WO2002081534A1 - Verfahren zur herstellung eines polymeren umsetzungsprodukts - Google Patents
Verfahren zur herstellung eines polymeren umsetzungsprodukts Download PDFInfo
- Publication number
- WO2002081534A1 WO2002081534A1 PCT/EP2002/003820 EP0203820W WO02081534A1 WO 2002081534 A1 WO2002081534 A1 WO 2002081534A1 EP 0203820 W EP0203820 W EP 0203820W WO 02081534 A1 WO02081534 A1 WO 02081534A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- reaction product
- polymeric reaction
- preparation
- radicals
- polymeric
- Prior art date
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Classifications
-
- 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
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
Definitions
- the invention relates to a process for the preparation of a polymeric reaction product, and to polymeric reaction products which can be prepared by a process according to the invention and their use according to the invention.
- the method according to the invention is particularly suitable for the production of copolymers, for example with block structures.
- Various processes for producing such polymers are known from the literature.
- WO 00/37507 describes a process for the preparation of a reaction product (A) by reaction under radical conditions, the reaction having features which are typical of a living polymerization system.
- the reaction of a radically convertible monomer takes place in the presence of at least one radical initiator and a compound (I) in the aqueous phase.
- the invention also relates to the reaction product per se, a process for producing a polymer using this reaction product, and its use in polymer dispersions.
- DE 10029695.5 and PCT / EP 00/12848 each relate to a process for the preparation of a polymeric reaction product (A) by a reaction under free radical conditions, and the corresponding reaction products and their use.
- DE 10029694.7 describes the use of such polymeric reaction products for various purposes.
- reaction product (A ') 5 comprising a reaction under free radical conditions of a reaction mixture comprising at least one free-radically convertible monomer (a) in the presence of at least one compound of the formula (II)
- PCT / EP 00/12848 describes processes for preparing a reaction product (A) comprising a reaction under free radical conditions of a reaction mixture comprising at least one free-radically convertible monomer (a) in the presence of at least one free radical initiator and a compound (I) of the formula
- DE 10029697.1 relates to binder compositions containing solids at least comprising block copolymers prepared by free-radical polymerization and at least 2% by weight of at least one non-magnetic and non-magnetizable inorganic or organic solid, a process for the preparation of such binder compositions and their use.
- the block copolymers have at least two blocks of different monomer compositions.
- the binder compositions according to the invention contain at least one block copolymer which can be prepared by free-radical polymerization and have at least two blocks of different monomer compositions and at least one magnetic or magnetizable pigment.
- WO 95/34586 describes a process for the preparation of styrene copolymers which is initiated by means of organometallic compounds.
- DE-A 199 10 339 describes the use of such polymers in thermoplastic molding compositions.
- the use for the production of glass fiber reinforced thermoplastic molding compositions is described in DE-A 198 05 586.
- Ionic processes in particular the anionic processes described above, must be carried out with strict exclusion of oxygen and water, which leads to high costs for the starting materials.
- the initiators used are mostly toxic.
- the present invention was therefore based on the primary object of providing a process for producing a polymeric reaction product in which inexpensive raw materials can be used and which can be used industrially.
- the present invention was also based on the object of making it possible to set the properties of polymers in a targeted manner and thereby to enable a wide range of uses for those polymers which are obtainable by simple radical polymerization.
- this object is achieved by a process for the preparation of a polymeric reaction product comprising a reaction under free radical conditions of a reaction mixture comprising at least one free-radically convertible monomer (a) in the presence of a compound (I) of the formula:
- R 1 to R 4 each independently of one another for hydrogen, straight-chain or branched-chain substituted or unsubstituted alkyl or cycloalkyl groups or substituted or unsubstituted aralkyl, alkylaryl or aryl groups, with the proviso that at least two of the radicals R 1 to R 4 represent a substituted or unsubstituted aromatic hydrocarbon having 6 to 18 carbon atoms or a functional group which is conjugated to CC Bond in the general formula I has a multiple bond between a carbon atom and a hetero atom, and
- R 5 and R 6 each independently represent a substituted or unsubstituted straight or branched chain alkyl group or a substituted or unsubstituted aralkyl, alkylaryl or aryl group, where the radicals R 5 and R 6 can also have a polymeric character, and
- - n stands for a number from 1 to 100, whereby the compound (I) is not produced by controlled radical polymerization.
- Controlled radical polymerization in the context of the present invention is understood to mean a radical polymerization which takes place in the presence of a compound which forms stable radicals and is characterized by a successively controlled monomer incorporation.
- the growing polymer radical does not terminate as in other reactions under radical conditions by combination or disproportionation, but instead reacts with the compound (I), which may result in a transfer of one of the radicals R 5 or R 6 .
- the radicals R 5 and R 6 have a polymeric character, copolymers are obtained which contain blocks of the monomer (a) and the radicals R 5 or R 6 .
- the compound (I) can be prepared by all known methods of organic chemistry, except by controlled radical polymerization. For example, radical methods as described in the Bulletin Chem. Soc. Jap., Vol. 40, p. 2569 (1967) and in J. Polymer Sei., Part B, Vol. 8, p. 499 (1970).
- ionic polymerization methods are also particularly suitable, in particular anionic methods as described in WO 95/34586, in which polymerization is initiated using organometallic compounds.
- Cationic polymerization methods as described, for example, by Feldhusen et al., Macromolecules, 1997, 31, 578, are also suitable.
- radicals R 1 and R 2 or the radicals R 3 and R 4 are in particular a substituted or unsubstituted aromatic hydrocarbon having 6 to 18 carbon atoms.
- the radicals R 1 and R 2 or R 3 and R 4 are phenyl derivatives.
- the radicals R 1 and R 2 or R 3 and R 4 represent a phenyl radical and the other radicals R 1 and R 2 or R 3 and R 4 each represent hydrogen.
- a polymeric character means that a residue consists of at least two repeat units.
- a residue with a polymeric character preferably consists of at least ten repeating units.
- the present invention relates in particular to a method for producing a polymeric reaction product, wherein R 5 or R 6 or both are composed of at least two repeating units.
- the radicals R 5 and R 6 can be constructed, for example, from 1 to 100,000 repetition units, in particular from 1 to 10,000 repetition units.
- Particularly preferred repeating units are those which are derived from a radical-convertible monomer (a).
- the reaction under radical conditions is in principle carried out under the usual conditions for radical polymerization, it being possible for suitable solvents to be present.
- aqueous phase in the context of the present text is understood to mean a phase which contains 10 to 100% by weight of water. If the water content of the aqueous phase is less than 10%, it is preferred in the context of the present invention if the aqueous phase contains a mixture of water and one or more water-miscible solvents such as THF, methanol, ethanol, propanol, butanol, acetone, methyl ethyl ketone or the like possible to carry out the reaction in the presence of a mixture of water and a water-immiscible solvent such as an aromatic solvent, for example toluene.
- water-miscible solvents such as THF, methanol, ethanol, propanol, butanol, acetone, methyl ethyl ketone or the like.
- reaction in an organic solvent or solvent-free (“in bulk”), for example in the melt.
- organic solvent or solvent-free in bulk
- one of these is used Understand ReaMonshrihrung that takes place in the presence of less than 10 wt .-%, preferably less than 5 wt .-% or less than 1 wt .-% water.
- the reaction is carried out anhydrous, that is, with a water content of less than 0.001% by weight
- water contents can be achieved, for example, by using commercially available solvents, as are usually used as organic solvents in radical polymerizations.
- Suitable solvents in the context of the present invention are in principle all polar and non-polar organic solvents in which the corresponding monomers and preferably also the resulting polymers are soluble, if appropriate at elevated temperature.
- Suitable solvents are, for example, C3 to C10 alkanes, cyclohexane, decalin, acetone, methyl ethyl ketone, diisobutyl ketone, tetrahydrofuran.
- methyl ketone or toluene are preferred as solvents.
- the reaction under free-radical conditions is generally carried out at temperatures above room temperature and below the decomposition temperature of the monomers, a temperature range from 50 to 150 ° C., more preferably 60 to 120 ° C. and in particular 75 to 95 ° C. being chosen.
- the reaction can be carried out at pressures from 1 to 300 bar, for example from about 1 to about 20 bar.
- the reaction is preferably carried out at atmospheric pressure.
- the reaction can also be carried out in the presence of a surface-active substance.
- the radical formation can take place according to the invention by different methods. For example, thermal, photo-chemical, electro-chemical or electron transfer-induced generation is possible, as is the use of oxidizing or reducing agents to generate radicals.
- the radicals can also be generated mechanically, for example by shear degradation or ultrasound.
- the invention accordingly relates to a process for the preparation of a polymeric reaction product, the reaction mixture additionally containing an initiator.
- initiators In addition to carrying out the reaction in the presence of at least one free radical initiator, it is also possible to use thermally, electrochemically or photochemically initiating monomers as initiators. All azo and / or peroxo compounds and / or compound compounds conventionally used in radical chain polymerization fertilize with homolytically cleavable CC bonds. Suitable initiators are described in WO 98/01478 on p. 10, lines 17 to p. 11, line 15, which in this regard is included in full in the context of the present application, and 3,4-dimethyl-3,4 -diphenylhexane or 2,3-dimethyl-2,3-diphenylbutane can be used. Initiators are preferably used which are soluble in the reaction system used in each case.
- oxidizing radical initiators such as, for example, potassium, sodium and ammonium peroxodisulfate, or a combination of a conventional, ie a non-oxidizing initiator with H 2 O 2 , are preferably used.
- Dicumyl peroxide, dibenzoyl peroxide, dilauryl peroxide and AIBN can also be used.
- a comparatively large amount of free-radical initiator is added, the proportion of free-radical initiator in the reaction mixture preferably being 0.1 to 50% by weight, more preferably 0.5 to 20% by weight, each based on the total amount of the monomer (a) and the initiator.
- the ratio (molar ratio) of initiator to the repeating unit R 5 C (R 1 R 2 ) C (R 3 R 4 ) R 6 of the compound (I) is preferably 5: 1 to 1: 5, for example 3: 1 to 1: 3, more preferably 2: 1 to 1: 2, and in particular 1.5: 1 to 1: 1.5.
- the present invention relates to a method for producing a polymeric reaction product, the polymeric reaction product being a block copolymer.
- a “block copolymer” is understood to mean a polymer which has at least two polymer blocks characterized by a different monomer composition.
- polymer blocks characterized in the context of the present invention is understood to be the finding that at least two regions of the block copolymer have at least two blocks with a different monomer composition. It is possible within the scope of the present invention that the transition between two blocks is continuous, that is to say that between two blocks there is a zone which has a statistical or regular sequence of the monomers constituting the blocks. However, it is also provided in the context of the present invention that the transition between two blocks is essentially discontinuous.
- An “essentially discontinuous transition” is understood to mean a transition zone which has a significantly shorter length than at least one of the blocks separated by the transition zone.
- the chain length of such a transition zone is less than 1/10, preferably less than 1/20 of the block length of at least one of the blocks separated by the transition zone.
- a “different monomer composition” means the finding that the monomers constituting the respective block differ in at least one feature, for example in their interlinking, in their conformation or constitution Invention block copolymers used which have at least two blocks, the monomer composition of which differs at least through the constitution of the monomers.
- the block copolymers that can be produced within the scope of the present invention have a polydispersity of less than about 5, for example less than about 4 or less than about 3.
- the block copolymers that can be produced according to the invention have, for example, a molecular weight (M n ) of 500 to 1,000,000 g / mol, in particular of 5,000 to 500,000 g / mol.
- M n molecular weight
- the molecular weights are determined by GPC in THF based on a polystyrene standard Suitable radically convertible monomer (a) are in particular ethylenically unsaturated monomers.
- Suitable monomers having at least one ethlyenically unsaturated group are: olefins such as ethylene or propylene, vinylaromatic monomers such as styrene, divinylbenzene, 2-vinylnaphthalene and 9-vinylanthracene, substituted vinylaromatic monomers such as p-methylstyrene, ⁇ -methylstyrene, o-chlorostyrene, p-chlorostyrene, 2,4-dimethylstyrene, 4-vinylbiphenyl and vinyltoluene, esters from vinyl alcohol and monocarboxylic acids containing 1 to 18 carbon atoms such as vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl laurate and vinyl stearate, anhydrides or esters from 3 to 6 ⁇ -monoethylenically unsaturated mono- and dicarboxylic acids containing C atoms, such as in particular acrylic acid
- Suitable styrene compounds are those of the general formula II:
- R 'and R "independently of one another are H or d- to C 8 -alkyl and n is 0, 1, 2 or 3.
- the monomers styrene, ⁇ -methylstyrene, divinylbenzene, vinyltoluene, N-vinylpyrrolidone and N-vinylformamide, C 1 -C 20 -alkyl acrylates and C 1 -C 12 -alkyl methacrylates, in particular n-, are particularly preferred in the process according to the invention.
- the present invention relates to a process for the preparation of a polymeric reaction product, the radically convertible monomer (a) being selected from the group consisting of: styrene compounds of the general formula (II)
- R 'and R "independently of one another are H or Q-Cs-alkyl and n is 0, 1, 2 or 3;
- the invention also relates to a polymeric reaction product A which can be produced by means of a process according to the invention.
- the polymeric reaction product A can be, for example, a copolymer with blocks consisting of polystyrene, methyl methacrylate, methacrylate, N-vinylpyrrolidone or poly (styrene-co-maleic anhydride) or olefins.
- the present invention furthermore relates to the use of a polymeric reaction product which can be prepared by a process according to the invention or a polymeric reaction product according to the invention for the production of moldings, films, fibers and foams.
- Poly (styrene-co-l, diphenylethene) was prepared according to WO 95/34586 on the anionic copolymerization of styrene and diphenylethene (DPE).
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/473,745 US20040116637A1 (en) | 2001-04-06 | 2002-04-05 | Method for producing a polymeric conversion product |
EP02759799A EP1392746A1 (de) | 2001-04-06 | 2002-04-05 | Verfahren zur herstellung eines polymeren umsetzungsprodukts |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10117276.1 | 2001-04-06 | ||
DE10117276A DE10117276A1 (de) | 2001-04-06 | 2001-04-06 | Verfahren zur Herstellung eines polymeren Umsetzungsprodukts |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2002081534A1 true WO2002081534A1 (de) | 2002-10-17 |
Family
ID=7680693
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2002/003820 WO2002081534A1 (de) | 2001-04-06 | 2002-04-05 | Verfahren zur herstellung eines polymeren umsetzungsprodukts |
Country Status (4)
Country | Link |
---|---|
US (1) | US20040116637A1 (de) |
EP (1) | EP1392746A1 (de) |
DE (1) | DE10117276A1 (de) |
WO (1) | WO2002081534A1 (de) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19524586A1 (de) * | 1994-07-16 | 1996-01-18 | Basf Ag | Wäßrige Dispersionen anionisch polymerisierter Polymerisate |
DE19701868A1 (de) * | 1997-01-21 | 1998-07-23 | Basf Ag | Schlagzäh thermoplastische Formmasse |
US5854353A (en) * | 1994-06-16 | 1998-12-29 | Basf Aktiengesellschaft | Thermoplastic molding compound |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3896099A (en) * | 1970-07-03 | 1975-07-22 | Akzo Nv | Polymerization of ethylenically unsaturated monomers with a 1,1,2,2-tetracarboalkoxy-diaryl-ethane |
US4581429A (en) * | 1983-07-11 | 1986-04-08 | Commonwealth Scientific And Industrial Research Organization | Polymerization process and polymers produced thereby |
US4675426A (en) * | 1986-06-11 | 1987-06-23 | General Electric Company | Free-radical, initiators, curable compositions, and methods |
DE19961063A1 (de) * | 1999-12-17 | 2001-07-12 | Basf Ag | Verfahren zur Herstellung eines polymeren Umsetzungsprodukts |
-
2001
- 2001-04-06 DE DE10117276A patent/DE10117276A1/de not_active Withdrawn
-
2002
- 2002-04-05 US US10/473,745 patent/US20040116637A1/en not_active Abandoned
- 2002-04-05 WO PCT/EP2002/003820 patent/WO2002081534A1/de not_active Application Discontinuation
- 2002-04-05 EP EP02759799A patent/EP1392746A1/de not_active Withdrawn
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5854353A (en) * | 1994-06-16 | 1998-12-29 | Basf Aktiengesellschaft | Thermoplastic molding compound |
DE19524586A1 (de) * | 1994-07-16 | 1996-01-18 | Basf Ag | Wäßrige Dispersionen anionisch polymerisierter Polymerisate |
DE19701868A1 (de) * | 1997-01-21 | 1998-07-23 | Basf Ag | Schlagzäh thermoplastische Formmasse |
Also Published As
Publication number | Publication date |
---|---|
EP1392746A1 (de) | 2004-03-03 |
US20040116637A1 (en) | 2004-06-17 |
DE10117276A1 (de) | 2002-10-10 |
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