Classifications

• • 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
  • C08F112/00—Homopolymers 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
  • C08F112/02—Monomers containing only one unsaturated aliphatic radical
  • C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
  • C08F112/06—Hydrocarbons
  • C08F112/08—Styrene
• • 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
  • C08J9/16—Making expandable particles
• • 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
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
• • 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

Definitions

• the present invention relates to a method of kinetic and static preparation of styrene polymers, in particular those intended for expanding and manufacturing of thermal insulation partitions with the required mechanical, geometrical and insulation parameters.
• the present invention relates also to styrene polymers so prepared. Polymers of styrene, in particular foamed (expanded), demonstrate very low resistance to heat streams of more than 85°C in which such polymers undergo physical and chemical degradation; this, through passage into the liquid phase and loss of thermal insulation properties, leads to their destruction.
• Expanded polystyrene is a polymer material which is most frequently used in thermal insulation, e.g. in construction. It is characterized, inter alia, by a very low thermal conductivity index and low density. In order to enhance expanded polystyrene resistance to the effects of heat radiation and high temperature streams, organic and mineral flame retardants and their compositions are used as well as agents and compounds released as a result of thermal decomposition of the components.
• Another concept type is the application - as flame retardant - of plastics or a halide-free composition containing monoammonium salts and/or various phosphorus compounds or phosphorus itself.
• JP92961 19 An example of such a concept is Japanese patent application JP92961 19 in which the inventors propose to combine a plastic, graphite (expanding in temperature) with red phosphorus and/or a phosphorus compound (in particular ammonium polyphosphate).
• EP08141 19 Another example of such a concept is application EP08141 19 in which flame resistant polystyrene is obtained through admixing a composition of metal hydroxide with phosphorus compounds.
• This group of materials also includes the plastic flame retardant described in application CA1201841 composed of: ammonium polyphosphate, ammonium monophosphate, anhydrous borax, borax, urea based amide, melamine.
• Other concepts are also known whereby the flame retardant composition includes ascorbic acid.
• Application KR20010096332 presents a composition based on a polyolefin polymer which uses natural compounds as anti-oxidants and/or flame resistant agents.
• Such a composition includes: polyolefin-based polymer resin, antioxidant (ascorbic acid or its derivatives, apple extract), a flame-resistant agent (lactic acid derivatives) and, additionally, an additive which reduces trickling, enhancing agent, plasticizer, compatibilizer, colouring agent, filler, antistatic agent, flame retardant, pigment, and/or dye.
• a stabilised composition with enhanced stability to thermal oxidation which comprises polyolefins, ascorbic acid and one or more tocopherols.
• thermoplastic polycarbonate compact formed as a result of polymer grafting in the presence of ascorbic peracid, redox acidic initiator or ascorbic acid.
• non-nano substances are applied as ingredients of flame retarding compositions.
• application CA2516292 which describes a flame retarding composition consisting of a polyolefin polymer, nanosilicates, metal hydroxide, calcium carbonate.
• application CA2592281 presents compact polystyrene foam containing multi-layer nanographite as an admixture enhancing the properties of the material.
• the aim of the invention is to provide a method of neutralizing preparation of styrene polymers, especially intended for expanding, and, at the same time, reducing the presence in styrene polymers of flame retardants applied to date which, during pyrolysis and thermal transformations resulting in their decomposition, may be transformed into toxic products.
• the aim of the invention is also to provide a prepared styrene polymer, especially intended for expanding, obtained according to the invention, during which energy centres generated by the polymer is neutralized, especially in the form of electrical friction charges with a known (+ or -) like sign which is an abhesive bridge for protective layers on the modified styrene polymer surface concerned.
• the aim of the invention is primarily preparation of styrene polymer through electrostatic neutralisation, homogenisation and adhesive activation of the surface of styrene polymer, especially intended for expansion, and introduction of preparing agents into the monomer before polymerization or the introduction of such agents into the polymer after polymerization, and also, using thermoplastic properties of styrene polymer, introduction of preparing agents during its redrawing, pressing in higher temperature and pre-assumed pressure.
• styrene polymers especially ones intended for expansion and production of thermal insulation partitions, containing styrene polymers, organic porophores, and, optionally, surface active agents or, optionally, technological additions such as plasticizers, characterised in that they also contain organic and/or inorganic neutralizing preparation in solid or liquid form of between 5 g/kg and 200 g/kg in relation to the mass of polymer, preferably with an addition of ascorbic acid of between 0.5 g/kg and 170 g/kg and, optionally, they contain an addition in the form of organic auxiliary preparations in solid or liquid form of between 0.3 g/kg and 220 g/kg in relation to the mass of styrene polymer, preferably with an addition of ascorbic acid of between 1g/kg and 230 g/kg in relation to the mass of styrene polymer.
• the neutralising preparation comprise ammonium bromide of between 0.1 and 18 parts by weight, and/or guanidine phosphate of between 0.1 and 19 parts by weight, monoammonium salt of sulphonic acid of between 0.1 and 15 parts by weight, and, optionally, ascorbic acid of between 0.1 and 17 parts by weight in relation to the styrene polymer.
• the auxiliary preparation is an acrylate- fluoroalkyl copolymer which contains dipropylene glycol ethyl ether.
• the quantity of the auxiliary preparation in the prepared polymer is between 0.1 and 16 parts by weight in relation to the styrene polymer.
• the quantity of ascorbic acid in the prepared polymer is between 0.05 - 9.5 parts by weight in relation to the styrene polymer.
• the proportions between the components of the neutralizing preparation vary.
• the neutralizing preparation is applied in solutions or water suspensions or in solid form; granulated, e.g.: in the form of powders with granularity of below 1500 pm.
• the granularity of the neutralizing preparation used in the preparation of styrene polymers in solid form is within the range of 2-100 pm;
• the quantity of the auxiliary preparation applied in the form of a solution is between 0.3 g/kg and 220 g/kg in relation to the styrene polymer.
• the aim of the invention is also a method of preparing styrene polymers, especially ones intended for expanding, whereby the neutralizing preparations and, optionally, the auxiliary preparations are introduced during one of the individual phases of obtaining styrene polymers, such as a) suspension polymerisation of the monomer; b) seasoning of the styrene polymer before expansion; c) preliminary expansion of the styrene polymer; d) drying and homogenization of the expanded styrene polymer; e) pneumatic transport of expanded styrene polymer to be block-formed; or, in the process of homogenization of the styrene polymer, through its extrusion, redrawing, pressing, characterised by that at the phase of suspension polymerisation of the monomer, the quantity of the neutralizing preparation introduced is between 0.1 and 18 parts by weight, with the neutralizing preparation in the dissolved form or in the form of a suspension, is introduced together with a typical water protective colloid at
• the neutralizing preparation in solid form, with the granularity of below 1500 pm or dissolved in water or in the form of a suspension of between 0.1 and 18 parts by weight is introduced directly into a known water protective colloid before the monomer is introduced or it is introduced directly into the monomer before it is introduced into the known water protective colloid.
• the neutralizing preparation in the form of a water solution or a suspension is introduced in the form of dispersion which is used to directly coat the styrene polymer surface during the mixing at a temperature of 10-35°C.
• the neutralizing preparation in the form of a water solution or a suspension is introduced by spraying directly onto the expanded styrene polymer containing porophore.
• the neutralizing preparation is introduced in the form of dispersion by spraying onto the surface of the expanded polystyrene.
• the neutralizing preparation is introduced in the form of dispersion and/or a solution by spraying onto the styrene polymer transported to the block-forming chamber.
• the neutralizing preparation is added in solid, granulated form.
• the neutralizing preparation is applied in water solutions and/or in solid form.
• the granularity of the neutralizing preparation in solid form is within the range of 2-200 pm;
• the neutralizing preparation in solid, granulated form, within the range of 2- 200 pm, is introduced into the pneumatic transport system using the difference between the pressure in the pneumatic transport duct (pipeline) and the pressure outside of the pipeline (injector principle).
• the neutralizing preparation is the agent which restricts the commencement of the burning of styrene polymer, and its addition makes it possible to considerably enhance the thermal resistance of expanded styrene polymer and restricts the transformation of expanded styrene polymer into the liquid phase (flowing, trickling).
• the auxiliary preparation is introduced together with the neutralizing preparation in form dissolved in water in the proportion of 3:10 to the typical protective colloid or in the form of water suspension of between 0.2 and 14 parts by weight in proportion to the typical protective colloid before the monomer is introduced.
• the auxiliary preparation together with the neutralizing preparation in total quantity between 0.2 and 16 parts by weight is introduced in the form of dispersion which is used to directly coat the styrene polymer surface during the mixing at a temperature of 36°C.
• the auxiliary preparation together with neutralizing preparation in total quantity between 0.1 and 16 parts by weight are introduced in the form of a water solution or dispersion by spraying onto the expanded styrene polymer.
• the auxiliary preparation together with neutralizing preparation in total quantity between 0.1 and 14 parts by weight are introduced in the form of dispersion by spraying onto the surface of expanded styrene polymer.
• the auxiliary preparation together with neutralizing preparation in total quantity between 0.1 and 14 parts by weight are introduced in the form of dispersion by spraying onto the styrene polymer transported to the block- forming chamber.
• the neutralizing preparation together with the auxiliary preparation in total quantity between 0.1 and 14 parts by weight are added in solid granulated form.
• the impact of the neutralizing preparation on styrene polymers consists in the use of the tension and current effects forming on the polymer surface (friction and electrolyte charges) and surface modification of the prepared polymer with like ions, through the diffusion of the ions on the area of excessive surface energy generated during the expansion, transport, especially pneumatic transport, technological seasoning and block-forming.
• Modification of styrene polymer in a mass consists in introducing neutralizing preparations in the process of homogenization of the styrene polymer through its extrusion, redrawnig, pressing. Owing to the preparation of styrene.
• energy streams are generated which offer the possibility to utilize "nano" effects with respect to the expanded polymer surface as a result of which the radicals and/or atoms produced are occluded on the dendritic surface of the expanded styrene polymer in elementary quantity particularly with respect to nitrogen in statu nascendi which leads to neutralisation of energy centres generated by the styrene polymer and the modifiers (neutralizing and auxiliary preparations) according to the invention.
• the neutralising preparation optionally with the auxiliary preparation, is added to the styrene polymer, it is modified on its surface and/or throughout its volume (in its mass).
• a result of the preparation according to the invention may also be an improvement of thermal resistance (reduction in the lambda coefficient), mechanical parameters (resistance to compression, elasticity) and elastic recovery.
• the application, in the method according to the invention of organic inserts of auxiliary preparations is an additional protection and compartment preventing the operation of external factors such as water, ultraviolet, ozone, finished expanded polystyrene elements in storage, transport and application on the construction site (assembly, gluing and fixing onto the required surfaces).
• the surfaces of expanded polystyrene beads were extended; after the block was cut through, the beads had very advantageous geometric properties characterised by an increased friction coefficient (grip) and the possibility to favourably store adhesive preparations (e.g. glues) limiting the generation of vacuums between the surface of e.g. the expanded polystyrene board and the protected plane (e.g. wall).
• grip friction coefficient
• adhesive preparations e.g. glues
• guanidine phosphate of: 20-30 % by weight.
• Ammonium bromide of: 50-75 % by weight.
• - DICRYLAN AC® is the trade name of the chemical produced by Huntsman Textile Effects with its seat in Germany consisting of acrylic copolymer.
• the total quantity of the aforementioned chemicals, both in the neutralizing preparation and the auxiliary preparation in relation to the styrene polymer is between 5 g/kg and 200 g/kg.
• the neutralizing preparation in the form of water solution is introduced, and then styrene monomer is introduced and suspension polymerization following the well known method is performed.
• the monomer to neutralizing preparation ratio is 1 :10, and the composition of the neutralizing preparation is as follows: 100 parts by weight of FLOVAN CWF®, 50 parts by weight of FLOVAN BU® and 10 parts by weight of water.
• the exothermic process is performed at a temperature of between 20°C and 1 10°C, obtaining the prepared styrene polymer according to the invention.
• the neutralizing preparation in the solid form with granulation of below 1500 ⁇ is introduced, and then, styrene monomer is introduced and suspension polymerization following the well known method is performed.
• the monomer to neutralizing preparation ratio is 10:0.6, and the composition of the neutralizing preparation is as follows: 0.1 parts by weight of FLOVAN CWF®, 0.3 parts by weight of FLOVAN BU®.
• the exothermic process is performed at a temperature of between 20°C do 1 10°C, obtaining the prepared styrene polymer according to the invention.
• styrene polymer intended for expanding 100 parts by weight of styrene polymer intended for expanding and 10 parts by weight of the neutralizing preparation which contains: 6.3 parts by weight of FLOVAN CWF®, 0.6 parts by weight of ascorbic acid, 3.1 parts by weight of water and 0.1 parts by weight of the auxiliary preparation consisting of FLUVAL Nl®
• the mixer is set to motion with the rotational speed of 0.5 m/s for 10 minutes. After the mixer is emptied, the styrene polymer with prepared surface, intended for expanding with the well-known method is seasoned.
• Example 4 In an expander provided with a mixing arm, during the expanding process - 100 parts by weight of polystyrene beads are dozed, 15 parts by weight of a solution of the neutralizing preparation are dozed by spraying, with the following composition: 5 parts by weight of FLOVAN CWF® 5 parts by weight of FLOVAN BU® and 5 parts by weight of water, and 0.1 parts by weight of the auxiliary preparation consisting of FLUVAL Nl®.
• the material is dried at a temperature of 85-95°C, cooled to the ambient temperature and seasoned for 24 hours, and then, after a pre-determined homogenization period, all is transferred to the forming element where, after consolidation in the presence of steam, finished material is obtained, modified according to the invention, in the form of a expanded polystyrene block.
• Example 5
• the tightness of the material in block and geometric formats (after cutting) is improved, anisotropy of the medium is reduced, and enhanced are resistance parameters (bending, compressing, tearing), elasticity, shape memory, vibration and noise damping, resistance to depolymerisation in oxygen, ozone and ultraviolet radiation conditions, and stabilisation of lambda coefficient.
• Styrene polymers obtained following the method according to the invention are used, inter alia, for thermal insulation, in thermal insulation partitions, vibroacoustic and hydroinsulation compartments used in construction, means of transport, shields, packaging, insulation of pipelines, etc.

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

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• 2010
  • 2010-01-14 PL PL390189A patent/PL219632B1/pl unknown
• 2011
  • 2011-01-12 WO PCT/PL2011/000003 patent/WO2011087384A1/en active Application Filing
  • 2011-01-12 EP EP11707228A patent/EP2523997A1/en not_active Withdrawn

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