WO2002032295A2 - Method for post-processing styrene polymers - Google Patents
Method for post-processing styrene polymers Download PDFInfo
- Publication number
- WO2002032295A2 WO2002032295A2 PCT/EP2001/011998 EP0111998W WO0232295A2 WO 2002032295 A2 WO2002032295 A2 WO 2002032295A2 EP 0111998 W EP0111998 W EP 0111998W WO 0232295 A2 WO0232295 A2 WO 0232295A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- styrene
- rubber
- polymer
- auxiliary
- impact
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- 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
- C08F6/00—Post-polymerisation treatments
- C08F6/001—Removal of residual monomers by physical means
- C08F6/005—Removal of residual monomers by physical means from solid polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions 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; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions 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; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions 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; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/14—Copolymers of styrene with unsaturated esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
Definitions
- the invention relates to a process for the aftertreatment of styrene polymers by mixing liquid stripping agents into the melt of the styrene polymer and subsequent degassing.
- This process is used on an industrial scale in the production of styrene polymers by bulk or solution polymerization for degassing residual monomers and solvent residues.
- the preferred stripping agent is water, see e.g. US-A 3 773 740, EP-A 584 926 and the publications "Static Vacuum Degassing Apparatus in the Production of Quality Enhancement of Plastics" by J.E. Juvet and F.A. Streiff in "Vacuum in Research and Practice” (1998), No. 4, pages 285.293, WILEY-VCH-Verlag.
- polymeric aids e.g. rubber-elastic toughness modifiers
- two process principles are usually used in styrene polymers.
- the rubbers are added on an industrial scale directly during the polymerization of the monomers; on the other hand, they can be incorporated into the finished polymers on an extruder, which, however, requires an additional work step.
- the polymeric auxiliary is mixed into the melt of the styrene polymer as a dispersion or solution in a liquid stripping agent.
- Styrene polymers are to be understood as: homopolystyrene (PS), impact-resistant modified polystyrene (HIPS) with polybutadiene rubber, styrene / butadiene block copolymers, copolymers of styrene with acrylonitrile (SAN), methyl methacrylate and maleic anhydride, and styrene / acrylonitrile copolymer which are modified with a polybutadiene or polyacrylate rubber (ABS or ASA).
- PS homopolystyrene
- HIPS impact-resistant modified polystyrene
- SAN acrylonitrile
- ABS polybutadiene or polyacrylate rubber
- the preferred stripping agent is water, and C 1 -C 4 alcohols are also suitable, in principle also gases in the supercritical state, such as carbon dioxide, nitrogen and C 4 -C 6 alkanes.
- Preferred polymeric auxiliaries are rubber-elastic impact modifiers, which are preferably used as an aqueous dispersion; According to the process of the invention, polyalkylene oxides, such as polyethylene glycol, which act as antistatic agents, can also be incorporated as aqueous solutions.
- Emulsion graft polymers which consist of at least one hard phase and at least one soft phase and have a shell structure are particularly preferred.
- the hard phase is formed primarily by monomers forming hard polymers, such as styrene, ⁇ -methylstyrene, methyl methacrylate, acrylonitrile, methacrylonitrile and maleic anhydride or mixtures thereof.
- the outer phase is preferably a hard phase.
- At least one of the inner phases is a soft phase, which is preferably formed from monomers forming soft polymers, such as butadiene, butyl acrylate or ethylhexyl acrylate.
- These emulsion graft polymers preferably have a glass transition temperature of less than 0 ° C., in particular of less than -20 ° C.
- those graft polymers are added whose hard phase is at least partially compatible with the polymer matrix of the melt.
- the selected proportions of stripping agent and polymeric auxiliary depend on the content of residual monomers and solvent residues to be degassed in the styrene polymer, and on the other hand on the desired amount of polymeric auxiliary in the styrene polymer.
- 0.5 to 20, in particular 1 to 10 parts by weight of the auxiliary dispersion or solution are preferably used per 100 parts by weight of styrene polymer.
- the solids content of the dispersion or solution is preferably 20 to 80, in particular 30 to 65,% by weight.
- a preferred graft consists of polybutadiene particles that contain occluded polystyrene cells, preferred emulsion grafts have a hard shell made of polystyrene or styrene copolymers and a soft core made of a polyacrylate rubber, polybutadiene or a butadiene / styrene copolymer.
- the stripping process is carried out according to known, e.g. carried out in the methods described above.
- the stripping agent is mixed into the polymer melt together with the polymeric auxiliary.
- the stripping agent is then withdrawn again together with the volatile impurities in a degassing device from the polymer melt.
- This process is preferably carried out continuously, preferably in static mixers or screw mixers, for example extruders. Heat is expediently added to the mixture or the components in order to facilitate the degassing process.
- the degassing is preferably carried out under reduced pressure. Suitable degassing devices can be, for example, flash degassers, degassing extruders or thin-film evaporators.
- auxiliaries and stripping agents are mixed into a polymer melt via a static mixer and the mixture is then expanded into a degassing pot operated under vacuum.
- the stripping process efficiently removes residual styrene and other volatile compounds.
- Polymers with a residual volatile compound content of less than 500, particularly preferably less than 300 ppm are preferably obtained.
- the residual styrene content is preferably less than 200 ppm, very particularly preferably less than 160 ppm.
- the rubber particles have an average particle size of 2.3 ⁇ m.
- Latex 1 is a polymer dispersion with a soft phase made from butadiene (60%) and a hard phase made from styrene and acrylonitrile (80/20; 40%). The solids content of the aqueous dispersion was 39.6%.
- Latex 2 is a polymer dispersion with a soft phase made from butyl acrylate and butanediol diacrylate (98/2; 60%) and a hard phase made from styrene (40%).
- the solids content of the aqueous dispersion was 34.3%.
- the rubber particles have an average particle size of 0.5 ⁇ m.
- the styrene polymer granules are introduced into a twin-screw extruder (ZSK 30, W & P) with two filler necks and a degassing neck and melted at a temperature of around 240 ° C.
- the polymer dispersion is pressed into this melt and mixed. Water, residual styrene and other volatile compounds are drawn off at a vacuum of 100 mbar through the expansion nozzle.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU1904202A AU1904202A (en) | 2000-10-18 | 2001-10-17 | Method for post-processing styrene polymers |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE2000151602 DE10051602A1 (en) | 2000-10-18 | 2000-10-18 | Post-treatment of polystyrene to modify the impact strength comprises mixing a melt with a liquid stripping agent containing a dispersed or dissolved polymer aid and degassing |
DE10051602.5 | 2000-10-18 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2002032295A2 true WO2002032295A2 (en) | 2002-04-25 |
WO2002032295A3 WO2002032295A3 (en) | 2002-07-04 |
Family
ID=7660189
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2001/011998 WO2002032295A2 (en) | 2000-10-18 | 2001-10-17 | Method for post-processing styrene polymers |
Country Status (3)
Country | Link |
---|---|
AU (1) | AU1904202A (en) |
DE (1) | DE10051602A1 (en) |
WO (1) | WO2002032295A2 (en) |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5899909A (en) | 1994-08-30 | 1999-05-04 | Medscand Medical Ab | Surgical instrument for treating female urinary incontinence |
US6273852B1 (en) | 1999-06-09 | 2001-08-14 | Ethicon, Inc. | Surgical instrument and method for treating female urinary incontinence |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4445141A1 (en) * | 1994-12-17 | 1996-06-20 | Basf Ag | Process for the production of impact modified polystyrene molding compounds |
ES2104481T3 (en) * | 1995-03-27 | 1997-10-01 | Basf Ag | PROCEDURE FOR OBTAINING THERMOPLASTICS. |
DE19713039A1 (en) * | 1997-03-27 | 1998-10-01 | Bayer Ag | Process for the production of elastomer-modified thermoplastics |
US5985997A (en) * | 1997-05-23 | 1999-11-16 | Chevron Chemical Company | In situ process for making a bimodal HIPS having both high gloss and high impact strength |
DE69813711T2 (en) * | 1997-09-30 | 2004-02-26 | Mitsui Chemicals, Inc. | Process for removing volatiles from a polymer composition |
-
2000
- 2000-10-18 DE DE2000151602 patent/DE10051602A1/en not_active Withdrawn
-
2001
- 2001-10-17 WO PCT/EP2001/011998 patent/WO2002032295A2/en active Application Filing
- 2001-10-17 AU AU1904202A patent/AU1904202A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5899909A (en) | 1994-08-30 | 1999-05-04 | Medscand Medical Ab | Surgical instrument for treating female urinary incontinence |
US6273852B1 (en) | 1999-06-09 | 2001-08-14 | Ethicon, Inc. | Surgical instrument and method for treating female urinary incontinence |
Also Published As
Publication number | Publication date |
---|---|
AU1904202A (en) | 2002-04-29 |
WO2002032295A3 (en) | 2002-07-04 |
DE10051602A1 (en) | 2002-04-25 |
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