Process for producing block copolymers

Block copolymers of (i) a polymer of ethylene or propylene, or copolymer of ethylene or propylene with another .alpha.-olefin and (ii) a polymer of an acrylic ester or a methacrylic ester are formed by polymerizing (i) in the presence of a titanium halide and an organic aluminum compound, and then adding in order (a), (b) and (c) to copolymerize a product so obtained with (a) an acrylic ester or a methacrylic ester, in the presence of (b) an organic phosphorus compound or tertiary amine and (c) a benzyl halide, a ring-alkylated benzyl halide, a benzyl halide in which a methylene hydrogen is replaced with an alkyl or aryl group, or an alkyl halide.

FIELD OF THE INVENTION 
This invention relates to a process for producing block copolymers and, 
more particularly, it relates to a process for producing block copolymers 
which are composed of a polymer of ethylene or propylene, or their 
copolymer with another .alpha.-olefin, and a polymer of an acrylic ester, 
or a methacrylic ester. 
BACKGROUND OF THE INVENTION 
Block copolymers of a polyolefin and a polymer of a vinyl compound possess 
desirable properties of polyolefins and furthermore are expected to 
improve dye-affinity, hydrophilicity and miscibility with other resins. 
Thus, various processes for producing the block copolymers have been 
proposed. For example, one process comprises polymerizing olefins in the 
presence of a stereospecific catalyst, and thereafter polymerizing vinyl 
compounds in the presence of an alkylene oxide (Japanese Patent 
Publication Gazette No. 8679/1969). However, by this process, an alkylene 
oxide may be incorporated into the copolymer and thus this process is not 
advantageous. Another process comprises polymerizing olefins using an 
anionic catalyst and block-copolymerizing vinyl compounds in the presence 
of a radical initiator (Japanese Patent Publication Gazette Nos. 
40055/1970 and 42385/1972). However, upon using a radical initiator, 
substantial amounts of homopolymers of vinyl compounds are produced as 
by-products and thus this process is also not advantageous. 
We have found that block copolymers can be prepared very efficiently from a 
polymer of ethylene or propylene or their copolymers, with another 
.alpha.-olefin, and a polymer of an acrylic ester or a methacrylic ester, 
by adding certain organic phosphorus compounds or tertiary amines and 
organic halides to specific catalyst systems for polymerization of said 
olefins described above. Thus, the present invention was achieved. 
SUMMARY OF THE INVENTION 
In accordance with the present invention, there is provided a process for 
producing block copolymers comprised of a polymer of ethylene or propylene 
or copolymers thereof, with another .alpha.-olefin, and a polymer of an 
acrylic ester or a methacrylic ester, which comprises polymerizing 
ethylene or propylene or copolymerizing them, with another .alpha.-olefin 
having from 2 to 7 carbon atoms in the presence of an organic aluminum 
compound represented by the formula AlR.sub.n X.sub.3-n, wherein R is an 
alkyl group having from 1 to 5 carbon atoms, X is halogen and n is an 
integer from 1 to 3, and titanium halide as a catalyst, to form a polymer 
or copolymer, and subsequently adding in order (a) an acrylic ester or a 
methacrylic ester, (b) an organic phosphorus compound or a tertiary amine, 
and (c) benzyl halide or a derivative thereof, or an alkyl halide, to 
copolymerize (a) with the polymer or copolymer first formed. 
DETAILED DESCRIPTION OF THE INVENTION 
The process of the present invention comprises two steps, that is, the 
first step is for polymerization of an olefin or olefins, and the second 
step is for block copolymerization of the polyolefin thus obtained and an 
acrylic ester or a methacrylic ester. 
In the first step, ethylene or propylene is normally polymerized or 
copolymerized with an .alpha.-olefin in a hydrocarbon solvent in the 
presence of an organic aluminum compound and a titanium halide under 
atmospheric pressure or medium to low pressure. Example of .alpha.-olefins 
having from 2 to 7 carbon atoms which are copolymerized with ethylene or 
propylene are ethylene, propylene, butene-1, pentene-1, 3-methyl butene-1, 
hexene-1, 4-methyl pentene-1, 3-ethyl butene-1, heptene-1, 4,4-dimethyl 
pentene-1 and 3,3-dimethyl butene-1. Copolymerization of ethylene or 
propylene with the above-described olefin can be done by random 
copolymerization or block copolymerization procedures. As to hydrocarbon 
solvents for polymerization, aliphatic hydrocarbons such as pentane, 
hexane, heptane, octane; alicyclic hydrocarbons such as cyclopentane, 
cyclohexane, methylcyclohexane; and aromatic hydrocarbons such as benzene, 
toluene, xylene are preferred examples. 
Two-component catalysts comprising an organic aluminum compound and a 
titanium halide are used for polymerization of the olefins described 
above. One component of the catalyst, an organic aluminum compound, is 
indicated by the above-described formula. When n is 2 or 3, alkyl groups 
are not necessarily the same. Among such compounds, trialkyl aluminums of 
short straight chain aliphatic alkyl groups such as trimethyl aluminum 
Al(CH.sub.3).sub.3, triethyl aluminum Al(C.sub.2 H.sub.5).sub.3, 
tri-n-propyl aluminum Al(C.sub.3 H.sub.7).sub.3 are preferred examples, 
and diethyl aluminum monochloride Al(C.sub.2 H.sub.5).sub.2 Cl, ethyl 
aluminum dichloride Al(C.sub.2 H.sub.5)Cl.sub.2 can also be used 
advantageously. Preferred examples of titanium halides, which comprise the 
other component of the catalyst for polymerization of olefins, are 
titanium tetrachloride, titanium trichloride and titanium dichloride. 
Titanium halides containing aluminum such as AA-type TiCl.sub.3, i.e. 
Aluminum activated TiCl.sub.3 can also be used effectively. 
The molar ratio of organic aluminum compound to titanium halide is from 0.6 
to 5.0, preferably 1.0 to 3.0. The amount of mixed catalyst of organic 
aluminum compound and titanium halide is not restrictive and is sufficient 
in an ordinary catalytic amount. Generally, the molar ration of titanium: 
ethylene or propylene or sum of ethylene or propylene and another 
.alpha.-olefin is 1:10- 100,000, preferably 1:500- 20,000. 
Polymerization or copolymerization can be done by blowing ethylene or 
propylene singly or in combination with another .alpha.-olefin under 
atmospheric pressure; when under pressurized conditions, at most 50 
atmospheres of pressure are required. Under these conditions, 
polymerization or copolymerization is achieved by reacting for 0.5 to 2 
hours at a temperature of from 30.degree. to 100.degree. C., preferably at 
50.degree. to 80.degree. C., and thus a partially inactivated polyolefin 
and a polyolefin having active terminal group are obtained. 
In the said second step, a block copolymer is prepared by adding, in the 
following order, (a) an acrylic ester or a methacrylic ester, (b) an 
organic phosphorus compound or a tertiary amine and (c) a benzyl halide or 
a derivative thereof or an alkyl halide to a polyolefin described above. 
Additive (a) is the starting material for formation of the desired block 
copolymer. On the other hand, additives (b) and (c) are used as catalysts 
for effecting copolymerization efficiently. When the order of addition of 
(a), (b) and (c) is altered from the above-described method, the yield of 
block copolymer is lowered greatly. 
Preferred examples of additive (a) include such acrylic esters as methyl 
acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl 
acrylate, 2-ethoxyethyl acrylate, ethyleneglycol ester of acrylic acid, 
1,3-propanediol ester of acrylic acid and 1,4-butanediol ester of acrylic 
acid. Methyl methacrylate is the best example of an ester of methacrylic 
acid, but ethyl methacrylate, propyl methacrylate, butyl methacrylate, 
2-ethylhexyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, 
benzyl methacrylate and alkylene glycol monomethacrylic esters, in which 
the number of carbon atoms present in the alkylene glycol group is from 2 
to 5, are also advantageous. Examples of alkylene glycol mono-methacrylic 
ester are 2-hydroxyethyl methacrylate, 1-hydroxyethyl methacrylate, 
3-hydroxypropyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl 
methacrylate, 3-hydroxybutyl methacrylate, 2-hydroxybutyl methacrylate, 
2-hydroxy-2-methylpropyl methacrylate and 1-hydroxy-2,2-dimethylpropyl 
methacrylate. 
Amounts of an ester of an acrylate or a methacrylate are not restrictive 
and can be varied suitably. Generally, the molar ratio of this compound to 
olefin is 0.01 to 10. 
Either an organic phosphorus compound or a tertiary amine is employed as 
additive (b). Examples of organic phosphorus compounds are: phosphines 
such as triethyl phosphine, tri-n-propyl phosphine, tri-n-butyl phosphine 
and triphenyl phosphine; phosphites such as trimethyl phosphite, triethyl 
phosphite and tri-n-butyl phosphite; phosphates such as trimethyl 
phosphate, triethyl phosphate and tri-n-butyl phosphate; phosphoramides 
such as hexamethyl phosphoramide. Organic phosphorus compounds described 
above are used singly or in combination. On the other hand, examples of 
tertiary amines are aliphatic tertiary amines such as triethyl amine, 
tri-n-propyl amine, tributyl amine, triamyl amine and trioctyl amine; 
amines with an unsaturated group such as triallyl amine; aromatic amines 
such as dimethyl aniline, diethyl aniline, toluidine and methyl diphenyl 
amine; tetramethyl ethylenediamine and 1,8-diaza-bicyclo-[5,4,0] 
undecene-7 or its phenolate, caproate or oleate. The present invention 
cannot be achieved by using primary or secondary amines. 
Examples of additive (c) include: benzyl halides such as benzyl chloride 
and benzyl bromide; their derivatives such as nuclear substitution 
products of benzyl halide with an alkyl group or groups, for example 
p-methylbenzyl chloride; substitution products of hydrogen other than on 
the benzene ring with an alkyl or an aryl group or groups, for example 
diphenylchloromethane; and alkyl halides such as carbon tetrachloride, 
chloroform, methylene chloride and t-butyl chloride. 
Amounts of additive (b) are from 0.5 to 50 by molar ratio, preferably 1.0 
to 30, to titanium halide. Additive (c) is employed in an amount of from 
0.1 to 5.0 by molar ratio, preferably 0.3 to 3.0. to organic phosphorus 
compound or tertiary amine. 
Under the above conditions, the desired block copolymers can be obtained by 
polymerizing at a temperature of from 30.degree. to 100.degree. C., 
preferably 50.degree. to 80.degree. C., for from 0.5 to 5 hours. 
According to the present invention, an acrylic ester or a methacrylic ester 
can be block polymerized with a polyolefin very efficiently. 
As described above, a copolymer obtained by the process of the present 
invention comprises a mixture of a small amount of inactivated olefin 
homopolymer, which is the product of the first step, the desired block 
copolymer and a small amount of homopolymer of an acrylic ester or a 
methacrylic ester. The mixture contains very low amounts of homopolymer, 
especially of acrylic ester or methacrylic ester compared with those 
produced by conventional methods. Therefore, the copolymers produced by 
this invention can be used as varius molding materials, composition 
compounds or starting material for paints, building materials, synthetic 
fiber paper, etc., without a further separation process. When an alkylene 
glycol mono-methacrylic ester is used as an example of an methacrylic 
ester, the block copolymer obtained is excellent in weatherproofing, 
hydrophilicity, adhesiveness and softness properties due to having an 
active hydroxy group therein.

The invention is explained in detail by means of the following illustrative 
examples and compartive examples. 
EXAMPLE 1 
To a 500 ml content flask the atmosphere of which is displaced with argon, 
250 ml. of purified n-heptane were placed as a solvent and then under a 
stream of argon, 0.5 millimole of 3 TiCl.sub.3 AlCl.sub.3 and 1 millimole 
of triethyl aluminum were added to form a catalyst for ethylene 
polymerization. Ethylene was blown through the mixture under normal 
pressure and polymerization was made at 70.degree. C. for 1 hour with 
agitation and subsequently ethylene was displaced with argon and argon was 
bubbled for 5 minutes. By this process, unreacted ethylene monomer other 
than dissolved in the solvent was removed, and then under the stream of 
argon 10 grams of methyl methacrylate (designated as MMA hereafter), 6.0 
millimoles of tri-n-butyl phosphine and 6.0 millinoles of benzyl bromide 
were added in this order and polymerization was continued for another 3 
hours. After the reaction, the catalyst was decomposed by adding small 
amounts of methanol and then a large amount of methanol was added to 
precipitate the polymer which had formed. The polymer was filtered and 
dried under reduced pressure. The polymer obtained was 21.7 grams and 
material extracted with hot acetone, which is considered to be a 
homopolymer of MMA, was only 0.9 weight percent. From the results of IR 
absorption spectrum, 38.7 % of MMA units were found to be present in the 
portion of copolymers insoluble in acetone. The conversion yield of MMA to 
homopolymer and copolymer was 85.2%. 
EXAMPLE 2 
This experiment was carried out in the same manner as described in Example 
1, except that 6 millimoles of benzyl bromide were replaced by 6 
millimoles of benzyl chloride. As a result, the amount of product was 16.4 
grams; the acetone-soluble part was 0.3%. In the acetone-insoluble 
copolymer, 13.0% of MMA units were found to be present. The conversion 
yield of MMA to homopolymer and copolymer was 21.7%. 
EXAMPLE 3 
This experiment was carried out in the same manner as described in Example 
1, except that 6 millimoles of benzyl bromide were replaced by 6 
millimoles of carbon tetrachloride. As a result, the amount of product was 
20.8 grams; the acetone-soluble material was 0.3%. In the 
acetone-insoluble copolymer, 9.1% of MMA units were found to be present. 
The conversion yield of MMA to homopolymer and copolymer was 19.5%. 
EXAMPLE 4 
This experiment was carried out in the same manner as Example 1, except 
that 6 millimoles of benzyl bromide were replaced by 6 millimoles of 
t-butyl chloride. As a result, the amount of product was 16.2 grams; the 
acetone-soluble part was 0.3%. In the acetone-insoluble copolymer, 1.0% of 
MMA units were found to be present. The conversion yield of MMA to 
homopolymer and copolymer was 2.1%. 
EXAMPLE 5 
This experiment was carried out in the same manner as Example 1, except 
that 6 millimoles of tri-n-butyl phosphine were replaced by 6 millimoles 
of triethyl phosphite and 6 millimoles of benzyl bromide were replaced by 
6 millimoles of benzyl chloride. As a result, the amount of product was 
13.2 grams; the acetone-soluble part was 0.2%. In the acetone-insoluble 
copolymer, 4.8% of MMA units were found to be present. The conversion 
yield of MMA to homopolymer and copolymer was 6.6%. 
EXAMPLE 6 
This experiment was carried out in the same manner as described in Example 
5, except that 6 millimoles of benzyl chloride were replaced by 6 
millimoles of carbon tetrachloride. As a result, the amount of the product 
was 16.4 grams; the acetone-soluble part was 0.9%. In the 
acetone-insoluble copolymer, 6.5% of MMA units were found to be present. 
The conversion yield of MMA to homopolymer and copolymer was 12.0%. 
EXAMPLE 7 
This experiment was carried out in the same manner as described in Example 
1, except that 1 millimole of triethyl aluminum was replaced by 1 
millimole of diethyl aluminum monochloride. As a result, the amount of the 
product was 19.3 grams; the acetone-soluble part was 13.6%. In the 
acetone-insoluble polymer, 42.8 weight percent of MMA units were found to 
be present. 
EXAMPLE 8 
This experiment was carried out in the same manner as Example 1, except 
that 10 grams of MMA were replaced by 10 grams of methyl acrylate. As a 
result, the amount of the product was 17.9 grams; the acetone-soluble part 
occupied 2.1%. In the acetone-insoluble copolymer, 30.6% of methyl 
acrylate units were found to be present. 
EXAMPLE 9 
To a 500 ml flask the atmosphere of which is displaced by argon, 100 ml of 
purified n-heptane were placed as a solvent and then under the stream of 
argon 0.5 millimole of 3 TiCl.sub.3 --AlCl.sub.3 and 1.0 millimole of 
triethyl aluminum were added to form the catalyst for ethylene 
polymerization. Ethylene was blown through the mixture under normal 
pressure and polymerization was made for 1 hour at 70.degree. C. with 
agitation. Subsequently, ethylene was displaced by argon and argon was 
bubbled for 5 minutes. By this process, unreacted ethylene monomer other 
than that dissolved in the solvent was removed, and then under the stream 
of argon 6 grams of MMA, 2 millimoles of hexamethyl phosphoramide and 2 
millimoles of carbon tetrachloride were added in this order and 
polymerization was continued for another 2 hours at 70.degree. C. After 
polymerization, the catalyst was decomposed by adding small amounts of 
methanol, and then a large amount of methanol was added to precipitate 
copolymer which had formed. The polymer obtained was filtered and dried 
under reduced pressure. The polymer obtained was 9.7 grams; no 
acetone-soluble part was present. In the acetone-insoluble copolymer, 2.9% 
of MMA units were found to be present. 
COMATIVE EXAMPLE 1 
This experiment was carried out in the same manner as described in Example 
1, except that benzyl bromide was not added. As a result, the amount of 
product was 15.5 grams. The acetone-soluble part was 0.3%. However, in the 
acetone-insoluble polymer almost no MMA unit was found. 
COMATIVE EXAMPLE 2 
This experiment was carried out in the same manner as Example 5, except 
that triethyl phosphite was not added. As a result, the amount of the 
product was 19.2 grams. The acetone-soluble part was 0.1%. In the 
acetone-insoluble polymer, no MMA unit was found to be present. 
COMATIVE EXAMPLE 3 
This experiment was carried out in the same manner as Example 1, except 
that tri-n-butylphosphine and benzyl bromide were not added. As a result, 
the amount of product was 17.4 grams. The acetone-soluble part was 0.3%. 
In the acetone-insoluble polymer, no MMA unit was found to be present. 
EXAMPLE 10 
A five-necked flask (500 ml content) with inlet for gas, cooler, 
thermometer, agitator and opening for pouring reagents was displaced by 
argon. Under the stream of argon, 250 milliliters of n-heptane as a 
solvent were added through a syringe, and then 0.5 millimole of AA-type 
titanium chloride and 1 millimole of triethyl aluminum were added. While 
introducing a small amount of argon, the temperature was raised to 
70.degree. C. with stirring, and then argon was replaced by ethylene which 
was introduced at the rate of 500 cubiic centimeter per minute, and 
polymerization was made for 1 hour. After the reaction, ethylene was 
displaced by argon and argon was bubbled for 5 minutes. By this process, 
unreacted ethylene was discharged from the flask. Subsequently, under the 
stream of argon 10 grams of butyl acrylate, 6 millimoles of triethyl amine 
and 6 millimoles of benzyl chloride were added in this order, and the 
polymerization was continued for 3 hours at 70.degree. C. After the 
reaction, the catalyst was decomposed by adding a small amount of methanol 
and then a large amount of methanol was added to precipitate polymer which 
had formed. The polymer was filtered and dried under reduced pressure. The 
polymer obtained was 29 grams. A part (3 grams) was weighed exactly and 
was extracted with boiling acetone using a Soxhlet extractor for 8 hours. 
The residues were examined by IR absorption spectroscopy. As a result, the 
content of homopolymer of butyl acrylate in the polymer formed was 0.7 
weight percent, and the content of butyl acrylate units in the block 
copolymer was 0.3 weight percent. 
EXAMPLE 11 
This experiment was carried out in the same manner as described in Example 
10, except that 6 millimoles of benzyl chloride were replaced by 6 
millimoles of carbon tetrachloride. As a result, the amount of polymer 
obtained was 26 grams. The content of homopolymer of butyl acrylate in the 
polymer was 1.7 weight percent. The content of butyl acrylate unit in the 
block copolymer was 1.8 weight percent. 
EXAMPLE 12 
This experiment was carried out in the same manner as Example 10, except 
that 10 grams of butyl acrylate was replaced by 10 grams of methyl 
acrylate. As a result, the amount of polymer obtained was 17.3 grams. The 
content of the homopolymer of methyl acrylate was 0.6 weight percent. The 
content of methyl acrylate unit in the block copolymer was 3.9 weight 
percent. The conversion yield of methyl acrylate to homopolymer of methyl 
acrylate and the block copolymer was 7.7%. 
EXAMPLE 13 
This experiment was carried out in the same manner as Example 12, except 
that 6 millimoles of benzyl chloride were replaced by 6 millimoles of 
carbon tetrachloride. As a result, the amount of polymer obtained was 21.4 
grams. The content of the homopolymer of methyl acrylate in the polymer 
formed was 1.0 weight percent. The content of methyl acrylate unit in the 
block copolymer was 19.4 weight percent. The conversion yield of methyl 
acrylate to homopolymer of methyl acrylate and the block copolymer was 
43.2%. 
COMATIVE EXAMPLE 4 
This experiment was carried out in the same manner as described in Example 
12, except that triethyl amine and benzyl chloride were not added. As a 
result, the amount of polymer obtained was 14.3 grams. The content of the 
homopolymer of methyl acrylate in the polymer formed was very small (0.4 
weight percent). However, the content of methyl acrylate unit in the block 
copolymer was less than 0.1 weight percent. 
EXAMPLE 14 
A five-necked flask (500 ml content) with inlet for introduction of gas, 
cooler, thermometer, agitator and opening for pouring reagents was 
displaced by argon. Under the stream of argon, 250 milliliters of 
n-heptane as a solvent were added through a syringe, and then 0.5 
millimole of AA-type titanium chloride and 1.0 millimole of triethyl 
aluminum were added. While introducing a small amount of argon, the 
temperature of the resulting mixture was raised to 70.degree. C. with 
stirring, and then argon was replaced by ethylene which was then 
introduced at the rate of 500 milliliters per minute, and polymerization 
was made for 1 hour. After the reaction, ethylene was displaced by argon 
and argon was bubbled for 5 minutes. By this process, unreacted ethylene 
was discharged from the flask. Subsequently, under the stream of argon, 10 
grams of MMA, 6 millimoles of triethyl amine and 6 millimoles of benzyl 
chloride were added in this order, and the polymerization was continued 
for 3 hours at 70.degree. C. After the reaction, the catalyst was 
decomposed by adding a small amount of methanol, and then a large amount 
of methanol was added to precipitate the polymer formed. The polymer was 
filtered and dried under reduced pressure. The polymer obtained was 21.7 
grams. A part of the polymer (3 grams) was weighed exactly and was 
extracted with boiling acetone using a Soxhlet extractor for 8 hours. 
Results were as follows: 
______________________________________ 
Extract MMA homopolymer* 
1.3 weight percent 
Residues 
Ethylene-MMA block 
98.7 weight percent 
copolymer + 
polyethylene 
Content of MMA 35.1 weight percent 
in the residues 
The conversion yield of MMA** 
78.0 percent. 
______________________________________ 
*confirmed by IR absorption spectroscopy 
**yield of MMA to MMA homopolymer and ethylene-MMA block copolymer 
EXAMPLE 15 
This experiment was carried out in the same manner as described in Example 
14, except that triethyl amine was replaced by another aliphatic tertiary 
amine shown in Table 1. Results are provided in Table 1. 
Table 1 
__________________________________________________________________________ 
Polymer MMA Content of MMA 
formed 
Conversion yield 
homopolymer 
in the residues 
Amine (grams) 
of MMA (%) 
(weight %) 
(weight %) 
__________________________________________________________________________ 
(CH.sub.3 CH.sub.2 CH.sub.2).sub.3 N 
18.4 22.3 0.7 11.5 
(CH.sub.3 (CH.sub.2).sub.4).sub.3 N 
16.4 4.3 0.6 2.0 
(CH.sub.3 (CH.sub.2).sub.7).sub.3 N 
22.6 13.9 0.5 5.7 
__________________________________________________________________________ 
EXAMPLE 16 
This experiment was carried out in the same manner as Example 14, except 
that triethyl amine was replaced by an aromatic tertiary amine shown in 
Table 2. Results are provided in Table 2. 
Table 2 
__________________________________________________________________________ 
Polymer MMA Content of MMA 
formed 
Conversion yield 
homopolymer 
in the residues 
Amine (grams) 
of MMA (%) 
(weight %) 
(weight %) 
__________________________________________________________________________ 
##STR1## 17.3 17.3 1.0 9.1 
##STR2## 17.5 8.0 0.8 3.8 
##STR3## 18.3 4.2 0.3 2.0 
__________________________________________________________________________ 
example 17 
this experiment was carried out in the same manner as Example 14, except 
that benzyl chloride was replaced by a derivative of benzyl halide shown 
in Table 3. Results are provided in Table 3. 
Table 3 
__________________________________________________________________________ 
Polymer MMA Content of MMA 
formed 
Conversion yield 
homopolymer 
in the residues 
Benzyl halide 
(gramm) 
of MMA (%) 
(weight %) 
(weight %) 
__________________________________________________________________________ 
##STR4## 29.2 100 3.0 37.5 
##STR5## 31.3 100 1.7 31.5 
##STR6## 21.1 7.4 2.5 1.0 
__________________________________________________________________________ 
EXAMPLE 18 
This experiment was carried out in the same manner as Example 14, except 
that amounts of triethyl amine and benzyl chloride were changed. Results 
are shown in Table 4. 
Table 4 
__________________________________________________________________________ 
Triethyl 
Benzyl Polymer 
Conversion 
MMA Content of MMA 
amine chloride 
formed 
yield of 
homopolymer 
in the residues 
(milli moles) 
(milli moles) 
(gramm) 
MMA (%) 
(weight %) 
(weight %) 
__________________________________________________________________________ 
2.0 1.0 17.1 19.6 0.8 10.7 
2.0 2.0 18.0 13.9 0.8 17.9 
2.0 6.0 17.3 5.7 0.4 2.9 
__________________________________________________________________________ 
COMATIVE EXAMPLE 5 
This experiment was carried out in the same manner as Example 14, except 
that benzyl chloride was not added. Results are as follows. 
______________________________________ 
Polymer formed 13.8 grams 
Conversion yield of MMA 
0.6 percent 
MMA homopolymer 0.4 weight percent 
Content of MMA in the residue 
0 percent. 
______________________________________ 
Comparative Example 6 
This experiment was carried out in the same manner as Example 14, except 
that triethyl amine was not added. Results are as follows. 
______________________________________ 
Polymer formed 19.2 grams 
Conversion yield of MMA 
0.2 percent 
MMA homopolymer 0.1 weight percent 
Content of MMA in the residues 
0 percent. 
______________________________________ 
COMATIVE EXAMPLE 7 
This experiment was carried out in the same manner as Example 14, except 
that triethyl amine and benzyl chloride were not added. Results are as 
follows. 
______________________________________ 
Polymer formed 17.4 grams 
Conversion yield of MMA 
0.5 percent 
MMA homopolymer 0.3 weight percent 
Content of MMA in the residues 
0 percent. 
______________________________________ 
COMATIVE EXAMPLE 8 
Inactivated polyethylene (10 grams) was placed in a 500 ml content 
five-necked flask, the atmosphere of which was displaced by argon (the 
same flask used in Example 14) and 250 milliliters of n-heptane were added 
to the flask. Furthermore, as a catalyst, 0.5 millimole of AA-type 
titanium chloride and 1.0 millimole of triethyl aluminum were added and 
the mixture was brought up to a temperature of 70.degree. C. Subsequently, 
10 grams of MMA, 6 millimoles of triethyl amine and 6 millimoles of benzyl 
chloride were added while stirring, and polymerization was effected for 
4.5 hours at 70.degree. C. After the completion of the reaction, a large 
amount of methanol was added to precipitate the polymer which was then 
filtered and dried under reduced pressure. The polymer thus obtained was 
analyzed by IR absorption spectroscopy. No absorption due to MMA was 
observed. 
EXAMPLE 19 
To a 500 ml content flask, the atmosphere of which was displaced by argon, 
250 ml of purified n-heptane were placed as a solvent. Then, under the 
stream of argon, 0.5 millimole of 3 TiCl.sub.3 -AlCl.sub.3 and 1 millimole 
of triethyl aluminum were added to form a catalyst for ethylene 
polymerization. Ethylene was blown through the mixture under normal 
pressure and polymerization was made for 1 hour at 70.degree. C. with 
stirring. Subsequently, ethylene was displaced by argon and argon was 
bubbled for 5 minutes. By this process, unreacted ethylene monomer other 
than that dissolved in the solvent was removed. Then, under the stream of 
argon, 10 grams of MMA, 6 millimoles of triethyl amine and 6 millimoles of 
carbon tetrachloride were added in this order, and polymerization was 
continued for another 3 hours. After polymerization, the catalyst was 
decomposed by adding a small amount of methanol, and then a large amount 
of methanol was added to precipitate the polymer formed. The polymer thus 
obtained was filtered and dried under reduced pressure. The amount of 
polymer was 25.7 grams. The hot acetone-soluble part which is considered 
to be homopolymer of methyl methacrylate comprised 1.9%. The content of 
MMA in the acetone-insoluble copolymer was found to be 36.7% by IR 
absorption spectroscopy. 
EXAMPLE 20 
This experiment was carried out in the same manner as described in Example 
19, except that 6 millimoles of triethyl amine were replaced by 6 
millimoles of tri-n-propyl amine. As a result, the amount of the polymer 
was 23.6 grams. The acetone-soluble part was 0.9%. The content of MMA in 
the acetone-insoluble copolymer was 26.5%. 
EXAMPLE 21 
This experiment was carried out in the same manner as Example 19, except 
that 6 millimoles of triethyl amine were replaced by 6 millimoles of 
dimethyl aniline. As a result, the amount of the product was 21.2 grams. 
The acetone-soluble part was 1.3%. The content of MMA in the 
acetone-insoluble copolymer was 4.6%. 
EXAMPLE 22 
This experiment was carried out in the same manner as described in Example 
19, except that 6 millimoles of triethyl amine were replaced by 6 
millimoles of tetramethyl ethylene diamine. As a result, the amount of the 
product was 17.1 grams. The actone-soluble part was 3.7%. The content of 
MMA in the acetone-insoluble copolymer was 22.5%. 
EXAMPLE 23 
This experiment was carried out in the same manner as Example 19, except 
that 6 millimoles of carbon tetrachloride were replaced by 6 millimoles of 
chloroform. As a result, the amount of the product was 18.7 grams. The 
acetone-soluble part was 0.7%. The content of MMA in the acetone-insoluble 
copolymer was 7.4%. 
COMATIVE EXAMPLE 9 
This experiment was carried out in the same manner as in Example 19, except 
that triethyl amine was not added. As a result, the amount of product was 
18.6 grams. However, no MMA was found either in the acetone-soluble or 
acetone-insoluble polymers. 
COMATIVE EXAMPLE 10 
This experiment was carried out in the same manner as Example 19, except 
that carbon tetrachloride was not added. As a result, the amount of the 
product was 19.2 grams. However, no MMA was found in the product. 
COMATIVE EXAMPLE 11 
This experiment was carried out in the same manner as Example 19, except 
that triethyl amine and carbon tetrachloride were not added. As a result, 
the amount of the product was 17.4 grams. However, no MMA was found in the 
product. 
EXAMPLE 24 
A five-necked flask (500 ml content) with inlet for introduction of gas, 
cooler, thermometer, agitator and opening for pouring reagents was 
displaced with argon. Under the stream of argon, 250 milliliters of 
n-heptane as a solvent were added through a syringe, and then 0.5 
millimole of AA-type titanium chloride and 1 millimole of triethyl 
aluminum were added. While introducing a small amount of argon, the 
temperature was raised to 70.degree. C. with stirring. Then, argon was 
replaced by ethylene which was then introduced at the rate of 500 
milliliters per minute, and polymerization was made for 1 hour. After the 
reaction, ethylene was displaced by argon, and argon was introduced for 5 
minutes. By this process, unreacted ethylene was discharged from the 
flask. Subsequently, under the stream of argon, 10 grams of 2-hydroxyethyl 
methacrylate, 6 millimoles of triethyl amine and 6 millimoles of benzyl 
chloride were added in this order, and polymerization was continued for 3 
hours at 70.degree. C. After the reaction, the catalyst was decomposed by 
adding a small amount of methanol, and then a large amount of methanol was 
added to precipitate the polymer formed. The polymer was filtered and 
dried under reduced pressure. The polymer obtained was 24.6 grams. A part 
of the polymer (3 grams) was weighed exactly and was extracted with 
boiling acetone using a Soxhlet extractor for 8 hours. The residues were 
examined by IR absorption spectroscopy. As a result, the content of 
2-hydroxyethyl methacrylate homopolymer in the product was 4.3 weight 
percent; the content of 2-hydroxyethyl methacrylate unit in the block 
copolymer was 33.3 weight percent. The conversion yield of 2-hydroxyethyl 
methacrylate to homopolymer and block copolymer was 89%. 
EXAMPLE 25 
This experiment was carried out in the same manner as described in Example 
24, except that 6 millimoles of benzyl chloride were replaced by 6 
millimoles of carbon tetrachloride. As a result, the amount of the product 
was 24.4 grams. The content of 2-hydroxyethyl methacrylate homopolymer in 
the polymer obtained was 3.6 weight percent. The content of 2-hydroxyethyl 
methacrylate unit in the block copolymer was 44.4 weight percent. The 
conversion yield of 2-hydroxyethyl methacrylate to homopolymer and block 
copolymer was 100%. 
EXAMPLE 26 
This experiment was carried out in the same manner as Example 24, except 
that the polymerization temperature for 2-hydroxyethyl methacrylate was 
set at 50.degree. C. As a result, the amount of the polymer was 21 grams. 
The content of 2-hydroxyethyl methacrylate homopolymer in the polymer 
obtained was 2.0 weight percent. The content of 2-hydroxyethyl 
methacrylate unit in the block copolymer was 40.8 weight percent. The 
conversion yield of 2-hydroxyethyl methacrylate to homopolymer and block 
copolymer was 88.2%. 
EXAMPLE 27 
This experiment was carried out in the same manner as described in Example 
24, except that 2-hydroxyethyl methacrylate was replaced by 
2-hydroxypropyl methacrylate. As a result, the amount of polymer obtained 
was 32.6 grams. The content of 2-hydroxypropyl methacrylate homopolymer in 
the polymer obtained was 2.7 weight percent. The content of 
2-hydroxypropyl methacrylate unit in the block copolymer was 11.0 weight 
percent. 
EXAMPLE 28 
This experiment was carried out in the same manner as Example 27, except 
that benzyl chloride was replaced by carbon tetrachloride. As a result, 
the amount of polymer obtained was 34.3 grams. The content of 
2-hydroxypropyl methacrylate homopolymer in the polymer obtained was 4.5 
weight percent. The content of 2-hydroxypropyl methacrylate unit in the 
block copolymer was 9.7 weight percent. 
COMATIVE EXAMPLE 12 
This experiment was carried out in the same manner as Example 26, except 
that triethyl amine and benzyl chloride were not added. As a result, the 
amount of polymer obtained was 13.0 grams. The content of 2-hydroxyethyl 
methacrylate homopolymer in the polymer obtained was 0.6 weight percent. 
The content of 2-hydroxyethyl methacrylate unit in the block copolymer was 
4.3 weight percent. The conversion yield of 2-hydroxyethyl methacrylate to 
homopolymer and block copolymer was 6.3%. 
EXAMPLES 29-35 
A five-necked flask (500 ml content) with inlet for introducing gas, 
cooler, thermometer, agitator and opening for pouring reagents was 
displaced by argon. Under the stream of argon, 250 milliliters of 
n-heptane as a solvent were added through a syringe, and then 0.5 
millimole of AA-type titanium chloride and 1 millimole of triethyl 
aluminum were added. While introducing a small amount of argon, 
temperature was raised to 70.degree. C. with stirring. Then argon was 
replaced by ethylene, which was then introduced at the rate of 500 
milliliters per minute, and polymerization was carried out for 1 hour. 
After the reaction, ethylene was displaced by argon, and argon was 
introduced for 5 minutes. By this process, unreacted ethylene was 
discharged from the flask. Subsequently, under the stream of argon, 10 
grams of prescribed additive (a), 6 millimoles of prescribed additive (b) 
and 6 millimoles of prescribed additive (c) were added in this order, and 
polymerization was made for 3 hours at 70.degree. C. After the reaction, 
the catalyst was decomposed by adding a small amount of methanol, and then 
a large amount of methanol was added to precipitate the polymer formed. 
The polymer was filtered and dried under reduced pressure. A part of the 
polymer (3 grams) was weighed exactly and was extracted with boiling 
acetone using a Soxhlet extractor for 8 hours. The residues were examined 
by IR absorption spectroscopy. Results are shown in Table 5. 
Table 5 
__________________________________________________________________________ 
Content of 
Amount of homopoly- 
Additive (a) 
mer of Additive (a) 
in the block- 
Conversion Yield* 
Additive 
Additive 
Additive Yield 
in the produced 
copolymer 
of Additive (a) 
No. 
(a) (b) (c) (grams) 
polymer (weight %) 
(weight %) 
(%) 
__________________________________________________________________________ 
1 methyl DBU** benzyl 42 0.4 1.5 -- 
methacrylate chloride 
2 " " carbon 28 0.7 1.3 -- 
tetrachloride 
3 butyl " benzyl 25 0.4 0.3 -- 
acrylate chloride 
4 methyl DBU " 12 0.5 5.7 -- 
methacrylate 
phenolate*** 
5 " DBU 2-ethyl 
" 36 0.3 1.3 -- 
caproate**** 
6 " DBU " 22.4 1.0 13.0 31.1 
7 " " carbon 15.0 2.6 13.8 24.1 
tetrachloride 
__________________________________________________________________________ 
*Total conversion yield to homopolymer and block copolymer 
##STR7## 
##STR8## 
##STR9## 
A pressure resistant glass autoclave (300 ml content) was displaced with 
argon. Under the stream of argon, 200 milliliters of n-heptane as a 
solvent, 0.5 gram of titanium trichloride and 6.0 millimoles of diethyl 
aluminum monochloride were added through a syringe. 
Propylene was blown into the resulting mixture under a pressure of 3 
kg/cm.sup.2, and polymerization was made at 70.degree. C. for 1 hour. 
Subsequently, argon was bubbled in for 10 minutes in order to remove 
unreacted propylene monomer from the autoclave. Then, under the stream of 
argon, 10 grams of MMA, 6.0 millimoles of tri-n-butyl phosphine and 6.0 
millimoles of benzyl bromide were added in this order, and polymerization 
was done at 70.degree. C. for 1.5 hours. After the reaction, the catalyst 
was decomposed by adding a small amount of methanol and then a large 
amount of methanol to precipitate the polymer formed. The polymer was 
filtered and dried under reduced pressure. The thus-obtained polymer was 
22.5 grams. A part (3 grams) was weighted exactly and was extracted with 
boiling acetone using a Soxhlet extractor for 8 hours. The residues were 
examined by IR absorption spectroscopy. As a result, the content of 
homopolymer of methyl methacrylate in the polymer formed was 5.0 weight 
percent, and the content of methyl methacrylate units in the block 
copolymer was 0.5 weight percent. 
EXAMPLE 37 
This experiment waas carried out in the same manner as described in Example 
36, except that benzyl chloride was replaced by carbon tetrachloride. As a 
result, the amount of polymer obtained was 24.1 grams, and the content of 
homopolymer of methyl methacrylate in the polymer was 2.6 weight percent. 
The content of methyl methacrylate units in the block copolymer was 0.3 
weight percent. 
EXAMPLE 38 
An autoclave (1000 ml content) was displaced with argon. Under the stream 
of argon, 400 milliliters of n-heptane as a solvent, 4.0 millimoles of 
titanium trichloride and 6.0 millimoles of diethyl aluminum monochloride 
were added through a syringe. Maintaining the temperature at 80.degree. 
C., hydrogen was introduced into the autoclave at a pressure of 4 
kg/cm.sup.2. Then, 5 grams of hexene-1 were introduced from a pressure 
resistant glass bomb into the autoclave, and ethylene was added to make 
the pressure of the reaction system 8 kg/cm.sup.2. Copolymerization 
reaction was done for 2 hours. 
Thereafter, argon was bubbled for 10 minutes in order to remove unreacted 
ethylene and hexene-1 from the autoclave. Then, under the stream of argon, 
50 grams of methyl methacrylate, 6.0 millimoles of triethyl amine and 6.0 
millimoles of carbon tetrachloride were added in this order, and 
polymerization was done at 80.degree. C. for 2 hours. After the reaction, 
the catalyst was decomposed by adding a small amount of methanol and then 
a large amount of methanol to precipitate the polymer formed. The polymer 
was filtered and dried under reduced pressure. The thus-obtained polymer 
was 228 grams. A part (3 grams) was weighed exactly and was extracted with 
boiling acetone using a Soxhlet extractor for 8 hours. The residues were 
examined by IR absorption spectroscopy. As a result, the content of 
homopolymer of methyl methacrylate in the polymer formed was 1.3 weight 
percent, and the content of methyl methacrylate units in the block 
copolymer was 14.5 weight percent. Further, the content of hexene-1in the 
poly-.alpha.-olefin chain was 0.28 mole percent.