WO1998023670A1 - Cavity containing moulded bodies made of thermoplastic moulding material - Google Patents
Cavity containing moulded bodies made of thermoplastic moulding material Download PDFInfo
- Publication number
- WO1998023670A1 WO1998023670A1 PCT/EP1997/006115 EP9706115W WO9823670A1 WO 1998023670 A1 WO1998023670 A1 WO 1998023670A1 EP 9706115 W EP9706115 W EP 9706115W WO 9823670 A1 WO9823670 A1 WO 9823670A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- thermoplastic molding
- molding compositions
- tert
- cavities
- alkyl
- Prior art date
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
- C08J9/02—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by the reacting monomers or modifying agents during the preparation or modification of macromolecules
-
- 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
- C08F8/00—Chemical modification by after-treatment
Definitions
- the invention relates to moldings containing cavities, obtainable from thermoplastic molding compositions which contain one or more compounds which are gaseous at elevated temperature or split off gaseous constituents.
- the invention relates to a process for the production of moldings containing cavities and their use for the production of office, household and sanitary articles, furniture and furniture elements as well as interior design components and design objects.
- Shaped bodies containing bubbles or pores are used, for example, as components of worktops because of their specific material properties and their characteristic aesthetic effects.
- EP-A 503 156 describes a process for the production of plastic moldings from a water-expanded polymer resin, in which the moldings obtained after the manufacturing process have essentially closed pores, the size of which is below 50 ⁇ m on average. These moldings are obtained by subjecting a curable mixture, the resin-forming component of which, in defined weight ratios, comprises a monomer component and an acrylate prepolymer based on acrylate, to a mass polyreaction as a water-in-oil emulsion. Because of the
- the reaction temperature is usually below 50 ° C.
- a disadvantage of the process according to EP 503 156 is that, due to the process, only a small number of components can be used in the selection of the molding compositions which are suitable for the shaped body. An additional drying step is also required to remove the water trapped in the pores. Another disadvantage is that the pore size can only be adjusted over a small range and that no transparent moldings are obtained.
- the invention was therefore based on the object of making molded articles made of thermoplastic molding materials accessible, in which cavities can be installed in a controlled manner using conventional processing conditions without additional process steps or special process parameters are required.
- thermoplastic molding compositions Accordingly, the molded articles defined at the outset were found from thermoplastic molding compositions.
- Shaped bodies made of thermoplastic molding compositions are preferred, on the surface of which the cavities appear only insignificantly and have no influence on the outer shape of the shaped body. Moldings which are transparent are particularly preferred.
- thermoplastic molding compositions are polymers and polymer mixtures which contain at least one compound which is gaseous at elevated temperature or releases gaseous constituents. This includes, for example, as volatile components physical blowing agents, such as pentane, heptane or octane, which are incorporated into the thermoplastic molding compositions.
- Compounds which split off gaseous components at elevated temperature can either be a component of the polymer composition forming the thermoplastic molding compositions, a polymer additive or a low molecular weight additive, as described in R. Gumbleter, H. Müller (ed.), Taschenbuch der Kunststoff-Additive, 3 Ed., Carl Hanser Verlag, Kunststoff, 1989, pp. 843 - 864.
- the compound which releases gaseous constituents preferably represents one or more polymer components of the thermoplastic polymer molding composition.
- Suitable monomer units of this polymer or copolymer component are ethylenically unsaturated carboxylic acid esters of the general formula (I):
- R 1 to R 3 independently of one another, hydrogen; C1 . -C 5 alkyl, whether or not substituted, in particular methyl, ethyl, propyl, butyl in straight-chain and branched form; -CH 2 C0 2 R 8 ,
- R 4 , R 5 independently of one another, C 1 -C 6 -alkyl, also substituted, in particular methyl, ethyl, propyl, butyl, pentyl, hexyl in straight-chain and branched form;
- Aryl in particular phenyl, optionally substituted with C 1 -C 4 -alkyl radicals,
- R 6 , R 7 independently of one another, hydrogen; C - to Cs -Alkyl, also substituted, in particular methyl, ethyl, propyl, butyl, pentyl, hexyl in straight-chain and branched form; Aryl, in particular phenyl, optionally substituted with Ci to C ⁇ alkyl residues,
- R8 hydrogen; Ci to C 4 alkyl, also substituted, such as methyl, ethyl, propyl.
- the radicals R 4 to R 7 can also be part of ring systems such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, furanyl or pyranyl.
- halogen such as chloride or bromide
- Cs-alkyl radicals such as methyl, ethyl or propyl
- the monomer units are particularly preferably tert. -Butyl acrylate and tert-butyl methacrylate.
- thermoplastic molding compositions can be composed either completely or partially of polymers which contain monomer units of the general formula (I).
- thermoplastic molding compositions are those
- the moldings according to the invention consist of thermoplastic molding compositions which comprise at least one polymer or at least one copolymer or at least one polymer and at least one copolymer which tert. -Butyl acrylate or tert.- Butyl methacrylate or a mixture of tert. -Butyl acrylate and tert-butyl methacrylate contains as monomer units.
- thermoplastic molding compositions which have at least one copolymer which tert. -Butyl acrylate and at least one methacrylate derivative or tert-butyl methacrylate and at least one acrylate or methacrylate derivative contains as monomer units.
- Preferred copolymers are those of tert-butyl methacrylate and other methacrylate derivatives, such as methyl methacrylate or 2-ethylhexyl methacrylate. These can be used alone or as a polymeric component of the thermoplastic molding compositions. Copolymers of tert-butyl methacrylate and methyl methacrylate are particularly preferred. The copolymers mentioned can contain further comonomers, the proportion of which is preferably below 20, particularly preferably below 10% by weight, based on the weight of copolymer.
- Suitable comonomer building blocks are, for example, esters of acrylic and methacrylic acid with Ci to C 20 carbon-organic ester groups, for example alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, 2- Ethylhexyl; C 2 - to C ⁇ -hydroxyalkyl methacrylates, such as 2-hydroxyethyl methacrylate; Vinyl aromatics such as styrene, ⁇ -methylstyrene and vinyl cyanides such as acrylonitrile and methacrylonitrile.
- the proportion of tert-butyl methacrylate and / or tert. -Butyl acrylate in the copolymer is usually in the range from 1 to 50% by weight, preferably in the range from 2 to 25% by weight.
- thermoplastic polymers and copolymers can be prepared by methods known per se, such as suspension, solution, bulk or emulsion polymerization (cf. "Acrylic and methacrylic compounds", H. Rauch-Puntigam, T. Völker, Springer Verlag, Berlin, 1967 and “Poly (eth) acrylate", PEP Report 65A, SRI International, Menlo Park, 1991 and literature cited there).
- suspension polymerization can be carried out analogously to the processes described in European patent applications EP-A 489 318, EP-A 584 632 and EP-A 632 069, bulk and solution polymerization as described in EP-A 457 355, and the Emulsion polymerization based on EP-A 245 647 and EP-A 693 501.
- the polymers and copolymers described can be processed as such or in a mixture with other thermoplastic molding compositions to give the moldings according to the invention.
- the gas-releasing components are in the thermoplastic parts advantageously in proportions of not less than 0.2% by weight, preferably not less than 0.5% by weight. However, this proportion is usually in the range from 1 to 50, preferably in the range from 2 to 25,% by weight, based on the total weight of the thermoplastic molding composition.
- thermoplastic mixture components used are in particular those which provide transparent or translucent moldings.
- Suitable materials are, for example, polystyrene, polymethyl methacrylate (PMMA), amorphous polyamide, transparent polyvinyl chloride, polycarbonate, transparent polyesters, cellulose derivatives, random polypropylene, styrene-butadiene-styrene copolymers, styrene-acrylonitrile copolymers (SAN), styrene-methyl methacrylate Copolymers, styrene-maleic anhydride copolymers, cycloolefin copolymers, styrene-acrylonitrile-methyl methacrylate terpolymers or the corresponding impact-modified materials, methyl methacrylate-acrylonitrile-butadiene-styrene polymer (MABS) and blends of SAN and PMMA.
- MABS methyl methacrylate-acrylonitrile-butadiene
- SAN SAN
- PMMA blends of SAN and PMMA or the corresponding impact-modified materials
- PMMA or impact-modified PMMA is very particularly preferably used.
- Emulsion graft copolymers as described in EP 62223, EP 512 333 and WO 9619509, are suitable for impact modification of the materials mentioned.
- non-transparent molding compositions for example acrylonitrile-styrene-acrylic ester (ASA) and acrylonitrile-butadiene-styrene polymers (ABS), and ASA / polycarbonate and polyphenylene ether / styrene-butadiene polymer blends are also suitable.
- ASA acrylonitrile-styrene-acrylic ester
- ABS acrylonitrile-butadiene-styrene polymers
- ASA polycarbonate and polyphenylene ether / styrene-butadiene polymer blends
- Suitable are conducted under the following trade names products including:
- Proven methods can also be used to produce the polymer blends described.
- thermoplastic molding compositions can be admixed with other stabilizers, pigments, dyes and auxiliaries known per se, such as antistatic agents, lubricants, mold release agents or flame retardants.
- the molding compositions can be processed by conventional methods to give the moldings according to the invention, for example by spraying, blowing, pressing, extruding, calendering or vacuum molding, with the proviso that the thermoplastic molding compositions at a temperature in the range from 140 ° C. to 300 ° C. are processed.
- the processing conditions should advantageously be selected such that the main amount of gaseous components is only released or split off in the last process step.
- the cavities forming in the shaped bodies are generally bubble-shaped and have a maximum average size of 1 cm, but preferably in the range from 5 ⁇ m to 0.5 cm in the shaped bodies.
- the shape and size of the cavities can be influenced by the processing conditions. In the case of injection molding processes, this is achieved in particular by varying the cooling rate, pressure and holding pressure, ie the pressure exerted on the solidifying melt. In principle, the injection molding process can operate over a pressure range from 0 to 3000 bar, but a pressure in the range from 50 to 2000 and in particular from 100 to 1000 bar is preferably set. The higher the pressure exerted on the melt, the smaller the cavities that form in the molded bodies.
- the number of cavities that form per unit volume is to be controlled via the amount of the gas-releasing polymer and the proportion of gas-releasing components contained therein as well as the processing temperature and duration.
- the number and size of the cavities contained in the moldings can also be influenced by the addition of additives.
- suitable additives are finely divided fillers, such as barium titanate, talc, chalk, kaolin, mica, silica, barium sulfate or aluminum hydroxide.
- the moldings containing cavities according to the invention have a density in the range from 0.5 to 1.5, preferably in the range from 0.8 to 1.3 and particularly preferably in the range from 1.0 to 1.2 g / cm 3 .
- thermoplastic molding compositions are suitable for the production of films and semi-finished products in the deep-drawing and blowing process. Accordingly, the moldings according to the invention can be used, for example, for the production of office, household and sanitary articles, furniture and furniture elements, as well as interior components and design objects. As products come e.g. Lampshades, skylights, salad bowls, shower handles or toothbrushes are possible.
- the present invention accordingly opens up an efficient access from a procedural and economic point of view to a large number of cavities containing thermoplastic molded articles.
- a solution of 5000 g of water, 3 g of the sodium salt of a copolymer of 64% by weight of methacrylic acid and 36% by weight of methyl methacrylate in the form of a 1.6% by weight aqueous solution and 3 g of sodium phosphate hydrate as a buffer were mixed with 4638 g Methyl methacrylate, 246 g of tert-butyl methacrylate, 4 g of dilauroyl peroxide, 2 g of 2, 2-bis (tert-butylperoxy) butane and 15 g of n-dodecyl mercaptan are mixed and flushed several times with nitrogen.
- the mixture was then heated to 125 ° C. with stirring and the system was kept at this temperature for 3 h. After cooling, the polymer was separated off, washed and dried.
- Example 1 was repeated with the difference that a mixture of 3655 g of methyl methacrylate and 1230 g of tert-butyl methacrylate was used as the monomer phase.
- B Other materials
- Polymer 3 was injected in a screw injection molding machine at a cylinder temperature of 220 ° C. and a mold temperature of 70 ° C. to form round disks with a thickness of 6 mm and a diameter of 10 cm. A crystal-clear, bubble-free molded part was obtained. Even when the injection or mold temperature was changed, no molded part containing bubbles was obtained.
- Polymer 1 was processed analogously to Example 1 at a cylinder temperature of 220 ° C. and a mold temperature of 70 ° C.
- the circular disc obtained had numerous bubble-shaped inclusions. Increasing the injection molding pressure to 600 bar reduced the size of the bubbles.
- a mixture of 90 parts of polymer 3 and 10 parts of polymer 1 was processed into round disks analogously to example 1 at a cylinder temperature of 240 ° C. and a mold temperature of 70 ° C. Crystal-clear molded parts were obtained which contained a few, statistically distributed bubbles.
- a mixture of 98 parts of polymer 3 and 2 parts of polymer 1 was processed analogously to Example 1 at 250 ° C cylinder temperature and 70 ° C mold temperature to round disks. Crystal-clear molded parts were obtained which contained a few, statistically distributed bubbles.
Landscapes
- 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)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP97951865A EP0960157A1 (en) | 1996-11-22 | 1997-11-05 | Cavity containing moulded bodies made of thermoplastic moulding material |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19648448.0 | 1996-11-22 | ||
DE1996148448 DE19648448A1 (en) | 1996-11-22 | 1996-11-22 | Molded articles made of thermoplastic molding compositions containing cavities |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1998023670A1 true WO1998023670A1 (en) | 1998-06-04 |
Family
ID=7812504
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1997/006115 WO1998023670A1 (en) | 1996-11-22 | 1997-11-05 | Cavity containing moulded bodies made of thermoplastic moulding material |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0960157A1 (en) |
DE (1) | DE19648448A1 (en) |
WO (1) | WO1998023670A1 (en) |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB864815A (en) * | 1957-07-30 | 1961-04-06 | Basf Ag | Porous plastics and their production |
GB1045229A (en) * | 1964-09-19 | 1966-10-12 | Roehm & Haas Gmbh | Foamable thermoplastic synthetic resins |
US3390105A (en) * | 1963-09-20 | 1968-06-25 | Sinclair Research Inc | Method of making a crosslinked polymer foam and product obtained therefrom |
US4291130A (en) * | 1980-01-02 | 1981-09-22 | The Dow Chemical Company | Process of making thermoset foams of acrylic polymers |
US4367290A (en) * | 1980-11-07 | 1983-01-04 | Agency Of Industrial Science & Technology | Method for manufacture of foamed article |
EP0532023A1 (en) * | 1991-09-13 | 1993-03-17 | Mitsubishi Rayon Co., Ltd. | Expandable polyacrylates and their foams |
-
1996
- 1996-11-22 DE DE1996148448 patent/DE19648448A1/en not_active Withdrawn
-
1997
- 1997-11-05 WO PCT/EP1997/006115 patent/WO1998023670A1/en not_active Application Discontinuation
- 1997-11-05 EP EP97951865A patent/EP0960157A1/en not_active Withdrawn
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB864815A (en) * | 1957-07-30 | 1961-04-06 | Basf Ag | Porous plastics and their production |
US3390105A (en) * | 1963-09-20 | 1968-06-25 | Sinclair Research Inc | Method of making a crosslinked polymer foam and product obtained therefrom |
GB1045229A (en) * | 1964-09-19 | 1966-10-12 | Roehm & Haas Gmbh | Foamable thermoplastic synthetic resins |
US4291130A (en) * | 1980-01-02 | 1981-09-22 | The Dow Chemical Company | Process of making thermoset foams of acrylic polymers |
US4367290A (en) * | 1980-11-07 | 1983-01-04 | Agency Of Industrial Science & Technology | Method for manufacture of foamed article |
EP0532023A1 (en) * | 1991-09-13 | 1993-03-17 | Mitsubishi Rayon Co., Ltd. | Expandable polyacrylates and their foams |
Also Published As
Publication number | Publication date |
---|---|
DE19648448A1 (en) | 1998-05-28 |
EP0960157A1 (en) | 1999-12-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE2726256C2 (en) | ||
EP1685186B2 (en) | Molding material containing a matting agent | |
EP0769524B2 (en) | Use of moulded parts from thermoplastic moulding compounds | |
DE2162485C3 (en) | Weather-resistant and impact-resistant resin mass | |
DE69936807T2 (en) | Crystalline resin blends with special effect surface appearance | |
EP2219843B1 (en) | Method for producing molded parts having reduced deposit formation | |
WO2004033824A1 (en) | Articles made of pmma molding compound | |
WO2008092517A1 (en) | Molded compounds for matt molded pmmi bodies | |
DE2503390B2 (en) | Rigid vinyl chloride polymer foam modifier system and method for making the same | |
DE69812360T2 (en) | PLASTIC COMPOSITION | |
EP0477726B1 (en) | Ternary mixtures of polymers | |
EP0264645B1 (en) | Compatible polymer compositions | |
JPH09104795A (en) | Syndiotactic polystyrene improved in impact resistance | |
DE19652758C2 (en) | Mixture or polymer composite containing methyl methacrylate-maleic anhydride copolymers | |
WO2006114430A1 (en) | Plastic objects having metal-like or mineral-like haptics and optics and good shaping properties | |
WO1998023670A1 (en) | Cavity containing moulded bodies made of thermoplastic moulding material | |
DE19906066A1 (en) | Thermoplastic molding compounds | |
DE2019945A1 (en) | Polystyrene moulding materials for prepnof foam bodies | |
CN102492239B (en) | AM mixture used for wood plastic products, and application methods thereof | |
EP0143321B1 (en) | Moulding masses with improved workability and aging-resistant polymeric foils prepared therefrom | |
DE19846244A1 (en) | Shaped body for the garden and animal husbandry area | |
DE4234296A1 (en) | Thermoplastic molding compound | |
DE3229131A1 (en) | MOLDS OF VINYL CHLORIDE POLYMER, SPECIFIC COPOLYMERS AND POLYMERS SOFTENERS WITH HIGH AGING RESISTANCE | |
WO2000047675A1 (en) | Thermoplastic molding materials | |
EP0591804A1 (en) | Transparent moulding matter |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): CN JP KR MX US |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 1997951865 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 1997951865 Country of ref document: EP |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 1997951865 Country of ref document: EP |