Isopropanolamines as catalyst deactivators in solution process for polymerization of alpha-olefins

A solution polymerization process for the preparation of high molecular weight polymers of alpha-olefins is disclosed. In the process, the coordination catalyst is deactivated using a solution of at least one trialkanolamine deactivating agent of the formula N(ROH)(R'OH).sub.2 where R is isopropyl and R' is alkyl of 2-4 carbon atoms, especially ethyl or isopropyl. The process is capable of producing polyers of improved color.

The present invention relates to the deactivation of the polymerization 
catalyst in a solution process for the polymerization of alpha-olefins, 
especially ethylene or mixtures of ethylene and higher alpha-olefins. In 
particular, the present invention relates to such deactivation in a 
process in which deactivated catalyst is not separated from the polymer. 
Polymers of ethylene, especially, homopolymers of ethylene and copolymers 
of ethylene and higher alpha-olefins, are used in large volumes for a wide 
variety of end uses, for example, in the form of film, fibres, moulded or 
thermoformed articles, pipe, coatings and the like. 
Processes for the preparation of homopolymers of ethylene and copolymers of 
ethylene and higher alpha-olefins are known. A particularly preferred 
process for the polymerization of alpha-olefins is the high temperature or 
"solution" polymerization process, an example of which is described in 
Canadian Pat. No. 660,869 of A. W. Anderson, E. L. Fallwell and J. M. 
Bruce, which issued Apr. 09, 1963. In a solution process the process 
parameters are selected in such a way that both the monomer and polymer 
are soluble in the reaction medium. Under such conditions accurate control 
over the degree of polymerization, and hence the molecular weight of the 
polymer obtained, may be achieved, for example, by control of the reaction 
temperature. Solution processes are also discussed in European patent 
publication No. 193,262 of V. G. Zboril, published Sept. 03, 1986. 
The polymerization reaction in a solution polymerization process is 
normally terminated by addition of a so-called "deactivator". A wide 
variety of compounds are capable of deactivating the coordination 
catalyst, especially at the high temperatures used in a solution 
polymerization process. However, a deactivator must meet other, more 
stringent, criteria in order to be acceptable for use in a commercial 
process. For instance, if a so-called catalyst removal process is used, 
both the deactivated catalyst residues and the deactivator must be capable 
of being removed from the reaction mixture in such a removal process. If 
the deactivated catalyst remains in the polymer, the deactivator and 
deactivated catalyst residues must not cause problems in the separation of 
polymer from solvent and unreacted monomers, in the processing of the 
polymer obtained and in the resultant fabricated articles. In any event, 
the polymer must have commercially-acceptable colour, odour and toxicity 
properties. It is particularly difficult to assess the possible effects of 
a potential deactivator at the high temperatures attained in a solution 
polymerization process, especially with regard to isomerization of 
comonomers, degradation of the deactivator, generation of coloured 
species, reaction with antioxidants and other stabilizers and the like. 
Moreover, the behavior of the deactivator may be quite sensitive to 
changes in the operation of a solution process. 
Deactivators for solution polymerization processes are usually admixed with 
hydrocarbon solvent, normally the solvent of the polymerization process, 
and fed into the polymerization mixture, usually shortly after that 
mixture passes from the reactor. Such processes are disclosed in, for 
instance, the aforementioned publication of V. G. Zboril and in Canadian 
Pat. No. 732,279 of B. B. Baker, K. M. Brauner and A. N. Oemler, which 
issued Apr. 12, 1966. 
Coordination catalyst containing vanadium may conveniently be deactivated 
by contacting the polymerization mixture with a solution of a salt of an 
alkaline earth metal or zinc and an aliphatic monocarboxylic acid 
dissolved in the hydrogen solvent used in the polymerization process. Such 
deactivation of coordination catalysts containing vanadium tends to result 
in polymer of improved colour, as is disclosed in Canadian Pat. No. 
1,165,499 of V. G. Zboril, which issued Apr. 10, 1984. Coordination 
catalysts may also be deactivated by sequentially contacting the 
polymerization mixture with a nitrogenous base, optionally in the form of 
an aqueous solution, water, carbon, dioxide, carbon monoxide, dialkyl 
carbonate or dioxolones, and then a solution of a salt of an alkaline 
earth metal or zinc and aliphatic monocarboxylic acid dissolved in a 
hydrocarbon solvent, as is disclosed in Canadian Pat. No. 1,173,599 of M. 
A. Hamilton, D. A. Harbourne and V. G. Zboril, which issued Aug. 28, 1984 
and in published European patent applications No. 193,261 of D. J. 
Mitchell and V. G. Zboril and No. 193,263 of V. G. Zboril and R. A. 
Zelonka, both published Sept. 03, 1986. 
The addition of alkanolamines, including triisopropanolamine and 
N,N-bis-(2-hydroxymethyl)soyamine, to polyolefins subsequent to catalyst 
deactivation and separation of polymer from solvent is disclosed in U.S. 
Pat. No. 4,454,270 of W. Kolodchin et al., which issued June 12, 1984. The 
use of triethanolamine for improving the colour of polyolefins is 
disclosed in U.S. Pat. No. 3,773,743 of O. C. Ainsworth et al., which 
issued Nov. 20, 1973. The use of diethanolamines in polyolefin 
compositions is disclosed in U.S. Pat. No. 3,349,059 of G. R. Lappin, 
which issued Oct. 24, 1967 and in U.S. Pat. No. 3,389,119 of R. W. 
Sherrill, which issued June 18, 1968. 
It has now been found that the colour of the polymer obtained may be 
improved if the polymerization mixture is deactivated with at least one 
trialkanolamine, as defined herein below. 
Accordingly, the present invention provides a solution polymerization 
process for the preparation of high molecular weight polymers of 
alpha-olefins selected from the group consisting of homopolymers of 
ethylene and copolymers of ethylene and C.sub.3 -C.sub.12 hydrocarbon 
alpha-olefins, said process comprising feeding monomer selected from the 
group consisting of ethylene and mixtures of ethylene and at least one 
C.sub.3 -C.sub.12 hydrocarbon alpha-olefin, a coordination catalyst and 
inert hydrocarbon solvent to a reactor, said catalyst being a 
titanium-based and/or vanadium-based coordination catalyst, polymerizing 
said monomer at a temperature of up to 320.degree. C. and a pressure of 
less than 25 MPa, deactivating the catalyst by admixing the solution so 
obtained with at least one trialkanolamine deactivating agent of the 
formula N(ROH)(R'OH).sub.2, where R is isopropyl and R' is alkyl of 2-4 
carbon atoms, separating the hydrocarbon solvent and other volatile matter 
from the resultant solution and recovering a composition of said high 
molecular weight polymer, the amount of deactivating agent being not more 
than 2.5 moles of deactivating agent per mole of halogen plus alkyl 
radicals in the coordination catalyst. 
In a preferred embodiment of the present invention, trialkanolamine is the 
sole deactivator. 
In another embodiment, the coordination catalyst is deactivated by 
sequentially admixing said solution with trialkanolamine followed by a 
solution of a salt of an alkaline earth metal or zinc with aliphatic 
monocarboxylic acid dissolved in hydrocarbon solvent. 
In yet another embodiment, the coordination catalyst is deactivated by 
admixing with said solution (a) a minor amount of a deactivating agent 
selected from the group consisting of water, a nitrogenous base, carbon 
dioxide, carbon monoxide, dialkyl carbonate and dioxolones, and mixtures 
thereof, and (b) trialkanolamine, optionally admixed with a solution of a 
salt of an alkaline earth metal or zinc with aliphatic monocarboxylic acid 
dissolved in hydrocarbon solvent. The minor amount of deactivating agent 
viz. (a) above, and the trialkanolamine viz. (b) above, may be admixed 
together prior to being admixed with the solution passing from the reactor 
but in preferred embodiments (a) and (b) are simultaneously admixed with 
the solution passing from the reactor or sequentially admixed with the 
solution in either order. The nitrogenous base is of the formula NR.sup.2 
R.sup.3 R.sup.4, where R.sup.2, R.sup.3 and R.sup.4 are independently 
selected from the group consisting of H, saturated alkyls having 1-20 
carbon atoms and --SiR.sup.5 R.sup.6 R.sup.7 where each R.sup.5, R.sup.6 
and R.sup.7 is independently selected from saturated alkyls having 1- 20 
carbon atoms, with the proviso that the nitrogenous base does not contain 
more than two --SiR.sup.5 R.sup.6 R.sup.7 groups. The dialkyl carbonate 
has 3-20 carbon atoms and the dioxolones have 3-20 carbon atoms. 
In a further embodiment, both of the R' groups of the trialkanolamine are 
the same, being isopropyl or ethyl. Alternatively, a mixture of 
trialkanolamines may be used, especially a mixture of trialkanolamines 
having both R' groups as isopropyl, both R' groups as ethyl and with one 
R' group being isopropyl and the other ethyl. 
The present invention is directed to a solution polymerization process for 
the preparation of high molecular weight polymers of alpha-olefins. In 
particular the polymers of alpha-olefins are homopolymers of ethylene or 
copolymers of ethylene and hydrocarbon alpha-olefins, especially such 
alpha-olefins having 3 to 12 carbon atoms i.e. C.sub.3 -C.sub.12, and 
especially C.sub.4 -C.sub.12, alpha-olefins, including bicyclic 
alpha-olefins, examples of which are propylene, butene-1, hexene-1, 
octene-1 and bicyclo-(2,2,1)2-heptene. In addition cyclic endomethylenic 
dienes may be fed to the process with the ethylene or mixtures of ethylene 
and C.sub.3 -C.sub.12 alpha-olefin, as described in Canadian Pat. No. 
980,498 of C. T. Elston, which issued Dec. 23, 1975. 
In a solution polymerization process of the present invention, monomer, a 
coordination catalyst and inert hydrocarbon solvent are fed to a reactor. 
Coordination catalysts for solution polymerization processes are known, 
for example those described in the aforementioned Canadian Pat. No. 
660,869, in Canadian Pat. No. 1,119,154 of A. N. Mollison and V. G. 
Zboril, which issued Mar. 02, 1982 and in European patent publication No. 
131,420 of M. A. Hamilton D. A. Harbourne, C. G. Russell, V. G. Zboril and 
R. A. Mulhaupt, published Jan. 16, 1985. Such coordination catalysts may 
be titanium-based and/or vanadium based catalysts, especially 
titanium-based or titanium/vanadium-based catalysts in which 20-100% of 
the transition metal is titanium. The monomer is ethylene or a mixture of 
ethylene and one or more of the higher alpha-olefins. 
Solution polymerization processes may be operated at temperatures of up to 
320.degree. C. and especially in the range 105.degree.-310.degree. C., the 
lower temperature being above the lowest solubilization temperature of the 
polymer, as will be understood by those skilled in the art of solution 
polymerization processes. The pressures used in the process of the present 
invention are those known for solution polymerization processes viz. less 
than 25 MPa and especially in the range of about 4-25 MPa. The pressure 
and temperature are controlled so that both the unreacted monomers and the 
polymer formed remain in solution. 
The hydrocarbon solvent used in the polymerization process is a hydrocarbon 
solvent that is inert with respect to the coordination catalyst. Such 
solvents are known and include hexane, heptane, octane, cyclohexane, 
methylcyclohexane and hydrogenated naphtha. The solvent used in the 
polymerization process is preferably also used in the preparation of the 
coordination catalyst. The hydrocarbon solvent is the major component of 
the polymerization mixture fed to the reactor, usually comprising at least 
60% by weight of the reaction mixture. In the process, the monomer is 
dissolved in the solvent. 
The mixture that passes from the polymerization reactor comprises polymer, 
unreacted monomers, coordination catalyst some of which remains in an 
active state, and hydrocarbon solvent. A deactivator is added to the 
mixture to terminate the polymerization process. 
In the process of the present invention, the deactivator is at least one 
trialkanolamine of the formula N(ROH)(R'OH).sub.2, where R is isopropyl 
and R' is alkyl of 2-4 carbon atoms. In a preferred embodiment both of the 
R' groups are the same, being either ethyl or isopropyl. Alternatively, 
the trialkanolamine may be a mixture of trialkanolamines, especially a 
mixture of a trialkanolamine having both R' groups as isopropyl, a 
trialkanolamine having both R' groups as ethyl and a trialkanolamine 
having one R' group as isopropyl and the other as ethyl. 
Triisopropanolamine is the preferred deactivator. 
The trialkanolamine(s) will usually be fed into the polymerization process 
in the form of a solution in hydrocarbon solvent, normally the same 
hydrocarbon solvent as is fed to the polymerization reactor. If a 
different solvent is used, it must be compatible with the solvent used in 
the polymerization process, not cause precipitation of any component of 
the polymerization mixture and not cause adverse effects on the solvent 
recovery system associated with the polymerization process. 
Trialkanolamine may be the sole deactivator used in the polymerization 
process. Alternatively, the coordination catalysts may be deactivated by 
sequentially admixing with the solution passing from the polymerization 
reactor (a) at least one trialkanolamine and (b) a solution of a 
non-stoichiometric salt of an alkaline earth metal or zinc with an 
aliphatic monocarboxylic acid dissolved in hydrocarbon solvent, especially 
a salt having excess acid to facilitate solubility. 
The salt of the second deactivator solution must be dissolved in the 
solvent in order to obtain intimate contact between the deactivator and 
the product of reaction of catalyst with the first deactivator, and to 
obtain uniform dispersion of the deactivator and catalyst residues i.e. 
the form of the catalyst after deactivation, throughout the polymer, 
thereby facilitating the production of polymer of uniform properties. 
In the salt of the second deactivator solution, the metal is an alkaline 
earth metal or zinc, especially magnesium or calcium. The remainder of the 
salt is derived from at least one aliphatic carboxylic acid, especially 
such an acid having 6 to 20 carbon atoms. In a preferred embodiment the 
acid has 8 to 12 carbon atoms. The acid is preferably a branched chain 
aliphatic acid although straight chain aliphatic acids and cycloaliphatic 
acids may be used. Moreover, the acids may be saturated or unsaturated 
acids. However, the acid must be such that the salt thereof that is used 
in the process of the present invention is soluble in the hydrocarbon 
solvent used therein. In preferred embodiments the salt is calcium 2-ethyl 
hexanoate, calcium naphthenate, calcium iso-stearate or the like. 
In an alternative embodiment, the solution passing from the polymerization 
reactor is deactivated with (a) a minor amount of a first deactivator and 
(b) trialkanolamine, optionally admixed with the salt of an alkaline earth 
metal or zinc with an aliphatic monocarboxylic acid described hereinabove. 
In this embodiment, the first deactivator may be a minor amount of water 
or of a nitrogenous base. The minor amount of deactivating agent viz. (a) 
above, and the trialkanolamine viz. (b) above, may be admixed together 
prior to being admixed with the reaction solution to deactivate the 
coordination catalyst, but in preferred embodiments (a) and (b) are 
simultaneously admixed with the reaction solution or independently admixed 
with that solution in either order. 
The nitrogenous base is of the formula NR.sup.2 R.sup.3 R.sup.4 where 
R.sup.2, R.sup.3 and R.sup.4 are independently selected from the group 
consisting of H, saturated alkyls having 1-20 carbon atoms and --SiR.sup.5 
R.sup.6 R.sup.7 where each of R.sup.5, R.sup.6 and R.sup.7 is 
independently selected from saturated alkyls having 1-20 carbon atoms, 
with the proviso that the nitrogenous base does not contain more than two 
--SiR.sup.5 R.sup.6 R.sup.7 groups. Preferably, each of R.sup.2, R.sup.3 
and R.sup.4 is H i.e. the nitrogenous base is ammonia. In a preferred 
embodiment, the nitrogenous base is in the form of an aqueous solution in 
which the ratio of water to nitrogenous base is not greater than 5. In 
embodiments, at least one of R.sup.2, R.sup.3 and R.sup.4 is methyl or 
ethyl. Alternatively, the deactivator of (a) above may be carbon dioxide, 
carbon monoxide, a dialkyl carbonate having 3-20 carbon atoms, especially 
dimethyl carbonate or diethyl carbonate, or a dioxolone which has 3-20 
carbon atoms. The preferred dioxolone is 1,3-dioxolan-2-one. Mixtures of 
deactivators may be used. In the event that the polymerization reaction 
involves the use of a comonomer, it is possible that some of the 
deactivators will be less preferred than other deactivators e.g. 
dioxolones and diethyl carbonate may cause isomerization of comonomers 
that are capable of being isomerized. 
The amount of first deactivating agent, or of trialkanolamine if it is the 
sole deactivating agent, is not more than 2.5 moles of deactivating agent 
per mole of halogen plus alkyl radicals in the coordination catalyst; as 
used herein a mole of catalyst component such as diethyl aluminum 
chloride, as used in the preparation of the catalyst, is deemed to contain 
two equivalents of ethyl groups and one equivalent of chlorine, the sum of 
such equivalents being referred to as "moles of halogen plus alkyl 
groups", and the calculation of the amount of the deactivating agent is to 
be made on such a basis. Preferably 0.25-1.5 moles of such deactivator are 
added per mole of halogen plus alkyl radicals in the catalyst. 
In the process of the present invention the thus deactivated and treated 
polymerization mixture is fed to a separator, which may be a multistage 
separator, to separate unreacted monomer, hydrocarbon solvent and any 
other volatile matter from the polymer. In contrast to the usual practice 
in a solution process, no steps are taken to remove catalyst residues from 
the polymer using adsorbents or other techniques. After separation from 
solvent and unreacted monomer, the polymer may be extruded into water and 
cut into pellets or other suitable comminuted shapes. 
The recovered polymer may then be treated with saturated steam, optionally 
admixed with air, at atmospheric pressure to, for example, reduce the 
amount of volatile materials and improve polymer colour. The treatment may 
be carried out for about 1 to 16 hours, following which the polymer may be 
dried and cooled with a stream of air for 1 to 4 hours. Pigments, 
antioxidants and other additives may be added to the polymer either before 
or after the polymer is initially formed into pellets or other comminuted 
shapes. 
The antioxidant incorporated into polymer obtained from the process of the 
present invention may, in embodiments, be a single antioxidant e.g. a 
hindered phenolic antioxidant, or a mixture of antioxidants e.g. a 
hindered phenolic antioxidant combined with a secondary antioxidant e.g. a 
phosphite. Both types of antioxidant are known in the art. For example, 
the ratio of phenolic antioxidant to secondary antioxidant may be in the 
range of 0.25:1 to 1:1 with the total amount of antioxidant being in the 
range of 400 to 2000 ppm. Examples of suitable hindered phenolic 
antioxidants are octadecyl-3,5,di-tert.butyl-4-hydroxy cinnamate, 
tetrakis-methylene-3-(3',5'-di-tert.butyl-4-hydroxyphenyl)propionate 
methane and octadecyl-3-(3,5-di-tert.butyl-4-hydroxyphenyl)propionate. 
Examples of secondary antioxidants are di(stearyl)pentaerythritol 
diphosphite, tris(2,4-di-tert.butyl phenyl)phosphite, dilauryl 
thiodipropionate and bis(2,4-di-tert.butyl phenyl)pentaerythritol 
diphosphite. 
In addition to antioxidants, other stabilizers especially stabilizers 
against the effect of ultra-violet light, may be incorporated into the 
polymer. Such other stabilizers are usually incorporated into the polymer 
before the polymer is initially formed into pellets. Examples of 
ultraviolet stabilizers are 2-hydroxy-4-n-octoxybenzophenone, 
2-(3'-tert.butyl-2'-hydroxy-5'-methylphenyl)-5-chlorobenzotriazole, 
bis-(2,2,6,6-tetramethyl-4-piperidyl)sebacate and 
poly-(N-hydroxyethyl-2-2,6,6-tetramethyl4-hydroxypiperidyl)succinate. 
The polymers produced by the process of the present invention are capable 
of being fabricated into a wide variety of articles, as is known for 
homopolymers of ethylene and copolymers of ethylene and higher 
alpha-olefins. The present invention provides such polymers of improved 
colour, especially when the polymers contain ultra-violet or related 
stabilizers. 
Unless otherwise noted, in the examples hereinafter the following 
procedures were used: 
The reactor was a 95 ml (depth=15.1 mm, diameter=88.9 mm) pressure vessel 
fitted with a six-bladed agitator having a diameter of 66.7 mm, a heating 
jacket, pressure and temperature controllers, three feed lines and an 
outlet line. Two of the feed lines were located adjacent to the tips of 
the agitator blades while the other feed line and the outlet line were 
adjacent to the centre of the agitator. The catalyst precursors and other 
ingredients were prepared as solutions in cyclohexane which had been 
purified, to remove water, oxygen, carbon dioxide and other oxygenated 
compounds. The monomer(s) was metered directly into the reactor. The rates 
of feed of the first and second components of the catalyst were adjusted 
to produce the desired conditions in the reactor. 
The reactor effluent was passed through 4.57 mm internal diameter (ID) 
tubing heated to a temperature of 296.degree. C. prior to injection of the 
first deactivator. The hold-up time in the tubing was about 0.2 minutes. 
After injection of a first deactivator, the resultant stream was passed 
through a further length of 4.57 mm ID tubing, which was heated to 
320.degree. C., for a hold-up time of about 2.8 minutes. A second 
deactivator was then injected into the stream. The deactivated polymer 
stream thus obtained was maintained at 320.degree. C. for about 1.2 
minutes and then flashed into the barrel of a ram extruder heated to about 
220.degree. C., the gaseous matter obtained being removed from the 
extruder. The molten polymer obtained was periodically extruded into a 
mould having a depth of 1 mm and a diameter of 40 mm and then rapidly 
cooled to ambient temperature. The plaques thus obtained were then 
stripped for eight hours with a mixture of saturated steam and air (7:1, 
by volume) at atmospheric pressure and then dried for 4 hours using air at 
100.degree. C. The colour of the plaques was then measured on a Hunter* 
L,a,b colorimeter, the measurement being on individual plaques using a 
white background. 
FNT *denotes trade mark 
The present invention is illustrated by the following examples. The solvent 
used in the examples was cyclohexane.

EXAMPLE I 
The catalyst was prepared by in-line mixing of (i) a solution of titanium 
tetrachoride (0.5 mmoles/liter) and vanadium oxytrichoride (0.5 
mmoles/liter) in cyclohexane with (ii) a solution of 1.9 mmoles/liter of 
diethylaluminum chloride in cyclohexane, the atomic ratio of aluminum to 
titanium plus vanadium being 1.67:1. After about 20 seconds, a stream of 
hot cyclohexane was injected into the catalyst mixture, the resultant 
stream having a temperature of 220.degree. C. The stream was maintained at 
this temperature for one minute. 
The catalyst obtained using the above procedure was fed into the reactor. 
The co-catalyst of triethyl dimethyl siloxalane was also fed to the 
reactor. The co-catalyst was used as a 4.0 mmole/liter solution in 
cyclohexane and the rate of feed to the reactor was the same as that of 
the solution of the transition metal mixture (i) above. The monomer was 
ethylene. The reactor effluent was treated as described hereinbefore. 
The first deactivator was dimethyl carbonate which was injected as a 30 
mmole/liter solution in cyclohexane. The rate of injection was such that 
the molar ratio of dimethyl carbonate to chlorine plus alkyl radicals in 
the catalyst was 0.35:1. The second deactivator was a 2.6:1 admixture 
(molar basis) of a deactivating agent, as specified in Table I below, and 
a non-stoichiometric mixture of calcium caprylate/caprate, the calcium 
caprylate/caprate solution being injected as a 6 mmole/liter solution in 
cyclohexane; the ratio of calcium to chlorine plus alkyl radicals in the 
catalyst was 0.18:1. 
Immediately prior to the flashing of the polymer solution into the 
extruder, a polymer additive solution containing octadecyl 
3-(3,5-di-tert.butyl-4-hydroxyphenyl)propionate, 
tris(2,4-di-tert.butylphenyl)phosphite, 
poly-(N-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy piperidyl succinate) 
and 2-hydroxy-4-n-octoxybenzophenone stabilizers, in a ratio of 
1.5:1:3.67:1.22 and at a total concentration of 3.1% by weight, in toluene 
was injected into the polymer solution at a rate such that the 
concentration of stabilizers in the polymer was 5440 ppm. Further details 
and the results obtained are given in Table I. The runs were made in the 
sequence shown in Table I. 
TABLE I 
______________________________________ 
Run Colour 
No. Deactivating Agent* 
"a" value "b"value 
______________________________________ 
1 Ca caprylate/caprate 
-1.53 3.01 
2 triisopropanolamine 
-1.24 2.26 
3 octadecyldiethanolamine 
-1.56 3.68 
4 Ca caprylate/caprate 
-1.46 2.75 
5 diethanolisopropanolamine 
-1.18 2.31 
6 N,N--bis(2-hydroxyethyl) 
-1.63 3.8 
soyamine 
7 Ca caprylate/caprate 
-1.55 3.05 
8 tris(3,6-dioxaheptyl) 
-1.47 3.06 
amine 
9 triisopropanolamine 
-1.25 2.33 
10 N,N,N',N'--tetrakis 
-1.49 5.62 
(2-hydroxypropyl)ethylene 
diamine 
11 Ca caprylate/caprate 
-1.48 3.17 
12 triethanolamine -1.2 2.87 
______________________________________ 
*a Ca caprylate/caprate is the "control" deactivating agent, the second 
deactivator being a solution of calcium caprylate/caprate, which was used 
at a ratio of calcium to chlorine plus alkyl radicals of 0.35:1. 
b octadecyldiethanolamine is available commercially as Ethomeen** 18/12 
from Armak Co., Industrial Chemicals Division. 
c N,N--bis(2hydroxyethyl)soyamine is available commerically as Ethomeen 
S/12. 
d Only Runs 2, 5 and 9 are of the present invention; all other runs are 
comparative runs. 
This example illustrates that only deactivating agents of the invention 
show significant improvements in the colour of the polymer, especially as 
measured by the "b" or yellowness value. 
EXAMPLE II 
The procedure of Example I was repeated except that the first and second 
deactivating agents were replaced with a sole deactivating agent which was 
dissolved in toluene solvent. The sole deactivating agent was injected 
into the process such that the molar ratio of deactivating agent to 
chlorine plus alkyl radicals in the catalyst was 0.47:1. 
Further details and the results obtained are given in Table II. The runs 
were made in the sequence shown in Table II. 
TABLE II 
______________________________________ 
Run Colour 
No.* Deactivating Agent 
"a" value "b" value 
______________________________________ 
13 triethanolamine -1.18 3.13 
14 trisopropanolamine 
-1.21 2.34 
15 octadecyldiethanolamine 
-1.37 4.78 
16 diethanolisopropanolamine 
-1.19 2.68 
17 tris(3,6-dioxaheptyl)amine 
-1.22 3.56 
______________________________________ 
*Runs 13, 15 and 17 are comparative runs. 
As in Example I only triisopropanolamine and diethanolisopropanolamine 
exhibited significantly superior performance in producing polymer of 
acceptable colour. 
EXAMPLE III 
Using the procedure of Example I of the aforementioned European patent 
publication No. 193 263 of V. G. Zboril and R. A. Zelonka, the effect of 
triisopropanolamine as the first deactivator on the isomerization of 
butene-1 to butene-2 in the copolymerization of ethylene and butene-1 was 
investigated. The results obtained were as follows, the runs being carried 
out in sequence: 
TABLE III 
______________________________________ 
Amount of 
Run Isomerization 
No. First Deactivator 
Ratio (%) 
______________________________________ 
18 dimethyl carbonate 
0.42 4.3 
19 triisopropanolamine 
0.65 1.3 
20 dimethyl carbonate 
0.39 3.0 
21 water 0.78 7.8 
22 water/- 0.78/0.65 
2.7 
triisopropanolamine 
23 triisopropanolamine 
0.65 1.8 
24 dimethyl carbonate 
0.36 3.2 
25 water 0.60 11.1 
______________________________________ 
*moles of first deactivator:moles of chlorine plus alkyl radicals in the 
catalyst. 
This example shows that triisopropanolamine as first deactivator causes 
less isomerization of butene-1 than the other first deactivators that were 
tested. 
EXAMPLE IV 
The procedure of Example I was repeated except that the first deactivator 
was either dimethyl carbonate or water and a single deactivator was used 
as the second deactivator. 
Further details and the results obtained are given in Table IV. The runs 
were made in the sequence shown in Table IV. 
TABLE IV 
______________________________________ 
Amount of 
Second Colour 
Run Second Deact- "a" "b" 
No.* Deactivator ivator value value 
______________________________________ 
26 triisopropanolamine 
0.47 -1.11 2.17 
27 N,N--bis(2-hydroxy- 
0.47 -1.46 5.35 
ethyl)soyamine 
28 triethanolamine 
0.47 -1.29 4.11 
29 diphenylamine 0.47 -1.21 3.56 
30 2,2'-bipyridine 
0.47 -1.30 3.51 
31 triisopropanolamine 
0.47 -1.12 2.23 
32 hexylamine 0.47 -1.31 3.32 
33 Ca caprylate/caprate 
0.35 -1.60 3.33 
34 triisopropanolamine 
0.47 -1.14 2.13 
35 hexylamine 0.47 -1.22 3.02 
36 N,N--bis(2-hydroxy- 
0.47 -1.41 5.21 
ethyl)soyamine 
37 2,2'-bipyridine 
0.47 -1.30 4.23 
38 triisopropanolamine 
0.47 -1.17 2.47 
39 Ca caprylate/caprate 
0.35 -1.48 3.10 
______________________________________ 
*Runs 26-33 used dimethyl carbonate as first deactivator, at a molar rati 
of dimethyl carbonate to chlorine plus alkyl radicals in catalyst of 0.35 
Runs 34-39 used water as first deactivator, at a molar ratio of water to 
chlorine plus alkyl radicals in catalyst of 0.53. 
Amount of Second Deactivator is molar ratio of second deactivator to 
chlorine plus alkyl radicals in catalyst. 
This example shows that triisopropanolamine gave significant improvement in 
the colour of the polymer obtained. 
EXAMPLE V 
Ethylene and either butene-1 or octene-1 were fed to a polymerization 
reactor and copolymerized in the presence of cyclohexane solvent and a 
catalyst. The catalyst was prepared using the procedure of Example I by 
admixing titanium tetrachloride/vanadium oxytrichloride with 
diethylaluminum chloride, heat treating, admixing with triethyl dimethyl 
siloxalane and feeding to the reactor without separation of any of the 
catalyst components. The catalyst components were fed at substantially the 
same rate, by volume. 
The monomers were polymerized under solution polymerization conditions. The 
reaction mixture passing from the reactor was deactivated and polymer was 
recovered from the resultant solution without separation of the 
deactivated catalyst. A mixture of additives viz, either 
antioxidant/ultraviolet (A/U) stabilizer or antioxidant/silica/slip agent 
(A/S), were added to the molten polymer. The polymer was recovered in the 
form of pellets and the pellets were treated with either steam (S) or a 
mixture of steam and air (SA) in order to reduce the level of residual 
cyclohexane solvent in the pellets. 
In the deactivation of catalyst, deactivator was injected at one or both of 
two inlet ports, which were sequentially located in the apparatus. 
Further details and the results obtained are given in Table V. 
This example illustrates the use of deactivators of the present invention, 
in comparison with other deactivators for solution processes. 
TABLE V 
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Run No.* 40 41 42 43 44 45 
______________________________________ 
Comonomer C4 C4 C4 C4 C4 C4 
Catalyst 
Ti 0.31 0.31 0.31 0.31 0.31 0.34 
V 0.34 0.34 0.34 0.34 0.34 0.37 
DEAC 1.02 0.79 0.79 0.79 0.84 1.07 
Siloxalane 
3.86 2.93 3.03 3.06 3.10 3.59 
Deactivator 
First Port 
A A A A A/B A 
Second Port 
-- -- -- B -- -- 
Deact. Conc. 
First Port 
0.49 0.49 0.32 0.32 0.34/ 0.25 
0.25 
Second Port 
-- -- -- 0.25 -- -- 
Polymer 
Density 0.924 0.924 0.924 
0.924 0.924 0.921 
Melt Index 
4.9 4.8 5.0 4.9 4.7 1.4 
Comonomer 7.8 7.8 7.8 7.8 7.8 7.8 
Content (%) 
Colour 
L 74.8 74.5 76.0 75.9 75.4 71.4 
b 0.10 0.07 0.22 0.16 0.48 2.06 
Stripping SA S SA SA SA SA 
Method 
Additives A/U A/U A/U A/U A/U A/S 
______________________________________ 
Run No.* 46 47 48 49 50 51 
______________________________________ 
Comonomer C4 C4 C4 C8 C8 C8 
Catalyst 
Ti 0.20 0.21 0.20 0.54 0.43 0.42 
V 0.24 0.20 0.24 0.58 0.66 0.64 
DEAC 0.75 0.82 0.83 1.73 1.56 1.52 
Siloxalane 
2.83 2.79 2.70 5.80 4.73 4.62 
Deactivator 
First Port 
C C C A A A 
Second Port 
A D -- -- -- A 
Deact. Conc. 
First Port 
0.34 0.37 0.37 0.43 0.30 0.11 
Second Port 
0.47 1.3 -- -- -- 0.22 
Polymer 
Density 0.921 0.921 0.921 
0.927 0.927 0.925 
Melt Index 
1.5 1.3 1.5 1.0 1.1 1.1 
Comonomer 7.8 7.8 7.8 6.3 6.3 6.3 
Content (%) 
Colour 
L 70.5 69.7 68.0 72.0 66.7 69.9 
b 0.42 2.25 3.31 5.67 5.70 3.97 
Stripping SA SA SA SA S S 
Method 
Additives A/S A/S A/S A/S A/S A/S 
______________________________________ 
*Catalyst concentration is reported in mmole/l 
DEAC = diethylaluminum chloride; 
The deactivators were as follows: 
A = triisopropanolamine; 
B = water; 
C = dimethyl carbonate; 
D = calcium 
caprylate/caprate: The deactivator concentration is expressed in moles of 
deactivating agent/moles of halogen plus alkyl plus R.sub.3 SiO, the 
latter being from the siloxalane; 
Polymer density expressed in g/cm.sup.3 
Melt index expressed in dg/min; 
L and b colour values were measured using the Hunter Colorimeter and the 
procedure described above, except that the measurements were conducted on 
100 ml samples of pellets instead of on plaques.