WO2016075567A1 - Préparation de polychlorure de vinyle chloré - Google Patents

Préparation de polychlorure de vinyle chloré Download PDF

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Publication number
WO2016075567A1
WO2016075567A1 PCT/IB2015/057966 IB2015057966W WO2016075567A1 WO 2016075567 A1 WO2016075567 A1 WO 2016075567A1 IB 2015057966 W IB2015057966 W IB 2015057966W WO 2016075567 A1 WO2016075567 A1 WO 2016075567A1
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WO
WIPO (PCT)
Prior art keywords
ranging
chamber
pvc
cpvc
baffles
Prior art date
Application number
PCT/IB2015/057966
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English (en)
Inventor
Pradip Munshi
Jayesh P VORA
Ninad Deepak INGLE
Pradeep Paresh KAPADIA
Raksh Vir Jasra
Shashikant RAJAN
Ajit Behari Mathur
Original Assignee
Reliance Industries Limited
Priority date (The priority date 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 date listed.)
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Publication date
Application filed by Reliance Industries Limited filed Critical Reliance Industries Limited
Publication of WO2016075567A1 publication Critical patent/WO2016075567A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/18—Introducing halogen atoms or halogen-containing groups
    • C08F8/20—Halogenation
    • C08F8/22—Halogenation by reaction with free halogens

Definitions

  • the present disclosure relates to chlorinated polyvinyl chloride (CPVC). Particularly, the present disclosure relates to an apparatus and a process for the preparation of CPVC.
  • CPVC chlorinated polyvinyl chloride
  • Chlorinated polyvinyl chloride is a thermoplastic polymer that is characterized by properties such as high glass transition (Tg), fire resistance, corrosion resistance, superior ductility, and good flexural and crush resistance, which enables its use in industrial liquid handling applications such as hot and cold water pipes.
  • CPVC is generally prepared by free radical chlorination reaction, wherein chlorine gas is initially decomposed into free radicals of chlorine by thermal or ultra violet (UV) energy, following which, the free radicals reacts with PVC to form CPVC.
  • Photo-chlorination of PVC in suspension form is a heterogeneous reaction which is primarily driven by mass transfer phenomenon and is controlled by diffusion of chlorine into the pores of the PVC particles.
  • chlorine diffusion is the rate limiting step
  • efforts have been directed towards increasing the rate of the reaction by using various strategies. Improved stirring is one such technique known in the art.
  • the pore size of PVC can also be increased to facilitate chlorine diffusion as recited in US patent 4412898.
  • US 4049517 discloses the use of ramping irradiation in order to control the rate of reaction. Elevating the temperature to enhance the rate of the reaction is also known in the art.
  • US 4377459 recites subjecting the PVC dissolved in organic solvent to chlorine gas at a high pressure so as to accelerate the rate of reaction.
  • the rate of the reaction can also be controlled by supplying controlled UV in the reactor as disclosed in US 4049517.
  • US 3328371 discloses the use of additives such as chlorinating agents (S0 2 C1 2 ) and swelling agents in order to further increase the rate of the reaction.
  • US 6197895 recites adding organic peroxide compounds to the PVC suspension in order to increase the rate of chlorination.
  • the inventors of the present disclosure envisage a simple apparatus and a relatively less expensive process to bring about photochlorination of PVC at an increased rate in order to mitigate the drawbacks associated with the prior art processes.
  • CPVC chlorinated polyvinyl chloride
  • CPVC chlorinated polyvinyl chloride
  • CPVC chlorinated polyvinyl chloride
  • CPVC chlorinated polyvinyl chloride
  • the present disclosure provides an apparatus for the preparation of chlorinated polyvinyl chloride (CPVC) comprising: i. a chamber for receiving polyvinyl chloride (PVC) and delivering CPVC; ii. at least one first inlet (6) leading into said chamber for introducing at least one fluid into said chamber (16); iii. at least one sparger (12) extending into said chamber for introducing fluid into said chamber (16); iv. at least one agitator fitted in said chamber; v. at least two baffles fitted in said chamber; and vi. a plurality of irradiation sources fitted to said baffles.
  • CPVC chlorinated polyvinyl chloride
  • the baffles can be in the form of transparent tubes, approximately equidistant from the center of the chamber and almost parallel to the wall of the chamber.
  • the irradiation source of the apparatus can be at least one selected from the group consisting of ultra violet (UV) lamps and light-emitting diodes (LEDs), having wavelength ranging from 250 nm to 550 nm, and may be fitted inside said transparent baffles.
  • UV ultra violet
  • LEDs light-emitting diodes
  • the present disclosure provides a process for the preparation of chlorinated CPVC using the apparatus disclosed herein above.
  • the rate of reaction can range from 1.50 to 2.63 mole of (Cl)/h/kg of PVC.
  • Figure 1 illustrates the apparatus for the preparation of CPVC in accordance with one embodiment of the present disclosure wherein:
  • thermocouple 10 represents a thermocouple
  • the process for the preparation of CPVC from PVC suspension is based on a gas-liquid- solid heterogeneous reaction.
  • diffusion of chlorine into the pore of the solid PVC particles is a major rate limiting step.
  • the inventors of the present disclosure have provided an apparatus, having a particular construction of its components, which increases the overall rate of the reaction.
  • the apparatus includes a chamber (16), at least one inlet (6) and a sparger (12), at least one agitator (2), at least two baffles (18) and a plurality of irradiation sources (20) fitted to said baffles (18).
  • the chamber (16) of the present apparatus further includes at least one inlet for receiving the polyvinyl chloride (PVC) and at least one outlet (4) for delivering the chlorinated PVC once the reaction of photochlorination is complete.
  • the chamber (16) includes at least one inlet (6) and sparger (12) for introducing at least one fluid into the chamberln accordance with the present disclosure, chlorine may be in gaseous or liquid form. In another embodiment, nitrogen is introduced in the chamber (16) via the sparger (12).
  • the agitator (2) of the present disclosure is fitted centrally in said chamber (16) in order to achieve optimum mass transfer.
  • the apparatus characteristically employs at least two baffles (18), which can be in the form of transparent tubes, typically made of glass or polymeric material.
  • the baffles comprise two transparent tubes, fitted opposite each other in the chamber (16), approximately equidistant from the center of the chamber (16) and almost parallel to the wall of the chamber (16).
  • the length of the tubes can be sufficient to cover from the top to the bottom wall of the chamber (16).
  • the length of the tube is equal to the length of the chamber (16).
  • these transparent tubes house a plurality of irradiation sources (20) along their length.
  • the irradiation sources (20) have a wavelength ranging from 250 nm to 550 nm, and can be selected from the group consisting of ultra violet (UV) lamps and light-emitting diodes (LEDs).
  • the transparent tubes thus, function both as baffles (18) and as irradiation sources (20), which facilitates good contact between the photons generated from the irradiation sources, chlorine and the PVC particles (both outer surface and pore surface). This effects faster chlorine diffusion inside the pores, which in turn leads to a faster reaction rate and a greater yield in a small time period.
  • the chamber (16) of the present disclosure further comprises at least one pocket for holding a thermocouple (10).
  • the chamber (16) also comprises at least one outlet (4) for discharging excess of chlorine and nitrogen from the chamber along with delivering CPVC.
  • the outlet (4) in another embodiment, can also be used for charging PVC and/ or water.
  • a process for the preparation of CPVC which is carried out in the afore-stated apparatus.
  • the process of the present disclosure includes reacting PVC with chlorine in the presence of a plurality of irradiation sources (20), under agitation at a speed ranging from 100 to 1600 rpm, for a time period ranging from 2 to 12 hours to obtain chlorinated polyvinyl chloride (CPVC).
  • CPVC chlorinated polyvinyl chloride
  • the PVC used in the present process may be in a dried form or in slurry form.
  • the dried PVC is characterized by 0.2 to 1 % loss on heating at 70 °C for 2 hours.
  • the PVC in slurry form is prepared by admixing water and PVC and has a concentration ranging from 10 to 25 % w/v.
  • the PVC is obtained by suspension polymerization of vinyl chloride monomer, having polymerization degree ranging from 200 to 15000, particle size ranging from 40 to 300 microns, surface area ranging from 1 to 3 m 2 /g, porosity ranging from of 0.02 to 0.40 mL/g and viscosity ranging from 0.9 to 1.2 dL/g.
  • PVC is reacted with chlorine gas to yield CPVC.
  • PVC is reacted with liquid chlorine to yield CPVC.
  • the irradiation sources (20) used in the present process can be selected from the group that includes ultra violet (UV) lamps and light-emitting diodes (LEDs) of wavelength ranging from 250 and 550 nm. The power input for these sources ranges from 0.01 to 0.04 Watt/ g of PVC.
  • the present process is carried out at a temperature ranging from 40 to 90 °C and at a pressure ranging from 0.5 to 4 atmospheres.
  • the tip speed of the agitator (2) can range from 0.5 m/s to 20 m/s.
  • the apparatus and process of the present disclosure bring about a faster rate of photo- chlorination in a much shorter time as compared to conventional apparatus, by increasing the probability of interactions between the photons, the reactive center of PVC and the chlorine radical, primarily by agitation or stirring of the PVC and creating obstacles (baffles) to the motion of the PVC. Moreover, by placing the irradiation source inside the chamber, the Reynolds number of the PVC in the slurry form remains in the range of 4000 to 3,00,000 which brings about accelerated photochlorination. Typically, the rate of reaction of the present process ranges from 1.50 to 2.63 mole of (Cl)/h/kg of PVC.
  • Flotation of CPVC during photochlorination of PVC in suspension form is another problem which results in uneven chlorination of PVC and creates difficulty during processing.
  • This problem of floatation of CPVC is also overcome by the process described in the present disclosure. This is because, as the irradiation sources also act as baffles, the CPVC remains homogeneously dispersed so that no flotation occurs during the reaction. Furthermore, during the photochlorination of PVC using chlorine, HC1 gets generated as a byproduct and remains firmly inside the pores of the CPVC particles.
  • HC1 in the final dried CPVC resin accelerates thermal degradation of CPVC as it is catalyzed by proton (H+) or any hydrated form of proton, making the CPVC thermally unstable. Therefore, it becomes necessary to reduce the amount of HC1 generated as well as to reduce the contact time between CPVC and HC1. As the present disclosure causes a reduction in the reaction time, the contact time between CPVC and HC1 reduces, which further reduces the diffusion of HC1 into the pores of CPVC particles.
  • Nitrogen purging was continued for another 40 minutes in order to remove both air or oxygen from the chamber and the slurry, while the temperature was maintained at 70 °C. Nitrogen purging was then replaced by purging of chlorine gas, (at flow rate of 200 g/h, while maintaining the same conditions. Irradiation (450 nm LED) having 7W as the input power was switched on when the chamber and the slurry were found to be saturated with chlorine (checked by means of the ammonia torch at the exit of the chlorine outlet on the chamber) and this was counted as the reaction starting time. The pressure was maintained at 1 atmosphere throughout the process. Periodically, the rate of reaction was monitored by withdrawing a sample in every hour and titrating the mother liquor against 0.1 N NaOH. The reaction was stopped at 5 hours. The titer value corresponded to 67% (by weight) chlorinated PVC.
  • the chorine present in 'A' grams PVC was 0.567A grams.
  • the result was validated by ASTM F 442M - 99, oxygen flask method, the results of which remained within + 0.5 %.
  • the thermal stability (sec) of the CPVC resin was measured by a conductivity meter using PVC thermomat (Metrohm 895), as per DIN53381, ISO 182-3 and it was found to be 612 sec.
  • Example 1 The experiment carried out in Example 1 was repeated, however, the agitation used in Example 2 was 400 rpm with the agitator tip speed of 1.745 m/s. The rest of the reaction parameters were the same as in Example 1. The reaction took 8 hours to reach 67 % chlorination. Moreover, the chlorination was uneven and flotation of CPVC occurred during reaction. The thermal stability was found to be 252 sec.
  • Example 1 The experiment carried out in Example 1 was repeated, however, the agitation used in Example 2 was 600 rpm and the agitator tip speed was 2.625 m/s. The rest of the reaction parameters were the same as in Example 1. The reaction took 7 hours to reach 67 % chlorination and flotation of CPVC did not occur during chlorination.
  • Example 1 The experiment carried out in Example 1 was repeated, however, the PVC amount was taken as 400 g. The rest of the reaction parameters were the same as in Example 1. The results obtained are demonstrated in Table 1.
  • Example 1 The experiment carried out in Example 1 was repeated, however, just one irradiation source was used instead of two. The reaction time increased to 7 hours.
  • Example 7 The experiment carried out in Example 1 was repeated, however, the irradiation source was kept above the slurry level. The reaction took more than 9 hours to achieve 67% by weight chlorination. The thermal stability was found to be 108 sec.
  • Example 7
  • Example 1 The experiment carried out in Example 1 was repeated, however, the irradiation source was inserted only till the mid-level of the slurry.
  • the reaction time increased to 7 hours (67% by weight chlorination).
  • the reaction rate was found to be 1.23 mole Cl/h/Kg PVC and the thermal stability by conductivity 324 sec.
  • Example 1 The experiment carried out in Example 1 was repeated, however, the irradiation source was removed from the transparent tube and kept outside the chamber, leaving the empty tube in position. The reaction took 7 hours to achieve 67% by weight chlorination.
  • Example 1 The experiment carried out in Example 1 was repeated, however, the light source was kept above the slurry level. After 9 hours, the reaction yield reached 66.8%.
  • the present disclosure provides an apparatus and a process for bringing about accelerated photochlorination of CPVC.
  • the apparatus uses irradiation sources (20) having input power of less than 5 Watt/g of PVC; thereby reducing the energy consumption.
  • the chlorine consumption of the present process is 50% less than the prior art processes and consequently the hydrogen chloride formation is also less.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente divulgation concerne un appareil et un procédé pour la préparation de polychlorure de vinyle chloré (PCVc). L'appareil comprend une chambre (16), au moins un tube d'aspersion (12), au moins un agitateur (2) et au moins deux déflecteurs (18) montés dans la chambre et une pluralité de sources de rayonnement (20) logées à l'intérieur des déflecteurs pour provoquer une accélération de la photochloration du polychlorure de vinyle. Le procédé comprend la réaction d'un polychlorure de vinyle (PVC) avec du chlore en présence d'un rayonnement d'une longueur d'onde de 250 à 550 nm et d'une puissance de 0,01 à 0,04 Watt/g de PVC, sous agitation à une vitesse de 100 à 1600 tours/minute, pendant une durée de 2 à 12 heures, pour obtenir un PVCc.
PCT/IB2015/057966 2014-11-11 2015-10-16 Préparation de polychlorure de vinyle chloré WO2016075567A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IN3542MU2014 2014-11-11
IN3542/MUM/2014 2014-11-11

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018138611A1 (fr) 2017-01-25 2018-08-02 Reliance Industries Limited Procédé destiné à la préparation de poly(chlorure de vinyle) chloré sec
US10081687B2 (en) 2015-07-29 2018-09-25 Reliance Industries Limited Process for chlorination of a polymer
CN109369829A (zh) * 2018-10-26 2019-02-22 山东高信化学股份有限公司 注塑用高性能氯化聚氯乙烯的制备方法
WO2021216940A1 (fr) * 2020-04-24 2021-10-28 Kansas Soybean Commission Synthèse en une étape de polyols de soja
US20220145061A1 (en) * 2019-03-29 2022-05-12 Sekisui Chemical Co., Ltd. Chlorinated vinyl chloride resin

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2085897A (en) * 1980-10-22 1982-05-06 Chloe Chemie Continuous process for the dry chlorination of polyvinyl chloride
EP0103769B1 (fr) * 1982-08-25 1988-08-10 The B.F. GOODRICH Company Procédé de chloruration de résines de polychlorure de vinyle
US20010014721A1 (en) * 1997-07-29 2001-08-16 Kaneka Corporation Process for production of chlorinated polyvinyl chloride resin
WO2014157346A1 (fr) * 2013-03-29 2014-10-02 株式会社カネカ Procédé de production et dispositif de production de résine à base de chlorure de vinyle chloré

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2085897A (en) * 1980-10-22 1982-05-06 Chloe Chemie Continuous process for the dry chlorination of polyvinyl chloride
EP0103769B1 (fr) * 1982-08-25 1988-08-10 The B.F. GOODRICH Company Procédé de chloruration de résines de polychlorure de vinyle
US20010014721A1 (en) * 1997-07-29 2001-08-16 Kaneka Corporation Process for production of chlorinated polyvinyl chloride resin
WO2014157346A1 (fr) * 2013-03-29 2014-10-02 株式会社カネカ Procédé de production et dispositif de production de résine à base de chlorure de vinyle chloré

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10081687B2 (en) 2015-07-29 2018-09-25 Reliance Industries Limited Process for chlorination of a polymer
WO2018138611A1 (fr) 2017-01-25 2018-08-02 Reliance Industries Limited Procédé destiné à la préparation de poly(chlorure de vinyle) chloré sec
CN109369829A (zh) * 2018-10-26 2019-02-22 山东高信化学股份有限公司 注塑用高性能氯化聚氯乙烯的制备方法
CN109369829B (zh) * 2018-10-26 2021-04-13 山东高信化学股份有限公司 注塑用高性能氯化聚氯乙烯的制备方法
US20220145061A1 (en) * 2019-03-29 2022-05-12 Sekisui Chemical Co., Ltd. Chlorinated vinyl chloride resin
WO2021216940A1 (fr) * 2020-04-24 2021-10-28 Kansas Soybean Commission Synthèse en une étape de polyols de soja

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