EP0236353A1 - Verfahren zur herstellung von geschäumten kunststoffen - Google Patents
Verfahren zur herstellung von geschäumten kunststoffenInfo
- Publication number
- EP0236353A1 EP0236353A1 EP19860904821 EP86904821A EP0236353A1 EP 0236353 A1 EP0236353 A1 EP 0236353A1 EP 19860904821 EP19860904821 EP 19860904821 EP 86904821 A EP86904821 A EP 86904821A EP 0236353 A1 EP0236353 A1 EP 0236353A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- component
- starting mixture
- monomeric
- oligomeric
- foamed
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 21
- 229920003023 plastic Polymers 0.000 title claims abstract description 6
- 239000004033 plastic Substances 0.000 title claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000000203 mixture Substances 0.000 claims abstract description 25
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 17
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 14
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 7
- 230000005855 radiation Effects 0.000 claims abstract description 7
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 4
- 125000003282 alkyl amino group Chemical group 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 3
- 150000003573 thiols Chemical group 0.000 claims abstract description 3
- 239000004604 Blowing Agent Substances 0.000 claims description 16
- 229920000642 polymer Polymers 0.000 claims description 8
- 229920002554 vinyl polymer Polymers 0.000 claims description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 7
- 238000005187 foaming Methods 0.000 claims description 5
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims description 4
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 4
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 claims description 4
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 239000000975 dye Substances 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- -1 hydroxyalkyl acrylates Chemical class 0.000 claims description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- IEVADDDOVGMCSI-UHFFFAOYSA-N 2-hydroxybutyl 2-methylprop-2-enoate Chemical compound CCC(O)COC(=O)C(C)=C IEVADDDOVGMCSI-UHFFFAOYSA-N 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004640 Melamine resin Substances 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- AQYSYJUIMQTRMV-UHFFFAOYSA-N hypofluorous acid Chemical compound FO AQYSYJUIMQTRMV-UHFFFAOYSA-N 0.000 claims description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- 150000003077 polyols Chemical class 0.000 claims description 2
- 239000000178 monomer Substances 0.000 abstract description 3
- 239000000470 constituent Substances 0.000 abstract 3
- 239000004088 foaming agent Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 8
- 239000003431 cross linking reagent Substances 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003380 propellant Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- DDMOUSALMHHKOS-UHFFFAOYSA-N 1,2-dichloro-1,1,2,2-tetrafluoroethane Chemical compound FC(F)(Cl)C(F)(F)Cl DDMOUSALMHHKOS-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 description 1
- 206010073306 Exposure to radiation Diseases 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 125000003396 thiol group Chemical class [H]S* 0.000 description 1
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
Definitions
- the invention relates to a process for the production of ge foamed plastics, in which a starting mixture of monomeric, oligomeric or polymeric compounds "polymerized with vinyl grouping in the presence of a blowing agent and a catalyst and then foamed by irradiation.
- a process for the manufacture of articles from polymethyl methacrylate in which a mixture of methyl methacrylate monomer, preferably liquid blowing agent and catalyst is polymerized to a solid body containing blowing agent in a first stage. This is carried out in a second stage foamed by heating to the softening temperature of the plastic, for example by means of microwaves.
- the acrylate polymers produced in this way are very difficult to foam with microwaves. In a commercially available microwave oven, the known material only begins after about 30 minutes to become soft and to inflate very slowly.
- GB-PS 1 348 552 describes a method for producing foams in which compounds containing vinyl groups are polymerized in the presence of a blowing agent, a catalyst and additionally a crosslinking agent.
- the polymers are foamed using radio waves of approximately 27 MHz. It is particularly pointed out that a crosslinking agent is necessary in order to be able to obtain a foamed material. If microwave radiation is used instead of radio waves in this process, no satisfactory results are obtained either. If the addition of crosslinking agents is dispensed with, the result is products which are too soft and are not stable foams.
- the present invention is based on the object of specifying a method with which the products can be fully foamed in a maximum of 5 minutes without the addition of crosslinking agents.
- the starting mixture is composed of at least three components, which consist of a component A of monomeric methyl methacrylate and / or styrene, optionally with a proportion of prepolymerized methyl methacrylate and / or styrene, of a component B consists of monomeric or oligomeric compounds containing a vinyl grouping and microwave-sensitive groups and a component C consists of monomeric, oligomeric or polymeric compounds containing microwave-sensitive groups without vinyl grouping, components B and C containing hydroxyl, thiol , Alkylamino- with 1 to 6 carbon atoms, amino or carboxyl groups are substituted, and that foaming by microwave radiation lung is brought about.
- a component A of monomeric methyl methacrylate and / or styrene optionally with a proportion of prepolymerized methyl methacrylate and / or styrene
- a component B consists of monomeric or oligomeric compounds containing a vinyl group
- the starting mixture has a special composition.
- the mixture component is methyl methacrylate and / or styrene. Some of these compounds can also be present in prepolymerized form.
- the amount of component A in the starting mixture is 50 to 95% by weight, preferably 70 to 8% by weight, based on the total weight of the starting mixture, i.e. without taking into account the proportions of blowing agent, catalyst and fillers or dyes that may also be present.
- the mixture components B and C can be monomeric, oligomeric or polymeric compounds and contain groups which are easily excitable by microwaves. Such groups are hydroxyl, thiol, alkylamino, amino or carboxyl groups.
- Component B furthermore has at least one vinyl grouping, while component C is free of vinyl groupings. It is also essential that the main part of the starting mixture forms methyl methacrylate and or styrene.
- the amount of component B i of the starting mixture is 5 to 50% by weight, preferably 10 to 2% by weight. -%, based on the total weight of the starting mixture.
- the amount of component C is 1 to 20% by weight. preferably 2 to 7% by weight, based on the total weight of the starting mixture.
- Hydroxyalkyl acrylates or methacrylates and / or hydroxyalkenes are preferably used as component B. Hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxybutyl acrylate, hydroxybutyl ethacrylate and allyl alcohol are particularly suitable fetch As component C, for example, hydroxyl-containing silicones, polyesters, ie polyols, melamine resin or urea precondensates are used. Particularly good results are achieved with silicones. Bisphenol A, nonylphenol, decanol and perfluoroalcohol are also suitable.
- Solid blowing agents can be used, which decompose when the temperature rises and thereby release the expanding gases.
- Liquid blowing agents are preferably used which have a boiling point of max. 100 ° C., preferably 50 ° C., evaporate when the temperature of the material rises and thereby inflate the material.
- the products contain 5 to 60 units. -%, preferably 40 to 50 wt. -% blowing agent, based on the total remaining portions in the reaction mixture. Frigen 1 and a mixture of Frigen 11 and Frigen 114 are preferably used.
- a conventional peroxide catalyst can be used as the polymerization initiator, which is effective when heated. If, for the purpose of polymerization, the reaction mixture has to be heated to a temperature above the evaporation temperature of the blowing agent, the polymerization can be carried out under pressure in order to prevent the blowing agent from being released prematurely.
- a photoinitiator is preferably used as the polymerization catalyst, which makes it possible to polymerize the mixture at low temperature, in particular at about room temperature, by exposure to radiation matched to a photoinitiator known for acrylate monomer, for example UV light of a wavelength of 350 nm.
- the polymerization can be controlled by switching the radiation sources on and off or by external cooling so that the temperature in the mass to be polymerized does not rise above a certain value in the course of the exothermic polymerization reaction which is below the evaporation temperature of the liquid blowing agent.
- fillers and / or dyes can be provided in the starting mixture, which can be selected depending on the area of use of the foamed product.
- An already polymerized, propellant-containing product can be stored as an intermediate product if it is not immediately fed into the second process stage, in which it is foamed by microwave radiation of approximately 2000 to 3000 MHz.
- the method according to the invention enables the products to be foamed by means of microwaves in a maximum of 5 minutes. Most of the products are fully foamed after only 2 minutes.
- non-substituted monomeric or prepolymeric vinyl compounds i.e. Methyl methacrylate and / or styrene, fast foaming products are thus obtained which also have well-formed pores.
- the foamed polymers according to the invention can also be transparent and in the form of sheets, sheets, moldings and multilayer bodies with a foam core.
- blowing agent Frigen 11
- the resulting blowing agent-containing polymer is then foamed by heating by means of high frequency in a commercially available microwave oven (2450 MHz, 720 W output power). The process of exhaustion was over after a minute.
- Example 1 The procedure of Example 1 is repeated using 4 parts of methyl methacrylate, 0.55 part of hydroxybutyl acrylate, 0.45 part of silicone, 0.05 part of nonylphenol, 0.03 part of UV polymerization initiator and 2.5 parts of blowing agent (Frigen 11) become. The polymer was fully foamed after about 2 minutes.
- Example 1 The procedure of Example 1 is repeated, except that 2.5 parts of methyl methacrylate, 1 part of styrene, 1 part of hydroxybutyl methacrylate, 0.25 part of nonylphenol, 0.25 part of bisphenol ⁇ , 0.07 part of UV polymerization initiator and 2 , 5 parts of blowing agent can be used.
- the duration of the foaming process using microwave radiation was less than 2 minutes.
Landscapes
- 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)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3532347 | 1985-09-11 | ||
| DE19853532347 DE3532347A1 (de) | 1985-09-11 | 1985-09-11 | Verfahren zur herstellung von geschaeumten kunststoffen |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0236353A1 true EP0236353A1 (de) | 1987-09-16 |
Family
ID=6280629
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19860904821 Pending EP0236353A1 (de) | 1985-09-11 | 1986-08-08 | Verfahren zur herstellung von geschäumten kunststoffen |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0236353A1 (enrdf_load_stackoverflow) |
| DE (1) | DE3532347A1 (enrdf_load_stackoverflow) |
| WO (1) | WO1987001710A1 (enrdf_load_stackoverflow) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3842305A1 (de) | 1988-12-16 | 1990-06-21 | Basf Ag | Verfahren zur herstellung von styrolpolymerisat-schaumstoffpartikeln |
| US5700844A (en) * | 1996-04-09 | 1997-12-23 | International Business Machines Corporation | Process for making a foamed polymer |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3432413A (en) * | 1964-11-02 | 1969-03-11 | Dow Chemical Co | Method for carrying out chemical reactions using microwave energy |
| GB1348552A (en) * | 1971-06-01 | 1974-03-20 | Dow Chemical Co | Composite sheet |
| US3923705A (en) * | 1974-10-30 | 1975-12-02 | Dow Corning | Method of preparing fire retardant siloxane foams and foams prepared therefrom |
| US4352854A (en) * | 1980-03-28 | 1982-10-05 | Phillips Petroleum Company | Molded sponge-like thermoplastic elastomer articles having thin, dense skins and a process for their production |
| DE3124980C1 (de) * | 1981-06-25 | 1987-07-09 | Fa. August Hohnholz, 2000 Hamburg | Verfahren zum Herstellen von Gegenständen aus geschäumtem Polymethylmethacrylat |
-
1985
- 1985-09-11 DE DE19853532347 patent/DE3532347A1/de active Granted
-
1986
- 1986-08-08 EP EP19860904821 patent/EP0236353A1/de active Pending
- 1986-08-08 WO PCT/EP1986/000471 patent/WO1987001710A1/de unknown
Non-Patent Citations (1)
| Title |
|---|
| See references of WO8701710A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3532347C2 (enrdf_load_stackoverflow) | 1989-03-02 |
| DE3532347A1 (de) | 1987-03-12 |
| WO1987001710A1 (en) | 1987-03-26 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE FR GB IT LI LU NL SE |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
| RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: WOLLMANN, KLAUS Inventor name: GUDJONS, JUERGEN Inventor name: GLINK, GERHARD |