3,477,999 United States Patent Office Patented Nov. 11, 1969

1. 2 3,477,999 powdery polymer which is rich in syndiotacticity and does METHOD FOR POLYMERIZATION OF not contain tetrahydrofuran-insoluble part or other im WNYL COMPOUNDS purities. It is still a further object of the present invention Saburo Takeda, 29-24. Mitsuzawashimocho, Hiromi Higa to provide a method for producing a polymer which shi, and Ryokichi Tarao, 44 Otsutomocho, Mikio Mi 5 affords a film Superior in transparency. It is still a further Zuno and Kazuyuki Watabe, 303 Termaecho, all of object of the present invention to provide a method which Kanazawa-ku Yokohamashi, Kanagawa-ken, Japan, can be applied to the copolymerization of vinyl chloride Michiaki Saito, 1938. Ookacho, Minami-ku, Yokohama or/and vinylidene chloride with a wide variety of polymer shi, Kanagawa-ken, Japan, Shigeo Namikawa, 44 Otsu izable unsaturated compounds while affording a homo tomocho, Kanazawa-ku, Yokohama-shi, Kanagawa-ken, Japan, and Takao Tsunoda, 28-15, 3-chome, Satae IO geneous copolymer containing hardly a homopolymer. machi, Tsurumi-ku, Yokohama-shi, Kanagawa-ken, These objects and other advantages can be attained by Japan the method of the present invention. No Drawing. Filed Apr. 11, 1967, Ser. No. 629,916 According to the method of the present invention, a Claims priority, application Japan, Apr. 11, 1966, lower aliphatic alcohol containing an amino radical, 41/22,794; Sept. 30, 1966, 41/64,536; Oct. 13, nitrile radical and a halogen atom as a substituent, is used 1966, 41/67,080; Oct. 22, 1966, 41/69,624; Dec. as a modifier of Ziegler type catalyst. In other words the 29, 1966, 42/323; Jan. 10, 1967, 42/1,908 present invention consists in a method for polymerizing or Int, C. C08g 1/56; B01j 1 1/84 copolymerizing a vinyl compound represented by a gen U.S. C. 260-78.5 12 Claims eral formula of 20 ABSTRACT OF THE DISCLOSURE A method for polymerizing or copolymerizing vinyl Yo! chloride or vinylidene chloride which comprises polymer wherein X is H or Cl atom, which comprises polymeriz izing or copolymerizing said compound by the use of a ing or copolymerizing said compound by the use of a modified Ziegler type catalyst consisting of a transition modified Ziegler type catalyst consisting of (a) a com metal compound, an organoaluminum compound and a pound of transition metal, (b) an organialuminum com lower aliphatic alcohol possessing, as a substituent, an pound and (c) a lower aliphatic alcohol possessing the amino radical, nitrile radical or a halogen atom, the cata above-mentioned substituent. lyst preferably consisting of a transition metal compound 30 The compound of transition metal, which is a constit and an isolated reaction product between an organo uent of the catalyst, includes halide, oxyhalide, alkoxide, aluminum compound and a lower alkanolamine. alkoxyhalide, alkoxyacetylacetonate, acetoxyhalide or acetylacetonate of titanium, , chromium, iron, cobalt, nickel, zirconium or manganese. This invention relates to a method for polymerizing 35 vinyl compound. More particularly it relates to a method Representative compounds are Ticli, Ticli, Ticlz, TiBra for polymerizing vinyl chloride or vinylidene chloride or copolymerizing vinyl chloride or/and vinylidene chlo ride in the presence of a modified Ziegler type catalyst. TiO(acac), Ti(ocochs).2cl2, VOCl3, Vcla, Vcla, Crcls, It has been known that the polymerization of vinyl 40 CrO2cl2, Cr(acac)3, Cocla, Co (acac)2, Co(acac)3, chloride or vinylidene chloride with a Ziegler type catalyst Fe(acac)2, Fe(acac)3, Ni(acac)2. Zrcla, Zrcla, yields a colored polymer due to the dehydrochlorination Zr(acac)4 acac is the abbreviation of acetylacetonate of the formed polymer. In order to overcome such a draw radical. The material such as Ticlis' /3 Alcla also is in back, the use of various modified Ziegler type catalysts cluded. - have been studied. With regard to such studies, collective 45 Illustrative oragnoaluminum compound includes com reports are found in "Vinyls and Polymers” (Japan), vol. pounds expressed by a general formula, AllRnX3-m, 5, No. 6, pp. 24–27 (1965) for vinyl chloride and “A.” wherein R is alkyl, cycloalkyl or aryl radical, X is halogen collection of lecture gists of the 14th discussion assembly and n is 3, 2, 1.5 or 1 such as trimethyl aluminum, on high molecular compounds' (Japan), pp. 281-286 triethyl aluminum, tricyclohexyl aluminum, triphenyl (1965) for vinylidene chloride. However it can hardly 50 aluminum diethyl aluminum chloride, ethyl aluminum say that anyone of the processes reported therein enables sesquichloride or ethyl aluminum dichloride. to overcome the above-mentioned drawback satisfactorily. The lower alcohol to be used in the present invention Accordingly, it is an object of the present invention to as a modifier contains halogen atom, nitrile radical or provide a method for producing a non-colored polymer or amino radical. Exemplary lower alcohols containing copolymer of vinyl chloride or vinylidene chloride which 55 halogen or nitrile are ethylene chlorohydrine, ethylene does not accompany the dehydrochlorination. It is another bromohydrine and ethylene cyanohydrine. object of the present invention to provide a method for The lower alcohols containing amino radical are producing the above-mentioned polymer or copolymer alkanolamine possessing N-substituted or non-substituted having a higher molecular weight by using a catalyst amino radical. As N-substituted radical, N-alkyl, N-cyclo possessing a sufficiently high activity even at a relatively 60 alkyl, N-aryl radical are useful and one or two substitu low temperature which can be handled safely and affords tions are possible. a high polymerization rate. It is a further object of the As alkanolamines possessing N-substituted amino radi present invention to provide a method for producing a cal, monoethanol amines possessing, as N-substituent, one 3,477,999 3 4. or two radicals such as N-methyl, N,N-dimethyl, N-ethyl, forms a stabilized catalyst system which can be handled N, N-diethyl, N-butyl, N, N-dibutyl, N-cyclohexyl, N, safely. N-dicyclohexyl, N-phenyl, N,N-diphenyl or the like are The polymerization can be carried out even at a tem perature generally used in the polymerization with a com illustrated.As alkanolamine possessing non-substituted aminoO mon radical polymerization catalysts. However since the radical, mono-ethanol amine (MEA), n-propanol amine catalytic system of the present invention is considerably (nPA), isopropanol amine (iPA), diethanolamine stable to heat, it exhibits a sufficient catalyst activity even (DEA), triethanolamine (TEA) or the like are illustrated. at a temperature of 80 C. or more. The reaction is car salts, and sulfuric acid salts of the ried out generally at -20° C. to 100° C., preferably at above-mentioned alkanol amines are also useful. 30° 70° C. In the polymerization, the above-mentioned three Con IO The reaction system shows grey, pale yellow or bright ponents (a), (b) and (c) can be added to the polyn violet color and does not show black color as in the case erization system as a mixed catalyst. It is also possible to of Ziegler type catalyst merely modified with a common react an organoaluminum compound with a substituted alcohol. When the catalyst activity is compared by using lower alcohol in advance and to use the isolated reaction 5 the polymerization velocity as a barometer, the present product together with a compound of a transition metal, catalytic system enables to complete the reaction in a as a catalysts. In order to attain the object of the present time considerably shorter than other catalytic systems. invention, the latter process is preferable. Such reaction Namely, reaction proceeds sufficiently in several to 10 products of organoaluminum compound with a substi hours with the present catalytic system. tuted lower alcohol include reaction products consisting 20 The polymerization reaction is carried out in the pres of AlMe-MEA (mol ratio 1:1), AEt3-MEA (1:1), ence or in the practical absence of solvent. As a solvent AlEt-nPA (1:1), AlEta-iPA (1:1), AlEta-MEA (1:2), to be used, a halogenated hydrocarbon is preferred. For AEt.-DEA (1:1), AlEta-DEA (2:1), AlBta-(N-MeMEA) example, tetrachloride, chloroform, tetrachloro (1:1), AlEta-(N,N-MeMEA) (1:1), AlEta-(N-EtMEA) ethylene, trichloroethylene, 1,2-dichloroethylene, 1,2-di (1:1), AlEt-(N,N-EtMEA) (1:1), AlEta-(N-PhMEA) chloroethane, amyl chloride, monochlorobenzene, mono (1:1), AlEta (N, N-Ph2MEA) (1:1), AlEta-(N-cyclo bromobenzene, dichlorobenzene or the like is used. Be hexyl MEA) (1:1), AlEta-(N, N-(cyclohexyl)2 MEA) sides halogenated hydrocarbon, tetrahydrofuran, n-hep 1:1). tane dimethyl formamide, acetone, ethyl acetate, acetyl ( Wii, regard to the mol ratio of these catalyst constitu acetone or the like is also useful, but the yield is generally ents, explanation is given in the case where an alkanol 30 lower than the case where chlorinated hydrocarbon is amine is selected as a (c)-constituent. used. Further when vinyl chloride and vinylidene chloride First of all, the organoaluminum compound is used gen is to be copolymerized, one of them as a comonomer, erally in a mol ratio of one or more relative to a con itself, can be used also as a solvent to perform simul pound of a transition metal. When an organoaluminum taneous function. If such a case is expressed by another compound is used in the form of isolated reaction product way, it is called the case of non-solvent polymerization. with an alkanol amine, the mol ratio of said reaction Not only in the case of copolymerization reaction, such product relative to a compound of a transition metal is a non-solvent polymerization reaction can be applied also in the range of one or more, preferably in the neighbour to the case of homopolymerization. Since each constituent hood of one to three (Organoaluminum compounds gen is prepared sometimes in a solution of n-, tolune erally exist as a dimer but the mol ratio is calculated as 40 or the like, the presence of such a small amount of solvent monomer throughout the specification and claims). It is is considered to belong to the non-solvent case where the also possible to add free organoaluminum compound to presence of solvent is substantially none. When com the above-mentioned reaction product with an alkanol pared with the solvent case, the non-solvent case has such amine. In such a case the activity of the resultant catalyst advantages that since it does not use the solvent, the increases further. However even in a mol ratio less than Solvent purification and recovery are unnecessary and the one, the catalysts possesses activity. For example when recovery of unreacted monomer is almost quantitative. a reaction product of AlEta-MEA (1:1) is used together Besides these, following advantages also are to be noted: with Ticli, the catalyst having a zero mol ratio of Al the reaction proceeds smoothly even at a relatively low compound to Ti-compound, hardly shows activity but temperature, the polymerization speed is high, and re with the increase of the ratio to 0.5, 1, 2, . . . in this 50 Sultant polymer is fine powder possessing high molecular order, the activity gradually increases and reaches a Weight which hardly contains tetrahydrofuran-insoluble, maximum value in the neighbourhood of 3 to 5. With the easy in shaping films and affords highly transparent films. mol ratio greater than this value, the catalytic activity It has been proved that the vinyl polymer is not colored does not increase but gradually decreases. Since the reac and shows hardly any dehydrochlorination. This fact will tion product of AlFt-MEA possesses, by itself, a certain be explained in the case of polyvinyl chloride. When other extent of catalytic activity, the activity does not drop to types of Ziegler catalyst are used, the chlorine content of zero even in a considerably increased mol ratio. resultant polyvinyl chloride is usually lower than the The mol ratio of organoaluminum compound to alka theoretical value of 56.73%. This shows the occurrence nolamine is selected in the range where one is a central of dehydrochlorination. Whereas the chlorine content of value. In the mixed catalyst system where the above 60 the polyvinyl chloride of the present invention is in the mentioned two constituents are used with a compound of range of 55.6-56.8% which is approximately identical transition metal in the mixed form of the three, the mol with the theoretical value. The ratio of the extinction de ratio of triethyl aluminum, diethyl aluminum monochloride gres at 638 cm. and 690 cm. -1 in the infra-red spectrum or the like to alkanol amine is generally in the range of is used in the calculation of the degree of syndiotacticity. 1-4. Whereas when a reaction product of the two con 65 Since this value is identical with or greater than the value stituents is used, the organoaluminum compound is used of the polyvinyl chloride obtained in the usual radical even in the mol ratio less than one as in the case of the polymerization, it can be said that the polyvinyl chloride reaction product of AlEta-MEA (1:2). of the present invention is rich in syndiotacticity. , Since the catalysts system loses its activity in the presence The present method can be applied not only to the of water or oxygen, the reaction must be carried out gen 70 homopolymerization of vinyl chloride or vinylidene chlo erally in the atomosphere of nitrogen. Though the reac ride, but also to the copolymerization. tion product of organoaluminum compound and alkanol Exemplary comonomers include vinyl compounds such amine decompose when exposed to the air, but it does not as vinyl acetate, vinyl chloride (to vinylidene chloride), ignite. Compared with trialkyl aluminum which has a vinylidene chloride (to vinyl chloride), styrenes such aS great ignition property, it affords an advantage that it 75 styrene, alkyl vinyl ethers such as cetyl vinyl ether, iso 3,477,999 5 6 butyl vinyl ether, alkyl acrylates or methacrylates such The value D638/D690 of the commercial polyvinyl chlo as methyl acrylate, methyl methacrylate, nitriles such as ride, obtained by the radical polymerization method was acrylonitrile, monoolefins such as ethylene, propylene, measured in the control run. It was 1.25. butene-1, 4-methyl pentene-1, trichloroethylene, diolefins such as butadiene and polymerizable unsaturated carboxy lic acid esters such as di(2-ethyl hexyl) maleate, ethyl EXAMPLES 8-19 crotonate. Resultant copolymers are isolated from homo polymers by fractionational precipitation using a solvent. The presence of comonomer constituent in the copolymer VC; non-solvent; M-- (AIEt-alkanolamine) is detected by the result of elementary analysis or infra O red spectrum. The characteristic point of the copolymeri Hundred ml. of vinyl chloride monomer was introduced zation reaction using the present catalyst system is to in a 200 ml. pressure resistant glass reaction tube equipped provide a homogeneous copolymer containing hardly with an electromagnetic stirrer, and two copper pipes one homopolymers. of which was used for connecting to a vacuum source or Following examples are given to illustrate the present nitrogen source or for introducing a monomer or a mono invention but they are by no means intended to limit the mer mixture and the other of which was used for con invention. necting to a manometer or for purging the unreacted In each examples the indices apeparing immediately monomer, after the operations of connecting the tube after the numbers of examples show the kind of monomer to the vacuum source then to the nitrogen source were used; whether or not solvent is used, and the kind of 20 repeated and the tube was cooled to -20° C. Then, 1-2 catalyst used, in this order. The part in the parenthesis ml. of toluene solution of the reaction product between means that the isolated reaction product between the triethyl aluminum and alkanolamine (1:1) and 1-2 ml. components in the parenthesis is used together with the of toluene Solution of a compound of transition metal other component outside of the parenthesis, that is, a were introduced in the reaction tube which was then transition metal compound which is abbreviated to M, 25 closed. The polymerization was carried out with vigorous here. agitation while maintaining the temperature of the bath EXAMPLES 1-7 of the reaction tube at 25-30° C. During the polymeriza tion which was continued for one to several hours, the VC; non-solvent; M-- (AIEt-MEA) Vapor pressure of vinyl chloride monomer indicated al Various amounts of the reaction product of triethyl 30 ways about 4 kg./cm... After the completion of the reac aluminum and monoethanolamine (mol ratio 1: 1) (here tion, the unreacted monomer was discharged and the inafter referred to AlEt-MEA, the method for preparing reaction product was dropped into methanol containing this product is disclose din the Japanese patent publication hydrochloric acid to be precipitated. (If the precipitate No. 2577/1967) and then 8.4 gr. of vinyl chloride mono was in the block form, it was chopped with a Waring mer were charged to a reaction tube cooled at -78 C. Blendor.) The precipitated reaction product, after being in the atmosphere of nitrogen. Further, 0.5 ml. of n-hex left to stand for over night, was washed with methanol, ane solution of Ticl having a concentration of 0.607 dried and weighed. If necessary, the polymer was purified millimole/ml, (abs. amount of Ticl:0.303 millimole) was by reprecipitation from tetrahydrofuran and methanol. added to the mixture. After closing the reaction tube by 40 The mean polymerization degree of the polymer was fusion, the polymerization was carried out at 30° C. for measured by the method shown in JISK-6721 (1959). 24 hrs. under shaking. Namely, 0.4 gr. of the polymer was dissolved in 100 ml. The reaction system took gradually a suspension state of nitrobenzene and the relative viscosity of the resultant showing greyish brown to greyish yellow color. With the Solution was measured with an Ubbelohde viscosimeter at advancement of the reaction, the whole system became 30 C. The mean polymerization degree of the polymer almost immobile state. After completion of the reaction, was calculated from this value. the reaction tube was cooled again to -78° C. and The reaction product of triethyl aluminum-alkanola opened. Then, reaction mixture was introduced in a large mine had been prepared by the following process. Tri amount of methanol containing hydrochloric acid to pre ethylaluminum-isopropanolamine (1:1) reaction product cipitate white material, which was then filtered, washed 50 with methanol and dried. Resultant product was, if neces (abbreviated as AlEtaiPA) sary, purified by reprecipitation from tetrahydrofuran and 3.27 gr. of triethylaluminum was diluted with a mixture methanol. The melting points of the products were meas liquid of 8 ml. of n-hexane and 4 ml. of toluene and the ured. The analysis of chlorine was also carried out to resultant solution was cooled to -78° C. 2.2 ml. of iso confirm whether or not dehydrochlorination of the poly propanolamine was gradually, added. As in the case of mer had occurred. The infrared spectrum of powdery monoethanolamine, the reaction product was treated to polymer in the region of 600 cm.-1 to 800 cm.-1 using yield 2.56 gr. of colorless needle crystal. The product has KBr disk was measured and the ratio of the optical den a solubility to toluene, or n-hexane, greater than the reac sities at 638 cm. I and 690 cm., D638/D690, was cal tion product between triethylaluminum and monoethanol culated by way of base line method in order to investigate 60 amine (1:1). the syndiotacticity of the polymer. Results are listed in Table 1. In these Examples, the effect of the mol ratio of the catalyst constituents (indicated by the ratio of (Triethylalminum-n-propanolamine reaction product Al/Ti) on the yield and properties of polymer was (1:1) (AlEt-n-PA) studied. v ; : TABLE1 Polymer As in the case of isopropanolamine, the reaction product AlTi between triethylaluminum and n-propanolamine (3-ami Example. (molar Product Yield Cl D638; M.P. Number ratio) (gr.) (percent) (percent) D690 (C.) no-n-propanol), (1:1), was prepared. - -

Isolated product was colorless plate crystal having a 0.6 0.79 9.5 ------O 0.9 0,90 10.7. 55.9 1.81. 140-145 M.P. of 90-92 C. Results are listed in Table 2. As evi 2.5 1,73 , 20.7 ------dent from the result, it can be seen that the mean polym 3, 4 2,51 30,0 56.1 49 37-5 4, 6 3,78 450 56. 81 152-159 erization degree of the resultant polymer was fairly high, . 1,95 23.2 56.0 66 50-56 and the catalyst activity is also sufficiently high com 10.0 1.54 8.4 55.6 1. 67 i48-160 75 pared with other catalyst systems. 3,477,999

TABLE 2 Polymerization Polyner Transition Al/Ti Example Alt3-alkanolamine reaction. Metal (molar) Temp. Time Product C D6381 M.P. -- Number product (mimol.) Compound ratio) (o C.) (hr.) (gr.) (percent) D690 (° C.) DP 8------AlEt3-MEA, 5.00------TiCl4------2.5 25 4.5 22.6 ------1.66 ------1,600 9---- 3.1 23 2.0 22.2 56.6 1.39 200-210 1,600 10--- 4.0 28 1.0 18.8 ------1.59 72-177 1,200 1.--- ... Altg-nPA, 8.00--- 4.0 30 5.0 24.8 ------1.57 175-180 1,200 12--- -- Altg-iPA, 4.08----- 3,0 23 2, O 4.9 56.2 ... 48 190-200 1,700 3.1 32 4.5 6.4 56. 1.57 150-155 1,900 ... 0 30 1.0 9, 1 56.5 1,60 120-130 1,580 2.0 30 1. () 15.9 56.0 ... 62 122-30 1,600 3.0 30 1... O 20, 56.1 , 53 125-131 1,250 6.0 30 1.0 20.0 56.3 1.57 124-128 680 10.0 30 ... O 18.3 55.9 .40 120-125 500 3.0 30 1. () 24.9 ------l, 51 ------2,300 - AlFt3,e 4.68--- 3.0 30 1.0 0 Alt3, 4.68-- 3.0 30 1.0 1.0 Ref. AlEt2(OEt), O 4. 3.0 30 1.0 40 Ref. - Alt2(OEt), a 4.68-- 3.0 30 10 3.7 a HCl salt of monoethanolamine was used. c The experiments carried out by the use of the catalyst described in b This aluminum compound was not crystalline but powdery. U. Giannini, S. Cesca, Chim. Ind. (Milan) 44, 371 (1962) and Belg. 611, 654 (Jan. 15, 1962).

The polymers obtained in the runs a and b were colored tion of the active ethyl radical being given by the number in pale yellow. of ethyl radical per aluminum atoms was effected by EXAMPLES 20-27 measuring the amount of ethane gas produced by the VC; non solvent; M-- (AlEta- N-substituted hydrolysis. The measurement of molecular weight was alkanolamine) 30 effected by the freezing point method using a solu Various amounts of triethyl aluminum was charged to tion. The results are shown in Table 3.

TABLE 3 Al (percent) Et-group Mol. Wit. N-substituted Alkanolamine Found Calcd. Found Calcd. Found Calcd. Monoethanolamine------. 18.4 18.60 2.0 2.0 290 45.2 N-methylethanolamine---- ... 16.94 16.95 2.0 2.0 323 59.2 N,N-dimethylethanolamine 5.54 15.58 2.0 2.0 ------173.2 N-ethylethanolamine.------15.13 5.58 18 2.0 338 173.2 N,N-diethylethanolamine--- 13.31 3.40 2.0 2.0 408 20.3 N,N-dicyclohexylethanolamine----- 8.83 8.72 2.2 2.0 733 309.5

N-phenylethanolamine------12.07 2.19 1.8 2.0 471 221.3 N,N-diphenylethanolamine.------8.95 9,07 2.0 2.0 605 297.4 NOTE.-The calculated values are obtained on the basis o he formula of Alt2(OCH - a glass vessel which had been flushed with nitrogen Sufi These compounds exist in benzene usually in the form ciently. Then the vessel was weighed. A 1:1 mixture of 50 of dimer. When they are used as a constituent of a cat toluene and n-hexane in an approximately equal amount alyst, all of the calculation of mol ratio is effected as a monomer. The NMR spectra of these compounds were to triethylaluminum was added to dilute triethylalumi also measured. num. After the vessel was cooled to -78 C., N-Sub The polymerization of vinyl chloride was carried out stituted alkanolamine was gradually added so as to 55 by the following process. amount to equimol to triethylaluminum. At this time, A 200 ml. pressure glass reaction vessel equipped with both react vigorously accompanying heat and gas evolu an electromagnetic stirrer was flushed with nitrogen, tion. After the completion of the addition of all the N evacuated and cooled to -20° C. Hundred gr. of vinyl substituted alkanolamine, the whole was further heated to chloride and then 5.45 millimole of the reaction product complete the reaction and to give a homogeneous trans- 60 of triethylaluminum and N-substituted alkanolamine parent solution. When the reaction liquid was cooled, (1:1) in toluene were introduced to the vessel. Then crystal was precipitated, and after the completion of the with stirring, a compound of transition metal was added precipitation, the supernatant liquid was removed by de to the mixture, so as to give a mol ratio of 1/3.5 (com cantation or by drawing with a syringe, and n-hexane was pound of trransition metal: reaction product). If nec newly added. The crystal was heated with stirring until 65 essary, further toluene was added so as to make the it was dissolved in n-hexane. The solution was cooled amount of toluene in the reaction system constant. In all again to precipitate crystal. After 3 to 5 times repetition the runs of these examples, the total amount of toluene of this operation for the purpose of purification, the crys used was 5 ml. and accordingly the polymerization was tal was dried at a reduced pressure to yield pure crystal carried out under the condition which could be called 70 practically non-solvent polymerization. line substance. Resultant crystals were all colorless in The reaction tube was heated to 30° C. and the polym the needle or plate form. The yield was 80 to 90% rela erization was started. The reaction system took gradually tive to the theoretical value. The aluminum content of the the Suspension state on account of the polymer pro resultant crystal was analyzed quantitatively by the oxine duced and finally reached the state where any liquid method using 8-oxyquinoline, The quantitative determina monomer could apparently be observed. After one hour 8,477,999 10 of polymerization, the resultant polymer was processed EXAMPLES 31 AND 32 as in the foregoing examples, dried to yield white powder polymer which was then weighed. The results are shown VC; nonsolvent; M--Al Et--COCH2CH2X (X: C1 or Br) in Table 4. In the table, R and R' indicate H or the N 1.22 gr. of triethyl aluminum was dissolved in a liquid substituent of the catalyst constituent expressed by the mixture of 5 ml. of toluene and 5 ml. of n-hexane, and general formula of Al-Et2(OCH2CH2NRR). the resultant solution was cooled to -78 C. 0.7 ml. of

TABLE 4 Polymer Transition Metal Product Cl D638 | M.P. - Example R, R' Compound (gr.) (percent) D690 ( C.) DP H, CH3------WOCl3----- 7.2 56.2 1.68 123-125 1,000 CH, CHI voCi. 13.8 56.5 , 62 19-24 980 CH3, CH3-...- TiCl4------4.3 56.8 i.77 15-119 260 - H, C2H5------VOCl3-...--- 9.0 56.8 1,66 130-35 990 24------H, C2H5---- TiCl4------12.5 56.1 i.77 20-125 330 CH5, CH5 WOCl3------12.9 56.4 .63 114-116 1,180 H, Colds------WOCl3------18.6 56.6 70 135-139 820

C6H5, CH5 VOCl3---- 5.6 56.0 1.66 123-125 1,100

As evident from theabove-mentioned result, it can be ethylene chlorohydrin was gradually added and the mix seen that the effect of N-substituent is great when the re ture was heated to 50-60° C. to complete the reaction action product of triehyl aluminum and N-substituted between the both components. The reacted mixture formed alkanolamine (1:1) combined with a compound of tran a colorless, transparent solution. sition metal is used and the catalyst activity is higher in Polymerizations were carried out in the same procedure the case of mono-substituent than in the case of di-sub 35 as in Examples 8-19, using a catalyst consisting of 9.60 stituent. millimoles of the reacted mixture and 2.40 millimoles EXAMPLE 28 of vanadium oxytrichloride. VC; M--(AlEta-N-ethyl-monoethanolamine) 19.5 gr. of polyvinyl chloride was obtained after the 40 polymerization for 1.5 hours at 24° C. This polymer had Fifty gr. of vinyl chloride was introduced at -20° C. a M.P. of 145-152 C., a chlorine content of 56.6%, in a reaction vessel flushed with nitrogen. 50 ml. of car D638/D690 of 1.48 and a mean polymerization degree bon tetrachloride was added thereto and stirred. After of 1400, 5 minutes later, 2.34 millimoles of the reaction product Except that ethylene bromohydrin was used instead of of triethylaluminum and N-ethyl-monoethanolamine 45 chlorohydrin, polymerization was carried out for one hour (1:1) in toluene and 0.78 millimole of vanadium oxy in almost the same procedure as in the above-mentioned trichloride in toluene were added and the polymerization 16.3 gr. of polymer was obtained. was carried out at 30° C. for one hour. 5.5 gr. of poly vinyl chloride was obtained. EXAMPLES 33-48 In this polymerization, when 4.68 millimoles of tri ethylaluminum, 9.36 millimoles of N-ethyl-monoethanol 50, VC; solvent; M--(AlEta-MEA) amine and 1.56 millimoles of vanadium oxytrichloride 100 ml of halogenated hydrocarbon, a given amount each in toluene were added to the monomer in this order of reaction product of triethyl aluminum and mono and the polymerization was carried out, 2.3 gr. of poly ethanol amine (1:1) and a given amount of a compound vinyl chloride was obtained. . . . . 55 of a transition metal, each by themselves or each in the form of benzene solutions were sealed into separate glass EXAMPLES 29 AND 30 ampoules, respectively. The sealed ampoules were charged VC; nonsolvent; M--AlEta-I-HOCH2CH2CN into a 300 ml. autoclave which effected up and down 4.41 gr. of triethyl aluminum was dissolved in a liquid stirring. The autoclave was closed under the nitrogen mixture of 8 ml. of toluene and 8 ml. of n-hexane, and 60 atmosphere and then flushed several times with dry nitro the resultant solution was cooled to -78° C. 2.6 ml. of gen gaS. purified ethylene cyanohydrin was added to prepare a The glass ampoules were crushed by nitrogen pressure catalyst component consisting of a mixture of triethyl of ten and odds kg./cm. applied to the autoclave and aluminum and ethylene cyanohydrin which was further then the autoclave was heated in an electric furnace to mixed with TiCl4 to give a molar ratio of 1:1. Polym 65 a given temperature with stirring for 10 minutes. There erizations were carried out in the same manner as in after, vinyl chloride monomer was introduced under pres sure and polymerization was started under 5 kg/cm2. Examples 1-7. Results thus obtained are shown in Table 5. After the polymerization for a given period, the autoclave TABLE5 was cooled. The content was poured into methanol (which Polymer 70 might contain a suitable amount of hydrochloric acid) TiCl Product Yield to precipitate polymer. After standing over night, the (mmol.) (gr.) (percent) polymer was washed with methanol, filtered and dried. l ber: White powder of polyvinyl chloride was obtained. The Exaple Number: 1.5 1,40 16.7 reaction conditions and results are shown in the following 30------0.8 1.53 18.2 Table 6. 3,477,999

TABLE 6 Polymerization Polymer Alts Example MEA Transition Metal Temp. in Product M.P. Number (immol.) Compound (immol.) Solvent (o C.) Chr.) (gr.) DP (o C.) 38------20.4 TiCl4, 2.05.------CCl4------80 O 16.9 ------50 34. 10.2 TiCl, 2.05-- - CC14-- 80 6 3.4 72 13 35. 20.4 TiCl, 2.05---- EDC * 80 6 16.2 160 37 36------34.2 TiCl3, 3.43.-- EDC------SO 5 lil ------60 37------17.3 TiCl3, 3.43. EDC------80 6 3.7 38------34.2 TiCl3, 3.43 -- CCl4------80 6 14, 6 39.-- 17.3 TiCl3, 3.43. -- CC14------80 8.3 17.3 TiCl3, 3.43. -- C6H5Cl------SO 5.5 7.3 VOCl3, 1.76--- -- El C------SO 21.3 10.0 Fe (acac)3, 2.00------EDC------60 6 2, O 10.0 Fe (acac)2, 2.00------EDC------60 6 3.0 10.0 Co (acac)3, 2.00------EDC------60 6 4.4 10.0 Co (acac)2, 2.00------EDC------O 5 3.8 10.0 Ni (acac)2, 2.00------EDC------60 6 2.0 10.0 Cr (acac)3, 2.00.------EC 60 6 3,8 10, O Zi (acac)4, 2.00------EDC------60 (5 3.6 *EDC; 1.2-dichloroethane.

EXAMPLES 49-56 reaction tube equipped with an electromagnetic stirrer 20 (as in Example 62) was used as a reaction vessel. 100 ml. VC; solvent; M--(AIEt-MEA) of 1,2-dichloroethane and a given amount of monoethanol Polymerizations of vinyl chloride were carried out using amine or diethanol amine and then given amounts of an a catalyst consisting of a reaction product between tri organic aluminum compound and a compound of transi ethyl aluminum and monoethanolamine (1:1) and a com tion metal, each by themselves or each in the form of solu pound of transition metal, each in a given amount. 2 5 tions were sealed into separate glass ampoules, respective A 200 ml. reaction tube of pressure resistant glass ly. These ampoules were charged into the reaction vessel. equipped with an electromagnetic stirrer was flushed with Polymerization and treatment of product were carried nitrogen. After 1,2-dichloroethane as a polymerization Sol out according to the procedure of Examples 33-48. White vent was poured into the tube, a compound of transition powder of polyvinyl chloride was obtained. The reaction metal and the above-mentioned reaction product as a conditions and results are shown in the following Table 8.

TABLE 8 Polymerization V Organo Al Polymer Example Transition Metal Compound Ethanolamine Solvent Press. Temp. Time Product Number Compound (m.mol.) (m.mol.) (mol.) (ml) (kg.fcm.2) (0 C.) (hr.) (gr.) 57------TiCld, 1.73------AlEt3, 17------MEA, 17------EDC, 100----- 5 80 6 10, - TiCl3, 54------AlEt3, 15------MEA, 15------EDC, 100-- 5 80 6 3. 8 Ti(OAc)3Cl21.40- ---. Alt2Cl, i4----- MEA, 14-----. EDC, 100- 5 80 6 20, - TiCl3, I-42. ------AlEt3, 14------DEA, 4------EDC, 100----- 5 80 6 2.0 Ti(OPr(acac), 7.88---- AEt3, 79. MEA, 79 -- ECC, 100. ---- 5 80 ... 7 62.------CrO2Cl2, 4.60------AIEt3, 10------MEA, 10.----- EDC, 100----- 2.5 62 8.5 *Ti(OEP) (acac): Titanium diisopropoxybisacetylacetonate.

catalyst component were added in that order. The tube 45 EXAMPLES 63-66 was closed. After nitrogen gas in the tube was replaced by vinyl chloride, vinyl chloride was introduced under VC; Solvent; M-- (AiBt-MEA)--AIEt or AlFtCl pressure with stirring. Polymerization was continued at After a 50 ml. pressures glass tube (ampoule) was a given pressure, a given temperature and for a given flushed with nitrogen gas, 20 ml. of 1,2-dichoroethane, 1.0 period. After completion of the reaction, the product 50 millinole of vanadium oxytrichloride and a given amount was treated as in Examples 33-48. Polyvinyl dichloride of various organic aluminum compounds were introduced of white powder was obtained. The reaction conditions into the ampoule in that order. and results are shown in the following Table 7. Next, the ampoule was connected to a vacuum source

TABLE 7 Transition Polymerization Polymer AEt3- Metal Example MEA Compound Solvent Press. Temp. line Product sm Number (immol.) (mumol.) (ml.) (kg.icm.) (o C.) (hr.) (gr.) IDP 5.2 VOCl3, 2.3------EDC, 75---- 2.0 18 3 0. 1,310 10.0 CrO2Cl2, 4.6----- EDC, 70-- 2.5 32 3 3.3 373 10. O CrO2Cl2, 4.6--- EPC, 70. 2.5 32 6 6.0 432 0.0 CrO2Cl2, 4.6----- EDC, 70. 2.5 32 24 24.9 1,140 10.0 CrO2Cl2, 4.6----- EDC, 70. 2.5 62 3. 7.7 245 10. O CrO2Cl2, 4.6----- EDC, 70- - 2.5 . 62 6 12.2 270 10.0 CoCl2, 2.0 ------EDC, 70. 2.5 62 3 4.4 225 10.0 CrO2Cl2, 4.6-- - - Il-C6, 70------2.5 62 6 2.2 ------Control----- 10.0 Nole------EDC, 70------2.5 62 3 0.1 ------

EXAMPLES 57-62 and 10.6 gr. of vinyl chloride monomer was introduced in the pressure-reduced ampoule from a distillation flask. VC: solvent; M--AIEt3-alkanolamine The ampoule was melt-sealed. A 300 ml. autoclave of up and down stirring type (used Polymerization was carried out at 60° C., for 6 hours, in Examples 57-61) or a 200 ml. pressure resistant glass 75 with shaking. Treatment of resultant polymer was carried 3,477,999 13 - 14 out as in Examples 33-48. Catalysts and results are shown EXAMPLES 76-83 in the following Table 9 below. The polymers obtained were all white. When the reac- VC-I-vinyl compound; solvent; M--(AlEta-MEA) tion product between triethyl aluminum and monaethanol amine (1:1) and additional triethyl aluminum or diethyl Copolymerization of vinyl chloride with other vinyl aluminum monochloride equimolecular to the reaction 5 compounds were carried out using a solvent.

TABLE 9 Polymer Number Organic Al Compound Component (percent)Yield -DP 63------AlEt3-MEA, 3.0 mmol.------46 230 64------AlFta-MEA, 1.5 mmol. plus AlEt3, 1.5 mmol.-- 63 400 65.-- --- Alta-MEA, 2.5 mmol. plus AEt3, 2.5 mmol.-- 74 20 66------AlEta-MEA, 1.5 mmol. plus Alet2Cl, 1.5 mmol------47 380 product were used together as in the present Examples 64- A given amount of 1,2-dichloroethane was poured into 66, it was observed from analysis of chlorine content, a 200-ml. pressure resistant glass reaction tube equipped infrared spectrum and nuclear magnetic resonance spec- 20 with an electro-magnetic stirrer after flushing the tube with trum of the polymers that dehydrochlorination did not nitrogen gas. Vinyl chloride monomer was dissolved in this occur also in these cases. 1,2-dichloroethane under pressure and was driven off. Next, given amounts of a catalyst and a comonomer were EXAMPLES 67-75 added into the tube with stirring, and the tube was closed. VC-I-vinyl compound; non solvent; M--(AlEta-MEA) 25 Vinyl chloride was introduced under pressure with stir Copolymerization of vinyl chloride with various com ring and polymerization was carried out under conditions pounds were carried out using, as one component of cata of given pressure, temperature and period. lyst, the reaction product between triethyl aluminum and After completion of the reaction, methanol (which monoethanolamine (1:1), in almost the same manner as in might contain a suitable amount of hydrochloric acid) Examples 8-19.5 ml. of comonomer was poured into vinyl 80 was poured into the reaction liquid, polymer being precipi chloride monomer excepting the Example 67 wherein tated. Resultant polymer was washed with methanol, 10 ml. of comonomer was used instead of 5 ml. In them filtered and dried at 40 C, in vacuo for 24 hours. The case of block copolymerization, a homopolymerization of polymer was white powder. The reaction conditions and vinyl chloride was at first carried out for a given period, results are shown in the following Table 11 below. and then the polymerization vessel was cooled to -20° C. 35 The unit of vinyl acetate, methyl acrylate or ethyl vinyl again to add a comonomer and to extend the polymer ether present in the copolymers of the present Examples chain by copolymerization. 76-83 was confirmed from infrared spectrum. The comon The results obtained are shown in the following Table omer contents in the copolymers were calculated from 10. analytical value of chlorine.

TABLE 10 Acetone Extraction Polymerization ------AEt3- Transition AlfTi -- Polymer Soluble Insoluble Example MEA Metal (molar Temp. Time Product (Weight (Weight Number (mmol.) Compound ratio) Comonomer (° C.) Chr.) (gr.) proent) percent) 4.75 3.12 Cetylvinyl ether 26 2 11.2 14.7 85.3 5. 70 3. i2. Vinyl acetate------23 1. 13.9 32.2 67.8 4.75 3.12 Isobutylvinyl ether 23 2 15. 31.7 68.3 4.75 3.12 ----- d 23 2-2 8.6 ------4.75 3.08 Winyl acetate.------23 0.5-1-2 17.9 8.0 92.0 4,75 3, 12 Maleic acid di-(2-ethylhexyl)------23 2 14.9 ------4.75 3.04 ----- do------27 2 30.2 -- 4.75 3.08 27 0.3--2 ... ------. 9.50 VOCl3------3,08 27 0.5-1-2.5 19.0 20.4 79.6

As seen in the table, in the cases of block copolymeriza- EXAMPLES 84-98 tions, the polymerization times are indicated in two steps; homopolymerization and copolymerization. VC--olefin; EMEAE-MEA) O The presence of comonomer unit was confirmed from in- --AlBt frared spectrum, in both the acetone-soluble parts and ace- Copolymerizations of vinyl chloride with olefins were tone-insoluble parts of the polymers in the cases of Ex- carried out using such a ctalyst system as in Examples amples 68, 69 and 71, and in the acetone-insoluble part of 60 84-90, consisting of a compound of transition metal, tri the polymer in the case of Example 67. ethyl aluminum and monoethanolamine, each in a given

TABLE 11 Polymerization Copolymer Transition Comonomer AlEta Metal Content Example MEA Compound Solvent Comonomer Press. Temp. Time Product (mol Number (mmol.) (mmol.) (ml.) (gr.) (kg/cm2) (° C.) (hr.) (gr.) DP percent)

5. 2 VOCl3, 2.3---- EDC, 75. --- Vinylacetate, 2.8------2.0 30 2 5.9 700 3.3 5.2 VOCl3,2,3--- EDC,75---- Methyl acrylate, 2.9- - 2.0 30 2 5.5 ------27.0 10.0 CrO2Cl2, 4.6--- EDC, 75---- Winyl acetate, 3.0-l. 2.5 32 3 5.7 510 3.0 10.0 CrO2Cl2, 4.6. EDC, 75---. Vinyl acetate, 10.0... 2.5 32 6 9.4 558 8.6 10.0 CrO2Cl2, 4.6--- EDC, 75---- Methyl acrylate, 3.0. 2.5 32 3 6.5 668 23. () 19.0 9r9292, 4.6--- EDC, 75---- Methyl acrylate, 100------2.5 32 6 13.7 1,029 36.3 10.0 CrO2Cl2, 4.6--- EDC, 75---- Ethyl vinyl ether, 5.0------2.5 32 6 l. 3 ------3.1 10.0 CrO2Cl2, 4.6--- None.------Vinyl acetate, 46.7...------2.5 32 9 8.7 ------34.8 3,477,999 15 16 amount, or such a catalyst system as in Examples 91-98, sultant filtrate was poured into thrice its amount of meth consisting of a compound of transition metal and the re anol, and allowed to stand for 4 hours. After the resultant action product between triethyl aluminum and mono precipitate was Iltered, the filterad polymer was dried in ethanolamine (1:1). A 300 ml. autoclave of up and down vacuo at 40° C. for 24 hours. stirring type was used. The copolymerization was carried out in the presence of 5 EXAMPLE 99 100 ml. of 1,2-dichloroethane as a polymerization sol vent, at a total pressure of 10 kg./cm. in which partial VC+CCl=CHCl; solvent; M--(AlEta-MEA) pressure of vinyl chloride was 5 kg./cm. and that of 70 ml. of trichloroethylene was poured into a 200 ml. olefin gas was 5 kg/cm., at a given temperature and 10 pressure resistant glass reaction tube equipped with an for a given period of time. In Examples 91.96, the co- electromagnetic stirrer, after flushing with nitrogen gas. polymerization was carried out at first at 80° C. for 2 Next, 4.6 millimole of chromyl chloride and 10.0 milli hours and then at 130° C. for 4 hours. mole of the reaction product between triethyl aluminum The reaction conditions and results are shown in the and monoethanolamine (1:1) were added thereto in that following Table 12. li5 order, and the tube was closed.

TABLE 12 Polymerizatlon Copolymer Cononomer Example Transition Metal AET MEA Temp. Time Product M.P. --- content Number Compound (mmol.) (mmol.) (mmol.) Comonomer (C.) (hr.) (gr.) (° C.) DP (mol percent) 84- ... TiCl3, 1.5- 2.13 100 85- TiCl4, 1.5 86. VOCl3, 1 87------TiCl3, 1.5---- 88------Ti(OAc)2Cl2, 1.5 89.------TiCl4, 1.5------15 90------VOCl3, 1.5------15 91------TiCl3, 1.5------AlFt3-MEA (Intol.), 15--- C2F4------80° C. (2 hrs.) plus 130° C. (4 hrs.). 92.------VOCl3, 1.5------AlBt3-MEA (mimol.), 15--- CFI------do------98------TiCl4, 1.5------AlFt3-MEA (namol.), 15--- C3H6------do------94- -- TiCl3, 1.5-- - AlBt3-MEA (mimol.), 15--- C3H6------do 95-- -- WOCl3, 1.5- - AlBt3-MEA (mmol.), 15--. C3H6------96. -- TiCl3, 1.5-- - Alist3-MEA (mmol.), 15--- n-C4H8---- 97------CrO2Cl2, 4.6------AllEt3-MEA (mmol.), 10--- C2FI4------80------6------98------CrO2Cl2, 4.6------AlEt3-MEA (mimol.), 10... C3H6------80------6------

Infrared spectra of the polymers obtained in Examples After the nitrogen gas in the tube was replaced by vinyl 91 and 94 were compared with that of the homopolymer chloride, vinyl chloride was charged under pressure with of vinyl chloride. It was observed that the absorption stirring, and polymerization was continued for 6 hours bands of 688 cm.1 and 635 cm. in the spectrum of the at 2.5 kg./cm. and 32 C. The product was treated as homopolymer of vinyl chloride changed to those of 683 in Examples 33-48 and 1.2 gr. of polymer was obtained. cm. 1 (shift), 635 cm. 1 (intensity is reduced) and 751 The result of elementary analysis was as follows. C: cm. (new absorption) in the spectrum of the vinyl 33.8%, H: 4.1%, Cl: 60.5%. chloride-ethylene copolymer of Example 91, and to those 45 It was confirmed from the above-mentioned chlorine of 683 cm. - (shift) and 635 cm. 1 (intensity is reduced) content that vinyl chloride-trichloroethylene copolymer in the spectrum of the vinyl chloride-propylene copolymer containing 8.06 mole percent of trichloroethylene was of Example 94. It was further observed that the spectrum formed. of the vinyl chloride-propylene copolymer had a new 50 EXAMPLES 100-106 absorption band at 1381 cm. - which was absent in the case of homopolymer of vinyl chloride. VDC; solvent; M--(AlEta-MEA) Also, the nuclear magnetic resonance spectra of the Polymerization of vinylidene chloride was carried out polymers obtained in Examples 91 and 94 were compared using as catalyst, 5.0 millimole of the reaction produce with that of homopolymer of vinyl chloride. It was ob 55 between triethyl aluminum and monoethanolamine (1:1) served that as for the signals of polyvinyl chloride, i.e. and 2.5 millinole of various compounds of transition a multiplet (CH) around t=5.61 and a multiplet (CH) metal. around t=7.91, their intensities in the part of higher 70 ml. of 1,2-dichloroethane was introduced into a 200 magnetic field side increased, whereas those in the part ml. pressure resistant glass reaction tube equipped with of lower magnetic field side decreased in both the vinyl 60 an electromagnetic type stirrer, after flushing with nitro chloride-ethylene copolymer obtained in Example 91 and gen gas. Next, a compound of transition metal and the the vinyl chloride-propylene copolymer obtained in Exam above-mentioned reaction product were added in that ple 94. This fact evidently shows that many units of vinyl order. Finally, 10 ml. of vinylidene chloride (0.125 mole, chloride adjasent to a unit of olefin exist in the polymer 12.1 gr.) was added and the tube was closed. Reaction chain and is a proof of the formation of copolymer. It 65 was carried out at a given temperature and for a given is also confirmed from the positions of the signals of period of time. After completion of the reaction, metha ethylene unit or propylene unit appearing in the spectra of nol (which might contain a suitable amount of hydro the polymers that not a mixture of polyvinyl chloride and chloric acid) was added to the reaction liquid to precipi polyolefin but a copolymer is formed. tate the polymer. After allowed to stand over night, re In the present examples, the separation and purification 70 Stiltant polymer was filtered, washed with methanol and of resultant copolymer of vinyl chloride with olefin were dried at 40° C. in vacuo for 24 hours. The polymers were carried out as follows. white powder, the infrared spectra of which accorded Raw polymer was added to 20 times its amount of tetra completely with those of a radical polymerization product hydrofuran and extracted at room temperature for 12 having good purity. The majority of white polymers pro hours. After insoluble polyolefin was filtered off, the re 75 duced using other modified Ziegler catalysts, have been 3,477,999 17 18 found from infrared spectrum to contain in their poly EXAMPLE 116 mer molecule chains such an irregular structure as seen in chlorinated polychloroprene or the like, on account VDC; solvent; M--(AlEta-N,N-Phe-MEA) of dehydrochlorination and various reactions accompa Polymerization was carried out in the same way as in nied. However, the above-mentioned fact cannot be seen Example 101, except that a reaction product between tri in the polymers obtained in the present examples. ethyl aluminum and N, N-diphenyl monoethanolamine The reaction conditions and results are shown in the (1:1) was used instead of the reaction product between following Table 13. triethyl aluminum and monoethanolamine (1:1) used in TABLE.13 Example 101. 2.11 gr. of polymer having a pale light blue Polymerization 10 color was obtained (yield: 17.3%). Polymer Example Transition Metal Temp. Time Yield EXAMPLE 117 Number Compound ( C.) Chr.) (percent) VDC; non solvent; M--(AIEt-MEA) - CrO2Cl2. 60 3 18.6 60 3. 24. 2.0 millimole of the reaction product between triethyl 60 3. 7.7 15 60 13 59. aluminum and monoethanolamine (1:1), 1.0 millimole of 60 40 82. Vanadium oxytrichloride and 8 ml. of vinylidene chloride 105------WOCl3------30 3. 13.0 were introduced in that order, under cooling, into a 18 106------WOCl3------90 3. 33.8 ml. pressure resistant glass reaction tube, after flushing with nitrogen gas. The tube was sealed, and then non-sol EXAMPLE 107 20 vent polymerization of vinylidene chloride was carried out with stirring, at 60° C., for 3 hours. The treatment VDC; solvent; M--AlEta--MEA after completion of the reaction was the same as in Ex 5.0 millimole of triethyl aluminum and 5.0 millimole ample 101. 4.45 gr. of white polymer was obtained (yield: of monoethanolamine were separately added to the re 45.7%). action system, instead of the reaction product between EXAMPLES 118-123 triethyl aluminum and monoethanolamine (1:1) used in Example 101. Other conditions in polymerization were VDC-VC; non solvent; M--(AIEt-MEA) the same as those in Example 101.2.1 gr. of white polymer 2.0 millimole of the reaction product between triethyl was obtained. aluminum and monoethanolamine (1:1), 1.0 millimole EXAMPLES 108-111 30 of vanadium oxytrichloride, a given amount of vinyli dene chloride and a given amount of vinyl chloride were VDC; solvent; M--(AlEta-MEA) (various amounts introduced in that order, under cooling, into a pressure of catalyst and VDC) resistant glass reaction tube, after flushing with nitrogen In the present examples, polymerizations were carried gas. The tube was sealed, and then non-solvent copolym out in the same Way as in Example 101 which the cata 35 erization of vinylidene chloride with vinyl chloride was lyst system (Al/V=2) consisting of the reaction product carried out at 60° C., for 20 hours, with stirring. The between triethyl aluminum and monoethanolamine (1:1) treatment after completion of the reaction was the same and vanadium oxytrichloride (polymerization: 60° C., 3 as in Example 101. Powdery polymer was obtained. The hours) was used except that the amount of the catalyst polymer was dissolved in tetrahydrofuran, filtered and and the amount of vinylidene chloride (VDC) charged 40 reprecipitated from distilled methanol for the purpose of were varied. In the examples in which the amount of the purification. Thus purified polymer was used for samples 'monomer was varied, the amount of 1,2-dichloroethane for elementary analysis, infrared spectrum and nuclear as a solvent was adjusted so as to give the total amount magnetic resonance spectrum. of the system consisting of solvent, monomer and cata The results are shown in the following Table 16. lyst, 85 ml. The reaction conditions and results are shown 45 TABLE 6 in the following Table 14. The polymers were all white Feed (ml.) Polymer WC Content powder. Yield in Copolymer TABLE 14 WDC WC (percent) (mo percent) Example No: WOCl3 WDC Polymer 50 118--- 7.0 0 22.5 17.6 Monomer Yield 19.-- 6.0 2.0 22.9 20.9 (mmol.) Feed (ml.) (percent) 20--- 50 3.1 6, 4 37.6 ExampleNumber: 121------4.0 4, 2 7.2 27.2 108------1.25 O 20.5 122------3.0 5.0 2.0 53.8 0.625 O 15.4 128------2. 60 5.5 74, 4 2.5 5 18.0 11l------2.5 5 249 55 *WC: Wolume at -78°C. The contents of vinyl chloride component in the co EXAMPLES 112-115 polymers were calculated from the analytical values of chlorine. The absorption band due to the deformation vi VDC; solvent; M--(AlEta-MEA) bration of CH in vinyl chloride unit can be seen clearly (Various solvents) 60 at 1205 cm. in every infrared spectra, (measured by the KBr tablet method), of the polymers obtained in Ex Polymerizations were carried out in the same way as amples 118-123. Since this absorption band is not found in Example 101, except that various solvents were used in polyvinylidene chloride and is supposed to appear at instead of 1,2-dichloroethane. The amounts of the sol 1250 cm. in polyvinyl chloride, the above-mentioned vents were all 70 ml. Resultant polymers were all white 65 result shows that the samples are not a mixture of homo powder. The solvents and results are shown in Table 15. polymers but copolymers. (Reference: J. Polymer Sci., A3, 3919 (1965)). Nuclear magnetic resonance spectra TABLE 1.5 of the samples were measured at 160 C. from 10% Polymer Yield chlorobenzene solutions thereof. Solvent (percent) 70 EXAMPLES 124-127 Example Number: 112------CCl4------24.2 VDC--vinyl compound or olefin; nonsolvent; n-Heptane. 7. M-4-(AlEta-MEA) Toluene- 14.9 --- THF------14.2 2.0 millimole of the reaction product between triethyl 75 aluminum and monoethanolamine (1:1), 1.0 millimole of 3,477,999 19 20 vanadium oxytrichloride, 4.0 ml. of vinylidene chloride 5. A method for polymerizing at least one vinyl com and 4.0 ml. of a specific comonomer were introduced in pound expressed by a general formula of this order, under cooling, into a 18 ml. pressure resistant X glass tube, after flushing with nitrogen gas. The tube was / sealed, and then non-solvent copolymerizations of vinyl CEEC idene chloride and several kinds of vinyl compounds were C carried out at 60° C. for 20 hours with stirring. The wherein X is a member selected from the group consist treatments after completion of the reaction were the same ing of hydrogen and chlorine atom, which comprises as in Example 101. White powder of polymer was ob polymerizing said vinyl compound by the use of a modi tained. The polymers were extracted with acetone or tetra fied Ziegler type catalyst consisting of (a) a compound of hydrofuran for 8 hours, or using successively the one of O a transition metal, (b) an organoaluminum compound the above-mentioned for 8 hours and then the other for and (c) a lower aliphatic alcohol having, as a substituent, 8 hours (total: 16 hours) and reprecipitated from distilled a member selected from the group consisting of an amino methanol for the purpose of purification. Thus obtained radical, nitrile radical and a halogen atom, in the presence polymers were used for the samples for elementary anal of a solvent the molar ratio of said alcohol component -ysis and infrared spectrum. (c) to said organoaluminum component (b) being within The results are shown in the following Table 17. the range of about 0.5 to 2.

TABLE 7 Solvent Extraction Comono Comono 8 mer in Comononer Acetone Acetone in TEF Acetone Soluble Acetone Insoluble TEE Soluble Polymer Solubie Fraction Insoluble o Fraction Soluble Fraction Example Yield (weight (nol (weight (nol (weight (mo Number Comonomer (percent) percent) percent) percent) percent) percent) percent) Propylene.-- 6.2 bX X X X 90.6 65.0

WinylAcetate 54.9 66.2 21.5 33.8 15.3 X X Me methacryla 100.0 75.2 50.8 24.8 27.0 X X

--- Me acrylate----- 94. 99.8 45.9 0.0 X X X a Feed volume: 4.0 ml. at -78 C. bX-Not extracted. c The Whole amounts of Acetone insoluble Fractions of No. 125-26 were THE Soluble. The contents of comonomer in the copolymers were 6. A method according to claim 5, wherein said solvent calculated from the analytical values of chlorine. It was 35 is a halogenated hydrocarbon. confirmed from the infrared spectra carried out by the 7. A method for polymerizing at least one vinyl com KBr tablet method and from the solubilities in acetone pound expressed by a general formula of or tetrahydrofuran of the polymers that the polymers were the copolymers of vinylidene chloride and a specific COOO 40 What is claimed is: 1. A method for polymerizing at least one vinyl com wherein X is a member selected from the group consisting pound expressed by a general formula of of hydrogen and chlorine atom, which comprising polym X erizing said vinyl compound by the use of a modified Ziegler type catalyst consisting of (a) a compound of a CH=c, transition metal, (b) an organoaluminum compound and Yol (c) a lower aliphatic alcohol having, as a constituent, a wherein X is a member selected from the group consist member Selected from the group consisting of an amino ing of hydrogen and chlorine atom, which comprises radical, nitrile radical and a halogen atom, in the absence polymerizing said vinyl compound by the use of a modi 50 of a solvent the molar ratio of said alcohol component fied Ziegler type catalyst consisting of (a) a compound (c) to said organoaluminum component (b) being within of transition metal, (b) an organoaluminum compound the range of about 0.5 to 2. and (c) a lower aliphatic alcohol having, as a substituent, 8. A method for polymerizing at least one vinyl com a member selected from the group consisting of an amino pound eXpressed by a general formula of radical, nitrile radical and a halogen atom the molar ratio of said alcohol component (c) to said organoalu minum component (b) being within the range of about 0.5 to 2. Cl 2. A method according to claim 1, wherein said com wherein X is a member selected from the group consist pound of a transition metal is selected from the group 60 ing of hydrogen and chlorine atom, which comprises consisting of halides, oxyhalides, alkoxides, alkoxyhalides, polymerizing said vinyl compound by the use of a catalyst alkoxyacetylacetonates, acetoxyhalides and acetylaceto consisting of a compound of a transition metal and an nate of titanium, vanadium, chromium, iron, cobalt, nick isolated reaction product between an organoaluminum el, zirconium and manganese and TiCl3/3 AlCl3. compound and an alkanolamine. 3. A method according to claim 1, wherein said organo 65 aluminum compound is selected from the group consist 9. A method for polymerizing at least one vinyl com ing of compounds expressed by a general formula, pound expressed by a general formula of AIRX-m, wherein R is a radical selected from alkyl, cycloalkyl and aryl radical, X is a halogen atom and n. is selected from 3, 2, 1.5 and 1. 70 4. A method according to claim 1, wherein said lower Yc aliphatic alcohol is selected from the group consisting of wherein X is a member selected from the group consist alkanol amines and compounds expressed by a general ing of hydrogen and chlorine atom, which comprises formula of HOCH2CH2X wherein X is selected from the polymerizing said vinyl compound by the use of a cata group consisting of Cl, Br atom and CN radical. 75 lyst consisting of a compound of a transition metal and 8,477,999 2. 22 an isolated reaction product between an organoaluminum compound and an alkanolamine in the presence of a free / organoaluminum compound further added the molar CH=C ratio of Said alkanolamine to said organoaluminum com Cl ponent being within the range of about 0.5 to 2. 10. A method for copolymerizing at least one vinyl 5 wherein X is a member selected from the group consisting compound expressed by a general formula of of hydrogen and chlorine atom, and a polymerizable un Saturated compound, which comprises copolymerizing CH-cC X Said compounds by the use of a catalyst consisting of a O compound of a transition metal and an isolated reaction C product between an organoaluminum compound and an wherein X is a member selected from the group consisting alkanolamine the molar ratio of said alkanolamine to of hydrogen and chlorine atom, and a polymerizable un said organoaluminum component being within the range Saturated compound, which comprises copolymerizing said of about 0.5 to 2. compounds by the use of a modified Ziegler type catalyst References Cited consisting of (a) a compound of a transition metal, (b) UNITED STATES PATENTS an organoaluminum compound and (c) a lower aliphatic alcohol having, as a substituent, a member selected from 2,932,633 4/1960 Juveland et al. ------260-94.9 the group consisting of an amino radical, nitrile radical 3,196,137 7/1965 Cain ------260-92.8 XR and a halogen atom the molar ratio of said alcohol com 3,219,648 11/1965 Hill ------260-94.9 XR ponent (c) to said organoaluminum component (b) be 3,251,810 5/1966 Bining ------260-78.5 ing within the range of about 0.5 to 2. FOREIGN PATENTS 11. A method according to claim 10, wherein said 620,226 5/1961 Canada. polymerizable unsaturated compound is selected from the group consisting of vinyl acetate, styrene, alkyl vinyl JOSEPH L. SCHOFER, Primary Examiner ethers, alkyl acrylate, alkyl methacrylate, acrylonitrile, ethylene, propylene, butene-1,4-methylpentene-1, tri JOHN KIGHT, Assistant Examiner chloroethylene, butadiene, maleic acid diesters and cro tonic acid alkyl esters. U.S. C1, X.R. 12. A method for copolymerizing at least one vinyl 252-429, 431; 260-33.8, 78.5, 82.1, 86.3, 87.1, 87.5, compound expressed by a general formula of 87.7, 91.7, 92.8