GB2035339A - Chemical reactors - Google Patents
Chemical reactors Download PDFInfo
- Publication number
- GB2035339A GB2035339A GB7913051A GB7913051A GB2035339A GB 2035339 A GB2035339 A GB 2035339A GB 7913051 A GB7913051 A GB 7913051A GB 7913051 A GB7913051 A GB 7913051A GB 2035339 A GB2035339 A GB 2035339A
- Authority
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- United Kingdom
- Prior art keywords
- ethylene
- vinyl
- vinyl acetate
- process according
- sodium
- 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.)
- Granted
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- 239000000126 substance Substances 0.000 title claims abstract description 10
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 26
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000005977 Ethylene Substances 0.000 claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 13
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 7
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 6
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 10
- 229920001038 ethylene copolymer Polymers 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000012429 reaction media Substances 0.000 claims description 2
- 229920001567 vinyl ester resin Polymers 0.000 claims description 2
- 229920001897 terpolymer Polymers 0.000 claims 1
- 239000000853 adhesive Substances 0.000 abstract description 4
- 230000001070 adhesive effect Effects 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 3
- 239000003973 paint Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 description 23
- 238000006116 polymerization reaction Methods 0.000 description 14
- 239000004160 Ammonium persulphate Substances 0.000 description 11
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 11
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 11
- 235000019395 ammonium persulphate Nutrition 0.000 description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- 239000003999 initiator Substances 0.000 description 7
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 7
- 235000010262 sodium metabisulphite Nutrition 0.000 description 7
- 239000004296 sodium metabisulphite Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000000872 buffer Substances 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 3
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 3
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- FKHNQSIOGWGQNY-UHFFFAOYSA-L [Na+].[Na+].[O-]S[O-] Chemical compound [Na+].[Na+].[O-]S[O-] FKHNQSIOGWGQNY-UHFFFAOYSA-L 0.000 description 3
- ALSTYHKOOCGGFT-UHFFFAOYSA-N cis-oleyl alcohol Natural products CCCCCCCCC=CCCCCCCCCO ALSTYHKOOCGGFT-UHFFFAOYSA-N 0.000 description 3
- 229940071826 hydroxyethyl cellulose Drugs 0.000 description 3
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 3
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- AKUNSTOMHUXJOZ-UHFFFAOYSA-N 1-hydroperoxybutane Chemical compound CCCCOO AKUNSTOMHUXJOZ-UHFFFAOYSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004159 Potassium persulphate Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- -1 ethylene, propylene, butene Chemical class 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- XULSCZPZVQIMFM-IPZQJPLYSA-N odevixibat Chemical compound C12=CC(SC)=C(OCC(=O)N[C@@H](C(=O)N[C@@H](CC)C(O)=O)C=3C=CC(O)=CC=3)C=C2S(=O)(=O)NC(CCCC)(CCCC)CN1C1=CC=CC=C1 XULSCZPZVQIMFM-IPZQJPLYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000028016 temperature homeostasis Effects 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/2415—Tubular reactors
- B01J19/2435—Loop-type reactors
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
A chemical reactor in the form of a closed loop has a section comprising a bundle of tubes leading back to a circulating pump. This is particularly suitable for polymerizing vinyl monomers. Polymeric dispersions so obtained from vinyl acetate alone or with ethylene or with ethylene and vinyl chloride give excellent adhesives, paints and surface coatings for paper. <IMAGE>
Description
SPECIFICATION
Chemical reactors
Description
The invention relates to chemical reactors suitable for polymerizing vinyl monomers, and is a development from our UK Patent Specification 1,482,148.
The invention provides a chemical reactor in the form of a closed loop comprising a number of sections detachably connected in sequence, the said sections comprising a pump for circulating reaction medium around the loop, a delivery section, a central section, and a further section comprising a bundle of tubes leading back to the pump.
The invention includes a process of polymerizing an unsaturated ester or vinyl monomer which is carried out in a chemical reactor according to the invention. The polymeric dispersions so produced from vinyl acetate or from a mixture thereof with ethylene or with ethylene and vinyl chloride have several advantages:
For employment in adhesives, a high adhesion and cohesive power which permit good performance within a wide range of temperatures; in water-soluble paints, a high resistance of the film to water and to alkalis; in the surface coating of paper, great smoothness and good printing characteristics.
Drawing:
Figure 1 shows a multitube reactor according to the invention: A chemical reactor 3 is in the overall form of a closed loop or annular tube, and comprises a number of sections detachably connected in sequence. The sections comprise a circulation pump 1 leading to the left into a delivery section. This is followed by a shorter central section at the top of the drawing, and a further section comprising a bundle of tubes leading back to the pump. The delivery and further sections are each provided with a thermoregulation jacket 2 having an inlet 6 and an outlet 6' forthermoregulating fluid. The reactor 3 has reagent inlets 5, 5' and outlets 4,4'.
The tube bundle makes it possible to have any desired height/width ratio for the loop; and a volume of the delivery section (the left hand vertical section and half of the lower horizontal section) smaller than 5% of the total reactor volume.
By the process of the invention it is possible to polymerize ethylenically unsaturated monomers, especially liquid and/or gaseous vinyl monomers. It is possible to copolymerize vinyl esters, for example vinyl acetate, propionate, butyrate or benzoate, or methyl, ethyl, butyl or octyl acrylate, or acrylic acid or styrene, with gaseous ethylenically unsaturated comonomers for example vinyl chloride, ethylene, propylene, butene, hexene or a mixture of two or more olefins having from 2 to 6 carbon atoms in the molecule.
Most advantageously, it is possible to prepare vinyl acetate/ethylene copolymers containing from 5 to 50% by weight of ethylene. Very interesting too - due to the properties of the products obtained - is the preparation of vinyl acetate/ethylene/vinyl chloride copolymers, containing from 5 to 40% by weight of ethylene and from 5 to 40% by weight of vinyl chloride, as well as the preparation of vinyl acetate/ethylene copolymers modified with a low percentage of copolymerized acrylic acid.
As catalysts it is possible to use the usual water-soluble initiators, such as potassium or ammonium persulphate, hydrogen peroxide, t.butyl-hydroperoxide, either alone or in a redox system with a reducing agent, for example sodium metabisulphite, ascorbic acid, an amine, or sodium sulphoxylate.
As protecting and thickening colloids it is possible to use the usual water-soluble products, both natural and synthetic: cellulose derivatives, polyvinyl alcohols of different molecular weight and hydrolysis degree, polyacrylamides, polyurethanes, sodium alginate.
As emulsifiers one can use, either individually or in combination with one another, the known commercial surfactants, both ionogenic and non-ionogenic.
The operating pressure may be from 1 to 300 kg/cm2 gauge, depending on the amoung of gaseous comonomer to be fixed. The reaction temperature may be from 10 to 1 50"C, preferably from 20 to 900C, depending on the operating technique and on the catalytic system utilized.
The following Examples are of discontinous polymerization in emulsion. The percentages in the Examples and in the Table below recording the properties of the products are by weight.
Example 1
Preparation of a vinyl acetate/ethylene copolymer
A "polymerization foot" consisting of: vinyl acetate 13.4 kg water 112.0 kg sodium vinyl-sulphonate 1.2 kg 10% aqueous solution of polyvinyl alcohol (Vinavilol 42-88 to Montedison) 10.6 kg sodium dodecylbenzene sulphonate 1.9 kg was introduced into a multitube 345 litre reactor as in the drawing having a tube bundle consisting of six tubes and including a rotary pump. After having flushed the reactor with an inert gas, ethylene was compressed into the reactor up to a pressure of 20 kg/cm' gauge, and this pressure level was maintained throughout the reaction by continuously feeding ethylene as it was consumed.A mass temperature of 55"C and at a liquid circulation flowrate of 15 m3/h were maintained throughout the reaction, the following 10% aqueous solutions of initiators and buffer were introduced: ammonium persulphate 1.6 kg sodium bicabonate 1.6 kg sodium metabisulphite 3.2 kg
After the reaction starting, 116 kg of vinyl acetate containing the solution 4.4 g of a condensate of ethylene oxide with oleic alcohol were injected during 5 hours. During the same period, the following 10% aqueous solutions of initiators and buffer were introduced: ammonium persulphate 7.5 kg sodium bicarbonate 7.5 kg sodium metabisulphite 16.0 kg
Polymerization was continued for 2 hours to finish the reaction and convert the last traces of monomer.
Example 2
Preparation of a vinyl acetate/ethylene copolymer.
Apparatus, operative technique and charge doses were the same as in Example 1, with the only exception that the polymerization foot had the following composition: vinyl acetate 14.4 kg water 112.0 kg sodium vinyl sulphonate 0.6 kg hydroxy-ethyl-cellulose having a mean molecular weight 0.8 kg dodecyl-benzene-sulphonicacid 0.6 kg sodium carbonate 0.12 kg
Example 3
Preparation of a vinyl acetate/vinyl chloride/ethylene copolymer.
A "polymerization foot" consisting of: vinyl acetate 10.2 kg vinyl chloride 4.2 kg water 112.0 kg sodium vinyl sulphonate 0.6 kg hydroxy-ethyl-cellulose having a mean molecular weight 0.8 kg 10% aqueous solution of polyvinyl alcohol (Vinavilol 42-88 of Montedison) 3.0 kg dodecyl-benzene-sulphonic acid 0.6 kg sodium carbonate 0.12 kg was introduced into the same multitube reactor used in Example 1. After flushing of the reactor with an inert gas, ethylene was compressed into the reactor up to a pressure of 30 kg/cm2 gauge, and this pressure was maintained throughout by continuously feeding ethylene as it was consumed. The reaction mixture was thermoregulated to 55"C and was circulated at a recycling pump flowrate of 15 m3/h.The following 10% aqueous solutions of initiators and of buffer were then introduced: ammonium persulphate 16 kg sodium bicarbonate 16 kg sodium sulphoxylate 3.2 kg
After the reaction starting, 83 kg of vinyl acetate containing in solution 4.4 g of a condensate of ethylene oxide with oleic alcohol and 34 kg of vinyl chloride were injected during 4.5 hours. Contemporaneously with the monomers, the following 10% aqueous solutions were introduced: ammonium persulphate 7.5 kg sodium bicarbonate 7.5 kg sodium sulphoxylate 16.0 kg
Polymerization was continued for 2 hours to finish the reaction and convert the last traces of monomer.
Example 4
Preparation of a vinyl acetate/ethylene copolymer.
Copolymerization of vi nyl acetate with ethylene was carried out as in Example 1 but with the following reagents and conditions.
a) Polymerization foot: vinyl acetate 12 kg water 100 kg sodium vinylsulphonate 0.9 kg sodium carbonate 0.06 kg formic acid 0.012 kg 10% aqueous solution of polyvinyl alcohol (Vinavilol 20-88 of Montedison 4.8 kg sodium dodecyl-benzene-sulphonate 0.3 kg b) Polymerization temperature 43-44"C c) Ethylene pressure 40 kg/cm2 gauge d) Initiators for starting the polymerization: 10% aqueous solution of ammonium persulphate 6.5 kg 10% aqueous solution of sodium metabisulphite 1.8 kg 3) Regularfeedduring 5.5 hours of: vinyl acetate 108 kg 10% aqueous solution of ammonium persulphate 10.5 kg 10% aqueous solution of sodium metabisulphite 13.0 kg 30% aqueous solution of a condensate of oleic acid with ethylene oxide 12.5 kg f) Finishing: 2 hours to convert the unreacted monomers.
g) Buffer (added at the conclusion ofthe reaction): aqueous solution at 5% of sodium bicarbonate 7 kg.
Example5
Preparation of a vinyl acetate/ethylene copolymer.
Copolymerization of vinyl acetate with ethylene was carried out as in Example 1 but the following reagents and conditions: a) Polymerization foot: vinyl acetate 11 kg water 115 kg sodium carbonate 0.4 kg 10% aqueous solution of polyvinyl alcohol (Vinavilol 42-88 of Montedison) 1.1 kg hydroxy-ethyl-cellulose having a mean viscosity 1.0 kg alkylphenol-polyoxyethylene sulphate 0.5 kg b) Reaction temperature 78"C c) Ethylene pressure 50 kg/cm2 gauge d) Initiator for starting the polymerization: 5% aqueous solution of ammonium persulphate 8.6 kg e) Feed during 4.5 hours at a constant flowrate of: vinyl acetate 100 kg 10% aqueous solution of ammonium persulphate 4.5 kg 25% aqueous solution of alkylphenolpolyoxyethylene sulphate 17.5 kg f) Finishing: 1.5 hours to convert the residual monomers.
Example 6
Preparation of a vinyl acetatelethylene copolyer modified with acrylic acid.
Copoymerization was carried out as in Example 1 but with the following reagents and conditions: a) Polymerization foot: vinyl acetate 6.2 kg water 95 kg 25% aqueous solution of sodium vinyl sulphonate 2.5 kg sodium carbonate 0.120 kg sodium dodecyl-benzene sulphonate 0.6 kg condensate of oleic alcohol with ethylene oxide 2.3 kg b) Polymerization temperature 63"C c) Ethylene pressure 30 kg/cm2 gauge d) Initiators for starting the polymerization: 10% aqueous solution of ammonium persulphate 5.0 kg 10% aqueous solution of sodium metabisulphite 6.0 kg e) Feed during 5 hours at a constant flowrate of: vinyl acetate 118 kg acrylic acid 3.8 kg 10% aqueous solution of ammonium persulphate 12.5 kg 10% aqueous solution of sodium metabisulphite 15.0 kg f) Finishing: 30 minutes to convert the last traces of monomers.
g) Buffer (introduced during the cooling): 10% aqueous solution of sodium bicarbonate 11.0 kg
TABLE
Example 1 2 3 4 5 6
Ethylene content in the copolymer% 14 14 15 20 25 15
Vinyl chloride content in the copolymer - - 25 Brookfield viscosity RVT at 20"C, 20 rpm cP 3500 200 3500 15000 4500 150 Intrinsic viscosity d1/g 1.8 1.9 1.7 1.8 0.7 0.9
Minimum film-forming temperature C +4 +4 +18 < 0 < 0 0
Average diameter of the particles p 0.15 0.15 0.10 0.8 0.45 < 0.10
Elongation at break of the film (23 C,50% of relative humidity) 710 700 400 750 > 1000 800
Tensile strength of the film 23"C 50% of relative humidity) kg/cm2 90 95 150 100 < 50 110
Resistance to alkalis (N/10 NaOH) ofthefilmofapaint% 100 100 100
Gardner abrasion of the paint film number of cycles 1100 1200 1200
PVC/wood adhesive power (at low, mean, high temperature) - global evaluation Excel-
lent
Plastics/paper adhesive powerglobal evaluation - excel
lent
LARSEN retention of the coat: ejected liquid ml 6.5
Heliotest (printing at 10 kg/cm of coated paper with the dispersion of the example) cm 6.2
Claims (8)
1. A chemical reactor in the form of a closed loop comprising a number of sections detachably connected in sequence, the said sections comprising a pump for circulating reaction medium around the loop, a delivery section, a central section, and a further section comprising a bundle of tubes leading back to the pump.
2. A chemical reactor as herein descibed with reference to the drawing.
3. A process of polymerizing an unsaturated ester or vinyl monomer which is carried out in a chemical reactor according to claim 1 or claim 2.
4. A process according to claim 3 in which a mixture of a vinyl ester with an ethylenically unsaturated gaseous monomer is polymerized.
5. A process according to claim 3 in which vinyl acetate/ethylene copolymers containing from 5 to 50% by weight of ethylene are prepared.
6. A process according to claim 3 in which vinyl acetate/ethylene/vinyl chloride terpolymers containing from 5 to 40% by weight of ethylene and 5 to 40% by weight of vinyl chloride are prepared.
7. A process according to claim 5 in which vinyl acetate/ethylene copolymers modified with a low percentage of copolymerized acrylic acid are prepared.
8. A copolymer prepared by a process according to any of claims 3 to 7.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT22644/78A IT1094930B (en) | 1978-04-24 | 1978-04-24 | PRESSURE POLYMERIZATION PROCEDURE IN ANOLAR TYPE EQUIPMENT |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2035339A true GB2035339A (en) | 1980-06-18 |
| GB2035339B GB2035339B (en) | 1982-09-22 |
Family
ID=11198775
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB7913051A Expired GB2035339B (en) | 1978-04-24 | 1979-04-12 | Chemical reactors |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS54155291A (en) |
| BE (1) | BE875777A (en) |
| DE (1) | DE2916556A1 (en) |
| FR (1) | FR2424287A1 (en) |
| GB (1) | GB2035339B (en) |
| IT (1) | IT1094930B (en) |
| NL (1) | NL186387C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0417893A1 (en) * | 1989-08-08 | 1991-03-20 | Crown Berger Limited | Polymerisation processes and reactors |
| EP1329259A2 (en) * | 2002-01-17 | 2003-07-23 | MERCK PATENT GmbH | Continuous method for hydrolysis of a solvent containing organic compound |
| CN1296392C (en) * | 2004-04-02 | 2007-01-24 | 北京化工大学 | Circulating tube tyre reactor and method for synthesizing acrylic copolymer emulsion |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4120203A1 (en) * | 1991-06-19 | 1992-12-24 | Basf Ag | METHOD FOR PRODUCING IMPACT POLYSTYRENE |
| DE19540645A1 (en) * | 1995-10-31 | 1997-05-07 | Basf Ag | Process and device for the continuous production of N-acylaminocarboxylic acids and N-acylaminosulfonic acids and their alkali metal salts |
| DE19640793A1 (en) * | 1996-10-02 | 1998-04-16 | Basf Ag | Method and device for the production of homopolymers and copolymers in emulsion polymerization technology |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1720524A1 (en) * | 1967-12-20 | 1971-07-08 | Dynamit Nobel Ag | Process for the continuous polymerization and copolymerization in emulsion of vinylidene, vinyl and / or acrylic compounds |
| NL181435B (en) * | 1973-10-17 | 1900-01-01 | Montedison Spa | PROCESS FOR POLYMERIZATION UNDER PRESSURE IN A TUBULAR REACTOR. |
-
1978
- 1978-04-24 IT IT22644/78A patent/IT1094930B/en active
-
1979
- 1979-04-12 GB GB7913051A patent/GB2035339B/en not_active Expired
- 1979-04-19 NL NLAANVRAGE7903087,A patent/NL186387C/en not_active IP Right Cessation
- 1979-04-23 BE BE0/194771A patent/BE875777A/en not_active IP Right Cessation
- 1979-04-23 JP JP4917179A patent/JPS54155291A/en active Granted
- 1979-04-24 DE DE19792916556 patent/DE2916556A1/en active Granted
- 1979-04-24 FR FR7910340A patent/FR2424287A1/en active Granted
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0417893A1 (en) * | 1989-08-08 | 1991-03-20 | Crown Berger Limited | Polymerisation processes and reactors |
| AU626706B2 (en) * | 1989-08-08 | 1992-08-06 | Crown Berger Europe Limited | Polymerisation processes and reactors |
| EP1329259A2 (en) * | 2002-01-17 | 2003-07-23 | MERCK PATENT GmbH | Continuous method for hydrolysis of a solvent containing organic compound |
| EP1329259A3 (en) * | 2002-01-17 | 2006-01-04 | MERCK PATENT GmbH | Continuous method for hydrolysis of a solvent containing organic compound |
| CN1296392C (en) * | 2004-04-02 | 2007-01-24 | 北京化工大学 | Circulating tube tyre reactor and method for synthesizing acrylic copolymer emulsion |
Also Published As
| Publication number | Publication date |
|---|---|
| NL186387C (en) | 1990-11-16 |
| JPS54155291A (en) | 1979-12-07 |
| DE2916556A1 (en) | 1979-10-31 |
| IT7822644A0 (en) | 1978-04-24 |
| NL7903087A (en) | 1979-10-26 |
| NL186387B (en) | 1990-06-18 |
| DE2916556C2 (en) | 1988-03-24 |
| BE875777A (en) | 1979-10-23 |
| GB2035339B (en) | 1982-09-22 |
| FR2424287A1 (en) | 1979-11-23 |
| JPH0321561B2 (en) | 1991-03-25 |
| FR2424287B1 (en) | 1981-12-18 |
| IT1094930B (en) | 1985-08-10 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 732 | Registration of transactions, instruments or events in the register (sect. 32/1977) | ||
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19940412 |