CH218277A - Process for the production of very high molecular weight polychloroprene. - Google Patents
Process for the production of very high molecular weight polychloroprene.Info
- Publication number
- CH218277A CH218277A CH218277DA CH218277A CH 218277 A CH218277 A CH 218277A CH 218277D A CH218277D A CH 218277DA CH 218277 A CH218277 A CH 218277A
- Authority
- CH
- Switzerland
- Prior art keywords
- dependent
- polymerization
- molecular weight
- high molecular
- alkali treatment
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 229920001084 poly(chloroprene) Polymers 0.000 title claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 6
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 3
- 239000003995 emulsifying agent Substances 0.000 claims description 3
- 239000000839 emulsion Substances 0.000 claims description 3
- 150000002896 organic halogen compounds Chemical class 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 230000001419 dependent effect Effects 0.000 claims 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 230000009965 odorless effect Effects 0.000 claims 1
- 230000000717 retained effect Effects 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 4
- 239000003518 caustics Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 206010029216 Nervousness Diseases 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- -1 ester acetals Chemical class 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002991 molded plastic Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000725 suspension Substances 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
-
- 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
-
- 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
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F36/14—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen
- C08F36/16—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen containing halogen
Landscapes
- 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)
Description
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Verfahren zur Herstellung von höchstmolekularem Polychloropren. Im Hauptpatent ist ein Verfahren zur Herstellung von höchst molekularem Poly- vinylchlorid beschrieben, gemäss welchem man das zu polymerisierende Vinylchlorid vor der Polymerisation weitgehend von den in ihm als Verunreinigungen enthaltenden organischen Halogenverbindungen anderer Art befreit, was durch eine ausreichende Vorbehandlung mit Alkali zu erreichen ist.
Es wurde nun gefunden, dass man in analoger Weise zu höchstmolekularem Poly- chloropren gelangt.
Gegenstand des vorliegenden Patentes ist daher ein Verfahren zur Herstellung von höchstmolekularem Polyehloropren, dadurch gekennzeichnet, dass man das monomere Chlorohren zunächst einer für eine weitgehende Entfernung von verunreinigenden, organischen Halogenverbindungen anderer Art ausreichenden Alkalibehandlung unterwirft und dann die Polymerisation, bevor sich neue Verunreinigungen gebildet haben, bei mässiger Temperatur durchführt und so rechtzeitig abbricht, dass praktisch keine Polymerisationsanteile niedrigen Molekulargewichte entstehen.
Man kann z. B. wie folgt verfahren: Zweckmässig verwendet man zur Reinigung des monomeren Chloroprens wässrige Natron- oder Kalilauge höherer Konzentration. Brauchbar sind 25 bis 60%ige Laugen, insbesondere 40 bis 50%ige. Die reinigende Wirkung kann durch Anwendung erhöhter Temperaturen befördert werden.
Nachdem das bZonomere mittels solcher Lauge gereinigt ist, ist es vor dem Entstehen neuer Verunreinigungen zu bewahren. Es ist deshalb vorteilhaft, es bald nach .der Reini- gung zu polymerisieren. Je nach den gegebenen Bedingungen soll die Lagerzeit nur wenige Stunden oder etwa einen Tag betragen.
Das auf diese Weise zur Polymerisation gelangende Chloropren zeigt seine besondere Polymerisationsfreudigkei.t schon darin, dass
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es in Behältern aus den verschiedensten nichtrostenden Materialien, wie beispielsweise V4 A, Aluminium, Blei, Nickel und dergl. glatt polymerisiert werden kann. Diese Polymerisationsfreudigkeit befähigt es auch, schon bei mässigen Temperaturen in einem Zuge in höchstmolekulares Polymerisat überzugehen, so dass man nur die Poly merisation rechtzeitig abzubrechen braucht, um das höchstmolekulare Produkt ohne Beimengung von Molekülen mit kleinerer Kette zu erhalten.
Zweckmässig führt man die Polymerisation bei Temperaturen unterhalb 40 , vorzugsweise bei 30 bis 35 durch und bricht sie ab. wenn noch etwa 40 bis 60% des Monomeren unverändert, vorhanden sind. Vorteilhaft für die Einheitlichkeit des Produktes ist es, die einmal gewählte Temperatur der Polymerisation in engsten Grenzen während der ganzen Polymerisationsdauer einzuhalten. Bei der Polymerisation von bereinigten Chloropren treten im Gegensatz zu den bisher bekannten Verfahren niemals Versager oder Spontanreaktionen auf; die Polymerisation verläuft vielmehr mit einer erstaunlichen Regelmässigkeit, und es fällt in stets gleichbleibenden Zeiten ein Polymerisat gleicher Art und Menge an.
In besonders glatter Weise verläuft die erfindungsgemässe Polymerisation zu dem höchstmolekularen Produkt, wenn man dabei in Gegenwart von nicht. lösenden Verdünnungsmitteln. insbesondere in wässriger Emulsion arbeitet. Vorteilhaft verwendet man dabei Emulgiermittel ohne verseifende Wirkung, insbesondere die wasserlöslichen partiellen Ester, Acetale, Esteracetale und Äther des Polyvinylalkohols.
Beispiel: 400 Teile eines mit 50 % iger Lauge bereinigten und am Licht anpolymerisierten Chlor-2-butadiens-1,3 wurden nach Zusatz von 1 % N - Phenyl - Naphthylamin unter starkem Rühren in 400 Teilen einer 2 % igen wässrigen Lösung eines bis zur Verseifungszahl 80 bis 100 verseiften Polyvinylacetats durch langsames Zulaufen emulgiert. Die Polymerisation wurde unter fortwährendem Rühren, um die Emulsion aufrecht zu erhalten, durch 15stündiges Erhitzen auf 30' C durchgeführt. Nach Abdestillieren des unver- änderten Monomeren hinterbleibt das benzollösliche Polymere in Form einer Suspension.
Nach dem neuen Verfahren erhält man ein Erzeugnis von überraschend verbesserten mechanischen Eigenschaften, insbesondere einer ganz ausserordentlichen Nervigkeit und Elastizität. sowie besonderer Wärme- und Kältebeständigkeit. Beispielsweise zeigt sich die erhöhte Wärmefestigkeit im Verhalten des Produktes beim Pressen oder auf der Heisswalze; es erfordert bei gleichem Mischungsverhältnis mit Weichmachern und Füllstoffen bedeutend höhere Plastifizierungs- temperaturen als Produkte, die nach den bisher bekannten Verfahren hergestellt werden. Es ist frei von dem Nachteil der bisherigen Produkte dieser Art, beim Lagern, insbesondere unter einer gewissen Belastung und bei höheren Temperaturen sich zu deformieren und zu fliessen.
Deshalb bedarf es keines grossen Gehaltes an Füllstoffen, der bisher zur Behebung dieser störenden Eigenschaft erforderlich war. Es zeichnet sich ferner durch eine weit überlegene Stabilität ans und erfordert deshalb keinen Zusatz von Stabilisatoren, die die elektrischen Eigenschaften beeinträchtigen. Durch die hervorragende Stabilität des neuen Produktes wird die auch sonst. bei Polycliloropren gegebene Nichtbrennbarkeit erst voll zur Geltung gebracht. Die Verarbeitung nach den beschriebenen Verfahren wirkt auch dein Entstehen lästiger Geruchsstoffe entgegen.
Die 0l-, Brennstoff- und Ozonfestig@7eit ist infolge des höchstmolekularen Zu;4andes gleichfalls noch gesteigert. Die Beständigkeit gegen konzentrierte Salpetersäure, 50 % ige Schwefelsäure, sogar oberhalb 100", konzentriertes Alkali. @Vasserstoffsuperoxvcl, Halogen und andere stark angreifende Stoffe lässt nichts mehr zu wünschen übrig.
Das neue Herstellungsverfahren eröffnet die 3iöglichkeit, geformte Kunststoffe verschiedenster Art mit den auf der höchst-
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molekularen Struktur des neuen Polymerisates beruhenden überragenden Eigenschaften herzustellen.
Das neue Polymerisat lässt sich nämlich unter zweckentsprechender Beimischung von Weichmachern und gegebenenfalls auch von Füllstoffen, beispielsweise auf Treibriemen, Transportbändern, Förderseile, Überzüge, Imprägnierungsmittel, Bodenbeläge, Auskleidungen von Behältern, Zeltbahnen, Schutzkleidung, Pressartikel verarbeiten, die sich durch überragende Nervigkeit und Elastizität, Wärme- und Kältebeständigkeit, Fehlen der Neigung zum Fliessen unter Belastung, Festigkeit gegen Öle und flüssige Brennstoffe, Ozon, Wasserstoffsuperoxyd, Alkalien, Säuren, Halogene und andere, stark angreifende Agentien sowie ihre hervorragenden elektrischen Eigenschaften auszeichnen.
<Desc / Clms Page number 1>
Process for the production of very high molecular weight polychloroprene. The main patent describes a process for the production of high molecular weight polyvinyl chloride, according to which the vinyl chloride to be polymerized is largely freed from the other types of organic halogen compounds contained in it as impurities, which can be achieved by adequate pretreatment with alkali.
It has now been found that very high molecular weight polychloroprene is obtained in an analogous manner.
The subject of the present patent is therefore a process for the production of very high molecular weight polychloroprene, characterized in that the monomeric chlorotube is first subjected to an alkali treatment sufficient for the extensive removal of contaminating, organic halogen compounds of other types and then the polymerization before new impurities have formed, carried out at a moderate temperature and terminated in such a timely manner that practically no polymerization components of low molecular weights arise.
You can z. B. proceed as follows: it is advisable to use aqueous sodium or potassium hydroxide solution of higher concentration to purify the monomeric chloroprene. 25 to 60% caustic solutions, in particular 40 to 50% caustic solutions, can be used. The cleaning effect can be promoted by using elevated temperatures.
After the bZonomer has been cleaned with such a lye, it must be protected from the formation of new impurities. It is therefore advantageous to polymerize it soon after cleaning. Depending on the given conditions, the storage time should be only a few hours or about a day.
The chloroprene that is polymerized in this way shows its particular joy in polymerizing in that
<Desc / Clms Page number 2>
it can be polymerized smoothly in containers made of a wide variety of stainless materials, such as V4 A, aluminum, lead, nickel and the like. This willingness to polymerize also enables it to transform into high molecular weight polymer in one go, even at moderate temperatures, so that you only need to terminate the polymerisation in good time to obtain the highest molecular weight product without adding molecules with a smaller chain.
The polymerization is expediently carried out at temperatures below 40, preferably from 30 to 35, and terminated. when about 40 to 60% of the monomer is still unchanged. It is advantageous for the uniformity of the product to keep the temperature of the polymerization chosen within the narrowest limits during the entire duration of the polymerization. In the polymerization of purified chloroprene, in contrast to the previously known processes, failures or spontaneous reactions never occur; Rather, the polymerization proceeds with astonishing regularity, and a polymer of the same type and amount is obtained at constant times.
The polymerization according to the invention proceeds in a particularly smooth manner to give the very high molecular weight product if it is not in the presence of. solvent thinners. especially works in aqueous emulsion. It is advantageous to use emulsifiers without a saponifying effect, in particular the water-soluble partial esters, acetals, ester acetals and ethers of polyvinyl alcohol.
Example: 400 parts of a chlorine-2-butadiene-1,3-chlorine purified with 50% caustic and polymerized in the light were, after adding 1% N-phenyl-naphthylamine, with vigorous stirring in 400 parts of a 2% aqueous solution of up to Saponification number 80 to 100, saponified polyvinyl acetate emulsified by slowly running in. The polymerization was carried out by heating at 30 ° C. for 15 hours with continued stirring to maintain the emulsion. After the unchanged monomer has been distilled off, the benzene-soluble polymer remains in the form of a suspension.
The new process gives a product with surprisingly improved mechanical properties, in particular very extraordinary nervousness and elasticity. as well as special heat and cold resistance. For example, the increased heat resistance can be seen in the behavior of the product during pressing or on the hot roll; With the same mixing ratio with plasticizers and fillers, it requires significantly higher plasticizing temperatures than products that are manufactured using the previously known processes. It is free from the disadvantage of previous products of this type, to deform and flow during storage, especially under a certain load and at higher temperatures.
Therefore, there is no need for a large amount of fillers, which was previously necessary to eliminate this disturbing property. It is also characterized by far superior stability and therefore does not require the addition of stabilizers that impair the electrical properties. Due to the excellent stability of the new product, the non-flammability which is otherwise given with polycliloroprene is fully brought to bear. Processing according to the procedures described also counteracts the formation of annoying odorous substances.
The oil, fuel and ozone resistance is also increased due to the extremely high molecular weight. The resistance to concentrated nitric acid, 50% sulfuric acid, even above 100 ", concentrated alkali. @Vasserstoffsuperoxvcl, halogen and other strongly aggressive substances leaves nothing to be desired.
The new manufacturing process opens up the possibility of using molded plastics of all kinds with the most
<Desc / Clms Page number 3>
molecular structure of the new polymer based on outstanding properties.
The new polymer can be processed with the appropriate admixture of plasticizers and, if necessary, fillers, for example on drive belts, conveyor belts, conveyor ropes, coatings, impregnating agents, floor coverings, linings of containers, tent sheets, protective clothing, pressed articles, which are characterized by outstanding nervousness and elasticity, Heat and cold resistance, lack of tendency to flow under load, resistance to oils and liquid fuels, ozone, hydrogen peroxide, alkalis, acids, halogens and other highly aggressive agents as well as their excellent electrical properties.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE209167X | 1937-04-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH218277A true CH218277A (en) | 1941-11-30 |
Family
ID=5794629
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH218277D CH218277A (en) | 1937-04-28 | 1938-04-27 | Process for the production of very high molecular weight polychloroprene. |
| CH223715D CH223715A (en) | 1937-04-28 | 1939-07-24 | Process for the production of a high molecular weight mixed polymer from chloroprene and vinyl acetate. |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH223715D CH223715A (en) | 1937-04-28 | 1939-07-24 | Process for the production of a high molecular weight mixed polymer from chloroprene and vinyl acetate. |
Country Status (3)
| Country | Link |
|---|---|
| BE (1) | BE427773A (en) |
| CH (2) | CH218277A (en) |
| NL (1) | NL48467C (en) |
-
0
- NL NL48467D patent/NL48467C/xx active
- BE BE427773D patent/BE427773A/xx unknown
-
1938
- 1938-04-27 CH CH218277D patent/CH218277A/en unknown
-
1939
- 1939-07-24 CH CH223715D patent/CH223715A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| NL48467C (en) | |
| BE427773A (en) | |
| CH223715A (en) | 1942-09-30 |
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