EP2981403A1 - Procédé de production en continu de mousse de polyméthacrylimide - Google Patents

Procédé de production en continu de mousse de polyméthacrylimide

Info

Publication number
EP2981403A1
EP2981403A1 EP14713047.0A EP14713047A EP2981403A1 EP 2981403 A1 EP2981403 A1 EP 2981403A1 EP 14713047 A EP14713047 A EP 14713047A EP 2981403 A1 EP2981403 A1 EP 2981403A1
Authority
EP
European Patent Office
Prior art keywords
blocks
pmi
foam
nir
foaming
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Withdrawn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
EP14713047.0A
Other languages
German (de)
English (en)
Inventor
Florian Becker
Wilfried Heberer
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.)
Roehm GmbH Darmstadt
Original Assignee
Evonik Roehm 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 Evonik Roehm GmbH filed Critical Evonik Roehm GmbH
Publication of EP2981403A1 publication Critical patent/EP2981403A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/20—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of indefinite length
    • B29C44/26—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of indefinite length using several expanding steps
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/3415—Heating or cooling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
    • B29C2035/0822—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using IR radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2033/00—Use of polymers of unsaturated acids or derivatives thereof as moulding material
    • B29K2033/26—Polymers of acrylamide or methacrylamide
    • 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
    • C08J2333/00—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/24—Homopolymers or copolymers of amides or imides

Definitions

  • the present invention relates to a novel process for the continuous production of PMI foam blocks.
  • this method has a high flexibility in terms of the size of the blocks.
  • individual prepolymerized PMI blocks are first, preferably by means of
  • the PMI foam foams continuously while passing through this station.
  • the PMI foam ends up as a continuous material and can be cut or sawn into individual pieces of any length and shape.
  • the advantage of this process beyond the continuous procedure is that the PMI foam material is almost stress-free and has a very uniform, closed-cell pore structure. This is accompanied by a uniform density distribution over the block thickness, since the foaming process does not progress from the outside to the center of the block, but evenly
  • DE 1 817 156 already describes a process by which foamable plastics are produced in sheet form by mixing mixtures of methacrylonitrile and methacrylic acid between two glass plates, which are sealed with a flexible cord, polymerized.
  • a blowing agent namely formamide or monoalkylformamide
  • free-radical generators are present, for example as a two-component mixture of tert-butyl perpivalate and benzoyl peroxide.
  • the foaming of the individual plates is carried out thermally in a heating oven at a temperature between 170 and 300 ° C. It is difficult to make the polymerization uniform because the temperature can very easily exceed the target temperature. Temperature fluctuations must therefore be controlled very precisely and compensated for by alternating cooling or warm-up phases. This usually leads to irregular pores and to
  • EP 1 175 458 describes the production of thick blocks in isothermal mode. This is achieved by using at least four
  • the initiator described at the highest temperature has a half-life of 1 h at 1 15 ° C to 125 ° C and acts mainly in a final annealing, but not during foaming.
  • This method also includes batch-wise foaming in an oven.
  • thicker material thicknesses can be foamed with this method, but since the foaming takes place from the outside to the inside, an insulating layer is formed on the surface which slows down the heating of the block center and, in the case of very thick blocks, also leads to an irregular pore structure and to stresses in the Material leads.
  • DE 3 630 930 (Röhm GmbH) describes another process for foaming the abovementioned copolymer plates of methacrylic acid and methacrylonitrile. In this case, the plates are made to foam with the aid of a microwave field.
  • the plate to be foamed, or at least its surface must first be heated to or above the softening point of the material. Since, under these conditions, of course, the foaming of the softened by the external heating material used, the foaming process alone by the influence of a microwave field is not controllable, but must by a accompanying heating be controlled from the outside. Thus, a microwave field is added to the normal single-stage hot air process to accelerate the foaming. However, the microwave method has proved to be too complicated and therefore not relevant to practice and is still not used.
  • Residual stress of the foam block is avoided by tempering the foam. Furthermore, the process should be simple, energy-saving and feasible without large investments. The method should also be adaptable so that comparable results can be achieved with different material properties and strengths. Other, not explicitly discussed at this point, may be further from the prior art, the description, the claims or
  • the described objects are achieved by a novel method for foaming P (M) I blocks in which P (M) I blocks are irradiated by irradiation with NIR radiation a wavelength between 0.78 and 1, 40 ⁇ are foamed in an infrared heater, solved.
  • PMI polymethacrylimides
  • PI polyacrylimides
  • NIR radiation so-called near infrared radiation is called.
  • PMI blocks are preferred according to the invention over P1 blocks.
  • Such PMI foams are normally prepared in a two-step process: e.g. Production of a cast polymer and foaming of this cast polymer. The present invention relates to this foaming of the cast polymer, wherein the invention does not
  • Cast polymers is to be understood limited, but also applicable to alternative production methods of P (M) I blocks.
  • monomer mixtures which contain (meth) acrylic acid and (meth) acrylonitrile, preferably in a molar ratio of between 2: 3 and 3: 2, as main constituents, are first prepared.
  • other comonomers may be used, such as e.g. Esters of acrylic or methacrylic acid, styrene, maleic acid or itaconic acid or their anhydrides or vinylpyrrolidone.
  • the proportion of the comonomers should not be more than 30% by weight.
  • Small amounts of crosslinking monomers, e.g. Allyl acrylate can also be used. However, the amounts should preferably be at most 0.05% by weight to 2.0% by weight.
  • the mixture for the copolymerization further contains blowing agents which are in
  • IR-A radiation ie radiation in the short-wave range of NIR radiation is used.
  • This radiation has a wavelength between 0.78 and 1.40 ⁇ .
  • P (M) I blocks are preferably connected to each other before the irradiation with said NIR radiation.
  • the irradiation with the NIR radiation then preferably takes place in one
  • the frontal interconnection of the P (M) I blocks takes place by means of mirror welding.
  • the method according to the invention preferably comprises the following process steps: a) mirror welding for connecting the end faces of P (M) I blocks, b) transferring the PMI blocks into an infrared heating station, in particular the transfer takes place continuously,
  • process step e) optional further cooling and removal of the finished block product.
  • the cooling of the foamed block product is preferably carried out in process step c1). Alternatively, however, it is also possible to completely cool only in process step e) or to cool it down to a slightly elevated temperature in process step c1) and finally to a removal temperature in process step e).
  • the intensity distribution of the NIR radiation in the infrared heating station is selected such that in the middle of the P (M) l block the highest radiation intensity is achieved.
  • This can be realized by means of individual controllable / controllable infrared emitters in the infrared heating station. This is a locally different
  • step e) it is possible to pass through a heating furnace between process step c) and process step d) in which the PMI foam is tempered.
  • This stove can also be equipped with NIR lamps. In general, however, it is a conventional heater, without radiation source. In such a variant, in particular, the cooling step in step e), regardless of whether the optional
  • Process step c1) has been carried out or not.
  • the damage to the subsequent hard foam surface to be observed does not occur if the present method is carried out properly.
  • the thermal radiation of the NIR spectral range used penetrates the gas phase of the forming foam cells without absorption and causes a direct heating of the P (M) I also in the forming cell wall matrix.
  • the inventive method is to perform low cycle times, economical and environmentally friendly. Due to the heating which can be carried out relatively quickly with the radiation mentioned and in particular with suitable temperature and intensity distribution of the NIR-stripping that can be deduced to the person skilled in the art with little effort, a stress-free, uniform heat distribution is achieved in the entire workpiece.
  • the intensity of the radiation can be varied in the range mentioned, depending on the P (M) I used, in particular as a function of the material thickness used.
  • the individual P (M) I foam blocks can be singulated before being transferred to the forming tool by means of a horizontal saw cut to tableware.
  • Cover layers for example made of fiber-reinforced thermoplastics or resins.
  • the P (M) I foam blocks, or panels made therefrom, may be partially compacted or into one
  • closed hollow sections can also be produced from two such P (M) l foam formats.
  • the forming tool is equipped with NIR heating technology.
  • NIR heating technology Such a shaping can be described in detail in the provisional application US 61 / 675,011 1
  • P (M) l foam materials produced by the process of the invention are also part of the present invention.
  • These P (M) l foam materials are distinguished from corresponding materials according to the prior art in that they are very uniform Pore structure at the same time have a lower thermal load, for example in relation to a yellowing.
  • the P (M) I foams produced according to the invention can be used very widely.
  • application areas are in particular automotive engineering - for example in the body shop or interior linings - air and
  • the PMI foam material produced according to the invention may additionally contain fire-protection additives, colorants, inorganic fillers and / or process additives.
  • fire-protection additives for example, fire-protection additives, colorants, inorganic fillers and / or process additives.
  • PMI block polymer in this case ROHACELL RIMA, was continuously foamed in a thickness of 33 mm in a heating section equipped with NIR lamps at a throughput speed of 5 cm / min.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)
  • Perforating, Stamping-Out Or Severing By Means Other Than Cutting (AREA)
  • Shaping Of Tube Ends By Bending Or Straightening (AREA)

Abstract

La présente invention concerne un procédé de production en continu de blocs de mousse de polyméthacrylimide (PMI) qui permet une grande flexibilité en termes de taille des blocs. Pour cela, on commence par assembler par leurs faces avant des blocs de PMI individuels prépolymérisés, de préférence par soudage en bout au moyen de réflecteurs, puis on les introduit dans un poste de chauffage fonctionnant dans le proche infrarouge où le polymère de PMI est expansé en continu à mesure qu'il traverse ce poste. La mousse de PMI sort à l'extrémité sous la forme d'une bande continue de matériau qui peut être découpée ou sciée pour obtenir des morceaux individuels de longueur et de forme quelconques. L'avantage de ce procédé par rapport au mode opératoire en continu est que le matériau en PMI expansé est pratiquement exempt de contraintes et qu'il possède une structure poreuse à cellules fermées très homogène. Ceci s'accompagne d'une distribution homogène de la densité sur l'épaisseur du bloc car le processus d'expansion ne progresse pas de l'extérieur jusqu'au centre du bloc, au contraire le polymère subit une augmentation de volume homogène.
EP14713047.0A 2013-04-04 2014-03-12 Procédé de production en continu de mousse de polyméthacrylimide Withdrawn EP2981403A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102013205963.9A DE102013205963A1 (de) 2013-04-04 2013-04-04 Verfahren zur kontinuierlichen PMI-Schaumfertigung
PCT/EP2014/054848 WO2014161707A1 (fr) 2013-04-04 2014-03-12 Procédé de production en continu de mousse de polyméthacrylimide

Publications (1)

Publication Number Publication Date
EP2981403A1 true EP2981403A1 (fr) 2016-02-10

Family

ID=50389398

Family Applications (1)

Application Number Title Priority Date Filing Date
EP14713047.0A Withdrawn EP2981403A1 (fr) 2013-04-04 2014-03-12 Procédé de production en continu de mousse de polyméthacrylimide

Country Status (11)

Country Link
US (1) US20160039986A1 (fr)
EP (1) EP2981403A1 (fr)
JP (1) JP2016520447A (fr)
KR (1) KR20150139512A (fr)
CN (1) CN105073371A (fr)
BR (1) BR112015024584A2 (fr)
DE (1) DE102013205963A1 (fr)
RU (1) RU2015147264A (fr)
SG (1) SG11201508268TA (fr)
TW (1) TW201504285A (fr)
WO (1) WO2014161707A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102013225132A1 (de) * 2013-12-06 2015-06-11 Evonik Industries Ag Vorschäumung von Poly(meth)acrylimid-Partikeln für das anschließende Formschäumen in geschlossenen Werkzeugen
CN112873353A (zh) 2014-11-18 2021-06-01 赢创运营有限公司 厚硬质泡沫板的切割
EP3911489A1 (fr) 2019-01-16 2021-11-24 Evonik Operations GmbH Nouveau procédé de moussage pour la production de matériaux en mousse
AU2021371895A1 (en) 2020-10-29 2023-06-22 Evonik Operations Gmbh Process for producing foam panels for the production of foam films

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3304882A1 (de) * 1983-02-12 1984-08-16 Röhm GmbH, 6100 Darmstadt Verfahren zur herstellung eines schaumstoffverbundkoerpers
DE3630930A1 (de) 1986-09-11 1988-03-24 Roehm Gmbh Verfahren zur herstellung eines hartschaumstoffes mittels eines mikrowellen- oder hochfrequenzfeldes
DE4036052C2 (de) * 1990-11-13 1997-05-07 Roehm Gmbh Verfahren zur Verminderung von Spannungen in Schaumstoffblöcken aus Polymethacrylimid
US5338765A (en) * 1993-11-23 1994-08-16 Schuller International, Inc. Method of and apparatus for continuously foaming a polyimide powder
DE19917987A1 (de) 1999-04-21 2000-10-26 Roehm Gmbh Verfahren zur Herstellung von blockförmigen Polymethacrylimidschaumstoffen
DE10141757A1 (de) 2001-08-29 2003-03-27 Roehm Gmbh Verbessertes Verfahren zur Herstellung von PMI-Schäumen
DE10350971A1 (de) 2003-10-30 2005-06-02 Röhm GmbH & Co. KG Wärmeformbeständige Polymethacrylimid-Schaumstoffe mit feinen Poren
JP2009013397A (ja) * 2007-06-04 2009-01-22 Nitto Denko Corp 熱可塑性樹脂発泡体、およびその製造方法
DE102010028695A1 (de) 2010-05-06 2011-11-10 Evonik Röhm Gmbh Polymethacrylimid-Schaumstoffe mit verminderter Entflammbarkeit sowie Verfahren zur Herstellung dieser
DE102010021120A1 (de) * 2010-05-19 2011-11-24 Faurecia Innenraum Systeme Gmbh Verfahren zum Herstellen eines Dekors auf einer Sichtseite eines Kunststoffteils sowie Kunststoffteil mit einem Dekor

Non-Patent Citations (1)

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Title
See references of WO2014161707A1 *

Also Published As

Publication number Publication date
JP2016520447A (ja) 2016-07-14
BR112015024584A2 (pt) 2017-07-18
WO2014161707A1 (fr) 2014-10-09
RU2015147264A (ru) 2017-05-16
US20160039986A1 (en) 2016-02-11
SG11201508268TA (en) 2015-11-27
KR20150139512A (ko) 2015-12-11
TW201504285A (zh) 2015-02-01
CN105073371A (zh) 2015-11-18
DE102013205963A1 (de) 2014-10-09

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