GB1572361A - Creación de Inventos y Patentes con Inteligencia Artificial

GB1572361A – Purification of polyvinyl chloride
– Google Patents

GB1572361A – Purification of polyvinyl chloride
– Google Patents
Purification of polyvinyl chloride

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Publication number
GB1572361A

GB1572361A
GB17986/77A
GB1798677A
GB1572361A
GB 1572361 A
GB1572361 A
GB 1572361A
GB 17986/77 A
GB17986/77 A
GB 17986/77A
GB 1798677 A
GB1798677 A
GB 1798677A
GB 1572361 A
GB1572361 A
GB 1572361A
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GB
United Kingdom
Prior art keywords
slurry
heated
polyvinyl chloride
added
process according
Prior art date
1976-05-25
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

Application number
GB17986/77A
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Tenneco Chemicals Inc

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Tenneco Chemicals Inc
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.)
1976-05-25
Filing date
1977-04-29
Publication date
1980-07-30

1977-04-29
Application filed by Tenneco Chemicals Inc
filed
Critical
Tenneco Chemicals Inc

1980-07-30
Publication of GB1572361A
publication
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patent/GB1572361A/en

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Expired
legal-status
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Classifications

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

C08F6/00—Post-polymerisation treatments

C08F6/001—Removal of residual monomers by physical means

Description

PATENT SPECIFICATION ( 1
_I ( 21) Application No 17986/77 ( 22) Filed 29th April 1977 = ( 32) Convention Application No ( 32) Filed 25th May 1976 in 690202 el ( 33) United States of America (US) C_ ( 44) Complete Specification Published 30th July 1980 __ ( 51) INT CL 3 CO 8 F 14/06 6/16 ( 52) Index at Acceptance:
C 3 L BA C 3 W 221 ( 54) IMPROVEMENTS IN OR RELATING TO PURIFICATION OF POLYVINYL CHLORIDE ( 71) We, TENNECO CHEMICALS INC, of Park 80 Plaza West-1, Saddle Brook New Jersey 07662, United States of America, a corporation organised and existing uner the laws of the State of Delaware, United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:-
This invention relates to a process for the purification of polyvinyl chloride More particularly, it relates to a procedure for minimizing or preventing discolouration of the polymer during the removal of residual vinyl chloride from polyvinyl chloride slurries by heating at temperatures of 70 ‘C and above.
When vinyl chloride is polymerized in an aqueous medium by suspension or emulsion polymerization techniques, a slurry is obtained which usually contains from 5 % to 50 % by weight of polyvinyl chloride and up to 5 % by weight of residual vinyl chloride Most of the unreacted monomer is usually removed by heating the slurry under vacuum to about 65 TC.
As it is ordinarily practised, this stripping procedure reduces the monomer content of the slurry to about 100 ppm to 20,000 ppm.
Further processing yields dry products which may contain 100 ppm or more of monomer.
In view of the recently-developed safety standards which require the amount of vinyl chloride in polyvinyl chloride and in the atmosphere to be maintained at very low levels, it is necessary for the monomer content of polyvinyl chloride slurries to be sufficiently reduced so that these requirements can be met.
Among the most effective procedures which have been developed for the removal of residual 4 o monomer from polyvinyl chloride slurries are those which involve maintaining the slurries at temperatures of 70 ‘C or above until the unreacted monomer has been removed One such process is disclosed in our copending application No 4713/77 (divided out of Application No 19208/75 Specifications Nos 1 490 152 and 1 490 151) In the process disclosed in Application No 4713/77, a polyvinyl chloride slurry or latex which contains, by weight, ppm to 15,000 ppm of vinyl chloride is 50 heated at 70 to 125 C and the evolved vinyl chloride vapour is removed until the slurry or latex contains less than 50 ppm and preferably less than 10 ppm of monomer While this heat treatment effectively removes vinyl 55 chloride from the slurry or latex, it often causes some deterioration of the polymer as is evidenced by its development of colour Although the slight decomposition which the polymer undergoes during heating to reduce its monomer 60 content does not detract to any appreciable extent from its physical and mechanical properties, the discolouration seriously restricts its use in many applications.
It has now been found that the discolour 65 ation which polyvinyl chloride undergoes when slurries containing this polymer are heated at temperatures above 70 TC for a sufficient time to reduce their monomer content to the required very low levels can be minimized or eliminated 70 by carrying out the heating step in the presence of an oxidizing agent This treatment results in the recovery of a lighter, brighter polymer, but it does not have a noticeable effect on the other properties of the polyvinyl chloride or of the 75 slurry which contains the polymer The effectiveness of oxidizing agents in preventing colour formation during the high temperature treatment of polyvinyl chloride slurries is surprising, inasmuch as the prior art teaches that oxygen 80 and oxygen equivalents must be excluded from polyvinyl chloride slurries containing vinyl chloride to prevent decomposition and discolouration of the polymer.
In accordance with the process of this inven 85 tion, an aqueous slurry comprising a suspension or emulsion which contains 5 % to 50 % by weight of polyvinyl chloride and 100 ppm to 15,000 ppm of vinyl chloride is maintained at a temperature in the range from 70 TC and 100 O C 90 1) 1 572 361 1 572 361 so as to remove monomer from the slurry until it contains less than 10 ppm (and preferably less than 1 ppm) of vinyl chloride, the polyvinyl chloride contacting an oxidizing agent during the heat treatment The treated slurry is then further processed to yield polyvinyl chloride that contains less than 10 ppm and preferably less than 1 ppm of vinyl chloride.
The oxidizing agents most preferably used in the process of this invention are those which are at least moderately soluble in water and form colourless or nearly colourless aqueous solutions They include oxygen, oxygen-containing gases, hydrogen peroxide, and compounds such as sodium perborate, potassium perborate, sodium persulfate, potassium persulfate, sodium carbonate peroxide, and sodium pyrophosphate peroxide that decompose in hot aqueous solutions to give oxygen or hydrogen peroxide Oxygen, air and other oxygen-containing gases, hydrogen peroxide, and sodium perborate are the preferred oxidizing agents because they are most readily available commercially and most economical to use.
The amount of the oxidizing agent preferably used is that which will prevent discolouration of polyvinyl chloride when a polyvinyl chloride slurry is heated at a temperature above C for a time sufficient to reduce its vinyl chloride content to less than 10 ppm without causing foaming or other handling problems It is dependent upon such factors as-the temperature at which the slurry is heated, the length of the heating period, and the monomer content of the slurry In most cases, 1 part to 10 parts by weight of the oxidizing agent per 100 parts by weight of polyvinyl chloride in the slurry will prevent discolouration of the polymer during the heating treatment Larger amounts of the oxidizing agents can be used, but they generally do not provide additional improvement in the colour of the product The oxidizing agent may be added to the polyvinyl chloride slurry before the heating of the slurry is begun, or it may be added either portionwise or continuously during the heating period.
When oxygen or an oxygen-containing gas is used, it is preferably sparged through the slurry during the heating period.
As used herein, the term «polyvinyl chloride» includes both the high molecular weight homopolymers of vinyl chloride and the high molecular weight copolymers formed by the copolymerization of vinyl chloride with an essentially water-insoluble ethylenically-unsaturated monomer that is copolymerizable therewith.
Suitable comonomers include vinyl acetate, vinyl propionate vinyl butyrate, vinyl stearate, vinyl benzoate, ethylene, propylene, ethyl acrylate, acrylic acid, acrylamide, acrylonitrile, methacrylonitrile, vinylidene chloride, dialkyl fumarates and maleates, vinyl ethers, and the like When one or more of these comonomers are used, the monomer component contains at least 70 % and preferably 80 % to 90 % of vinyl chloride.
The polyvinyl chloride slurries that are treated in accordance with the process of this invention to prevent discolouration of the polymer during processing to remove residual vinyl 70 chloride from them may be prepared by the well-known suspension or emulsion polymerization processes In the suspension polymerization processes, the monomer is suspended in water by a suspending agent and agitation The 75 polymerization is initiated with a suitable free radical generating polymerization initiator, such as lauroyl peroxide, benzoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, tertiary butyl peroxy 80 pivalate, azobisisobutyronitrile, azobis-2,4dimethylvaleronitrile, and mixtures thereof.
Suspending agents that may be used include methylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydrolyzed polyvinyl 85 acetate, gelatin, methyl vinyl ether-maleic anhydride copolymers, and the like In emulsion polymerization processes, the polymerization initiator may be hydrogen peroxide, an organic peroxide, a persulfate, or a redox system 90 Surface-active agents, such as sulfates, alkane sulfonates, alkyl aryl sulfonates, and fatty acid soaps are used as emulsifiers in these processes The reaction mixtures produced by these processes are usually heated under vacuum to 95 about 60 C to 65 C to remove most of the unreacted monomer from them The resulting stripped slurries generally contain 5 % to 50 % and preferably 15 % to 40 % by weight of polyvinyl chloride as particles that range in size 100 from about 5 microns to 200 microns and from about 100 ppm to 15,000 ppm of vinyl chloride.
Following the removal of vinyl chloride from them by the process of this invention, the slurries may be dewatered, for example, on a 105 rotary drum filter, and then dried, or they may be spray dried The polyvinyl chloride prepared in this way has excellent brightness and color and usually contains less than 1 ppm of vinyl chloride 110 The invention is further illustrated by the following examples In these examples, all parts are by weight and all percentages are percentages by weight.
EXAMPLE 1 115
A An aqueous slurry of polyvinyl chloride was prepared by polymerizing vinyl chloride using a mixture of lauroyl peroxide and di-2ethylhexyl peroxydicarbonate as the initiator, hydroxypropylmethylcellulose as the suspend 120 ing agent, and trichloroethylene as the chain transfer agent The slurry was heated under vacuum at a temperature below 65 C to reduce its vinyl chloride content to less than 5,000 ppm 125 B Fifteen hundred grams of the slurry, which contained approximately 35 % of polyvinyl chloride, was heated to 75 C After the addition of 15 grams of 30 % hydrogen peroxide solution to it, the slurry was heated to 130 1 572361 O C Another 15 grams of 30 % hydrogen peroxide solution was added, and the slurry was heated at 95 C to 100 C for 1 hour, cooled to 70 ‘C, heated at 70 C for 5 hours, and then filtered The polyvinyl chloride, after drying at 50 C for 12 hours, contained less than 1 ppm of vinyl chloride.
The color of the dry polyvinyl chloride was measured by reflectance using a Hunter Colornmeter, Model D-25, which gives readings directly from the polymer surface The results obtained are given in Table 1 In this table, the L value relates to the brightness of the polymer, that is, to the percentage of the light that is 1 5 reflected, with perfectly white polymer having an L value of 100 The a and b values relate to hue Positive a denotes red, negative a denotes green, positive b denotes yellow, and negative b denotes blue.
EXAMPLE 2
Five grams of sodium perborate was added to 500 grams of a polyvinyl chloride slurry that has been prepared by the procedure described in Example 1 A The treated slurry was heated at 95 C to 100 C for 30 minutes and then at 70 C for 5 hours After filtration, the polyvinyl chloride was dried at 50 C for 12 hours The dry polymer contained less than 1 ppm of vinyl chloride Its color, as measured by reflectance, is given in Table 1.
EXAMPLE 3
Five hundred grams of a polyvinyl chloride slurry that has been prepared by the procedure described in Example 1 A was heated at 95 C.
while air was sparged into it through a fritted glass dispersion tube at the rate of 840 ml / minute The heating at 95 C and the air sparging were continued for 2 5 hours The slurry was then cooled and filtered, and the recovered polyvinyl chloride was dried at 50 C.
for 12 hours The dry polymer contained less than 1 ppm of vinyl chloride Its color, as measured by reflectance, is given in Table 1.
COMPARATIVE EXAMPLE A Five hundred grams of a polyvinyl chloride slurry that had been prepared by the procedure described in Example 1 A was heated at 95 C for 3 hours, cooled to room temperature, and filtered After drying at 50 C for 12 hours, the recovered polyvinyl chloride had a monomer content of less than 1 ppm Its color, as measured by reflectance, is given in Table 1.
COMPARATIVE EXAMPLE B Five hundred grams of a polyvinyl chloride slurry that had been prepared by the procedure described in Example 1 A was heated at 95 C for 30 minutes and then at 70 C for hours After filtration, the product was dried at 50 C for 12 hours Its monomer content was less than 1 ppm Its color, as measured by reflectance, is given in Table 1.
COMPARATIVE EXAMPLE C Five hundred grams of a polyvinyl chloride slurry that has been prepared by the procedure described in Example l A was sparged with nitrogen for 30 minutes The sparging with nitrogen was continued while the slurry was heated at 95 -100 «C for 30 minutes and then at 70 O C for 5 hours After filtration, the product was dried at 50 TC for 12 hours.
Its monomer content was less than 1 ppm Its color, as measured by reflectance, is given in Table 1.
The data in Table 1 show that the addition of an oxidizing agent to a polyvinyl chloride slurry that is maintained at elevated temperatures until its monomer content has fallen below 1 ppm results in the recovery of lightercolored and brighter polyvinyl chloride than is obtained in the absence of an oxidizing agent.
The products prepared using either hydrogen peroxide (Example 1) or sodium perborate (Example 2) were appreciably brighter than those prepared in the absence of an oxidizing agent (Comparative Example A and B) The product of Example 3, which was prepared by sparging the heated slurry with air, was brighter and less red than that of Comparative Example B, which was heated in the absence of an oxidizing agent, while the product of Comparative Example C, from which oxygen was removed by sparging with nitrogen, was considerably duller than the products of both Example 3 and Comparative Example B. EXAMPLE 4
Three 500 gram portions of a polyvinyl chloride slurry prepared by the procedure described in Example 1 A were heated to 95 TC.
Small amounts of 30 % hydrogen peroxide solution were added to two of the heated portions of slurry; the third portion served as the control The three portions of slurry were heated at 95 -100 TC for 1 hour, cooled to -C, heated at 70 TC for 5 hours, and then filtered The polyvinyl chloride, which was dried at 50 TC for 12 hours, contained less than 1 ppm of vinyl chloride The amounts of hydrogen peroxide that were added to two of the portions of slurry, and the colors of the products are given in Table 2.
From the data in Table 2, it will be seen that the products recovered from the portions of slurry that had been treated with hydrogen peroxide before heating were brighter and had better color than the control Increasing the amount of hydrogen peroxide added gave brighter polymer with less yellow and less red hue.

Claims (9)

WHAT WE CLAIM IS:-

1 A process for the removal of vinyl chloride from an aqueous slurry comprising a suspension or emulsion which contains 5 % to % by weight of polyvinyl chloride and 100 ppm to 15,000 ppm of vinyl chloride, which comprises maintaining the slurry at a temperature in the range from 70 to 100 ‘C so as to remove monomer from the slurry until it contains less than 10 ppm of vinyl chloride, the polyvinyl chloride contacting an oxidizing agent during the heat treatment.
Table 1 Ex Reflectance of PVC No Treatment of Slurry L a b 1 0 85 PHR of H 202 added; slurry 97 8 0 2 2 3 heated to 95 C; 0 85 PHR of H 202 added; slurry heated at -100 C for 1 hour and at C for 5 hours.

2 2 8 PHR of sodium perborate 97 7 0 8 1 6 added; slurry heated at 95 C for 0 5 hour and at 70 C.
for 5 hours.
3 Slurry heated and air-sparged at 97 8 0 8 1 9 C for 2 5 hours.
Comp.
Ex.
No.
A Slurry heated at 95 -100 Cfor 950 1 9 6 2 3 hours.
B Slurry heated at 95 -100 C for 97 3 1 1 1 8 0.5 hour and at 70 C for 5 hours.
C Slurry sparged with N 2 for O 5 96 7 1 3 2 8 hour, and then heated and N 2sparged at 95 -100 C for 0 5 hour and at 70 ‘C for 5 hours.
Table 2 Ex Amount (PHR) of Reflectance of PVC No H 202 Added L a b 4 a 3 4 98 1 0 3 1 9 4 b 1 7 97 7 0 8 2 4 4 c 0 96 4 1 5 2 7 2 A process according to claim 1, wherein the oxidizing agent is selected from oxygen, oxygen-containing gases, hydrogen peroxide and compounds which decompose in hot aqueous solutions to give oxygen or hydrogen peroxide.

3 A process according to claim 2, wherein the oxidizing agent is sodium perborate.

4 A process according to any preceding claim, wherein the amount of oxidizing agent added is that which will prevent discoloration of the polyvinyl chloride.

A process according to any preceding claim, wherein 1 to 10 parts by weight of oxidizing agent is added per 100 parts by weight of polyvinyl chloride in the slurry.

6 A process according to any preceding claim, wherein the oxidizing agent is added and then the slurry is heated to 70 to 100 C 120

7 A process according to any of claims 1 to 5, wherein the oxidizing agent is added continuously while the slurry is maintained at to 100 C.

8 A process according to claim 1, substan 125 tially as herein described.

9 A polyvinyl chloride slurry containing less than 10 ppm of vinyl chloride, when prepared by a process according to any preceding claim 130 1 572 361 1 572 361 5 (POLLAK MERCER & TENCH) Chartered Patent Agents Eastcheap House, Central Approach, Letchworth, Hertfordshire, SG 6 3 DS and High Holborn House, 52/54 High Holborn, London WC 1 V 6 RY Agents for the Applicants Printed t’or Hler Majesty’s Stationery Office by MULI’IPLLX techniques ltd, St Mary Cray Kent 1980 Published at the Patent Office, 25 Southampton Buildings London WC 2 1 AY, from which copies may be obtained.

GB17986/77A
1976-05-25
1977-04-29
Purification of polyvinyl chloride

Expired

GB1572361A
(en)

Applications Claiming Priority (1)

Application Number
Priority Date
Filing Date
Title

US05/690,202

US4220754A
(en)

1976-05-25
1976-05-25
Process for the purification of polyvinyl chloride with oxidizing agents

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Publication Number
Publication Date

GB1572361A
true

GB1572361A
(en)

1980-07-30

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ID=24771530
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Application Number
Title
Priority Date
Filing Date

GB17986/77A
Expired

GB1572361A
(en)

1976-05-25
1977-04-29
Purification of polyvinyl chloride

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US
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US4220754A
(en)

JP
(1)

JPS52144081A
(en)

CA
(1)

CA1094734A
(en)

DE
(1)

DE2723377A1
(en)

GB
(1)

GB1572361A
(en)

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* Cited by examiner, † Cited by third party

Publication number
Priority date
Publication date
Assignee
Title

GB1588991A
(en)

1977-04-06
1981-05-07
Tenneco Chem
Vinyl chloride resin slurry purification

JPS5814453B2
(en)

1979-07-16
1983-03-19
信越化学工業株式会社

Surface treatment method for plastic molded products

DE4110058A1
(en)

1991-03-27
1992-10-01
Hoechst Ag

METHOD FOR REDUCING THE RESIDUAL MONOMER CONTENT IN AQUEOUS PLASTIC DISPERSIONS BASED ON POLYVINYL ESTER

DE4425625C1
(en)

1994-07-20
1996-01-04
Degussa

Process for the preparation of unglazed, low-monomer homo- or copolymers of methyl methacrylate, an emulsion polymer of polymethyl methacrylate obtainable by this process with a comonomer content of less than 5% by weight and the use of the emulsion polymer

US5498693A
(en)

1994-09-26
1996-03-12
The Goodyear Tire & Rubber Company
Method of reducing the residual unsaturated monomer content of an aqueous dispersion of a saturated polymer

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BE465917A
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1945-01-10

US3077371A
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1956-02-14
1963-02-12
Celanese Corp
Treatment of knitted fabrics

DE1301996B
(en)

1964-04-09
1969-09-25
Degussa

Method of bleaching

US3600366A
(en)

1969-12-10
1971-08-17
Procter & Gamble
Bleaching of polymaleate homopolymers and copolymers

US3697495A
(en)

1970-08-05
1972-10-10
Du Pont
Preparation of polyvinyl alcohol having improved color properties by treating the polyvinyl ester with ozone

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(en)

1970-12-29
1973-05-31
American Cyanamid Company
Process for producing lac toni zed acrylic polymer products

FR2235952A1
(en)

1973-06-15
1975-01-31
Ugine Kuhlmann
Chlorinated (co)polymers with carboxylic end gps – prepd by reacting macromolecular chain with ozone

US4015065A
(en)

1974-05-17
1977-03-29
The British Petroleum Company Limited
Treatment of vinyl halide polymers

IL47420A
(en)

1974-06-24
1978-07-31
Tenneco Chem
Process for the removal of vinyl chloride from pvc slurries and latexes and pvc thus obtained

US3956249A
(en)

1974-06-24
1976-05-11
Tenneco Chemicals, Inc.
Manufacture of polyvinyl chloride of low vinyl chloride monomer content by treatment of wet polyvinyl chloride

ES438975A1
(en)

1974-08-14
1977-02-16
Solvay
Removal of residual vinyl chloride

1976

1976-05-25
US
US05/690,202
patent/US4220754A/en
not_active
Expired – Lifetime

1977

1977-04-29
GB
GB17986/77A
patent/GB1572361A/en
not_active
Expired

1977-05-09
CA
CA278,014A
patent/CA1094734A/en
not_active
Expired

1977-05-23
JP
JP5891777A
patent/JPS52144081A/en
active
Pending

1977-05-24
DE
DE19772723377
patent/DE2723377A1/en
not_active
Withdrawn

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Publication number
Publication date

DE2723377A1
(en)

1977-12-08

CA1094734A
(en)

1981-01-27

JPS52144081A
(en)

1977-12-01

US4220754A
(en)

1980-09-02

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