DE1021165B - Process for the production of easily plasticizable polyvinyl chloride suspension polymer - Google Patents
Process for the production of easily plasticizable polyvinyl chloride suspension polymerInfo
- Publication number
- DE1021165B DE1021165B DEF20372A DEF0020372A DE1021165B DE 1021165 B DE1021165 B DE 1021165B DE F20372 A DEF20372 A DE F20372A DE F0020372 A DEF0020372 A DE F0020372A DE 1021165 B DE1021165 B DE 1021165B
- Authority
- DE
- Germany
- Prior art keywords
- production
- polyvinyl chloride
- suspension polymer
- chloride suspension
- plasticizable
- 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
- 229920000642 polymer Polymers 0.000 title claims description 12
- 238000000034 method Methods 0.000 title claims description 8
- 239000000725 suspension Substances 0.000 title claims description 7
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 229920000915 polyvinyl chloride Polymers 0.000 title claims description 5
- 239000004800 polyvinyl chloride Substances 0.000 title claims description 5
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 3
- 239000001273 butane Substances 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000004908 Emulsion polymer Substances 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- UKIMGCJPCFNHHF-UHFFFAOYSA-N 2-methylpropyl naphthalene-1-sulfonate;sodium Chemical compound [Na].C1=CC=C2C(S(=O)(=O)OCC(C)C)=CC=CC2=C1 UKIMGCJPCFNHHF-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C08F14/00—Homopolymers and 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 a halogen
- C08F14/02—Monomers containing chlorine
- C08F14/04—Monomers containing two carbon atoms
- C08F14/06—Vinyl chloride
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 leichtplastifizierbarem Polyvinylchlorid-Suspensionspolymerisat Man kann Vinylchlorid nach den bekannten Verfahren der Block-, Lösungs,- Emulsions- und Suspensionspolymerisation polymerisieren (Literatur: C. E. Schildknecht, Polymer Processes, 1956). Die Polymerisate unterscheiden sich zum Teil in ihrer äußeren Form und in ihren Eigenschaften. Eine anwendungstechnisch besonders wichtige Eigenschaft ist die Plastifiziergeschwindigkeit. Diese ist temperaturabhängig, sie nimmt mit steigender Temperatur zu, Da die Zersetzungsgeschwindigkeit von Polyvinylchlorid mit steigender Temperatur und mit der Dauer der Verarbeitung zunimmt, ist man bestrebt, die Verarbeitung bei möglichst niedriger Temperatur und kurzen Zeiten vorzunehmen.Process for the production of easily plasticizable polyvinyl chloride suspension polymer Vinyl chloride can be polymerized by the known processes of block, solution, emulsion and suspension polymerization (literature: CE Schildknecht, Polymer Processes, 1956). The polymers differ partly in their external shape and in their properties. A particularly important property from an application point of view is the plasticizing speed. This is temperature-dependent; it increases with increasing temperature. Since the rate of decomposition of polyvinyl chloride increases with increasing temperature and with the duration of processing, endeavors are made to carry out processing at the lowest possible temperature and with the shortest possible times.
Beim Vergleich von Produkten mit gleichem Molekulargewicht (gleicher spezifischer Viskosität) ist das Produkt bezüglich Plastifiziergeschwindigkeit am wertvollsten, das sich am schnellsten bei gegebener Temperatur plastifizieren läßt oder das die Anwendung der tiefsten Verarbeitungstemperatur erlaubt bei gleicher Plastiflziergeschwindigkeit.When comparing products with the same molecular weight (same specific viscosity) is the product in terms of plasticizing speed am most valuable that can be plasticized fastest at a given temperature or that allows the use of the lowest processing temperature for the same Plasticizing speed.
Es ist nun allgemein bel, annt, daß Ernulsionspolymerisate besonders leicht verarbeitbar sind. Die Produkte weisen jedoch, wenn sie noch Emulgatorreste enthalten, verschiedene Nachteile auf, die z. B. ihre Verwendung im Elektrosektor oder für die Herstellung glasklarer Artikel ausschließen. Besser geeignet für diese Anwendungsgebiete sind die sogenannten Suspensions- oder Perlpolymerisate. Neben ihren hervorragenden elektrischen Eigenschaften, die ihre Verwendung auf dem Isolationsgebiet gestatten, kann man sie zur Herstellung von glasklaren Folien oder anderen Artikeln verwenden. Ein Nachteil der Suspensionspolymerisate ist ihre langsamere Plastifizierung und daraus resultierende schwierigere Verarbeitbarkeit im Vergleich zu Emulsionspolymerisaten von gleichem K-Wert.It is now generally unlikely that emulsion polymers especially are easy to process. However, if the products still contain emulsifier residues contain various disadvantages, e.g. B. their use in the electrical sector or exclude for the production of clear articles. More suitable for this Areas of application are the so-called suspension or pearl polymers. Next to their excellent electrical properties, which makes their use in the field of insulation they can be used for the production of crystal-clear foils or other articles use. A disadvantage of the suspension polymers is their slower plasticization and the resulting more difficult processability compared to emulsion polymers of the same K value.
Neben der schlechten Plastifizierbarkeit treten in den Walzfolien sogenannte Stippen ("fish-eyes"; s. USA.-Patentschrift 2 528 469) auf, die sich sehr störend auswirken. Man kann das Auftreten dieser Stippen zum Teil verhindern bzw. reduzieren, wenn man bei der Polymerisation neben den wasserlöslichen Schutzkolloiden geringe Mengen von kapillaraktiven Stoffen zusetzt (britische Patentschriften 627 235 und 622 944, USA.-Patentschrift 2 528 469). Weiterhin ist bekannt, daß man ein leichtplastifizierbares Suspensionspolymerisat von poröser Struktur herstellen kann (französische Patentschrift 1099 238), wenn die Polymerisation unterhalb des Sättigungsdruckes von Vinylchlorid durchgeführt wird.(USA. Patent 2,528,469 s "fish-eyes".) That affect very disturbing Besides the poor plasticizability called specks appear in the roll films. One can prevent or reduce the occurrence of these specks in some cases when low in the polymerization in addition to the water-soluble protective colloids amounts of capillary-active substances are added (British patent specifications 627 235 and 622 944, USA. Patent 2,528,469). It is also known that an easily plasticizable suspension polymer with a porous structure can be produced (French patent 1099 238) if the polymerization is carried out below the saturation pressure of vinyl chloride.
Durch Zusatz von kapillaraktiven Stoffen (Emulgatoren) wird die Plastifiziergeschwindigkeit nicht verbessert. Die Polymerisation unterhalb des Sättigungsdruckes reduziert in erheblichem Maß die Polymerisationsgeschwindigkeit.The plasticizing speed is increased by adding capillary-active substances (emulsifiers) not improved. The polymerization below the saturation pressure reduces in the rate of polymerization to a considerable extent.
Es wurde nun gefunden, daß man überraschenderweise ein sehr leicht plastifizierbares Polyvinylchlorid-Suspensionspolymerisat herstellen kann, wenn die Suspensionspolymerisation in Gegenwart von geringen Mengen eines gesättigten Kohlenwasserstoffs, dessen Siedepunkt zwischen - 110 und + 150', vorzugsweise zwischen - 40 und + 50', liegt, und zwar in Mengen von 0,5 bis 40"/" vorteilhaft 3 bis 120/" bezogen auf das monomere Viiiylchlorid, durchgeführt wird. Als Kohlenwasserstoffe kann man z. B. Methan und Äthan verwenden. Besonders günstig ist die Verwendung von Propan, n-Butan und n-Pentan bzw. deren Isomerer, z. B. 2-Methylbutan. Man kann jedoch auch höhere Kohlenwasserstoffe, z. B. Hexan, Heptan und ihre isomeren Formen, ferner Oktan und seine Isomere, einsetzen. Die genannten Paraffine können auch in Mischung untereinander bzw. mit ihren Isomeren angewandt werden. Auch technische Gemische dieser Verbindungen sind anwendbar, wobei das erfindungsgemäße Verfahren nicht gestört wird, wenn geringe Anteile ungesättigter Kohlenwasserstoffe anwesend sind. Kohlenwasserstoffe, deren Siedepunkte höher als 150' liegen, sind weniger gut geeignet, da zu ihrer Entfernung aus dem Polymerisat Temperaturen erforderlich sind, bei denen die Qualität der Polvmerisate nachteilig verändert werden 'kann. Beispiel In einem Rührautoklav werden zu 180 Gewichtsteilen Wasser, 0,5 Gewichtsteilen Polyvinylalkohol, 0,03 Gewichtsteileri isobutylnaphthalinsulfosaurem Natrium und 0,5 Gewichtsteilen Benzoylperoxyd oder Lauroylperoxyd 100 Gewichtsteile Vinylchlorid und 3 Gewichtsteile n-Butau hinzugefügt. Die Reaktion wird bei einer Temperatur von 52' durchgeführt. Nach 8 Stunden erhält man 75 Gewichtsteile Polymeres vom K-Wert 70 und von sehr einheitlicher Kornverteilung zwischen 50 und 150 Korndurchmesser. Das Produkt läßt sich mit 30 0/, Dioctylphthalat als Weichmacher schon bei 130' leicht plastifizieren. Für die Plastifizierung eines Produktes, das ohne Butanzusatz hergestellt wurde, ist die dreifache Zeit erforderlich.It has now been found that, surprisingly, can produce a very easily plasticizable polyvinyl chloride suspension polymer, when the suspension polymerization in the presence of small amounts of a saturated hydrocarbon having a boiling point between - 110 and + 150 ', preferably between - 40 and + 50', is , namely in amounts of 0.5 to 40 "/" advantageously 3 to 120 / "based on the monomeric vinyl chloride. Methane and ethane, for example, can be used as hydrocarbons. The use of propane is particularly advantageous, n-butane and n-pentane or their isomers, for example 2-methylbutane, but it is also possible to use higher hydrocarbons, for example hexane, heptane and their isomeric forms, and also octane and its isomers can also be used as a mixture with one another or with their isomers.Industrial-grade mixtures of these compounds can also be used, the process according to the invention not being disturbed if small amounts of unsaturated hydrocarbons are present. Hydrocarbons whose boiling points are higher than 150 ' are less suitable because their removal from the polymer requires temperatures at which the quality of the polymer can be adversely affected. EXAMPLE 100 parts by weight of vinyl chloride and 3 parts by weight of n-butau are added in a stirred autoclave to 180 parts by weight of water, 0.5 parts by weight of polyvinyl alcohol, 0.03 parts by weight of sodium isobutylnaphthalenesulfonate and 0.5 parts by weight of benzoyl peroxide or lauroyl peroxide. The reaction is carried out at a temperature of 52 '. After 8 hours, 75 parts by weight of polymer with a K value of 70 and a very uniform particle size distribution between 50 and 150 particle diameters are obtained. The product can be easily plasticized with 30 % dioctyl phthalate as a plasticizer at 130 °. Three times the time is required to plasticize a product that was manufactured without the addition of butane.
Claims (2)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BE557790D BE557790A (en) | 1956-05-24 | ||
| DEF20372A DE1021165B (en) | 1956-05-24 | 1956-05-24 | Process for the production of easily plasticizable polyvinyl chloride suspension polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF20372A DE1021165B (en) | 1956-05-24 | 1956-05-24 | Process for the production of easily plasticizable polyvinyl chloride suspension polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1021165B true DE1021165B (en) | 1957-12-19 |
Family
ID=7089652
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEF20372A Pending DE1021165B (en) | 1956-05-24 | 1956-05-24 | Process for the production of easily plasticizable polyvinyl chloride suspension polymer |
Country Status (2)
| Country | Link |
|---|---|
| BE (1) | BE557790A (en) |
| DE (1) | DE1021165B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1098714B (en) | 1956-11-15 | 1961-02-02 | Basf Ag | Process for the production of polymers and copolymers of vinyl chloride in aqueous suspension |
-
0
- BE BE557790D patent/BE557790A/xx unknown
-
1956
- 1956-05-24 DE DEF20372A patent/DE1021165B/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1098714B (en) | 1956-11-15 | 1961-02-02 | Basf Ag | Process for the production of polymers and copolymers of vinyl chloride in aqueous suspension |
Also Published As
| Publication number | Publication date |
|---|---|
| BE557790A (en) |
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