EP0387273A1 - Procede de production de mousses dures a partir de polymerisats d'acryle et/ou de methacryle, sans l'utilisation de fluorocarbones comme agents moussants - Google Patents

Procede de production de mousses dures a partir de polymerisats d'acryle et/ou de methacryle, sans l'utilisation de fluorocarbones comme agents moussants

Info

Publication number
EP0387273A1
EP0387273A1 EP88909748A EP88909748A EP0387273A1 EP 0387273 A1 EP0387273 A1 EP 0387273A1 EP 88909748 A EP88909748 A EP 88909748A EP 88909748 A EP88909748 A EP 88909748A EP 0387273 A1 EP0387273 A1 EP 0387273A1
Authority
EP
European Patent Office
Prior art keywords
weight
foam
mixture
polymerization
acrylic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP88909748A
Other languages
German (de)
English (en)
Inventor
Stefan Meinhardt
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 Forderung der Angewandten Forschung eV
Original Assignee
Fraunhofer Gesellschaft zur Forderung 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 Forderung der Angewandten Forschung eV filed Critical Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Publication of EP0387273A1 publication Critical patent/EP0387273A1/fr
Ceased legal-status Critical Current

Links

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
    • C08J9/06—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 chemical blowing agent
    • C08J9/10—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 chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/102—Azo-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
    • 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
    • C08J9/143—Halogen containing compounds
    • C08J9/147—Halogen containing compounds containing carbon and halogen atoms only
    • 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

Definitions

  • the invention relates to a process for the production of hard foam from acrylic and / or methacrylic poly-merisates by polymerizing and foaming acrylic acid and / or methacrylic acid compounds at elevated temperature in a mold and removing the foams from the mold.
  • the process involves polymerizing the monomers in the presence of a small amount of azobisisobutyronitrile in a first stage at a low temperature of about 40 to 45 ° C. over a period of 6 to 15 hours to give a bubble-free product.
  • the polymerization product obtained is heated at a temperature in the range from 170 ° to 190 ° C. in vacuo.
  • thermosets and elastomers there are three different foaming processes for the production of foamed plastics, which are based on either a chemical, physical or mechanical basis.
  • vaporization pressure of the blowing agent is polymerized at the polymerization temperature to form a plate-shaped body in particular.
  • the body obtained is then foamed in a second stage by heating to a sufficiently high temperature (cf. DE-PS 3 124 980).
  • a sufficiently high temperature cf. DE-PS 3 124 980
  • Inert blowing agents are volatile fluorocarbons such as trichlorofluoromethane and trichlorotrifluoroethane used.
  • volatile hydrofluorocarbons as a blowing agent is increasingly encountering concerns and resistance for environmental reasons.
  • 35 DE-PS 3 001 205 describes a process for the production of foam from methacrylic acid ester.
  • DE-OS 3,412,142 a process for the preparation is lung, of fire-resistant products from Acrylpoly- merisaten described. This process is carried out under positive pressure and both foamed and non-foamed products can be produced. The foamed products obtained in this process have no smooth surfaces.
  • Foams made of acrylic and / or methacrylic polymers are of increasing interest as building materials because they are transparent, i.e. let the light through, but are impermeable to heat. They are particularly well suited as panels, for example for greenhouses. When such foams are used, it is essential that the foams have a smooth surface, so that it is no longer necessary to cover them with glass or plastic plates. If the foams do not have a smooth surface, dirt and moisture can easily penetrate, and the boards become unsightly after a short time. It is also advantageous if the foams obtained have smooth edges so that window frames are no longer required for their processing.
  • the invention has the object of providing a simple process for the production of foams from polyacrylates and poly ethacrylates th to make available to the r without the use of added hydrofluorocarbons as blowing agent manages.
  • a method for. Be provided, according to which a foam can be obtained in a reproducible manner in a short time according to a one-step process.
  • the process should be able to be carried out continuously and discontinuously. The process is said to be difficult
  • REPLACEMENT LEAF flammable foam products can be obtained.
  • the products produced by the process according to the invention should be transparent, with transparency being understood to mean that they have a light transmission of up to 60 to 70%.
  • the products should be hard so that they can be nailed and meltable with a heating wire.
  • the surface should be smooth and non-porous, and • the mechanical strength of the foam should be high.
  • the products produced by the process of this invention are for exterior insulation to protect against cold, rain, etc., insulation materials as the transparent RUER perennial ⁇ , preferably in plate form, in particular for: greenhouses, and are used in the construction sector as skylights.
  • foams can be produced from acrylates and / or methacrylates in a simple manner in a short time if a mixture is used which contains monomeric and oligomeric acrylic and / or methacrylic compounds and N-releasing agents.
  • a mixture which contains monomeric and oligomeric acrylic and / or methacrylic compounds and N-releasing agents.
  • the invention relates to a process for the production of hard foam from acrylic and / or methacrylic polymers by polymerization and foaming of acrylic acid and / or methacrylic acid compounds at elevated temperature and removal of the product from the mold after the polymerization has ended is characterized in that
  • an oligomer mixture from the group consisting of acrylic acid, methacrylic acid, acrylic acid or methacrylic acid-C. -C fi alkyl esters or mixtures thereof, 5 to 20% by weight of flame retardants,
  • N_-releasing catalysts 0.2 to 1.5% by weight of N_-releasing catalysts, , '' 1 to 2% by weight line regulating agent,
  • foam stabilizer or foam regulator 0.5 to 3% by weight of foam stabilizer or foam regulator
  • the invention further relates to the hard foam obtained in the process and its use.
  • the oligomers consist a.us dimers, trimers, etc. up to hexamers and have viscosities ⁇ ranging from 300 cps to 1200 cps, preferably 300 cps to 800 cps. -Preferably preferred. Prepolymers used with viscosities ranging from 300 cps to 350 cps ⁇ .
  • the prepolymer mixtures are crystal-clear liquids. Such mixtures of prepolymers are commercially available.
  • alkyl esters of acrylic and methacrylic acids examples of the alkyl esters of acrylic and methacrylic acids
  • Acid are the .Methyl, ethyl, n-propyl, isopropyl and n-buty esters.
  • the C.-C, esters of acrylic acid and methacrylic acid are preferred.
  • the methacrylic acid methyl ester is particularly preferred because it is easily and cheaply available.
  • the reaction mixture which is polymerized contains 65.5 to 92.7% by weight, preferably 70 to 85% by weight, of oligomers, based on the reaction mixture to be polymerized.
  • the amount which is used in practice will depend on the density and the amount of the fluorocarbon used. If, for example, a foam with a very low density is desired, the amount of oligomer mixture will be in the lower range. It can be determined by the expert by simple preliminary tests.
  • flame retardants for plastics all the products which are commercially available as flame retardants for plastics can be used as flame retardants.
  • Known flame retardants for plastics are: chlorinated paraffins, chlorinated b ⁇ cyclic compounds, pentabro diphenyl ether, tetrabromobi ⁇ phenol A, tetrahalophthalic anhydrides, tris (2,3-dibromopropyl) phosphate (see the overview in Jenker (Plaste Kautschuk 24 (1977), 415 -418) and Kerscher. (Kunst ⁇ Kunststoff-Journal 13 (1979); No. 1, pp. 6-14). Also see organic compounds, phosphorus compounds, organic phosphonic acids,
  • Phosphines and halogenated phosphoric acid esters are suitable as flame retardants for the foam according to the invention (Dang and Wortmann, Kunststoff-Journal 10 (1976), No. 1/2, pp. 8-10).
  • phosphorus-containing flame retardants are particularly preferred for transparent plastics and films, as described by R. Wolf (Kunststoffe 76 (1986), p. 943).
  • Sandotlam 5087 and Fryol CEF (tris ( ⁇ -chloroethyl) phosphate) are particularly preferably used.
  • all flame retardants which give adequate flame protection and do not adversely affect the transparency of the foam obtained can be used.
  • Particularly preferred are those compounds which are recommended for cast polymethacrylate, unsaturated polyesters and polyurethanes which give transparent products.
  • the amount of flame retardant is 5 to 20% by weight and preferably 10 to 15% by weight.
  • mixtures of flame retardants which contain at least two different flame retardants can also be used.
  • catalysts are used as catalysts which split off nitrogen and decompose in the range from 40 ° C. to 70 ° C.
  • a suitable catalyst has, for example, a half-life of 12 hours at 52 ° C. Examples of suitable ca
  • REPLACEMENT LEAF Talisators are the compounds commercially available under the name VAZO ® - such as 2,2'-azobis (2-methylpropannitrile), 2,2'-azobis (2,4-dimethylpentanitrile), 2,2'- Azobi ⁇ - (2-methylbutanenitrile), 1,1'-azobis- (cyclohexane
  • Catalysts which split off 15 N not only cause the reaction mixture to polymerize, but at the same time cause foaming.
  • the catalysts are used in very small quantities and it was not foreseeable that they would cause foaming.
  • line regulating agents are used in the process according to the invention.
  • Such line regulating agents are commercially available.
  • the line regulating agent affects the size
  • silicone polyether which are commercially available and are available for the production of polyurethane foams, are preferably used.
  • the amount 35 is 1 to 2% by weight, preferably 1.5% by weight.
  • the mixture to be polymerized contains 0.5 to 3% by weight, preferably 1 to 2% by weight, of foam stabilizer or foam regulator.
  • foam stabilizers or foam regulators are commercially available. Those which are commercially available for polyurethane foams are preferably used. Examples include silicones modified with polyether. An example of a commercial product is Tegostab 8300, an alkylene oxide modified dimethyl siloxane.
  • Silicone foam stabilizers or foam regulators based on silicone oils are preferably added. These silicone compounds have functional groups, in particular functional acrylic polymers of the following general formulas bonded to a silicone skeleton:
  • X means a carboxy, hydroxyl or epoxy group.
  • polyether silicones which contain functional carboxy or epoxy groups and polyether 1,3-diols such as polyetherols with longer alkyl side chains, polyetherols with aromatic structural units and higher molecular weight polypropylene oxides, provided that that they are compatible with the foams formed from the monomers and oligomers.
  • Polyether silicones copolymers
  • foam stabilizers or foam regulators are commercially available in a variety of ways.
  • crosslinking agents 0.5 to 6% by weight, preferably 1 to 3% by weight, of crosslinking agents are used.
  • Such products are commercially available for the polymerization of acrylic and methacrylic derivatives. Virtually all products that are offered in the trade can be used.
  • An example of a crosslinking agent is Pleximon 786 ' , a trimethylolpropane trimethacrylate.
  • wetting agents which are commercially available for methacrylic acid ethers can be used as wetting agents for acrylate and methacrylate foams. These are non-ionic alkylphenyl ethoxylates. The interfacial activity of such wetting agents is given by the presence of a hydrophilic and hydrophobic portion. The chemical-physical properties and performance characteristics are determined by the ratio of the hydrophilic 'polyglycol ether to the hydrophobic alkylphenol. Different degrees of ethoxylation give rise to products with different properties, which are for different ones. Applications can be used. According to the invention, degrees of ethoxylation between 6 and 9, preferably 8, have proven successful. Virtually all products offered in this way can be used. ' The Lutensol AP brands from BASF are examples of commercial products that can be used. The Lutensol AP brands sell ethoxylation products based on nonylphenol.
  • the mixture of the above constituents can additionally contain up to 3 parts by weight, preferably up to 1 part by weight, based on 100 parts by weight of the above reaction mixture, customary additives such as dyes, UV Stabilizers etc. included. All of the above components are weighed in the required amounts and placed in a tank. There they are mixed well.
  • the mixture can additionally contain up to 3 parts by weight, preferably up to 1 part by weight, based on 100 parts by weight of the above reaction mixture, customary additives such as dyes, UV Stabilizers etc. included. All of the above components are weighed in the required amounts and placed in a tank. There they are mixed well.
  • the mixture of the above constituents can additionally contain up to 3 parts by weight, preferably up to 1 part by weight, based on 100 parts by weight of the above reaction mixture, customary additives such as dyes, UV Stabilizers etc. included. All of the above components are weighed in the required amounts and placed in a tank. There they are mixed well.
  • the mixture can additionally contain up to
  • a TZBLATT 11 is heated, for example passed through a heating tube, and preheated to a temperature in the range from 30 to 45 ° C., preferably 40 ° C., and brought into the mold.
  • the mixture may discontinuously in a predetermined amount into molds, preferably closed molds, were ⁇ passed the or 'can ⁇ continuously on a tape a ⁇ s such, which is in the form of a mold or onto a mold on a tape in a specific metered amount be brought up.
  • the mold is preferably provided with a lid '.
  • the mixture is at. a temperature in the range of '50 ° C. kept up to 70 ° C. At this temperature, polymerization and foaming take place simultaneously.
  • the temperature is measured continuously, and since the reaction is exothermic, it is generally not necessary to continue heating. In the process according to the invention, care must be taken to ensure that a temperature of 80 ° C. is not exceeded, since there is then a risk that the foam formed will become cloudy. Cooling must be achieved at the latest when 80 ° C. is reached, preferably already at 70 ° C. In a preferred embodiment of the invention, the mold into which the reaction mixture is passed is preheated to the same temperature to which the reaction mixture is preheated.
  • the process according to the invention can be carried out continuously and batchwise.
  • a 'particular be ⁇ ferred embodiment of the method according to the invention is its continuous operation.
  • the reaction mixture is passed freely from the container through a heating pipe onto a conveyor belt. It is particularly noteworthy and advantageous that the process according to the invention is carried out under atmospheric pressure and that it is not necessary to work under excess pressure.
  • the polymerization and foaming are complete within a period of 20 to 60 minutes, normally up to 30 minutes.
  • the product obtained is cooled in air and removed from the mold.
  • the products obtained in the process according to the invention have a smooth surface, they are hard and can be nailed, for example. They have a density in the range of 50 to 100 g / 1, preferably 80 g / 1.
  • the pore size is within a relatively large range and can be in the range from 1 to 8 mm, preferably in the range from 3 to 5 mm. If the foams Erfin dung produced in accordance with thermal insulation comparable • applies, the pore size is not a major - role - because the insulation does not depend on the size of the pores ⁇ and the differences in the thermal insulation of large and small cells are relatively low. However, the larger the cells are, the better the light permeability, ie the transparency, and the lower the weight of the room.
  • the size of the pores can be regulated by the amount of foam regulating agent, the amount of blowing agent and the amount of mass which is added to the mold, and the appropriate amounts can easily be determined on the basis of preliminary tests.
  • the products obtained have a high light transmission and a smooth, pore-free surface. Such products could not be produced by any of the known processes.
  • ATZBLATT alkylene oxide-modified dimethylsiloxane which is commercially available under the name Tegostab 8300, - as a line regulating agent, 0.5 part by weight of silicone acrylate, which is commercially available under the name RC 710, as a stabilizer, 0.5 part by weight
  • nonionic wetting agent based on nonylphenol with 8 ethylene oxide units, which is commercially available under the name Lutensol AP 8-, as wetting agent and 0.5 part by weight of polyglycol-400-dimethacrylate and 1 part by weight.
  • the mixture is preheated to 3.5 ° C in a mixing container and heated via a. Supply line on a revolving endless conveyor belt
  • the mixture is heated to a temperature of 60 ° C to 70 ° C. At this temperature, the reaction mixture foams and polymerizes. The temperature is continuously measured using temperature sensors. The polymerization and foaming are completed in about 20 minutes. You get a good
  • plates 30 are cut off after 1 m, plates 30 x 100 cm can be produced. According to Example 1, plates with a thickness of 10 mm are produced.
  • ER ⁇ of the methacrylic acid methyl ester which is commercially available from Degussa under the name DEGALAN S 340, are mixed with 5 parts by weight of chlorinated alkyl phosphate, a flame retardant (Fryol F 2; Stauffer Chemical Corp.) and 7 parts by weight of phosphorinane (Sandotlam 5087), a flame retardant, mixed well.
  • a flame retardant Fluor F 2; Stauffer Chemical Corp.
  • phosphorinane Sandotlam 5087
  • alkyleno 'xidmod es dimethylsiloxane under the name Tegostab 8300 commercially as Zeilreguliersch 0.8 parts by weight of silicone acrylate
  • the un ⁇ ter called RC 705 is commercially available, as a stabilizer, 0 , 5 parts by weight of nonionic wetting agent based on Nonylpheno.l with 8 ethylene oxide units, which is commercially available under the name Lutensol AP 8, as a wetting agent and 1 part by weight of trimethoxysilane, which is available under the name GF 31 , added as a crosslinking agent.
  • Example 1 was repeated, but a mold with a height of 15 was now used. It was found that temperatures of 70 ° C. were obtained during the polymerization. The belt was therefore cooled in such a way that it did not exceed 75 ° C. The polymerization. was finished nac '30 minutes.
  • a coarser foam is obtained than in Example 1 with a medium-fine cell structure.
  • the polymerization and foaming time is about 15 minutes.
  • the catalyst is added.
  • the catalyst is commercially available under the name Vazo 52.
  • Vazo 52 for this purpose, 2.0 parts by weight of alkylene oxide-modified dimethylsiloxane, which is commercially available under the name Tegostab 8300, are used as cell regulating agents, 0.8 parts by weight of silicon acrylate, which is
  • Drawing RC 710 is commercially available, as a stabilizer, 2.0 parts by weight of nonionic wetting agent based on nonylphenol with 8 ethylene oxide units, which is on the market.
  • Drawing Lutensol AP 8 as wetting agent and 1 , 0 parts by weight of polyglycol-400-dimethacrylate and 1.5 parts by weight - • 15 parts of ' trimethoxysilane, which is commercially available under the name GF 31, are given as crosslinking agents.
  • Example 2 The procedure is as described in Example 1. A coarse structured foam with a density of 20 • 80 g / 1 is obtained. This foam has a very stable outer skin. The polymerization and foaming is completed in 15 minutes.

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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)
  • General Chemical & Material Sciences (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

Selon un procédé de production de mousses dures à partir de polymérisats d'acryle et/ou de méthacryle par polymérisation et moussage de composés d'acide acrylique et/ou d'acide méthacrylique à des températures élevées, on provoque la polymérisation et la formation d'une mousse dans un moule à partir d'un mélange d'oligomères, avec un agent ignifuge, et un catalyseur de clivage d'azote, un régulateur des pores, un stabilisateur ou régulateur de la mousse, un agent de réticulation et un agent mouillant pendant une durée comprise entre 20 et 60 minutes.
EP88909748A 1987-11-13 1988-11-04 Procede de production de mousses dures a partir de polymerisats d'acryle et/ou de methacryle, sans l'utilisation de fluorocarbones comme agents moussants Ceased EP0387273A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3738624 1987-11-13
DE3738624 1987-11-13

Publications (1)

Publication Number Publication Date
EP0387273A1 true EP0387273A1 (fr) 1990-09-19

Family

ID=6340463

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88909748A Ceased EP0387273A1 (fr) 1987-11-13 1988-11-04 Procede de production de mousses dures a partir de polymerisats d'acryle et/ou de methacryle, sans l'utilisation de fluorocarbones comme agents moussants

Country Status (6)

Country Link
US (1) US5026738A (fr)
EP (1) EP0387273A1 (fr)
JP (1) JPH03503059A (fr)
AU (1) AU2786789A (fr)
IL (1) IL88245A0 (fr)
WO (2) WO1989004342A1 (fr)

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US5399593A (en) * 1993-10-14 1995-03-21 Edwards; Bill R. Acrylic/lactam resin compositions and method of producing same
DE4344224A1 (de) * 1993-12-23 1995-06-29 Stockhausen Chem Fab Gmbh Vernetzte synthetische Polymerisate mit poröser Struktur, hoher Aufnahmegeschwindigkeit für Wasser, wäßrige Lösungen und Körperflüssigkeiten, ein Verfahren zu ihrer Herstellung und ihre Verwendung zur Absorption und/oder Retention von Wasser und/oder wäßrigen Flüssigkeiten
EP1364985A1 (fr) * 1994-12-08 2003-11-26 Nippon Shokubai Co., Ltd. Résine absorbant l'eau, son procédé de production et composition de résine absorbant l'eau
US5605717A (en) * 1995-06-01 1997-02-25 Morgan Adhesives Company Process for foaming an adhesive using moisture in a backing
US6960619B2 (en) * 2003-03-06 2005-11-01 Acryfoam Ltd. Foamable photo-polymerized composition
EP3365385B1 (fr) * 2015-10-20 2019-12-11 Basf Se Système et procédé de fabrication d'une mousse moulée sur place

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Also Published As

Publication number Publication date
IL88245A0 (en) 1989-06-30
WO1989004343A1 (fr) 1989-05-18
US5026738A (en) 1991-06-25
AU2786789A (en) 1989-06-01
JPH03503059A (ja) 1991-07-11
WO1989004342A1 (fr) 1989-05-18

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