CA1251600A - Preparation of chlorinated polyolefins - Google Patents
Preparation of chlorinated polyolefinsInfo
- Publication number
- CA1251600A CA1251600A CA000483529A CA483529A CA1251600A CA 1251600 A CA1251600 A CA 1251600A CA 000483529 A CA000483529 A CA 000483529A CA 483529 A CA483529 A CA 483529A CA 1251600 A CA1251600 A CA 1251600A
- Authority
- CA
- Canada
- Prior art keywords
- polyolefin
- vessel
- chlorine
- chlorine gas
- plug
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Method and apparatus for the chlorination of polyolefins in aqueous suspension are disclosed. The method includes subjecting the suspension of the poly-olefin to a submerged jet of chlorine gas at a velocity sufficient to atomize the chlorine; i.e., at least 18.3 m/s (about sixty feet per second). By this method a very intimate mixture of chlorine and aqueous suspension is formed, whereby the chlorination proceeds more efficiently and at a lower chlorine pressure. Further advantages include a more uniformly-substituted product.
Method and apparatus for the chlorination of polyolefins in aqueous suspension are disclosed. The method includes subjecting the suspension of the poly-olefin to a submerged jet of chlorine gas at a velocity sufficient to atomize the chlorine; i.e., at least 18.3 m/s (about sixty feet per second). By this method a very intimate mixture of chlorine and aqueous suspension is formed, whereby the chlorination proceeds more efficiently and at a lower chlorine pressure. Further advantages include a more uniformly-substituted product.
Description
~ 5 ~ O ~
PREPARATION OF CHLORINATE~ POLYOLEFINS
The present invention relates to the pre-paration of chlorinated polyolefins. More particularly, the invention relates to an improved method for chlori-nating polyethylene and polypropylene in aqueous suspension.
The patent and journal literature is repletewith descriptions of various methods for preparing chlorinated polyolefins. In generall however, the description merely states th~t the polyolefin is chlor-inated in aqueous suspension by introducing a stream ofchlorine gas beneath the liguid level of the suspension.
In the absence of a method for efficiently dispersing the chlorine gas in the suspension, the chlorination is not as efficient nor the product as uniform as it would be if the chlorine were better dispersed. The present invention provides an improved method for the introduction of chlorine gas into an aqueous suspension of a polyolefin.
The present invention is a method ~or preparing a chlorinated polyolefin, comprising the steps of:
32,112-F
~:5~1.600 (a) suspending a particulate mass of a polyolefin or chlorinated polyolefin in an aqueous medium;
and (b) injecting a submerged jet of chlorine gas traveling at a linear velocity of at least 18.3 meters per second (m/s) into the suspension, thereby atomizing the chlorine, and chlorinating the polyolefin or chlorinated polyolefin.
In general, the present invention provides a met'hod and suitable apparatus for the more efficient chlorination of a particulate polyolefin or chlorinated polyolefin suspended in an aqueous medium. The method comprises subjecting the suspension of the polyolefin or chlorinated polyolefin to a submerged jet of chlorine gas traveling at a velocity sufficient to atomize the chlorine into extremely finely-divided bubbles intimately mixed with the aqueous suspension.
In general, a linear velocity of at least 18.3 meters per second (m/s) or about sixty feet per second is required~ The upper practical limit of the gas velocity is the sonic velocity. After the desired degr0e of chlorination has been achieved, the product may be separated and dried by any of several well-known m2ans. The term "atomize" as used herein means to disperse the stream of chlorine gas into such minute bubbles that the gas is intimately mixed with the aqueous suspension, forming in effect a separate phase near the point of introduction of the gas. The term "submerged" means below the liquid level of the suspension.
32,112-F -2-5 ~6 ~ 0 The present invention also is an apparatus for contacting a particulate polyolefin or chlorinated polyolefin solid suspended in a liquid with a gas, comprising: a vessel defining an interior space and including an agitator for keeping the solid suspended in the liquid; inlet means located in a bottom wall of said vessel for introducing chlorine gas into said vessel, said inlet means including a tubular member attached at one end to said bottom wall and extending outwardly and away from the bottom wall, jet-forming means disposed in the tubular member for forming a jet of chlorine gas introduced into the vessel, said jet-forming means including a plug disposed within the tubular member, said plug having an internal passageway through which the chlorine gas is introduced into the vessel, the plug having an end defining a surface which is tapered and extends into the interior space of the vessel rom an inner surface of the bottom wall, with the tapered surface of the end of the plug defining with the inner surface of the bottom wall an angle of between about 120 degrees to about 150 degrees; and means for connecting the tubular member to a chlorine gas delivery line.
Suitable apparatus for the practice of the present invention includes a vessel equipped with an agitator for keeping a particulate solid suspended in a liquid. In the vessel a port extends outwardly from the interior of the vessel for introducing chlorine gas into the vessel. Means for forming the high velocity jet of chlorine introduced into the vessel through the port is also included in the apparatus. This means should provide the jet of gas at sufficient linear velocity to atomize the gas in the aqueous suspension.
32,112-F -3-.. . .
~s~
-3a-Figure 1 is a cross sectional elevation view of a portion of an apparatus according to the present invention.
Figure 2 is a graph showing improved temperature-pressure conditions achieved for the chlorinat;on of polyethylene with the method and apparatus of the present invention.
More specifically, Figure 1 shows a small section of a chlorination reactor 1 made according to the present invention. The reactor 1 includes a vessel 32,112-F -3a-~S~L6~
wall 2, only a small portion of which is shown in the drawing. The reactor 1 is equipped with means (not shown) for keeping a particulate mass of solids suspen-ded in a liguid. Suspension means for this purpose are well-known in the art, and include for example mechanical and electrical agitators or mixers. A port 3 extends through and outwardly from the interior of the vessel wall 2. Disposed within the port 3 is an internal plug .~ 4 with an internal passageway 5. The plug 4 forms a gas tight seal with the port 3 and with a gas-delivery line 6. .One end Sa of the passageway 5 widens and forms a continuation of the enlarged end 6a of the gas-delivery line 6. The other end of the passageway 5 opens into the interior of the reactor 1. The exit end 4b of the plug 4 extends obliquely a short distance into the interior of the reactor 1. By a short dis-tance is meant a distance that is small compared with the total length of the plug 4 and passageway 5. The exit end 4b of the plug 4 defines an angle ~ of between
PREPARATION OF CHLORINATE~ POLYOLEFINS
The present invention relates to the pre-paration of chlorinated polyolefins. More particularly, the invention relates to an improved method for chlori-nating polyethylene and polypropylene in aqueous suspension.
The patent and journal literature is repletewith descriptions of various methods for preparing chlorinated polyolefins. In generall however, the description merely states th~t the polyolefin is chlor-inated in aqueous suspension by introducing a stream ofchlorine gas beneath the liguid level of the suspension.
In the absence of a method for efficiently dispersing the chlorine gas in the suspension, the chlorination is not as efficient nor the product as uniform as it would be if the chlorine were better dispersed. The present invention provides an improved method for the introduction of chlorine gas into an aqueous suspension of a polyolefin.
The present invention is a method ~or preparing a chlorinated polyolefin, comprising the steps of:
32,112-F
~:5~1.600 (a) suspending a particulate mass of a polyolefin or chlorinated polyolefin in an aqueous medium;
and (b) injecting a submerged jet of chlorine gas traveling at a linear velocity of at least 18.3 meters per second (m/s) into the suspension, thereby atomizing the chlorine, and chlorinating the polyolefin or chlorinated polyolefin.
In general, the present invention provides a met'hod and suitable apparatus for the more efficient chlorination of a particulate polyolefin or chlorinated polyolefin suspended in an aqueous medium. The method comprises subjecting the suspension of the polyolefin or chlorinated polyolefin to a submerged jet of chlorine gas traveling at a velocity sufficient to atomize the chlorine into extremely finely-divided bubbles intimately mixed with the aqueous suspension.
In general, a linear velocity of at least 18.3 meters per second (m/s) or about sixty feet per second is required~ The upper practical limit of the gas velocity is the sonic velocity. After the desired degr0e of chlorination has been achieved, the product may be separated and dried by any of several well-known m2ans. The term "atomize" as used herein means to disperse the stream of chlorine gas into such minute bubbles that the gas is intimately mixed with the aqueous suspension, forming in effect a separate phase near the point of introduction of the gas. The term "submerged" means below the liquid level of the suspension.
32,112-F -2-5 ~6 ~ 0 The present invention also is an apparatus for contacting a particulate polyolefin or chlorinated polyolefin solid suspended in a liquid with a gas, comprising: a vessel defining an interior space and including an agitator for keeping the solid suspended in the liquid; inlet means located in a bottom wall of said vessel for introducing chlorine gas into said vessel, said inlet means including a tubular member attached at one end to said bottom wall and extending outwardly and away from the bottom wall, jet-forming means disposed in the tubular member for forming a jet of chlorine gas introduced into the vessel, said jet-forming means including a plug disposed within the tubular member, said plug having an internal passageway through which the chlorine gas is introduced into the vessel, the plug having an end defining a surface which is tapered and extends into the interior space of the vessel rom an inner surface of the bottom wall, with the tapered surface of the end of the plug defining with the inner surface of the bottom wall an angle of between about 120 degrees to about 150 degrees; and means for connecting the tubular member to a chlorine gas delivery line.
Suitable apparatus for the practice of the present invention includes a vessel equipped with an agitator for keeping a particulate solid suspended in a liquid. In the vessel a port extends outwardly from the interior of the vessel for introducing chlorine gas into the vessel. Means for forming the high velocity jet of chlorine introduced into the vessel through the port is also included in the apparatus. This means should provide the jet of gas at sufficient linear velocity to atomize the gas in the aqueous suspension.
32,112-F -3-.. . .
~s~
-3a-Figure 1 is a cross sectional elevation view of a portion of an apparatus according to the present invention.
Figure 2 is a graph showing improved temperature-pressure conditions achieved for the chlorinat;on of polyethylene with the method and apparatus of the present invention.
More specifically, Figure 1 shows a small section of a chlorination reactor 1 made according to the present invention. The reactor 1 includes a vessel 32,112-F -3a-~S~L6~
wall 2, only a small portion of which is shown in the drawing. The reactor 1 is equipped with means (not shown) for keeping a particulate mass of solids suspen-ded in a liguid. Suspension means for this purpose are well-known in the art, and include for example mechanical and electrical agitators or mixers. A port 3 extends through and outwardly from the interior of the vessel wall 2. Disposed within the port 3 is an internal plug .~ 4 with an internal passageway 5. The plug 4 forms a gas tight seal with the port 3 and with a gas-delivery line 6. .One end Sa of the passageway 5 widens and forms a continuation of the enlarged end 6a of the gas-delivery line 6. The other end of the passageway 5 opens into the interior of the reactor 1. The exit end 4b of the plug 4 extends obliquely a short distance into the interior of the reactor 1. By a short dis-tance is meant a distance that is small compared with the total length of the plug 4 and passageway 5. The exit end 4b of the plug 4 defines an angle ~ of between
2.1 radians ~120 degrees) and 2.6 radians (150 degrees) with the interior surface 2a of the vessel wall 2.
Preferably, the angle ~ so defined is between 2.3 radians (rad) and 2.4 rad and even more preferably it is between 2.34 rad and 2.37 rad (134 degrees and 136 degrees). The entran~e end 4a of the plug 4 tapers outwardiy to conform to the enlarged end 6a of the gas-delivery line 6, thereby forming a gas-tight seal when the f~anges 7, 8 and 9 of the plug 4, port 3 and line 6 are fastened together as shown.
The preparation of chlorinated polyolefins is carried out by suspending in water the polyolefin used as reactor feed and the chlorinated polyolefin formed, while subjecting the suspension to a jet of chlorine 32,112-F -4-6~
_5.
gas i~jected beneath the surface of the suspension from the passageway 5 at a rate sufficient to atomize the chlorine and form an intimate mixtur~ of the chlorine and the suspension. In order to atomiæe the chlorine it is necessary that the linear velocity of the gas stream as it leaves the passageway 5 be at least 18.3 m/s. Preferably, the linear velocity of the gas is between 30.5 and 91.4 m/s.
, Besides forming a gas-tight seal between the gas-delivery line 6 and the port 3, the plug 4 provides needed protection of the passageway 5 from liquid forces and from abrasion encountered in the environment inside the reactor 1. Keeping the solids in suspension requires that the slurry be vigorously agitated, with the re~sult that any objects protruding into the reactor l beyond the vessel wall 2 below the liquid level are subjected to intense mechanical wear. By extending the exit end 4b of the plug g into the interior of the reactor 1 and by lnclining the exit end 4b of the plug 4 away from the insidè surf~ce 2a of the vessel wall 2, the swirling mass of suspended solids is directed inward into the reactor 1 and into the jet of chlorine gas, thereby forming a combined stream of gas, liquid, and solids in which the thxee phases are intimately mixed.
~ he temperature at which the reactio~ is caxried out is generally between 93 and 149C (about 200 and about 300F). Preferably, the reaction is initiat.ed at a lower temperature, which is increased as the reaction progresses. A trace amount of a wetting agent may beneficially be dissolved in the water used to suspend the particulate polyolefin and chlorinated polyolefin.
32,112-F -5-~5 ~6~3 While the present invention is most advanta-geously applied to the preparation of chlorinated polyolefins, especially polyethylene and polypropylene, it should be recognized that the invention is applicable to any process requiring efficient contact between a gas and a solid suspended in a liquid. Advantages of the present invention for the chlorination of polyole-fins include a more uniform distribution of chlorine in ,; the final chlorinated product; a drastic reduction in frequency of chlorine feed line-plugging; and the capability of operating the chlorination reactor at a lower pressure, at a faster flow rate of chlorine, or both.
T'ae invention will now be illustrated by the following experiments. Experiment 1 is a comparative experiment not according to the invention in which high-density polyethylene was chlorinated using conven-tional technology by introducing the chlorine into the suspension at a rate less than that required to atomize the chlorine. Experiment 2 is an expe,riment illustra-ting the invention, and showing the improved ,results obtained with the invention.
Experiment 1' Chlorine was fed through a gas-delivery line which extended below the surface of an agitated suspen-'~ sion of high-density polyethylene powder in water, at a :
rate of 0.82 kilograms (k~) per hour per kg of polyethyl-ene, and a linear flow velocity of 3.35 m/s ~11 feet per second). The chlorine flow was continued for about 1~ hours, with the reactor temperature rising over that period of time from an initial value of 99~C (210F) to a final value of about 138C (280F). The composition 32,112-F -6-~ ~i ~L60(~
of the chlorinated polyethylene separated and recovered as product comprised 36 percent chlorine by weight.
The relationship between reactor temperature and pressure is shown as the upper curve in Figure 2.
Experiment 2 Using the apparatus shown in Figure 1, a chlorination was carried out using the same conditions . and same temperature-time schedule used in Experiment . 1, except the linear flow velocity of the chlorine was changed to 54.9 m/s (180 feet per second). The final pxoduct, after separation and drying, contained 36 percent chlorine by weight. The temperature-pressure relationship observed in this example is shown as the lower curve in Figure 2. Examination of the resulting curves in Figure 2 shows that the use of the present invention made it possible to achieve the same degree of chlorination under otherwise identical conditions while employing significantly lower pressures for delivering chlorine to the reactcr. Instead of chlori-nating the polyethylene at the same flow rate and alower pressure of chlorine, it is of course also pos-sible to chlorinate at a faster flow rate and the same pressure, thereby substantially decreasing the time re~uired to produce the chlorinated polyethylene.
Other ways of utilizing the improvements inherent in the present invention, including for example the prepa-.ration of a mora uniformly substituted product, will beapparent to those skilled in the art.
32,112-F -7-
Preferably, the angle ~ so defined is between 2.3 radians (rad) and 2.4 rad and even more preferably it is between 2.34 rad and 2.37 rad (134 degrees and 136 degrees). The entran~e end 4a of the plug 4 tapers outwardiy to conform to the enlarged end 6a of the gas-delivery line 6, thereby forming a gas-tight seal when the f~anges 7, 8 and 9 of the plug 4, port 3 and line 6 are fastened together as shown.
The preparation of chlorinated polyolefins is carried out by suspending in water the polyolefin used as reactor feed and the chlorinated polyolefin formed, while subjecting the suspension to a jet of chlorine 32,112-F -4-6~
_5.
gas i~jected beneath the surface of the suspension from the passageway 5 at a rate sufficient to atomize the chlorine and form an intimate mixtur~ of the chlorine and the suspension. In order to atomiæe the chlorine it is necessary that the linear velocity of the gas stream as it leaves the passageway 5 be at least 18.3 m/s. Preferably, the linear velocity of the gas is between 30.5 and 91.4 m/s.
, Besides forming a gas-tight seal between the gas-delivery line 6 and the port 3, the plug 4 provides needed protection of the passageway 5 from liquid forces and from abrasion encountered in the environment inside the reactor 1. Keeping the solids in suspension requires that the slurry be vigorously agitated, with the re~sult that any objects protruding into the reactor l beyond the vessel wall 2 below the liquid level are subjected to intense mechanical wear. By extending the exit end 4b of the plug g into the interior of the reactor 1 and by lnclining the exit end 4b of the plug 4 away from the insidè surf~ce 2a of the vessel wall 2, the swirling mass of suspended solids is directed inward into the reactor 1 and into the jet of chlorine gas, thereby forming a combined stream of gas, liquid, and solids in which the thxee phases are intimately mixed.
~ he temperature at which the reactio~ is caxried out is generally between 93 and 149C (about 200 and about 300F). Preferably, the reaction is initiat.ed at a lower temperature, which is increased as the reaction progresses. A trace amount of a wetting agent may beneficially be dissolved in the water used to suspend the particulate polyolefin and chlorinated polyolefin.
32,112-F -5-~5 ~6~3 While the present invention is most advanta-geously applied to the preparation of chlorinated polyolefins, especially polyethylene and polypropylene, it should be recognized that the invention is applicable to any process requiring efficient contact between a gas and a solid suspended in a liquid. Advantages of the present invention for the chlorination of polyole-fins include a more uniform distribution of chlorine in ,; the final chlorinated product; a drastic reduction in frequency of chlorine feed line-plugging; and the capability of operating the chlorination reactor at a lower pressure, at a faster flow rate of chlorine, or both.
T'ae invention will now be illustrated by the following experiments. Experiment 1 is a comparative experiment not according to the invention in which high-density polyethylene was chlorinated using conven-tional technology by introducing the chlorine into the suspension at a rate less than that required to atomize the chlorine. Experiment 2 is an expe,riment illustra-ting the invention, and showing the improved ,results obtained with the invention.
Experiment 1' Chlorine was fed through a gas-delivery line which extended below the surface of an agitated suspen-'~ sion of high-density polyethylene powder in water, at a :
rate of 0.82 kilograms (k~) per hour per kg of polyethyl-ene, and a linear flow velocity of 3.35 m/s ~11 feet per second). The chlorine flow was continued for about 1~ hours, with the reactor temperature rising over that period of time from an initial value of 99~C (210F) to a final value of about 138C (280F). The composition 32,112-F -6-~ ~i ~L60(~
of the chlorinated polyethylene separated and recovered as product comprised 36 percent chlorine by weight.
The relationship between reactor temperature and pressure is shown as the upper curve in Figure 2.
Experiment 2 Using the apparatus shown in Figure 1, a chlorination was carried out using the same conditions . and same temperature-time schedule used in Experiment . 1, except the linear flow velocity of the chlorine was changed to 54.9 m/s (180 feet per second). The final pxoduct, after separation and drying, contained 36 percent chlorine by weight. The temperature-pressure relationship observed in this example is shown as the lower curve in Figure 2. Examination of the resulting curves in Figure 2 shows that the use of the present invention made it possible to achieve the same degree of chlorination under otherwise identical conditions while employing significantly lower pressures for delivering chlorine to the reactcr. Instead of chlori-nating the polyethylene at the same flow rate and alower pressure of chlorine, it is of course also pos-sible to chlorinate at a faster flow rate and the same pressure, thereby substantially decreasing the time re~uired to produce the chlorinated polyethylene.
Other ways of utilizing the improvements inherent in the present invention, including for example the prepa-.ration of a mora uniformly substituted product, will beapparent to those skilled in the art.
32,112-F -7-
Claims (9)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS
FOLLOWS:
1. A method for preparing a chlorinated polyolefin, comprising the steps of:
(a) suspending a particulate mass of a polyolefin or chlorinated polyolefin in an aqueous medium;
and (b) injecting a submerged jet of chlorine gas traveling at a linear velocity of at least 18.3 meters per second (m/s) into the suspension, thereby atomizing the chlorine, and chlorinating the polyolefin or chlorinated polyolefin.
(a) suspending a particulate mass of a polyolefin or chlorinated polyolefin in an aqueous medium;
and (b) injecting a submerged jet of chlorine gas traveling at a linear velocity of at least 18.3 meters per second (m/s) into the suspension, thereby atomizing the chlorine, and chlorinating the polyolefin or chlorinated polyolefin.
2. The method of Claim 1, wherein the linear velocity of the chlorine gas is between 30.5 and 91.4 m/s.
3. The method of Claim 2, wherein the temperature of the suspension is between 93°C and 149°C.
4. The method of Claim 1, wherein the polyolefin is polyethylene or polypropylene.
5. The method of Claim 2, wherein the polyolefin is polyethylene or polypropylene.
6. The method of Claim 3, wherein the polyolefin is polyethylene or polypropylene.
7. The method of Claim 1 including the step of separating and recovering the chlorinated polyolefin product.
8. An apparatus for contacting a particulate polyolefin or chlorinated polyolefin solid suspended in a liquid with a gas, comprising: a vessel defining an interior space and including an agitator for keeping the solid suspended in the liquid; inlet means located in a bottom wall of said vessel for introducing chlorine gas into said vessel, said inlet means including a tubular member attached at one end to said bottom wall and extending outwardly and away from the bottom wall, jet-forming means disposed in the tubular member for forming a jet of chlorine gas introduced into the vessel, said jet-forming means including a plug disposed within the tubular member, said plug having an internal passageway through which the chlorine gas is introduced into the vessel, the plug having an end defining a surface which is tapered and extends into the interior space of the vessel from an inner surface of the bottom wall, with the tapered surface of the end of the plug defining with the inner surface of the bottom wall an angle of between about 120 degrees to about 150 degrees; and means for connecting the tubular member to a chlorine gas delivery line.
9. The apparatus of Claim 8, wherein the angle is from about 130 degrees to about 140 degrees.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000483529A CA1251600A (en) | 1985-06-10 | 1985-06-10 | Preparation of chlorinated polyolefins |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000483529A CA1251600A (en) | 1985-06-10 | 1985-06-10 | Preparation of chlorinated polyolefins |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1251600A true CA1251600A (en) | 1989-03-21 |
Family
ID=4130674
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000483529A Expired CA1251600A (en) | 1985-06-10 | 1985-06-10 | Preparation of chlorinated polyolefins |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1251600A (en) |
-
1985
- 1985-06-10 CA CA000483529A patent/CA1251600A/en not_active Expired
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |