Source: http://www.google.com/patents/US5147907?ie=ISO-8859-1
Timestamp: 2015-03-04 17:45:48
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Matched Legal Cases: ['application no. 134', 'arts   30', 'arts   70', 'arts   0', 'arts   0', 'arts   14']

Patent US5147907 - Process of producing aqueous polymer dispersions - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsA process is described for the production of an aqueous polymer dispersion by polymerization of ethylenically unsaturated compounds by means of free-radical initiators in the presence of starch and/or starch derivatives and optional further conventional adjuvants, and which the dispersions are coagulate-free,...http://www.google.com/patents/US5147907?utm_source=gb-gplus-sharePatent US5147907 - Process of producing aqueous polymer dispersionsAdvanced Patent SearchPublication numberUS5147907 APublication typeGrantApplication numberUS 07/550,630Publication dateSep 15, 1992Filing dateJul 10, 1990Priority dateJul 11, 1989Fee statusLapsedAlso published asDE3922784A1, EP0408099A1, EP0408099B1Publication number07550630, 550630, US 5147907 A, US 5147907A, US-A-5147907, US5147907 A, US5147907AInventorsGunter Rinck, Knut Moller, Sigismund Fullert, Frank Krause, Helmut KochOriginal AssigneeSynthomer Chemie Gmbh, Cerestar Holding B.V.Export CitationBiBTeX, EndNote, RefManPatent Citations (7), Referenced by (37), Classifications (34), Legal Events (7) External Links: USPTO, USPTO Assignment, EspacenetProcess of producing aqueous polymer dispersions
US 5147907 AAbstract
1. A process for the production of an aqueous polymer dispersion comprising:polymerizing an ethylenically unsaturated diene monomer or a mixture of monomers consisting of20% to 100% by weight of a diene monomer, 0% to 80% by weight of a vinyl-aromatic monomer, and 0% to 50% by weight of an ethylenically unsaturated monomer, by means of one or more free radical initiators in the presence of an aqueous dextrin solution or dispersion containing 10 parts to 200 parts by weight dextrins, wherein the content of said dextrins having a molecular weight in excess of 5000 is at least 50% by weight and the content of said dextrins having a molecular weight in excess of 10,000 is not in excess of 5% by weight of the dextrin component. 2. The process of claim 1, wherein said dextrins are chemically modified
15. The process of claim 14, wherein said polymerization is carried out at a temperature of 0� C. to 120� C.
16. The process of claim 15, wherein said polymerization is carried out at a temperature of from 40� C. to 100� C.
19. The process of claim 17, wherein said mixed monomers comprise,20% to 70% by weight 1,3-butadiene, 30% to 80% by weight styrene, 0% to 15% by weight acrylonitrile, and 0% to 5% by weight ethylenically unsaturated mono- or dicarboxylic acid. 20. The process of claim 18, wherein said ethylenically unsaturated mono- or dicarboxylic acid is selected from acrylic acid and itaconic acid or a mixture thereof.
21. A polymer dispersion prepared by the process of claim 1, 4 or 5, wherein the average particle diameter is less than about 250 nm, the viscosity measured at a solids content of 50�1% by weight is less than 2000 mpas, and the solids concentration is at least 50% by weight.
Published European patent application no. 134,449 discloses a process of producing an aqueous polymer dispersion by the emulsion polymerization of ethylenically unsaturated compounds in the presence of starch and at least 0.6% by weight starch derivatives. Before the polymerization begins, 0.5% by weight starch derivatives acting as a protective colloid are added to the reaction mixture. In this process, organic hydroperoxides are used as radical-forming initiators at reaction temperatures of 10� C. to 100� C. The resulting polymer dispersions have relatively large particle diameters of 235 nm to 3500 nm. The polymer dispersions produced by the aforesaid process may be used, e.g., as adjuvants in the production of textiles and paper.
Dextrins are starch decomposition products having the general formula (C6 H10 O5)n �H2 O. They are formed by an incomplete hydrolysis of starch with dilute acids or by an action of heat, and consist of glucose chains.
Dextrins are used in the present invention in an amount of 10 parts to 200 parts by weight, and preferably in an amount of 25 parts to 100 parts by weight, solids per 100 parts by weight of monomer or mixed monomers. Polymerization is effected at temperatures of 0� C. to 120� C., and preferably 40� C. to 100�C.
As mentioned hereinabove a reaction temperature between 0� C. and 120� C. during polymerization is maintained. Such a reaction temperature is preferably chosen such that the half-life of the free-radical initiators is so short that sufficiently fast reactions will be ensured. For example, if peroxydisulfates are employed, the preferred temperature range is between 40� C. and 100� C. The pressure is not controlled during the polymerization reaction and will amount to the sum of the partial pressures of the reaction components at a selected reaction temperature. When the reaction has been terminated the reaction mixture is subjected to conventional water vapor distillation methods to remove the residue monomers. The average particle diameter of the polymer dispersions is below 250 nm. The Brookfield viscosity of the polymer dispersions according to the invention, measured at a solids content of 50�1% by weight, is below 2000 mPa s and the solids concentration is at least 50% by weight.
Mixture A is charged into a 4-liter stirrer-autoclave and the reactor is subsequently heated up. When a reaction temperature of 90� C. has been reached, mixture B is added. Immediately thereafter, mixtures C, D and E are metered into the reactor at the same time. Before mixtures C and D enter the autoclave they are passed through an in-line mixer by which said two streams are thoroughly mixed. Mixture E is separately metered. Mixtures C, D and E are metered into the autoclave at a constant rate within 6 hours. After a subsequent afterreaction time of one hour, a dextrin-containing polymer dispersion is obtained, which has the properties summarized in Table 2 below. The resulting properties of the obtained polymer dispersions after the residual monomers have been removed by water vapor distillation (stripping) and the pH value has been increased to 6 are also summarized in Table 2.
TABLE 1______________________________________       Number    Proportion of       average of                 molecular weight             molecular   &gt;5000 &gt;100,000Dextrin           weight      % by  % byType    Designation             g/mole      weight                               weight______________________________________I       07082 2)  4,700       66.0  0II      07380 2)  3,300       68.7  0.5III     08320 2)  3,400       66.5  0IV      08380 2)  3,400       66.1  2.8V       Tackidex  4,100       70.4  0.6   JO 55 K 3)VI      acetylated             5,830       79.8  0   dextrin 4)VII     carboxyl- 5,900       78.2  3.6   ated dextrin   No. 1 4)VIII 1) 07321 2)  4,700       83.8  6.9IX 1)   carboxyl- 10,900      86.0  14.6   ated dextrin   No. 2 4)______________________________________ 1) No dextrin present such as required in accordance with the invention 2) Corn dextrin of Cerestar GmbH, Krefeld 3) Corn dextrin of Roquette, Lille, France 4) Chemically modified dextrins of Cerestar GmbH, Krefeld
Mixture A is charged into a 4-liter stirrer-autoclave and the reactor is subsequently heated up. When a reaction temperature of 90� C. has been reached, mixture B is added. Immediately thereafter, mixtures C and D are metered at the same time. The mixtures are separately metered into the autoclave at a constant rate within 6 hours. After a subsequent afterreaction time of one hour, a dextrin-containing polymer dispersion is obtained. The respective properties of the resulting dispersion as a reactor effluent and after stripping are summarized below in Table 3.
For this purpose, four colored paper-coating compositions composed as summarized below in Table 4 are prepared and by use of a laboratory doctor are coated onto a woodpulp-containing raw paper (weight 36 g/m2). The applied coating composition weighs 12 g/m2. The coated sheets are then dried (3 minutes, 110� C.), calendered (70� C., 700 N/cm) and subjected to the following tests:
TABLE 4______________________________________         Composition/Experiment No.Component       16      17      18    19______________________________________Calcium carbonate       parts   30.0    30.0  30.0  30.0(Hydrocarb 90 + 1)       by       weightClay SPS    parts   70.0    70.0  70.0  70.0(Speswhite + 2)       by       weightDispersing agent       parts   0.25    0.25  0.25  0.25(Polysalz F + 3)       by       weightCa stearate (Om-       parts   0.1     0.1   0.1   0.1brelube FC 544 + 4)       by       weightDispersion 11       parts   14.0    --    --    --(see Table 3)       by       weightDispersion 14       parts   --      14.0  --    --(see Table 3)       by       weightControl dis-       parts   --      --    9.5   9.5(spersion + 5)       by       weightDextrin No. III       parts   --      --    4.5   --(see Table 1)       by       weightControl starch + 6)       parts   --      --    --    4.5       by       weightSolids content       % by    55.0    55.0  55.0  55.0       weightpH value            9.0     9.0   9.0   9.0Viscosity of coat-       mPa s   173     165   60    1790ing compositionsResistance to       %       11.9    15.3  54.5  39.5picking in wet       remis-state       sionResistance to       cm/s    115     115   105   105picking in drystate______________________________________ + 1) Omya Gmbh, Cologne; + 2) ECC, Dusseldorf; + 3) BASF, Ludwigshafen; + 4) Munzig Chemie GmbH, Heilbronn; + 5) Starchfree polymer dispersion in other respects composed like Dispersion 11; + 6) Commercially available starch (Amysol 5582 of Cerester GmbH, Krefeld)
The solids contents were determined after the products are dried to a constant weight at 140� C.
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ethylenically unsaturated carboxylic acid nitrileWO1996015187A1 *Nov 9, 1995May 23, 1996Wacker Chemie GmbhRedispersable polymer powder compositions containing cyclodextrin or cyclodextrin derivativesWO2002084028A1 *Apr 12, 2002Oct 24, 2002Miettinen PaeiviNovel coating color compositionWO2009079254A1 *Dec 8, 2008Jun 25, 2009Johns ManvilleBase interlining, methods for their manufacture and application thereofWO2010060863A1 *Nov 20, 2009Jun 3, 2010Basf SeMethod for preparing aqueous polymer dispersions from a vinyl aromatic compound, a conjugated aliphatic diene and an ethylenically unsaturated carboxylic acid nitrileWO2012000609A1 *Jun 15, 2011Jan 5, 2012Cargill, IncorporatedStarch-based compositions for latex replacement* Cited by examinerClassifications U.S. Classification524/48, 524/836, 526/200, 524/822, 524/819, 524/821, 524/734, 524/47International ClassificationD06M15/11, C09J121/02, D21H19/54, D06M15/05, C08F36/00, C08F236/10, D06N7/00, D21H19/58, C08F236/04, C08F2/20, C09J109/10, C08F2/18, C08F251/00, C08F12/00, C08F4/40, D06M15/21, C08F4/30, C08F2/44Cooperative ClassificationC08F236/04, C08F251/00, D21H19/58, D21H19/54European ClassificationC08F236/04, D21H19/58, C08F251/00, D21H19/54Legal EventsDateCodeEventDescriptionNov 21, 2000FPExpired due to failure to pay maintenance feeEffective date: 20000915Sep 17, 2000LAPSLapse for failure to pay maintenance feesApr 11, 2000REMIMaintenance fee reminder mailedApr 23, 1996REMIMaintenance fee reminder mailedFeb 23, 1996FPAYFee paymentYear of fee payment: 4Mar 1, 1994CCCertificate of correctionOct 15, 1990ASAssignmentOwner name: CERESTAR HOLDING B.V., NIJVERHEIDSSTRAAT 1 P.O. BOFree format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:RINCK, GUNTER;MOLLER, KNUT;FULLERT, SIGFSMUND;AND OTHERS;REEL/FRAME:005467/0951;SIGNING DATES FROM 19900920 TO 19901001Owner name: SYNTHOMER CHEMIE GMBH REUTERWEG 14 D-6000 FRANKFURFree format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:RINCK, GUNTER;MOLLER, KNUT;FULLERT, SIGFSMUND;AND OTHERS;REEL/FRAME:005467/0951;SIGNING DATES FROM 19900920 TO 19901001RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services