounts are about 0.5 to 25 Wt .-%, in particular 3 to 15 wt .-%, based on the total weight of the polymer.
  • elemental sulfur or a sulfur compound e.g. Melamine thiosulfate [bis (1,3,5-triazine-2,4,6-triamine) thiosulfate] or para-tertiobutylphenol disulfide polymer (Vultac TB7 from Arkema Inc.) may be included as a synergist.
  • a sulfur compound e.g. Melamine thiosulfate [bis (1,3,5-triazine-2,4,6-triamine) thiosulfate] or para-tertiobutylphenol disulfide polymer (Vultac TB7 from Arkema Inc.) may be included as a synergist.
  • the flame retardant system comprises a combination of at least one phosphorus compound as flame retardant and at least one sulfur compound as additional flame retardant agent or synergist.
  • the effect of the flame retardant system can be further increased if, in addition to the gas-phase-active flame retardant, flame retardants such as aluminum hydroxide, magnesium hydroxide, borates, boron salts, melamine cyanurate, meiamine, ammonium phosphate, ammonium polyphosphate, ammonium succinate, trisodium phosphate, hexamate phosphate, dipentaerythydrite, in each case alone or be added in mixtures.
  • flame retardants such as aluminum hydroxide, magnesium hydroxide, borates, boron salts, melamine cyanurate, meiamine, ammonium phosphate, ammonium polyphosphate, ammonium succinate, trisodium phosphate, hexamate phosphate, dipentaerythydrite, in each case alone or be added in mixtures.
  • At least one infrared opacifier preferably selected from the group of carbon black, metal oxides, Metal powder, petroleum coke, anthracite and / or graphite.
  • Advantageous polymers are characterized in that the individual granules have an average particle size of 0.2 to 5 mm and / or that the granules are substantially round.
  • a coating layer in particular of glycerol stearates, metal stearates, silicates, etc.
  • a nucleating agent preferably selected from the group of polyolefin waxes, paraffins, Fischer-Tropsch waxes, the esters and amides of fatty acids or inorganic particles with a particle size between 1 and 20 ⁇ m or combinations thereof.
  • An advantageous process procedure provides that a polymer melt containing cellulose acetate butyrate and polystyrene, and a blowing agent mixed by means of a dynamic or static mixer and then granulated, wherein the Granui réelle of the particles using a pressurized Unterwassergranuiierers at a pressure greater than 3 bar and A water temperature between 20 and 100 ° C takes place.
  • cellulose acetate butyrate and polystyrene are melted by means of a dynamic or static mixer, and the melt is subsequently mixed with propellant and granulated, the granulation of the particles being effected with the aid of a pressurized underwater granulator at a pressure of greater than 3 bar and a water temperature between 20 and 100 ° C takes place.
  • the cellulose acetate butyrate is mixed with a mixer into still granular expandable polystyrene (EPS) and then the mixture is melted, optionally with additionalmaschinemiitel and granulated, the granulation of the particles by means of a pressurized Unterwassergranuiierers at a pressure greater than 3 bar and a water temperature between 20 and 100 ° C takes place.
  • EPS granular expandable polystyrene
  • the granules are produced by suspension polymerization of styrene in aqueous suspension in the presence of cellulose acetate butyrate and a propellant.
  • a polymer foam is proposed, which consists of a mixture of cellulose acetate butyrate and a styrene polymer or of a a polymer mixture containing a Celluioseacetatbutyrat (CAB) and a Styrolpolyme- risat is formed.
  • CAB Celluioseacetatbutyrat
  • the polymer foam advantageously has all those characteristics which are predetermined by the polymers, for example special polymer mixtures, concentration ratios, types, ingredients or additives of the polymers or CA8 and / or the styrene polymers.
  • Advantageous polymer foams therefore have the features of at least one of claims 1 to 7 and 9 > 10, 11 and 14.
  • a foam which is formed from the expandable polymers according to one of claims 1 to 14, in particular by foaming and sintering these polymers into a particle foam is particularly advantageous.
  • an advantageous foam can also be obtained by extrusion of the polymer mixture, analogously to XPS.
  • the foam may be open-cell, closed-cell or mixed. Such a foam has the initially mentioned advantages of a good
  • the polymer foam can be prepared either by extrusion. Alternatively, it is advantageously also possible to form the polymer foam in the form of a particle foam. In this case, the expandable polymers described above by means of conventional methods, in particular by foaming and sintering of the particles, further processed to foam.
  • the foam has a uniform cell structure with average cell sizes between 20 and 500 pm.
  • the foam has a density of 8 to 250 kg / m 3 .
  • the foam is non-biodegradable according to EN 13432: 2000.
  • a particularly advantageous embodiment of the polymer foam provides that particles and particles containing infrared opacifying agents without infrared opacifiers are sintered with one another in regular or irregular distribution.
  • Such a foam has a low thermal conductivity, combined with a high dimensional stability, especially in sunlight.
  • the preparation of some of the phosphorus compounds mentioned initially results, for example, from AT 508.507, AT 508.304 or WO 2011/000018 A1.
  • the phenylphosphonate salts are prepared according to WO 201 1/003773, the oligophosphorus compounds or oiigophosphines according to WO 201/029901.
  • Thermometer 92.8 g of DOPO-OH were suspended in 400 g of water and treated at 25 ° C with 50.4 g of melamine. Subsequently, the suspension was heated to 90 ° C and held for 4 h at this temperature. Thereafter, it was cooled to room temperature. The precipitate was filtered off and washed with water. The drying was carried out at 160 ° C, and the yield was 141, 4 g [98.7% d, Th.] Of a white, crystalline solid.
  • Thermometer a mixture of 100.0 g of water, 100 g of ethanol and 36.0 g of guanidinium carbonate was prepared and heated to 75 ° C. Subsequently, 92.8 g of DOPO-OH were added in portions over a period of 5.5 h. After CO evolution was no longer detectable, the reaction mass was concentrated by distillation. The remaining Rohkristailbrei (135.6 g) was applied to a drying cup and dried at 1 10 ° C. The yield was 100.5 g [86.0% d. Th.] Of a white, crystalline solid.
  • Example 1 The invention is illustrated below with reference to some particularly advantageous, non-limiting examples: Example 1
  • Example 3 50% cellulose acetate butyrate and 50% styrene polymer
  • Example 6 (comparison)
  • Example 2 metered addition of 4% graphite
  • the polymer granules from Examples 1 to 6 were analyzed by gas chromatography for their pentane retention capacity. The pentahands were determined at intervals of 24 hours. The results are shown in Table 1. The starting contents of the granules were all at 5.5% by weight and the initial value was calculated as 100%. The granules were stored in open packaging.
  • the polymer granules obtained from experiments 1 to 8 were prefoamed by means of a pressure prefoamer (Kurtz X1.5). After an intermediate storage time of 6 hours, plates of approx. 30 x 30 x 5 cm were produced in a molding machine (Erlenbach C87 / 67/1). These were tested for weld quality with a FA meter. Erlenbach (welding measuring device type EM 840 / PE from Erlenbach). The results are shown in Table 2.
  • Example 7 The foam samples of Example 7 thus obtained were tested in accordance with DIN 4 02-B2 and according to EN 13501 (fire class E) in order to check the fire protection properties.
  • Fig. 1 shows the diagram to Tabe
  • the molded parts produced from Examples 7 and 8 passed the small burner tests according to DIN 4102-B2 and according to EN 13501.
  • the molded article produced from Example 8 achieved a thermal conductivity of 30.4 mW / (m * K) at a density of 20 kg / m 3 .

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

L'invention concerne des polymérisats ou des granulats polymères expansibles ainsi qu'une mousse polymère, composés d'un mélange polymère contenant un acétate-butyrate de cellulose (CAB) et un polymérisat de styrène, ainsi que leur préparation.
EP12721401.3A 2011-04-18 2012-04-17 Polymérisats expansibles composés d'acétate-butyrate de cellulose et de polymérisat de styrène Withdrawn EP2699628A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT5462011A AT511509A1 (de) 2011-04-18 2011-04-18 Expandierbare polymerisate aus celluloseacetatbutyrat und styrolpolymerisat
PCT/AT2012/000102 WO2012151596A2 (fr) 2011-04-18 2012-04-17 Polymérisats expansibles composés d'acétate-butyrate de cellulose et de polymérisat de styrène

Publications (1)

Publication Number Publication Date
EP2699628A2 true EP2699628A2 (fr) 2014-02-26

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EP (1) EP2699628A2 (fr)
AT (1) AT511509A1 (fr)
WO (1) WO2012151596A2 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015135835A1 (fr) 2014-03-11 2015-09-17 Smartpolymer Gmbh Articles moulés en cellulose difficilement inflammable, fabriqués selon un procédé de dissolution directe
NL2014258B1 (en) * 2015-02-06 2016-10-13 Synbra Tech B V A process for producing foam mouldings.
ES2938007T3 (es) * 2018-11-13 2023-04-03 Nouryon Chemicals Int Bv Microesferas a base de celulosa térmicamente expandibles
KR102860849B1 (ko) * 2020-05-20 2025-09-16 누리온 케미칼즈 인터내셔널 비.브이. 낮은 팽창 온도를 갖는 열 팽창성 셀룰로오스계 미소구체
CN117623274B (zh) * 2023-12-07 2025-02-25 北京化工大学 一种煤基功能碳材料的制备方法及其应用

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3857729A (en) * 1972-09-21 1974-12-31 H Burwasser Indicia receiving matte sheet materials having an outermost antistatic layer
JPS565273B2 (fr) * 1973-05-24 1981-02-04
WO1999012723A1 (fr) 1997-09-05 1999-03-18 Teijin Limited Mousses d'acetate de cellulose biodegradables et leur procede de production
DE102004044380A1 (de) 2004-09-10 2006-03-30 Basf Ag Halogenfreie, flammgeschützte Polymerschaumstoffe
NL1033719C2 (nl) 2007-04-19 2008-10-21 Synbra Tech Bv Deeltjesvormig expandeerbaar polymelkzuur, werkwijze voor het vervaardigen hiervan, geschuimd vormdeel op basis van deeltjesvormig expandeerbaar polymelkzuur evenals werkwijze voor het vervaardigen hiervan.
WO2011000018A1 (fr) 2009-07-03 2011-01-06 Sunpor Kunststoff Ges.M.B.H. Polymérisats expansibles, retardateurs de flamme
JP5631392B2 (ja) 2009-07-06 2014-11-26 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ フェニルホスホネート難燃性組成物
CN102482445A (zh) 2009-09-14 2012-05-30 巴斯夫欧洲公司 含有至少一种低聚磷化合物的不含卤素的阻燃聚合物泡沫
AT510312B1 (de) * 2010-08-27 2013-02-15 Sunpor Kunststoff Gmbh Polymerschaumkörper oder teilchenförmige expandierbare polymerisatpartikel und verfahren zu deren herstellung
AT510311B1 (de) * 2010-08-27 2013-02-15 Sunpor Kunststoff Gmbh Flammgeschützte, wärmedämmende polymerisate und verfahren zu deren herstellung

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2012151596A2 *

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AT511509A1 (de) 2012-12-15
WO2012151596A2 (fr) 2012-11-15

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