EP2340274A1 - Continuous production of copolymers suitable as flow agents - Google Patents
Continuous production of copolymers suitable as flow agentsInfo
- Publication number
- EP2340274A1 EP2340274A1 EP09783837A EP09783837A EP2340274A1 EP 2340274 A1 EP2340274 A1 EP 2340274A1 EP 09783837 A EP09783837 A EP 09783837A EP 09783837 A EP09783837 A EP 09783837A EP 2340274 A1 EP2340274 A1 EP 2340274A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- different
- represented
- reaction surface
- same
- unbranched
- 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.)
- Withdrawn
Links
- 229920001577 copolymer Polymers 0.000 title claims abstract description 33
- 238000010924 continuous production Methods 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims abstract description 91
- 239000000203 mixture Substances 0.000 claims abstract description 37
- 239000002253 acid Substances 0.000 claims abstract description 36
- 239000000178 monomer Substances 0.000 claims abstract description 33
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 23
- 229920000570 polyether Polymers 0.000 claims abstract description 23
- 239000010409 thin film Substances 0.000 claims abstract description 20
- 230000001678 irradiating effect Effects 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 35
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 7
- 125000003161 (C1-C6) alkylene group Chemical group 0.000 claims description 6
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 4
- 239000011976 maleic acid Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 claims description 3
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000010408 film Substances 0.000 claims description 2
- CPJRRXSHAYUTGL-UHFFFAOYSA-N isopentenyl alcohol Chemical compound CC(=C)CCO CPJRRXSHAYUTGL-UHFFFAOYSA-N 0.000 claims description 2
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 239000007870 radical polymerization initiator Substances 0.000 claims 1
- 125000002348 vinylic group Chemical group 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000011541 reaction mixture Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- -1 methyl benzoyl Chemical group 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 239000012736 aqueous medium Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XVZXOLOFWKSDSR-UHFFFAOYSA-N Cc1cc(C)c([C]=O)c(C)c1 Chemical group Cc1cc(C)c([C]=O)c(C)c1 XVZXOLOFWKSDSR-UHFFFAOYSA-N 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000010327 methods by industry Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000008030 superplasticizer Substances 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
- B01J19/122—Incoherent waves
- B01J19/123—Ultraviolet light
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J10/00—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor
- B01J10/02—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor of the thin-film type
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
- B01J19/1887—Stationary reactors having moving elements inside forming a thin film
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/247—Suited for forming thin films
-
- 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
- C08F267/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00
-
- 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
- C08F267/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00
- C08F267/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00 on to polymers of anhydrides
-
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
-
- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
-
- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/14—Polymers provided for in subclass C08G
- C08F290/142—Polyethers
-
- 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
- C08L51/08—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 otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
Definitions
- the present invention relates to a process for the preparation of
- Acid monomer structural units and copolymers containing polyether macromonomer structural units and also copolymer which can be prepared by this process and the use of the copolymer.
- aqueous slurries of powdered inorganic or organic substances such as clays, silicate, chalk, carbon black, rock flour and hydraulic binders to improve their processability, d. H. Kneadability, spreadability, sprayability, pumpability or flowability, often added additives in the form of dispersants.
- Such additives are able to break up solid agglomerates, to disperse the particles formed and thus to improve the processability.
- This effect is also exploited specifically in the production of building material mixtures containing hydraulic binders such as cement, lime, gypsum, hemihydrate or anhydrite.
- additives are used which are generally referred to as water reducers or flow agents.
- water reducers or flow agents in particular copolymers are used in practice, which are prepared by free-radical copolymerization of acid monomers with Polyethermakromonomeren.
- the copolymerization is usually carried out in the semi-batch mode.
- WO 2005/075529 describes a semicontinuous preparation process for said copolymers, in which the polyether macromonomer is initially charged and subsequently the acid monomer is added over the time of the template.
- the method described is already cost-effective and high-performance flow agents are obtained as the process product, there continues to be a desire to further improve the quality of the process product and the economic efficiency of the process.
- the object underlying the present invention is therefore to provide an economical process for the preparation of copolymers which show good performance as dispersants for hydraulic binders, especially as flow agents / water reducing agents.
- the solution to this problem is a process for preparing acid monomer structural units and copolymers containing polyether macromonomer structural units, which is carried out in continuous operation in a reactor comprising
- ⁇ ) a body B rotating about a rotation axis, having a reaction surface, ⁇ ) a dosing system, and Y) a device for irradiating the reaction surface,
- the components of a starting reaction composition are applied individually and / or as a mixture by means of the dosing system in a thin film to an inner region of the reaction surface of the rotating body B, so that the thin film over the reaction surface of the rotating body B to an outer region of the Reaction surface of the rotating body B flows, wherein the thin film on the reaction surface by means of
- the thin film leaves the reaction surface as the reaction composition, the acid monomer structural units and
- an acid monomer, a polyether macromonomer and a photoinitiator are present and the temperature of the reaction surface is 0 to 60 0 C.
- Acid monomer to be understood as meaning radically copolymerizable monomers having at least one carbon double bond, which contain at least one acid function and in the aqueous medium as the acid react. Furthermore, the acid monomer should also be taken to mean free-radically copolymerizable monomers having at least one carbon double bond which, owing to the hydrolysis reaction, form at least one acid function in the aqueous medium and react as an acid in the aqueous medium (Example: maleic anhydride). Polyethermakromonomere in the sense of the present
- the invention relates to free-radically copolymerizable compounds having at least one carbon double bond, which have at least two ether oxygen atoms, with the proviso that the polyether macromonomer structural units contained in the copolymer have side chains containing at least two ether oxygen atoms.
- the reactor in which the method according to the invention is carried out makes it possible to carry out a process in which, due to the formation of a very thin film on the pane, a particularly efficient and uniform irradiation by the UV light is made possible.
- particularly good mixing ratios within the film lead to intensive contact of the active species.
- Short and controllable residence times allow control over the molecular weight even at high viscosities, which has a positive effect on product properties.
- positive properties, such as a short residence time, intensive mixing and high mass transfer also lead to economic benefits.
- the method according to the invention offers the possibility of a flexible and simple process optimization.
- the scale-up which is often problematic in process engineering, is particularly simple due to the simplicity and usually relatively small size of the reactor used, and it should be mentioned that the investment costs as well as the maintenance costs (purification, etc.) of said reactor are quite low
- the quality of the resulting product ie the copolymer-containing reaction composition, can be varied in a targeted manner by changing the process parameters (residence time, temperature, metering of the components of the starting reaction composition).
- the rotating body B is formed as a turntable having the reaction surface at the top, in which the components of the Ninre forceskomposition be applied individually and / or as a mixture with the aid of the dosing system in the middle region as a thin film and preferably a wall surrounding the turntable before, with the the the
- Reaction composition is collected after leaving the reaction surface.
- a reaction surface having body B is generally in front of a horizontal or a slightly different from the horizontal (at an angle of up to about 30 °) before rotating disk.
- this body B may also be vase-shaped, ring-shaped or conical.
- the body B has a diameter of 0.10 m to 3.0 m, preferably 0.20 m to 2.0 m and more preferably from 0.20 m to 1, 0 m.
- the reaction surface can be smooth or have alternatively riffel- or spiral-shaped projections, which exert influence on residence time of the reaction mixture.
- the body B is installed in a respect to the conditions of the method resistant container.
- the temperature of the reaction surface is between 5 and 45 ° C., preferably between 10 and 30 ° C.
- the temperature of the reaction surface is an important parameter, which is coordinated by the person skilled in the art with other relevant influencing variables, such as residence time, type and amount of the components of the starting reaction mixture should.
- photoinitiators are suitable, for example:
- Irgacure® 369 2-Benzyl-2-dimethylamino-1- [4- (4-morpholinyl) phenyl] -1-butanone
- Irgacure® 651 alpha, alpha-dimethoxy-alpha-phenylacetophenone
- Irgacure® 2022 phosphine oxide, phenylbis (2,4,6-trimethylbenzoyl) (20%) and 2-
- Irgacure® 2100 phosphine oxide
- Irgacure® 819 DW Phosphine Oxide Phenyl bis (2,4,6-trimethylbenzoyl) (45% FS dispersed in water)
- Irgacure® 2959 1- (4- (2-hydroxyethoxy) -phenyl) -2-hydroxy-2-methyl-1-propan-1-one
- Esacure KIP EM oligo [2-hydroxy-2-methyl-1-4- (1-methylvinyl) phenyl] propanone], emulsion in water based on 32% active photoinitiator Esacure DP 250: 2,4,6-trimethylbenzoyldiphenylphosphine oxide + alpha - Hydroxy ketone + benzophenone derivative
- 0.1 to 0.0005, preferably 0.01 to 0.1 mol, of photoinitiator is used per mole of acid monomer.
- solvents are also used as components of the starting reaction composition.
- the use of water as a solvent is particularly useful.
- the device for irradiating the reaction surface is present as a UV lamp, with which the thin film on the reaction surface is irradiated with light in a wavelength range of 10 to 700 nm, preferably 280 to 400 nm electromagnetically.
- the process parameters set are a layer thickness of the thin film applied by the metering system of 10 ⁇ m to 1.0 mm, preferably 100 to 200 ⁇ m, and a mean residence time of the components of the starting reaction composition on the reaction surface of 0.1 to 20 seconds, preferably from 1 to 10 seconds.
- the rotational speed of the body B as well as the dosage rate of the components of the starting reaction mixture are variable.
- the rotational speed in revolutions per minute is 1 to 20,000, preferably 100 to 5000 and particularly preferably 500 to 2000.
- Reaction mixture which is per unit area of the reaction surface on the rotating body B, is typically 0.1 to 10 mL / dm 2 , preferably 1, 0 to 5.0 mL / dm 2 .
- the average residence time (frequency means of the residence time spectrum) of the reaction mixture is, inter alia, on the size of the reaction surface, on the type and amount of the components of
- Starting reaction mixture of the reaction surface and the rotational speed of the rotating body B dependent and is normally 0.01 to 100 s, preferably 0.1 to 10 s, more preferably 1 to 10 s and is thus considered to be extremely short. This ensures that the level of undesirable side reactions is greatly reduced and products of consistent quality are produced. In particular, the molecular weight can be well controlled even in the case of high viscosities.
- the dosing system employed in a preferred embodiment allows the components of the starting reaction composition to be added at any position on the reaction surface. A portion or all of the components of the starting reaction composition may be premixed and then applied to the reaction surface by the dosing system. Not infrequently, however, the acid monomer and the polyether macromonomer are separated, i. E. not premixed with each other, applied to the reaction surface.
- the reaction surface may extend to further rotating bodies so that the reaction composition, before leaving the reaction surface of the rotating body B, reaches the reaction surface of at least one further rotating body having the reaction surface.
- the other rotating bodies are suitably designed according to the body B.
- body B practically feeds the other bodies with the reaction mixture, ie, the thin film flows from the body B to at least one other body, leaves this at least one other body, and then be collected as a reaction product.
- R 1 is identical or different and represented by H and / or an unbranched or branched C 1 -C 4 -alkyl group
- R 2 is the same or different and represents C 6 H 4 -SO 3 H substituted by OH, SO 3 H, PO 3 H 2, O-PO 3 H 2 and / or para, with the proviso that if X is a non-existent moiety, R 2 is represented by OH;
- R 4 is the same or different and represents C 6 H 4 -SO 3 H substituted by SO 3 H, PO 3 H 2, O-PO 3 H 2 and / or para;
- R 5 is identical or different and is represented by H and / or an unbranched or branched C 1 -C 4 -alkyl group
- Z is identical or different and represented by O and / or NH;
- R 6 is identical or different and is represented by H and / or an unbranched or branched C 1 -C 4 -alkyl group
- Q is the same or different and represented by NH and / or O;
- the acid monomer used is methacrylic acid, acrylic acid, maleic acid, maleic anhydride, a half ester of maleic acid or a mixture of several of these components.
- the acid monomer used may also be an ester compound which can be converted (in particular as a structural unit incorporated in the copolymer) by alkaline saponification (for example in the alkaline medium of the concrete) to the corresponding acid compound.
- the acid monomer not only such an alkaline saponifiable ester compound is used, but typically the ester compound together with an acid monomer having free acid functions (e.g., acrylic acid).
- polyether macromonomer structural unit derived from the reaction of the polyether macromonomer of the copolymer according to one of the general formulas (IIa), (IIb) and / or (Nc)
- R 10 , R 11 and R 12 are each the same or different and are independently represented by H and / or an unbranched or branched C 1 -C 4 -alkyl group;
- E is identical or different and represents C ⁇ H 4 and / or a non-existing unit substituted by an unbranched or branched C 1 -C 6 -alkylene group, a cyclohexyl group, CH 2 -CeHiO, ortho, meta or para;
- G is the same or different and is represented by O, NH and / or CO-NH with the proviso that if E is a non-existent unit, G is also present as a non-existing unit;
- n is the same or different and represented by 0, 1, 2, 3, 4 and / or 5;
- a is the same or different and represented by an integer from 2 to 350 (preferably 10-200);
- R 13 is identical or different and represents H, an unbranched or branched C 1 -C -alkyl group, CO-NH 2, and / or COCH 3;
- R 14 is identical or different and is represented by H and / or an unbranched or branched C 1 -C -alkyl group;
- E is the same or different and is represented by an unbranched or branched C 1 -C 6 -alkylene group, a cyclohexyl group, C 2 -C 6 H 10, ortho, meta or para substituted C6H4 and / or by a non-existent moiety;
- G is the same or different and represented by a non-existent moiety, O, NH and / or CO-NH with the proviso that if E is a non-existent moiety then G is also present as a non-existent moiety;
- n is the same or different and represented by 0, 1, 2, 3, 4 and / or 5
- a is the same or different and represented by an integer from 2 to 350;
- R 15 are identical or different and are represented by H, a straight or branched Ci - C 4 alkyl group, CO-NH2, and / or COCH3;
- R 16 , R 17 and R 18 are each the same or different and are independently represented by H and / or an unbranched or branched C 1 -C 4 -alkyl group;
- E is identical or different and represents CeH 4 substituted by an unbranched or branched C 1 -C 6 -alkylene group, a cyclohexyl group, C 2 -C 6 H 10, ortho, meta or para and / or by a non-existing unit;
- n is the same or different and represented by 0, 1, 2, 3, 4 and / or 5;
- a is the same or different and represented by an integer from 2 to
- d is the same or different and represented by an integer from 1 to 350;
- R 19 is identical or different and represented by H and / or an unbranched or branched C 1 -C 4 -alkyl group
- R 20 is identical or different and is represented by H and / or an unbranched C 1 -C 4 -alkyl group.
- the polyether macromonomer used is vinylated methyl polyethylene glycol, alkoxylated isoprenol and / or alkoxylated hydroxybutyl vinyl ether and / or alkoxylated (meth) allyl alcohol, preferably each having an arithmetic average number of oxyalkylene groups of 4 to 340.
- the starting reaction composition there may be a vinyl unsaturated compound which is reacted by polymerization to thereby produce a structural unit in the copolymer represented by the general formulas (IIIa) and / or (NIb)
- R 21 is identical or different and is represented by H and / or an unbranched or branched C 1 -C 4 group;
- W is the same or different and represented by O and / or NH;
- R 22 is identical or different and represented by a branched or unbranched C 1 -C 8 monohydroxyalkyl group
- R 23 , R 24 and R 25 are each the same or different and each independently represented by H and / or an unbranched or branched C 1 - C 1 alkyl group;
- n is the same or different and represented by 0, 1, 2, 3 and / or 4;
- R 26 is identical or different and represented by (C ⁇ Hs), OH and / or -COCH 3 .
- Most components of the starting reaction composition used are as much polyether macromonomer per mole of acid monomer that an arithmetic average molar ratio of acid monomer structural units to polyether macromonomer structural units of from 20: 1 to 1: 1, preferably from 12: 1 to 1: 1, is established in the copolymer formed.
- At least 45 mole percent, but preferably at least 80 mole percent, of all the structural units of the copolymer are present as acid monomer structural units and polyether macromonomer structural units.
- a chain regulator which is preferably in dissolved form, may be present as a further component of the starting reaction composition.
- the monomeric starting materials and / or the initiator may be presented in the form of their aqueous solutions as components of the Ninre syndrome.
- the invention further relates to a copolymer which can be prepared according to the method described above.
- the present invention relates to the use of this copolymer as a dispersant for hydraulic binders.
- a reactor cascade consisting of three reactors of the reactor type Protensive Limited. The diameter of the respective disc was 20 cm.
- a monomer solution consisting of 57.5% macromonomer (prepared by ethoxylation of 4-hydroxybutyl vinyl ether with 22 moles of EO), 6.4% acrylic acid (99.5%), 1.6% KOH (40%), 0.1% 3-mercaptopropionic acid, 33.9 % Water and 0.5% initiator (Irgarcure 500, Ciba - chemical: mixture of 1-hydroxy-cyclohexyl-phenyl ketone and
- Benzophenone in the molar ratio of 1: 1) prepared in a reservoir and metered through the housing opening in the middle of the disc of the first reactor.
- the flow rate was 1 ml / s and the rotational speed 800 revolutions / min.
- the thin film forming on the rotating disk was irradiated with UV light (wavelength between 280 and 400 nm).
- the reaction solution leaving the first reactor was then sequentially metered onto the reaction surfaces of the second and third reactors of the cascade, on each of which the process described on the first disk was repeated with the same parameters.
- the temperature of the reaction surface was about 22 ° C. After leaving the disk of the third reactor, the reaction mixture was collected and then analyzed.
- the aqueous solution of a copolymer having an average molecular weight of Mw 39700 g / mol and a polydispersity of 1.80 was obtained.
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Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP09783837A EP2340274A1 (en) | 2008-10-10 | 2009-10-08 | Continuous production of copolymers suitable as flow agents |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP08166298 | 2008-10-10 | ||
EP09783837A EP2340274A1 (en) | 2008-10-10 | 2009-10-08 | Continuous production of copolymers suitable as flow agents |
PCT/EP2009/063070 WO2010040794A1 (en) | 2008-10-10 | 2009-10-08 | Continuous production of copolymers suitable as flow agents |
Publications (1)
Publication Number | Publication Date |
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EP2340274A1 true EP2340274A1 (en) | 2011-07-06 |
Family
ID=41395701
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP09783837A Withdrawn EP2340274A1 (en) | 2008-10-10 | 2009-10-08 | Continuous production of copolymers suitable as flow agents |
Country Status (3)
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US (1) | US20110306696A1 (en) |
EP (1) | EP2340274A1 (en) |
WO (1) | WO2010040794A1 (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
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EP2310157B1 (en) * | 2008-07-23 | 2013-04-10 | Construction Research & Technology GmbH | Method for producing metal nanoparticles in polyols |
EP2313445B1 (en) * | 2008-08-08 | 2011-11-02 | Construction Research & Technology GmbH | Production of silylated polyurethane and/or polyurea |
EP2742995A1 (en) | 2012-12-11 | 2014-06-18 | Construction Research & Technology GmbH | Continuous method for manufacturing copolymers |
CN105778007A (en) * | 2014-12-22 | 2016-07-20 | 辽宁奥克化学股份有限公司 | Polymer, preparation method thereof, and water reducer comprising same |
CN113929836B (en) * | 2021-11-01 | 2024-03-26 | 湖北凌安科技有限公司 | High-dispersion viscosity-reducing water reducer and preparation method thereof |
Family Cites Families (5)
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GB9903474D0 (en) * | 1999-02-17 | 1999-04-07 | Univ Newcastle | Process for the conversion of a fluid phase substrate by dynamic heterogenous contact with an agent |
JP2003241032A (en) * | 2002-02-21 | 2003-08-27 | Dainippon Ink & Chem Inc | Resin composition for coating optical fiber and optical fiber using the same |
US6582510B1 (en) * | 2002-04-16 | 2003-06-24 | Arco Chemical Technology, L.P. | Use of comb-branched copolymers as pigment dispersants |
DE102004005434A1 (en) * | 2004-02-04 | 2005-08-25 | Construction Research & Technology Gmbh | Copolymers based on unsaturated mono- or dicarboxylic acid derivatives and oxyalkylene glycol-alkenyl ethers, process for their preparation and their use |
US8541518B2 (en) * | 2008-03-19 | 2013-09-24 | Construction Research & Technology Gmbh | Semi continuous operational method for producing copolymers |
-
2009
- 2009-10-08 EP EP09783837A patent/EP2340274A1/en not_active Withdrawn
- 2009-10-08 WO PCT/EP2009/063070 patent/WO2010040794A1/en active Application Filing
- 2009-10-08 US US13/122,663 patent/US20110306696A1/en not_active Abandoned
Non-Patent Citations (1)
Title |
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See references of WO2010040794A1 * |
Also Published As
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WO2010040794A1 (en) | 2010-04-15 |
US20110306696A1 (en) | 2011-12-15 |
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