Effects of phosphorous oxychloride, phosphorous trichloride and dichlorophenylphosphine on the radical polymerisation of acrylonitrile under heterogeneous conditions
TL;DR: In this paper, the effects of C6H5PCl2, POCl3, and PCl3 on the free radical polymerisation of acrylonitrile initiated bya,a′-azobisisobutyronitrile were kinetically investigated in benzene and trichloroethylene solutions.
Abstract: The effects of C6H5PCl2, POCl3, and PCl3 on the free radical polymerisation of acrylonitrile initiated bya,a′-azobisisobutyronitrile were kinetically investigated in benzene and trichloroethylene solutions. With PCl3 rates of polymerisation were unaffected but the degrees of polymerisation were found to decrease with increasing PCl3. With C6H5PCl2 and POCl3 however both rates and degrees of polymerisation were adversely affected. Thus PCl3 acts as a chain transfer agent while the other two phosphorous compounds function as degradative chain transfer agents.
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24 Jul 2009TL;DR: In this paper, an aqueous pigment dispersion containing at least a pigment, water, a high-molecular dispersant, and an alkali is described, and a production method and use of the aQP dispersion is discussed.
Abstract: Disclosed are an aqueous pigment dispersion containing at least a pigment, water, a high-molecular dispersant, and an alkali. The high-molecular dispersant is a diblock polymer having a formula (1) of A-B or a triblock polymer having a formula (2) of A-B-C. The diblock or triblock polymer is a diblock or triblock polymer obtained by polymerizing addition-polymerizable monomers with a radical generator while using an organic iodide as a polymerization initiating compound and an organic phosphorus compound, organic nitrogen compound or organic oxygen compound as a catalyst. Also disclosed are a production method and use of the aqueous pigment dispersion. With the high-molecular dispersant obtained by a simple living radical polymerization process free of the problems of conventional living radical polymerization and having a precisely-controlled molecular structure, the aqueous pigment dispersion can be obtained with the pigment dispersed in it.
55 citations
Patent•
02 May 2008TL;DR: A highly active and environment-friendly catalyst for use in a living radical polymerization is provided in this article, which comprises a central element, which is selected from nitrogen and phosphorus, and at least one halogen atom which is bound to the central element.
Abstract: A highly active and environment-friendly catalyst for use in a living radical polymerization is provided. A catalyst for use in a living radical polymerization method is provided. The catalyst comprises a central element, which is selected from nitrogen and phosphorus, and at least one halogen atom, which is bound to the central element. A monomer having a radical reactive unsaturated bond is subjected to a radical polymerization reaction in the presence of the catalyst, thereby it is possible to obtain a polymer having narrow molecular weight distribution. The present invention has the merits such as low toxicity of the catalyst, a small amount of the catalyst being required, high solubility of the catalyst in the polymerization media, mild reaction conditions, no coloration, no odor (unnecessary post-treatment of molded products). The method of the present invention is more environment-friendly and economical than other living radical polymerization methods.
15 citations
Patent•
10 May 2010
TL;DR: In this article, a low-cost, highly active, environmentally friendly living radical polymerization catalyst which does not require a radical initiator is presented, which is significantly more environmentally friendly and economically excellent than conventional living radical polymers.
Abstract: Provided is a low-cost, highly active, environmentally friendly living radical polymerization catalyst which does not require a radical initiator. An organic compound having an oxidation-reduction capability is used as a catalyst. Even if a radical initiator is not used, a monomer can be subjected to a radical polymerization to obtain a polymer having narrow molecular weight distribution. The cost of the living radical polymerization can be remarkably reduced. It is made possible to prevent adverse effects of using a radical initiator. The present invention is significantly more environmentally friendly and economically excellent than conventional living radical polymerization methods, due to advantages of the catalyst such as low toxicity of the catalyst, low amount of the catalyst necessary, high solubility of the catalyst, mild reaction conditions, and no coloration/no odor (which do not require a post-treatment for a molded article), etc.
12 citations
TL;DR: In this paper, the effect of 2-Chloro-1,3,2-dioxaphospholane on the AIBN initiated polymerisation of acrylo was investigated kinetically in benzene at 60 − 80°C.
Abstract: The effect of 2-Chloro-1,3,2-dioxaphospholane on the AIBN initiated polymerisation of acrylo — nitrile , methyl methacrylate and styrene was investigated kinetically in benzene at 60 – 80°C. With acrylonitrile normal kinetic orders with respect to monomer and AIBN could be observed with the phospholane behaving as a chain transfer agent. With methyl methacrylate and styrene it was observed that the phospholane causes enhancement of the rates due to concurrent radical and ionic polymerisation besides functioning as a chain transfer agent.
3 citations
Patent•
13 Mar 2013TL;DR: In this article, an aqueous pigment dispersion containing at least a pigment, water, a high-molecular dispersant, and an alkali is described, and a production method and use of the aQP dispersion is discussed.
Abstract: Disclosed are an aqueous pigment dispersion containing at least a pigment, water, a high-molecular dispersant, and an alkali. The high-molecular dispersant is a diblock polymer having a formula (1) of A-B or a triblock polymer having a formula (2) of A-B-C. The diblock or triblock polymer is a diblock or triblock polymer obtained by polymerizing addition-polymerizable monomers with a radical generator while using an organic iodide as a polymerization initiating compound and an organic phosphorus compound, organic nitrogen compound or organic oxygen compound as a catalyst. Also disclosed are a production method and use of the aqueous pigment dispersion. With the high-molecular dispersant obtained by a simple living radical polymerization process free of the problems of conventional living radical polymerization and having a precisely-controlled molecular structure, the aqueous pigment dispersion can be obtained with the pigment dispersed in it.
1 citations
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TL;DR: Weight-average molecular weights and intrinsic viscosities in dimethyl formamide at 25° have been measured for four unfractionated low-conversion acrylonitrile polymers covering the molecular weight range 30 to 250 thousand as mentioned in this paper.
Abstract: Weight-average molecular weights and intrinsic viscosities in dimethyl formamide at 25° have been measured for four unfractionated low-conversion acrylonitrile polymers covering the molecular weight range 30 to 250 thousand. The results follow the equation:
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TL;DR: In this paper, the effect of polymerization temperature on the molecular conformation of polyacrylonitrile was investigated. But the results were not analyzed with aid of the recent viscosity theory of StOCKCMAYER and FIXMAN.
Abstract: Um den Einflus der Polymerisationstemperatur auf die Molekulformation des Polyacrylnitrils zu untersuchen, werden zwei Praparate bei zwei verschiedenen Temperaturen unter Verwendung eines Redoxsystems hergestellt. Die Molekulargewichte von sieben Fraktionen des bei −30°C hergestellten Polymerisates („T„-Reihe) und von sechs Fraktionen des bei +60°C gewonnenen („S„-Reihe) werden nach dem Ultrazentrifugen-Verfahren von ARCHIBALD bestimmt.
Zwischen der Viskositatszahl in Dimethylformamid (DMF) und dem Molekulargewicht gelten folgende Beziehungen:
Die Viskositatsgleichung fur die „S„-Reihe stimmt mit der von CLELAND und STOCKMAYER sehr gut uberein.
Die Mesdaten werden mit Hilfe der neuen Viskositatstheorie von STOCKMAYER und FIXMAN analysiert, um die ungestorten Knaueldimensionen der beiden polymerhomologen Reihen miteinander zu vergleichen. Die dieser Theorie entsprechende Form der [η]-M-Beziehung lautet fur die „S„-Reihe:
Es wird gefunden, das die ungestorte Knaueldimension der „S„-Reihe um etwa 10% kleiner ist als die der „T„-Reihe. Der sterische Faktor σ, der als Verhaltnis der ungestorten Knaueldimension zu der bei freier Drehbarkeit zu erwartenden definiert wird, liegt bei 2,10 fur die „S„-Reihe und bei 2,30 fur die „T„-Reihe. Dieser Tatsache wird entnommen, das der syndiotaktische Anteil des Polyacrylnitrils durch Erniedrigung der Polymerisationstemperatur vergrosert wird.
In order to study the influences of polymerization temperature upon the molecular conformation of polyacrylonitrile, two types of samples are prepared at two different temperatures using a redox system. By employing the ARCHIBALD ultracentrifugal procedure the molecular weight determination is made for seven fractions from a sample polymerized at −30°C. (“T”-series) and for six ones from that obtained a t +60°C. (“S”-series).
Between the intrinsic viscosity in dimethyl formamide (DMF) and the molecular weight the following relations are found:
The viscosity equation for the “5”-series is in good agreement with that of CLELAND and STOCKMAYER.
These results are analysed with aid of the recent viscosity theory of STOCKCMAYER and FIXMAN to evaluate the unperturbed dimension of these two homologous series. The [η]- M-relation for the “S”-series in the STOCKMAYER-FIXMAN form is:
The unperturbed dimension of the „S”-series is found to be smaller than that of the “T”-series. The steric factor σ, defined as the ratio of unperturbed dimension to that corresponding to the free rotation, is about 2.10 and 2.30 for the “S”- and “T”-series, respectively. This leads to the conclusion that the syndiotactic part in the chain of polyacrylonitrile will be increased by a lowering of the temperature of polymerization.
19 citations
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