GB2078237A - Suspension polymerization of vinyl chloride - Google Patents
Suspension polymerization of vinyl chloride Download PDFInfo
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- GB2078237A GB2078237A GB8118207A GB8118207A GB2078237A GB 2078237 A GB2078237 A GB 2078237A GB 8118207 A GB8118207 A GB 8118207A GB 8118207 A GB8118207 A GB 8118207A GB 2078237 A GB2078237 A GB 2078237A
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- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000010557 suspension polymerization reaction Methods 0.000 title claims abstract description 14
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 103
- 239000000203 mixture Substances 0.000 claims abstract description 76
- 239000000178 monomer Substances 0.000 claims abstract description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 21
- 239000012736 aqueous medium Substances 0.000 claims abstract description 4
- 229920000642 polymer Polymers 0.000 claims description 22
- 238000002474 experimental method Methods 0.000 claims description 13
- 239000000375 suspending agent Substances 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000004904 shortening Methods 0.000 abstract description 4
- 239000003999 initiator Substances 0.000 description 22
- 230000008021 deposition Effects 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000013019 agitation Methods 0.000 description 6
- 239000002270 dispersing agent Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- -1 tertbutylperoxy neodecanoate Chemical compound 0.000 description 5
- 239000000243 solution Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 3
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 3
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 3
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003708 ampul Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- NMHPKVDFYDXHHV-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOOC(C)(C)C NMHPKVDFYDXHHV-UHFFFAOYSA-N 0.000 description 1
- GMLYXPGQZVOYNT-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethylperoxy)ethane Chemical group CCOCCOOCCOCC GMLYXPGQZVOYNT-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 description 1
- YPIFGDQKSSMYHQ-UHFFFAOYSA-M 7,7-dimethyloctanoate Chemical compound CC(C)(C)CCCCCC([O-])=O YPIFGDQKSSMYHQ-UHFFFAOYSA-M 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 229920005682 EO-PO block copolymer Polymers 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920001213 Polysorbate 20 Polymers 0.000 description 1
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 1
- 239000004147 Sorbitan trioleate Substances 0.000 description 1
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- CIQVOHYWIBJUIK-UHFFFAOYSA-N carboxy 2,2-diethoxyethylperoxy carbonate Chemical compound CCOC(COOOC(=O)OC(=O)O)OCC CIQVOHYWIBJUIK-UHFFFAOYSA-N 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- BSVQJWUUZCXSOL-UHFFFAOYSA-N cyclohexylsulfonyl ethaneperoxoate Chemical compound CC(=O)OOS(=O)(=O)C1CCCCC1 BSVQJWUUZCXSOL-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 description 1
- ZFTFAPZRGNKQPU-UHFFFAOYSA-N dicarbonic acid Chemical compound OC(=O)OC(O)=O ZFTFAPZRGNKQPU-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003028 elevating effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- UPWGQKDVAURUGE-UHFFFAOYSA-N glycerine monooleate Natural products CCCCCCCCC=CCCCCCCCC(=O)OC(CO)CO UPWGQKDVAURUGE-UHFFFAOYSA-N 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- OCWMFVJKFWXKNZ-UHFFFAOYSA-L lead(2+);oxygen(2-);sulfate Chemical compound [O-2].[O-2].[O-2].[Pb+2].[Pb+2].[Pb+2].[Pb+2].[O-]S([O-])(=O)=O OCWMFVJKFWXKNZ-UHFFFAOYSA-L 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229940082004 sodium laurate Drugs 0.000 description 1
- 229940035044 sorbitan monolaurate Drugs 0.000 description 1
- 235000019337 sorbitan trioleate Nutrition 0.000 description 1
- 229960000391 sorbitan trioleate Drugs 0.000 description 1
- 238000012956 testing procedure Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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
- C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F14/02—Monomers containing chlorine
- C08F14/04—Monomers containing two carbon atoms
- C08F14/06—Vinyl chloride
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The productivity of the suspension polymerization of vinyl chloride in an aqueous medium, especially in a large polymerization reactor, is improved by shortening the time taken for completing polymerization run. In this method, the polymerization initiator is dissolved in the monomer to form a uniform mixture and the mixture is introduced into the polymerization reactor simultaneously with pre-heated water to form a hot polymerization mixture in the reactor at a temperature substantially equal to the prescribed polymerization temperature so that the time otherwise necessary for the temperature elevation of the cold polymerization mixture to the prescribed polymerization temperature can be mostly saved.
Description
SPECIFICATION
Method for the suspension polymerization of vinyl chloride
The present invention concerns an improvement in the suspension polymerization of vinyl chloride in an aqueous medium.
As is well known, suspension polymerization of vinyl chloride monomer is usually carried out in a batch-wise process. In the conventional method for the suspension polymerization of vinyl chloride, water as the aqueous polymerization medium, dispersing agent or suspending agent, polymerization initiator and the vinyl chloride monomer are introduced into the polymerization reactor with addition of optional additives to form a polymerization mixture which is then heated to a prescribed temperature to start the polymerization reaction. The polymerization temperature is usually maintained constant throughout the time to complete a polymerization run.
When improvement in the productivity of the suspension polymerization is desired by shortening the overall time taken for a polymerization run, therefore, it is necessary to shorten the time for the introduction of the ingredients of the polymerization mixture into the polymerization reactor and the reaction time as well as the time necessary for elevating the temperature of the cold polymerization mixture to the prescribed polymerization temperature.The temperature elevation of the polymerization mixture contained in the polymerization reactor is carried out usually solely by means of the heating jacket surrounding the reactor, but a large sized polymerization reactor sometimes has an insufficient heating capacity because the surface area, i.e. the area for heat transfer, of such a large reactor is small relative to the volume thereof so that it has been desired to develop an efficient means for the temperature elevation of the polymerization mixture contained in a large polymerization reactor.
An alternative method for the solution of the above problem is the introduction of water or vinyl chloride monomer heated in advance. When the polymerization initiator is introduced together with the water at an elevated temperature, however, the initiator is rapidly decomposed before the introduction of the vinyl chloride monomer so that certain difficulties are encountered in the control of the polymerization reaction. When the vinyl chloride monomer and the polymerization initiator are introduced into the polymerization reactor already containing the water heated in advance, on the other hand, the polymerization of the monomer begins during introduction of the monomer so that a large amount of polymer scale deposits on the walls of the polymerization reactor resulting in inferior quality of the polymer product which has an extremely large number of fish-eyes.
Further, the amount of fish-eyes is increased by adding the polymerization initiator after introduCtion of the pre-heated water and the vinyl chloride monomer into the reactor. Similar disadvantages are unavoidable in the case of the introduction of pre-heated monomer.
The problem from which the present invention arose, was therefore to provide a method for the improvement of productivity in the suspension polymerization of vinyl chloride monomer by shortening the overall time taken for completing a polymerization run.
The method of the present invention is based on the principle that the most effective way for shortening the time before the start of the polymerization reaction is the simultaneous introduction of pre-heated water and a uniform mixture composed of the vinyl chloride monomer and the polymerization initiator together into the polymerization reactor to form a hot polymerization mixture in which the polymerization reaction can immediately start. It is desirable that the polymerization mixture formed in the reactor during and at the end of the introduction of the pre-heated water and the uniform mixture of the monomer and the initiator is at a temperature substantially equal to the prescribed polymerization temperature. In particular, the temperature of the polymerization mixture should not exceed the prescribed polymerization temperature by 20C or more.
Preferred embodiments of the invention will now be described.
In practicing the method of the present invention, vinyl chloride monomer and the polymerization initiator are first mixed together to form a uniform mixture before they are introduced into the polymerization reactor. There are several ways for forming the uniform mixture of the monomer and the initiator in advance. For example, they are mixed together in advance in a separate vessel to form a uniform mixture and the mixture is then introduced into the polymerization reactor. Alternatively, they are mixed together on the way to the polymerization reactor in a continuous line mixer so that they arrive at the reactor as a uniform mixture.
As will be readily understood from the above requirement that the monomer and the polymerization initiator are introduced into the polymerization reactor as a uniform mixture, the initiator naturally should be selected from monomer-soluble ones. In this regard, conventional initiators used for the suspension polymerization may be used in the present invention such as organic peroxides and azo compounds as exemplified by diisopropylperoxy dicarbonate, diethoxyethylperoxy dicarbonate, tertbutylperoxy neodecanoate, br-cumylperoxy neodecanoate, tert-butylperoxy neodecanoate, acetyl cyclohexylsulfonyl peroxide, 2, 4, 4-trimethylpentyl 2-peroxyphenoxy acetate and the like as examples of the former class and azobis-2, 4-dimethylvaleronitrile, azobis (4-methoxy-2, 4-dimethyívaleronitrile) and the like as the examples of the latter class.These initiators may be used either alone or as a combination of two or more according to need. The amount of the polymerization initiator relative to the
monomer is conventional.
When the monomer and the initiator are mixed together to form a uniform mixture and introduced
into the polymerization reactor simultaneously with the pre-heated water, the temperature of the
mixture should be kept sufficiently low before contacting with the pre-heated water so as not to cause
premature decomposition of the initiator before the polymerization mixture is formed in the reactor. As a
result of investigations to establish the effect of this temperature, it was noted that the temperature of
the mixture of the monomer and the initiator should be such that the conversion of the monomer in the
mixture is 5% or less or, preferably, 3% or less after 2 hours at the temperature. If the above condition is
not satisfied, deposition of polymer scale on the reactor walls is remarkably increased and the polymer
product contains a large amount of fish-eyes.
As the uniform mixture of the monomer and the polymerization initiator as introduced into the
polymerization reactor, pre-heated water is simultaneously introduced into the reactor to form a
polymerization mixture at an elevated temperature so that the polymerization reaction may start. In this case, it is essential that the temperature of the thus formed polymerization mixture at the end of the
introduction of both of the monomer-initiator mixture and the pre-heated water is substantially equal or as close as possible to the prescribed polymerization temperature. In particular, the temperature of the polymerization mixture should not be higher than the polymerization temperature by 20C or more since an excessively high temperature of the polymerization mixture causes a danger of a violent polymerization reaction only controllabie with difficulty.On the other hand, a lower temperature of the polymerization mixture than the polymerization temperature involves no problems of safety but the advantages of the present invention, viz improved productivity, are reduced in proportion to the temperature difference since the temperature of the polymerization mixture must be elevated by an outer heating means so that a time elapses before the start of the polymerization reaction. A temperature difference of 50C or smaller may be practically tolerable.Though not limited thereto, it is
practically convenient that the temperatures of the monomer-initiator mixture and the pre-heated water are both kept constant throughout their period of introduction into the reactor and their introduction is begun at the same time and continued at constant rates in proportion to the ratio of their total amounts so that their introduction comes to an end at approximately the same time. In this
manner, the temperature of the polymerization mixture is kept approximately constant during and at
the end of the introduction of the monomer-initiator mixture and the pre-heated water.
The simultaneous introduction of the monomer-initiator mixture and the pre-heated water should be carried out under agitation and completed within a time as short as possible or, usually, within 30 minutes or less. If their introduction is prolonged, deposition of the polymer scale on the reactor walls is increased resulting in inferior quality of the polyvinyl chloride resin product with remarkably increased fish-eyes.
Needles to say, the suspension polymerization of vinyl chloride monomer is performed by dispersing the monomer in the aqueous medium with the aid of a dispersing agent or a suspending agent. When the dispersing agent is soluble in the monomer, it can be introduced into the polymerization reactor together with the monomer and dissolved therein. When the dispersing agent is soluble in water, on the other hand, it may be introduced into the reactor together with the pre-heated water and dissolved therein or, alternatively, it may be introduced into the reactor separately as an aqueous solution of a relatively high concentration, preferably, at the initial stage of or prior to the introduction of the pre-heated water.If the introduction of the dispersing agent is too iate the amount of the polymer scale deposition is increased resulting in inferior quality of the polymer product with
increased fish-eyes.
The above mentioned dispersing agent or suspending agent may be a conventional one used in the suspension polymerization of vinyl chloride exemplified by water-soluble polymeric materials such
as water-soluble cellulose ethers, e.g. methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose,
hydroxypropyl methylcellulose and the like, partially saponified polyvinyl alcohols, polymers of acrylic
acid, gelatin and the like, monomer-soluble emulsifying agents such as sorbitan monolaurate, sorbitan
trioleate, block copolymers of ethyleneoxide and propyleneoxide and water-soluble emulsifying agents
such as polyoxyethylene sorbitan monolaurate, polyoxyethylene glycerin oleate, sodium laurate and the
like. These suspending agents may be used either alone or as a combination of two or more.
Furthermore, the suspension polymerization according to the present invention may be carried out
with addition of various additives conventionally used in the prior art polymerization of vinyl chloride
such as polymerization controlling agents, chain transfer agents, gelation improvers, anti-static agents,
pH controlling agents and the like.
The method of the present invention is applicable not only to the homopolymerization of vinyl
chloride but also to the copolymerization of a monomer mixture of which the main component, say,
50% by weight or more, is vinyl chloride. The comonomers copolymerizable with vinyl chloride are
exemplified by vinyl esters such as vinyl acetate, vinyl propionate and the like, esters of acrylic acid and
methacrylic acid such as methyl acrylate, ethyl acrylate, methyl methacrylate and the like, olefins such
as ethylene, propylene and the like, maleic anhydride, acrylonitrile, styrene and vinylidene chloride.
In practicing the method of the present invention, the weight ratios of the individual ingredients.
polymerization temperature and other conditions may be determined in accordance with the conditions conventionally undertaken in the prior art methods of the suspension polymerization of vinyl chloride.
Using the method of the present invention, an advantage can be obtained in that the time taken for completion of a polymerization run can be greatly shortened so that the method is particularly effective in giving high productivity, especially in the case of polymerization with a large polymerization reactor having a relatively small heating capacity in relation to the volume capacity thereof, such that, in a conventional method, a long time is taken for the temperature elevation of the cold polymerization mixture up to the prescribed polymerization temperature.
EXAMPLE 1 (Experiments No. 1 to No. 8)
In each of the experiments, the polymerization of vinyl chloride was performed in a polymerization reactor of 1.2 m3 capacity equipped with a stirrer and provided with a heating jacket.
In the first place, a mixture of the monomer and the polymerization initiator was prepared by dissolving 200 g of di-2-ethylhexylperoxy dicarbonate in 350 kg of vinyl chloride monomer without heating. The temperature of the mixture in each of the runs before introduction into the reactor was as indicated in Table 1 below together with the estimated conversion of the monomer in % to the polymer after 2 hours in the mixture at the temperature.
Separately, an aqueous solution of a suspending agent was prepared by dissolving 1 50 g of a partially saponified polyvinyl alcohol and 50 g of a hydroxypropyl methylcellulose in 480 kg of preheated water. The temperature of the thus prepared aqueous solution was as indicated in the table.
The above prepared cold monomer-initiator mixture and the pre-heated aqueous solution of the suspending agent were introduced separately but simultaneously at constant rates into the polymerization reactor through separate inlets to form a hot polymerization mixture with continuous agitation. The temperatures of the polymerization mixture during and at the end of the introduction of the monomer-initiator mixture and the aqueous solution in the reactor were as indicated in the table.
When the above given temperature of the polymerization mixture at the end of the introduction of the monomer-initiator mixture and the aqueous solution was lower than the prescribed polymerization temperature of 570C, the temperature of the polymerization mixture was further increased up to 57CC by means of the heating jacket taking a time shown in Table 1 in minutes and the polymerization reaction was started with continuous agitation.
When the polymerization reaction came near to the end and the pressure inside the reactor had dropped to 7 kg/cm2G, the unreacted monomer was recovered and the aqueous polymerizate slurry discharged out of the reactor was dehydrated and dried to give a polyvinyl chloride resin product.
In Experiment No. 8 shown in Table 1, the monomer initiator mixture was introduced into the polymerization reactor simultaneously with the pre-heated water containing no suspending agent dissolved therein followed by the separate addition of the suspending agent as an aqueous solution of a relatively high concentration.
In each of the experiments, the state of the polymer scale deposition on the reactor walls andthe number of fish-eyes in the polymer product were recorded according to the following criteria or the testing procedure.
Conversion of the monomer in the monomer-initiator mixture to the polymer after 2 hours (in%): 20 ml of the uniform mixture of the monomer and the polymerization initiator were sealed in a glass ampoule and the conversion was determined after 2 hours of standing of the glass ampoule at the temperature indicated.
Number of fish-eyes (pieces): a resin compound was prepared by blending 100 parts by weight of the resin product, 1 part by weight of tribasic lead sulfate, 1.5 parts by weight of lead stearate, 0.2 part by weight of titanium dioxide, 0.1 part by weight of carbon black and 50 parts by weight of dioctyl phthalate and 25 g of the compound were milled in a roller mill at 1 450C for 5 minutes and shaped into a sheet of 0.2 mm thickness. The number of translucent spots in 100 cm2 of this sheet was counted and recorded as the number of pieces of fish-eyes.
State of polymer scale deposition: A... almost no polymer scale deposition B... polymer scale deposition on the vapor-liquid interfacial region
C . . . polymer scale deposition all over the walls of the polymerization reactor
TABLE 1
Experiment No. 1 2 3 4 5 6 7 | 8 Monomerinitiator mixture Temperature, "C 25 12 18 23 22 36 30 25 Monomer conversion after 2 hours, % 1.5 < 1 < 1 1.5 1.5 7 4.5 1.5 Temperature of aqueous solution, "C 65.5 68 67 61.3 55.3 62.5 63 65 Charge time, minutes 10 20 40 15 15 10 5 15 Temperature of polymerization mixture, "C During charging 56-57 55-57 55-57 52-53 48-4955-57 55-56 55-56 At the end of charging 57 56 57 53 48 57 56 56 Time for temperature elevation to 57"C, minutes 0 5 0 20 45 0 5 5 Fish-eyes, pieces 9 12 > 500 23 > 500 > 500 28 > 500 Polymer scale deposition A A C A C C B C EXAMPLE 2 (Experiments No. 9 to No. 13)
Into a polymerization reactor of 40 m3 capacity equipped with a condenser having an area for heat transfer of 40 m2 were introduced simultaneously 13 tons of vinyl chloride monomer and 1 8 m3 of pre-heated water at constant rates of 0.65 ton/minute and 0.9 m3/minute, respectively, with agitation taking 20 minutes.
In the piping line for the transfer of the vinyl chloride monomer to the reactor, 14 kg of a toluene solution containing 50% by weight of di(ethoxyethyl)peroxy dicarbonate were injected into the stream of the monomer at a rate of 0.7 kg/minute with agitation by a static mixer so that the initiator was uniformly blended with the monomer when arriving at the reactor.
Similarly, 100 liters of an aqueous solution containing 3.0 kg of a partially saponified polyvinyl alcohol and 2.5 kg of a hydroxypropyl methylcellulose dissolved therein were injected into the preheated water in the piping line at a rate of 5 liters/minute.
When the temperature of the polymerization mixture thus formed in the polymerization reactor
was lower than 57"C, the temperature was further increased up to 570C by means of the heating jacket
and the polymerization reaction was started with continuous agitation.
The polymerization reaction was terminated when the pressure inside the reactor had dropped to
7 kg/cm2G by recovering the unreacted monomer, and the aqueous polymerizate slurry discharged out of the reactor was dehydrated and dried to give a polyvinyl chloride resin product.
Table 2 given below shows the temperature of the monomer-initiator mixture at the inlet to the reactor, the monomer conversion in the monomer-initiator mixture at such a temperature after 2 hours, the temperature of the pre-heated water at the inlet to the reactor after admixing of the solution of the suspending agents, the temperature of the polymerization mixture at the end of the introduction of the monomer and the pre-heated water, the time taken for the temperature elevation of the polymerization mixture up to 570C and the polymerization time as well as the state of polymer scale deposition on the reactor walls and the number of fish-eyes in the polymer product in each of the experiments. In Table 2,
Experiment No. 12 was undertaken for comparative purpose according to the conventional procedure in which the water as the aqueous polymerization medium containing the suspending agents, polymerization initiator and vinyl chloride monomer were introduced into the reactor successively one by one.
For further comparison, substantially the same procedure was repeated as in Experiment No. 9 except that the vinyl chloride monomer and the toluene solution of the polymerization initiator were introduced into the reactor not as a uniform mixture but separately through separate inlets omitting the static mixer in the piping. The increased number of fish-eyes in the resin product obtained in this experiment as shown in Table 2 clearly indicates the significance of the introduction of the monomer and the initiator as a uniform mixture (Experiment No. 1 3).
TABLE 2
Experiment No. 9 10 ' 11 12 13 Monomerbinitiator mixture Temperature, 1C 18 8 16 22 18 Monomer conversion after 2 hours, % 1 1 1 - I Temperature of pre-heated water, "C 67 67.5 19 25 67 Temperature of polymerization mixture at the end of charging, C 57 55 18 24 57 Time for temperature elevation to 57 .C, minutes 0 10 55 50 O Polymerization time, hours 4.8 5.0 5.7 6.2 4.8 Fish-eyes, pieces 8 9 5 8 > 500 Polymer scale deposition A A A A A
Claims (9)
1. A method for the suspension polymerization of vinyl chloride monomer or a monomer mixture mainly composed of vinyl chloride in an aqueous medium containing a suspending agent in a polymerization reactor in the resence of a polymerization initiator at a prescribed elevated polymerization temperature, which comprises introducing the monomer or monomer mixture and the polymerization initiator as a uniform mixture simultaneously with the introduction of pre-heated water into the polymerization reactor to form a polymerization mixture therein to start the polymerization reaction, the temperature of the polymerization mixture during and at the end of the introduction of the uniform mixture of the monomer and the polymerization initiator and the pre-heated water being substantially equal to the prescribed polymerization temperature.
2. The method as set forth in claim 1 wherein the temperature of the polymerization mixture at the end of the introduction of the uniform mixture of the monomer and the polymerization initiator and the pre-heated water is not higher than the prescribed polymerization temperature by 20C or more.
3. The method as set forth in claim 1 or 2 wherein the uniform mixture of the monomer and the polymerization initiator before introduction into the polymerization reactor is kept at such a temperature that, when the mixture is kept at this temperature, the conversion of the monomer to polymer does not exceed 5% after 2 hours.
4. The method as set forth in any preceding claim wherein the introduction of the uniform mixture of the monomer and the polymerization reactor is completed within a time not exceeding 30 minutes.
5. The method as set forth in claim 1, 2, 3 or 4 wherein the suspending agent is dissolved in the pre-heated water prior to the introduction of the pre-heated water into the polymerization reactor.
6. The method as set forth in claim 1, 2, 3 or 4 wherein the suspending agent is introduced into the polymerization reactor in a form of an aqueous solution prior to the introduction or the uniform mixture of the monomer and the polymerization initiator and the pre-heated water into the polymerization reactor.
7. The method as set forth in any preceding claim wherein the introduction of the uniform mixture of the monomer and the polymerization initiator and the introduction of the pre-heated water are performed at constant rates beginning and ending at substantially the same time.
8. The method as set forth in Claim 1, substantially as described in any of Experiments 1,2,4,7,9,10,11 or 12.
9. A vinyl chloride polymer prepared by a method as set forth in any preceding claim.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8114980A JPS575704A (en) | 1980-06-16 | 1980-06-16 | Suspension polymerization of vinyl chloride monomer |
Publications (2)
Publication Number | Publication Date |
---|---|
GB2078237A true GB2078237A (en) | 1982-01-06 |
GB2078237B GB2078237B (en) | 1984-07-25 |
Family
ID=13738367
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB8118207A Expired GB2078237B (en) | 1980-06-16 | 1981-06-12 | Suspension polymerization of vinyl chloride |
Country Status (6)
Country | Link |
---|---|
JP (1) | JPS575704A (en) |
BE (1) | BE889218A (en) |
DE (1) | DE3123015A1 (en) |
FR (1) | FR2484420A1 (en) |
GB (1) | GB2078237B (en) |
IT (1) | IT1137251B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0129803A2 (en) * | 1983-06-23 | 1985-01-02 | Occidental Chemical Corporation | Novel polyvinyl chloride suspension polymerization process |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3451985A (en) * | 1964-03-26 | 1969-06-24 | Monsanto Co | Method of polymerizing vinyl monomers |
DE2212962C2 (en) * | 1972-03-17 | 1985-01-24 | Basf Ag, 6700 Ludwigshafen | Process for the polymerization of vinyl chloride in aqueous suspension |
DE2442574A1 (en) * | 1974-09-05 | 1976-03-25 | Huels Chemische Werke Ag | PROCESS FOR PRODUCING POLYVINYL CHLORIDE WHICH AVOID VINYL CHLORIDE EMISSIONS BY DISCONTINUOUS POLYMERIZATION IN SUSPENSION |
DE2458024B2 (en) * | 1974-12-07 | 1979-10-04 | Hoechst Ag, 6000 Frankfurt | Process for the aqueous suspension polymerization of vinyl chloride |
CH611632A5 (en) * | 1975-02-13 | 1979-06-15 | Solvay | |
DE2639343A1 (en) * | 1976-09-01 | 1978-03-02 | Dynamit Nobel Ag | Suspension polymerisation of vinyl! chloride - with catalyst addn. between initiation and polymerisation temps., to reduce crust formation |
-
1980
- 1980-06-16 JP JP8114980A patent/JPS575704A/en active Granted
-
1981
- 1981-06-10 DE DE19813123015 patent/DE3123015A1/en active Granted
- 1981-06-11 IT IT22256/81A patent/IT1137251B/en active
- 1981-06-12 GB GB8118207A patent/GB2078237B/en not_active Expired
- 1981-06-15 BE BE889218A patent/BE889218A/en not_active IP Right Cessation
- 1981-06-15 FR FR8111724A patent/FR2484420A1/en active Granted
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0129803A2 (en) * | 1983-06-23 | 1985-01-02 | Occidental Chemical Corporation | Novel polyvinyl chloride suspension polymerization process |
EP0129803A3 (en) * | 1983-06-23 | 1986-06-11 | Occidental Chemical Corporation | Novel polyvinyl chloride suspension polymerization process |
Also Published As
Publication number | Publication date |
---|---|
BE889218A (en) | 1981-10-01 |
DE3123015A1 (en) | 1982-04-22 |
IT8122256A0 (en) | 1981-06-11 |
GB2078237B (en) | 1984-07-25 |
FR2484420B1 (en) | 1983-04-15 |
JPS6239601B2 (en) | 1987-08-24 |
JPS575704A (en) | 1982-01-12 |
IT1137251B (en) | 1986-09-03 |
DE3123015C2 (en) | 1992-11-05 |
FR2484420A1 (en) | 1981-12-18 |
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Legal Events
Date | Code | Title | Description |
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711A | Proceeding under section 117(1) patents act 1977 | ||
PE20 | Patent expired after termination of 20 years |
Effective date: 20010611 |