DE1147754B - Process for the production of emulsion polymers - Google Patents
Process for the production of emulsion polymersInfo
- Publication number
- DE1147754B DE1147754B DEB64239A DEB0064239A DE1147754B DE 1147754 B DE1147754 B DE 1147754B DE B64239 A DEB64239 A DE B64239A DE B0064239 A DEB0064239 A DE B0064239A DE 1147754 B DE1147754 B DE 1147754B
- Authority
- DE
- Germany
- Prior art keywords
- water
- emulsion
- polymerization
- polymers
- production
- 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.)
- Pending
Links
- 239000004908 Emulsion polymer Substances 0.000 title claims description 6
- 238000000034 method Methods 0.000 title claims description 6
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- 239000003995 emulsifying agent Substances 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 239000000839 emulsion Substances 0.000 claims description 5
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 claims description 5
- 150000004668 long chain fatty acids Chemical class 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000007720 emulsion polymerization reaction Methods 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- KHJWSKNOMFJTDN-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;sodium Chemical compound [Na].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KHJWSKNOMFJTDN-UHFFFAOYSA-N 0.000 description 1
- -1 Fatty acid salt Chemical class 0.000 description 1
- PMVSDNDAUGGCCE-TYYBGVCCSA-L Ferrous fumarate Chemical compound [Fe+2].[O-]C(=O)\C=C\C([O-])=O PMVSDNDAUGGCCE-TYYBGVCCSA-L 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Natural products OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- SELIRUAKCBWGGE-UHFFFAOYSA-N hexadecanoic acid;octadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O SELIRUAKCBWGGE-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
Description
Verfahren zur Herstellung von Emulsionspolymerisaten Gegenstand der Erfindung ist ein Verfahren zur Herstellung von Emulsionspolymerisaten. Insbesondere betrifft die Erfindung die Verwendung eines besonderen Emulgators bei der Emulsionspolymerisation. Process for the preparation of emulsion polymers The invention is a process for the production of emulsion polymers. In particular the invention relates to the use of a particular emulsifier in emulsion polymerization.
Die Polymerisation von polymerisierbaren Verbindungen in wäßriger Emulsion ist bekannt. Sie wird unter Verwendung von Polymerisationsbeschleunigem und von Emulgiermitteln vorgenommen. Die üblichen Emulgiermittel sind wasserlöslich. Bei der Aufarbeitung der Emulsionspolymerisate verbleiben die Emulgatoren im allgemeinen im Polymerisat. Dadurch wird die Wasseraufnahmefähigkeit dieser Polymerisate erhöht. Wenn man die Emulgatoren jedoch bei der Gewinnung der Festpolymerisate entfernt, ist man auf umständliche und kostspielige Verfahren angewiesen. The polymerization of polymerizable compounds in aqueous Emulsion is known. It is made using polymerization accelerator and made of emulsifiers. The usual emulsifiers are water-soluble. When the emulsion polymers are worked up, the emulsifiers generally remain in the polymer. This increases the water absorption capacity of these polymers. However, if the emulsifiers are removed when the solid polymers are obtained, one is dependent on cumbersome and costly procedures.
Polymerisate mit geringer Wasseraufnahmefähigkeit kann man bekanntlich durch Polymerisation in wäßriger Suspension herstellen. Als Suspensionsstabilisator kann man dabei wasserunlösliche Verbindungen verwenden, so daß durch diese die Wasseraufnahmefähigkeit nicht beeinflußt wird. Die Suspensionen setzen sich jedoch rasch ab, bedingt durch die im Vergleich zur Emulsionspolymerisation größeren Teilchen. Dies erschwert oftmals die weitere Bearbeitung, z. B. das Abmischen mit anderen Dispersionen. It is known that polymers with a low water absorbency can be used prepared by polymerization in aqueous suspension. As a suspension stabilizer you can use water-insoluble compounds, so that the water absorption capacity through them is not affected. However, the suspensions settle quickly, to a limited extent the larger particles compared to emulsion polymerization. This often makes it difficult further processing, e.g. B. mixing with other dispersions.
Es wurde nun gefunden, daß man Emulsionspolymerisate, die sich durch eine besonders geringe Wasseraufnahme auszeichnen, vorteilhaft herstellen kann, wenn man äthylenisch ungesättigte, polymerisierbare Verbindungen in an sich üblicher Weise in wäßriger Emulsion polymerisiert, jedoch als Emulgiermittel ein wasserlösliches Komplexsalz aus Natriumäthylendiamintetraacetat und einem wasserunlöslichen Salz einer langkettigen Fettsäure verwendet. It has now been found that you can emulsion polymers through have a particularly low water absorption, can advantageously produce, if you have ethylenically unsaturated, polymerizable compounds in per se Polymerized in an aqueous emulsion, but a water-soluble emulsifier Complex salt of sodium ethylenediaminetetraacetate and a water-insoluble salt a long-chain fatty acid.
Der wasserlösliche Komplex aus Natriumäthylendiamintetraacetat und einem wasserunlöslichen Salz einer langkettigen Fettsäure bildet sich durch einfaches Zusammengeben der beiden Komponenten in wäßriger Phase schon beim leichten Erwärmen. In kaltem Wasser ist das Komplexsalz unlöslich, in der Wärme dagegen löslich. Die Polymerisate, die unter Verwendung dieses Komplexsalzes als Emulgator in wäßriger Emulsion hergestellt wurden und die in üblicher Weise aus den wäßrigen Dispersionen als Festprodukte gewonnen wurden, enthalten den Komplex nicht mehr in wasserlöslicher Form. The water-soluble complex of sodium ethylenediamine tetraacetate and a water-insoluble salt of a long-chain fatty acid is formed by simple Combination of the two components in the aqueous phase even with slight warming. The complex salt is insoluble in cold water, but soluble in warm water. the Polymers made using this complex salt as an emulsifier in aqueous Emulsion were prepared and in the usual manner from the aqueous dispersions When solid products were obtained, the complex no longer contained in water-soluble Shape.
Äthylenisch ungesättigte, polymerisierbare Verbindungen, die erfindungsgemäß polymerisiert werden können, sind insbesondere Styrol, das am Kern durch Alkyl oder Halogen substituiert sein kann, sowie andere Vinyl- und Acrylverbindungen. Solche Verbindungen sind beispielsweise Vinylchlorid, Vinyliden- chlorid, Acryl- und Methacrylsäure sowie deren Ester, Amide und Nitrile oder auch Vinyläther und Vinylester. Diese monomeren Verbindungen können allein oder auch mischpolymerisiert werden. Auch Fumar-und Maleinsäure können als Comonomere verwendet werden. Ethylenically unsaturated, polymerizable compounds according to the invention can be polymerized, are in particular styrene, which is on the core by alkyl or Halogen can be substituted, as well as other vinyl and acrylic compounds. Such Compounds are, for example, vinyl chloride, vinylidene chloride, acrylic and methacrylic acid as well as their esters, amides and nitriles or also vinyl ethers and vinyl esters. These monomeric compounds can be polymerized alone or as a copolymer. Also fumar and Maleic acid can be used as comonomers.
Als wasserunlösliche Salze langkettiger Fettsäuren, die mit Natriumäthylendiamintetraacetat in Komplexform als Emulgiermittel verwendet werden, kommen beispielsweise die Salze der Metalle der II. und III. Hauptgruppe sowie der II. Nebengruppe des Periodensystems mit höheren Fettsäuren in Frage. As water-insoluble salts of long-chain fatty acids with sodium ethylenediaminetetraacetate are used in complex form as emulsifiers, come for example the salts of metals of II. and III. Main group as well as the II. Subgroup of the periodic table with higher fatty acids in question.
Höhere Fettsäuren sind insbesondere Laurylsäure, Stearinsäure oder Palmitinsäure.Higher fatty acids are in particular lauric acid, or stearic acid Palmitic acid.
Das in Wasser lösliche Komplexsalz wird in solchen Mengen bei der Emulsionspolymerisation angewendet, daß etwa 0,5 bis 2 Gewichtsprozent des wasserunlöslichen Fettsäuresalzes, bezogen auf die zu polymerisierenden Monomeren, während der Polymerisation anwesend sind. Die Menge an Natriumäthylendiamintetraacetat wird so bemessen, daß der sich bildende Komplex bei etwa 500 C in Wasser gelöst ist. The water-soluble complex salt is used in such amounts in the Emulsion polymerization applied that about 0.5 to 2 percent by weight of the water-insoluble Fatty acid salt, based on the monomers to be polymerized, during the polymerization are present. The amount of sodium ethylenediamine tetraacetate is calculated so that the complex that forms is dissolved in water at about 500 C.
Als Polvmerisationsinitiatoren werden die üblichen angewendet, also beispielsweise Radikale bildende Verbindungen, wie Peroxyde, Persäuren oder Azoverbindungen. Auch die anderen Polymerisationsbedingungen, wie die Polymerisationstemperatur oder die Verwendung von Polymerisationsreglem, entsprechen den bei der Emulsionspolymerisation üblichen. The usual polymerisation initiators are used, ie for example compounds which form free radicals, such as peroxides, peracids or azo compounds. The other polymerization conditions, such as the polymerization temperature or the use of polymerization rules correspond to those for emulsion polymerization usual.
Das erfindungsgemäße Verfahren ermöglicht es, an sich wasserunlösliche Verbindungen als Emulgatoren bei der Emulsionspolymerisation zu verwenden. Da die im Polymerisat verbleibenden Emulgiermittel wiederum wasserunlöslich sind, wird die Wasseraufnahmefähigkeit derPolymerisate dadurch nicht erhöht. The method according to the invention enables water-insoluble per se Compounds as emulsifiers in emulsion polymerization use. Since the emulsifiers remaining in the polymer are again insoluble in water the water absorption capacity of the polymers is not increased as a result.
Die in dem Beispiel genanriten Teile sind Gewichtsteile Beispiel 1 Teil Zinkstearat und 1 Teil äthylendiamintetraessigsaures Natrium werden bei PH 10 unter Erwärmen auf 500 C in 195 Teilen Wasser gelöst.The parts specified in the example are parts by weight of Example 1 Part of zinc stearate and 1 part of ethylenediaminetetraacetic acid sodium are at pH 10 dissolved in 195 parts of water while heating to 500.degree.
Hierzu werden 20 Teile einer Mischung aus 72 Teilen Styrol und 28 Teilen Acrylnitril und 1,5 Teile einer Lösung von 0,4 Teilen Kaliumpersulfat in 7,5 Teilen Wasser gegeben. Die unter Rühren entstehende Emulsion wird auf 900 C erwärmt und innerhalb von 2Stunden bei 900 C die restliche Mischung aus Styrol und Acrylnitril sowie die Kaliumpersulfatlösung zulaufen gelassen. For this purpose, 20 parts of a mixture of 72 parts of styrene and 28 Parts of acrylonitrile and 1.5 parts of a solution of 0.4 parts of potassium persulfate in 7.5 parts of water are given. The emulsion formed while stirring is heated to 900.degree heated and within 2 hours at 900 C the remaining Mixture of styrene and Acrylonitrile and the potassium persulfate solution are allowed to run in.
Man erhält eine Dispersion mit etwa 32 0/o Feststoffgehalt in einer etwa 960/obigen Ausbeute. Das daraus erhaltene Polymerisat zeichnet sich durch geringe Wasseraufnahme aus. A dispersion with about 32% solids content is obtained in one about 960 / above yield. The polymer obtained therefrom is characterized by low Water absorption off.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB64239A DE1147754B (en) | 1961-10-05 | 1961-10-05 | Process for the production of emulsion polymers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB64239A DE1147754B (en) | 1961-10-05 | 1961-10-05 | Process for the production of emulsion polymers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1147754B true DE1147754B (en) | 1963-04-25 |
Family
ID=6974309
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEB64239A Pending DE1147754B (en) | 1961-10-05 | 1961-10-05 | Process for the production of emulsion polymers |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1147754B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1271889B (en) * | 1958-04-14 | 1968-07-04 | Monsanto Co | Device for the continuous treatment of endless strands of fibers or threads with a pressure chamber |
-
1961
- 1961-10-05 DE DEB64239A patent/DE1147754B/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1271889B (en) * | 1958-04-14 | 1968-07-04 | Monsanto Co | Device for the continuous treatment of endless strands of fibers or threads with a pressure chamber |
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