DE1227236B - Process for the production of copolymers from vinyl chloride and esters of unsaturated carboxylic acids - Google Patents
Process for the production of copolymers from vinyl chloride and esters of unsaturated carboxylic acidsInfo
- Publication number
- DE1227236B DE1227236B DED41772A DED0041772A DE1227236B DE 1227236 B DE1227236 B DE 1227236B DE D41772 A DED41772 A DE D41772A DE D0041772 A DED0041772 A DE D0041772A DE 1227236 B DE1227236 B DE 1227236B
- Authority
- DE
- Germany
- Prior art keywords
- vinyl chloride
- copolymers
- hydrogen peroxide
- water
- chloride
- 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.)
- Pending
Links
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims description 14
- 229920001577 copolymer Polymers 0.000 title claims description 9
- 238000000034 method Methods 0.000 title claims description 7
- 150000002148 esters Chemical class 0.000 title claims description 4
- 238000004519 manufacturing process Methods 0.000 title description 5
- 150000001735 carboxylic acids Chemical class 0.000 title description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims description 6
- 150000002978 peroxides Chemical class 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- CSKNSYBAZOQPLR-UHFFFAOYSA-N benzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC=C1 CSKNSYBAZOQPLR-UHFFFAOYSA-N 0.000 claims description 4
- 150000004820 halides Chemical class 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000007900 aqueous suspension Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- -1 ethylhexyl ester Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011049 pearl Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
-
- 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
-
- 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
- C08F214/00—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
- C08F214/02—Monomers containing chlorine
- C08F214/04—Monomers containing two carbon atoms
- C08F214/06—Vinyl chloride
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/28—Oxygen or compounds releasing free oxygen
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polymerization Catalysts (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
DEUTSCHESGERMAN
PATENTAMTPATENT OFFICE
AUSLEGESCHRIFTEDITORIAL
Int, CL:Int, CL:
C08fC08f
Deutsche Kl.: 39 c-25/01 German class: 39 c -25/01
Nummer: 1227 236Number: 1227 236
Aktenzeichen: D 41772IV d/39 cFile number: D 41772IV d / 39 c
Anmeldetag: 15. Juni 1963Filing date: June 15, 1963
Auslegetag: 20. Oktober 1966Opened on: October 20, 1966
Es ist bereits bekannt, daß bei der Suspensionspolymerisation von Vinylchlorid mit öllöslichen Katalysatoren aus ungleichmäßigen porösen Körpern bestehende Produkte entstehen. Stellt man jedoch Mischpolymerisate des Vinylchlorids her, so fallen die Produkte vielfach nicht in Form solcher porösen Partikeln an. Beispielsweise verschwindet diese Teilchenform bei der Mischpolymerisation von Vinylchlorid mit ungesättigten Monocarbonsäureestern '■'■·' oder ungesättigten α,^-Diearbonsäureestern im Maße ίο der Verminderung des Vinylchloridanteils. --···;.It is already known that the suspension polymerization of vinyl chloride with oil-soluble catalysts results in products consisting of non-uniform porous bodies. If, however, copolymers of vinyl chloride are produced, the products are often not obtained in the form of such porous particles. For example, this particle disappears during the copolymerization of vinyl chloride with unsaturated Monocarbonsäureestern '■' ■ * 'or unsaturated α, ^ - Diearbonsäureestern the extent ίο the reduction of vinyl chloride content. - ··· ;.
Gerade im interessanten Gebiet, bei Anteilen von Vinylchlorid zwischen 80 und 95 %> entstehen Polymerisatkörner, die rund oder länglich sein können, aber eine glatte Oberfläche besitzen. Der Nachteil eines solchen Granulats liegt darin, daß die Aufnahmefähigkeit für Zusatzstoffe vor der Verarbeitung, wie z. B. Stabilisatoren, sehr gering ist.Especially in the interesting area, with a proportion of vinyl chloride between 80 and 95%> the result is polymer grains that can be round or elongated, but have a smooth surface. The disadvantage of such a granulate lies in the fact that the absorption capacity for additives before processing, such as B. stabilizers, is very low.
Es wurde nun gefunden, daß man bei Wahl bestimmter Katalysatoren die Polymerisate als poröses, ao ungleichmäßiges Granulat erhalten kann.It has now been found that if certain catalysts are chosen, the polymers can be used as porous, ao may get uneven granules.
Gegenstand der Erfindung ist ein Verfahren zur Herstellung von Mischpolymerisaten aus Vinylchlorid und Estern ungesättigter Carbonsäuren, besonders «,^-ungesättigter Carbonsäuren, durch Mischpolymerisation der Monomeren in wäßriger Suspension in Gegenwart einer basischen Substanz und eines ein wasserlösliches Peroxyd, besonders Wasserstoffsuperoxyd, enthaltenden Katalysators, das dadurch gekennzeichnet ist, daß man einen Katalysator verwendet, der aus einem wasserlöslichen Peroxyd und einem Säurehalogenid, besonders Sulfurylchlorid oder Benzolsulfochlorid, besteht.The invention relates to a process for the production of copolymers from vinyl chloride and esters of unsaturated carboxylic acids, especially «, ^ - unsaturated carboxylic acids, by copolymerization of the monomers in aqueous suspension in the presence of a basic substance and one Catalyst containing water-soluble peroxide, especially hydrogen peroxide, characterized in that is that a catalyst is used, which consists of a water-soluble peroxide and a Acid halide, especially sulfuryl chloride or benzenesulfochloride, consists.
Der erfindungsgemäß verwendete Katalysator setzt sich aus einem wasserlöslichen Peioxyd und einem Säurehalogenid zusammen. Außerdem muß dem Polymerisationsgemisch eine basische Substanz, z. B. Erdalkalihydroxyd oder Alkalicarbonat, zugegeben werden. Es werden z. B. Mischungen aus Wasserstoffsuperoxyd und Sulfurylchlorid sowie Calciumhydroxyd oder Natriumcarbonat eingesetzt. Dabei verwendet man vorzugsweise Wasserstoffperoxyd und Säurehalogenid in molaren Verhältnissen zwischen 2:1 und 4:1, während die Menge der basischen Substanz etwa 1 bis 6 Äquivalente in bezug auf das abspaltbare Halogen des Säurechlorids beträgt.The catalyst used according to the invention is composed of a water-soluble peioxide and a Acid halide together. In addition, the polymerization mixture must contain a basic substance, e.g. B. Alkaline earth hydroxide or alkali carbonate, may be added. There are z. B. Mixtures of hydrogen peroxide and sulfuryl chloride and calcium hydroxide or sodium carbonate are used. Used in this hydrogen peroxide and acid halide are preferably used in molar ratios between 2: 1 and 4: 1, while the amount of the basic substance is about 1 to 6 equivalents with respect to the cleavable Halogen of the acid chloride.
Die Polymerisation wird dabei in einem wäßrigen Medium als Dispergiermittel durchgeführt, die Temperatur richtet sich nach der Reaktionsfähigkeit der Monomeren. Die eingesetzten Mengen an Wasserstoffsuperoxyd (30 Gewichtsprozent) betragen im allgemeinen weniger als 0,5 Gewichtsprozent der Mono-Verfahren zur Herstellung von Mischpolymerisaten aus Vinylchlorid und Estern ungesättigter CarbonsäurenThe polymerization is carried out in an aqueous medium as a dispersant, the temperature depends on the reactivity of the monomers. The amounts of hydrogen peroxide used (30 percent by weight) are generally less than 0.5 percent by weight of the mono processes for the production of copolymers from vinyl chloride and esters unsaturated carboxylic acids
Anmelder:Applicant:
Deutsche Solvay-WerkeGerman Solvay works
Gesellschaft mit. beschränkter Haftung,Society with. limited liability,
Solingen-Ohligs .-< . ; ·, . '.·-..r \: ..'.Solingen-Ohligs .- <. ; ·,. '. · - .. r \: ..'.
Als Erfinder benannt:Named as inventor:
Dr.-Ing. Gerhard Faerber, Rheinberg (RhId.)Dr.-Ing. Gerhard Faerber, Rheinberg (RhId.)
meren und liegen am zweckmäßigsten zwischen etwa 0,1 und 0,5%.mers and are most suitably between about 0.1 and 0.5%.
Bei Verwendung von Wasserstoffsuperoxyd allein erhält man in unvollständiger Reaktion nur geringe Mengen eines klebrigen Produktes.If only hydrogen peroxide is used, only a small amount is obtained in an incomplete reaction Amounts of a sticky product.
Vergleichsversuch:Comparative experiment:
Herstellung eines glatten Perlpolymerisates mitProduction of a smooth bead polymer with
15 Gewichtsprozent Acrylsäureäthylhexylester nach15 percent by weight of ethylhexyl acrylate
bekanntem Verfahrenknown method
In einem 3-1-Edelstahlautoklav werden in einer Mischung von 425 g Vinylchlorid und 75 g Acrylsäureäthylhexylester 4 g Lauroylperoxyd durch Umrühren aufgelöst. Dann wird eine Lösung von 1500 g entmineralisiertem Wasser mit 4,5 g teilacetyliertem Polyvinylalkohol und einigen Tropfen Siliconöl zugedrückt. Es wird auf 55° C aufgeheizt. Wenn der Innendruck auf 2 atü abgefallen ist, gilt die Polymerisation als beendet. Das gebildete Polymerisat besteht aus glatten Perlen.In a 3-1 stainless steel autoclave, in a Mixture of 425 g of vinyl chloride and 75 g of ethylhexyl acrylate and 4 g of lauroyl peroxide by stirring dissolved. Then a solution of 1500 g of demineralized water with 4.5 g of partially acetylated Squeeze polyvinyl alcohol and a few drops of silicone oil. It is heated to 55 ° C. If the The internal pressure has dropped to 2 atmospheres, the polymerization is considered to have ended. The polymer formed exists made of smooth pearls.
Herstellung eines Mischpolymeiisates mit poröser StrukturProduction of a mixed polymer with a porous structure
1. Zu einer Lösung von 1500 g Wasser mit 4,5 g teilacetyliertem Polyvinylalkohol und einigen Tropfen Siliconöl in einem 3-1-Edelstahlautoklav werden gegeben: 816 mg Wasserstoffsuperoxyd (30°/oig), 173 mg Siliconöl in einem 3-1-Edelstahlautoklav werden Calciumhydroxyd und 270 mg Sulfurylchlorid. Dann wird verschlossen, der Sauerstoff entfernt und eine Mischung von 425 g Vinylchlorid und 75 g Acrylsäure-1. To a solution of 1500 g water with 4.5 g teilacetyliertem polyvinyl alcohol and a few drops of silicone oil in a 3-1 stainless steel autoclave are placed: 816 mg of hydrogen peroxide (30 ° / o solution), 173 mg of silicone oil in a 3-1- A stainless steel autoclave uses calcium hydroxide and 270 mg sulfuryl chloride. Then it is closed, the oxygen is removed and a mixture of 425 g vinyl chloride and 75 g acrylic acid
■ Ϊ, Ui■ Ϊ, Ui
609 707/409609 707/409
äthylhexylester zugedrückt. Die Polymerisation wird bei 55 0C durchgeführt. Das- entstehende Mischpolymerisat stellt ein poröses Granulat dar.ethylhexyl ester pressed. The polymerization is carried out at 55 0 C. The resulting copolymer is a porous granulate.
2. Zu einer Lösung von 1500 g Wasser mit 4,5 g teilacetyliertem Polyvinylalkohol werden gegeben: 1,34 g Natriumcarbonat (10H2O), 1,632 g-Wasserstoffsuperoxyd (30%) und 540 mg Sulfurylchlorid. Der Autoklav wird verschlossen und der Luftsauerstoff entfernt. Dann werden nacheinander 425 .g Vinylchlorid und 75 gAcrylsäureäthylhexylester zugedrückt. Die Polymerisationstemperatur ist 55° C, wobei man durch Rühren eine Suspension aufrechterhält. Nach 21 Stunden ist der Druck auf 2 atü gefallen. Die erhaltenen 445 g Mischpolymerisat bestehen aus porösen Teilchen.2. To a solution of 1500 g of water with 4.5 g of partially acetylated polyvinyl alcohol are added: 1.34 g of sodium carbonate (10H 2 O), 1.632 g of hydrogen peroxide (30%) and 540 mg of sulfuryl chloride. The autoclave is closed and the atmospheric oxygen is removed. Then 425 g of vinyl chloride and 75 g of ethylhexyl acrylate are pressed in one after the other. The polymerization temperature is 55 ° C., a suspension being maintained by stirring. After 21 hours the pressure has dropped to 2 atmospheres. The 445 g of copolymer obtained consist of porous particles.
3. In einem 3-1-Edelstahlautoklav werden zu einer Lösung von 1500 g Wasser und 4,5 g teilacetyliertem Polyvinylalkohol nacheinander zugefügt: 1,412 g Benzolsulfochlorid, 0,312 g Ca(OH)2 und 1,890 g H2O2 (30%ig)· Dann wird der Autoklav verschlossen, das Rührwerk in Gang gesetzt und der Sauerstoff durch Spülen mit Stickstoff entfernt. Nach Eindrücken einer Mischung aus 425 g Vinylchlorid und 75 g Acrylsäurebutylester wird auf 55° C aufgeheizt. Nach etwa 18 Stunden ist die Polymerisation beendet. Es haben sich 475 g eines Mischpolymerisates mit etwa 14% Acrylsäurebutylester gebildet von stark poröser Struktur.3. In a 3-1 stainless steel autoclave, the following are added in succession to a solution of 1500 g water and 4.5 g partially acetylated polyvinyl alcohol: 1.412 g benzene sulfochloride, 0.312 g Ca (OH) 2 and 1.890 g H 2 O 2 (30%) · The autoclave is then closed, the stirrer started and the oxygen removed by purging with nitrogen. After a mixture of 425 g of vinyl chloride and 75 g of butyl acrylate has been pressed in, the mixture is heated to 55.degree. The polymerization has ended after about 18 hours. 475 g of a copolymer with about 14% butyl acrylate have formed and have a highly porous structure.
Claims (3)
Deutsche Auslegeschriften Nr. 1100 958, 1110 872.Considered publications:
German Auslegeschriften No. 1100 958, 1110 872.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DED41772A DE1227236B (en) | 1963-06-15 | 1963-06-15 | Process for the production of copolymers from vinyl chloride and esters of unsaturated carboxylic acids |
| FR977209A FR1411049A (en) | 1963-06-15 | 1964-06-05 | Process for the preparation of polymers, in particular of vinyl chloride |
| GB2391564A GB1025719A (en) | 1963-06-15 | 1964-06-09 | Polymerisation process |
| BE649045D BE649045A (en) | 1963-06-15 | 1964-06-10 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DED41772A DE1227236B (en) | 1963-06-15 | 1963-06-15 | Process for the production of copolymers from vinyl chloride and esters of unsaturated carboxylic acids |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1227236B true DE1227236B (en) | 1966-10-20 |
Family
ID=7046312
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DED41772A Pending DE1227236B (en) | 1963-06-15 | 1963-06-15 | Process for the production of copolymers from vinyl chloride and esters of unsaturated carboxylic acids |
Country Status (3)
| Country | Link |
|---|---|
| BE (1) | BE649045A (en) |
| DE (1) | DE1227236B (en) |
| GB (1) | GB1025719A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109467633A (en) * | 2018-10-10 | 2019-03-15 | 中国石油化工股份有限公司 | A kind of preparation method of vinyl chloride-acrylate copolymer |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4952650A (en) * | 1987-07-27 | 1990-08-28 | Minnesota Mining And Manufacturing Company | Suspension polymerization |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1100958B (en) * | 1959-08-01 | 1961-03-02 | Hoechst Ag | Process for the production of polymer dispersions |
| DE1110872B (en) * | 1956-04-09 | 1961-07-13 | Us Rubber Co | Process for the preparation of stable aqueous dispersions of copolymers containing vinyl chloride and maleic acid dialkyl ester |
-
1963
- 1963-06-15 DE DED41772A patent/DE1227236B/en active Pending
-
1964
- 1964-06-09 GB GB2391564A patent/GB1025719A/en not_active Expired
- 1964-06-10 BE BE649045D patent/BE649045A/xx unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1110872B (en) * | 1956-04-09 | 1961-07-13 | Us Rubber Co | Process for the preparation of stable aqueous dispersions of copolymers containing vinyl chloride and maleic acid dialkyl ester |
| DE1100958B (en) * | 1959-08-01 | 1961-03-02 | Hoechst Ag | Process for the production of polymer dispersions |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109467633A (en) * | 2018-10-10 | 2019-03-15 | 中国石油化工股份有限公司 | A kind of preparation method of vinyl chloride-acrylate copolymer |
| CN109467633B (en) * | 2018-10-10 | 2022-04-08 | 中国石油化工股份有限公司 | Preparation method of vinyl chloride-acrylate copolymer |
Also Published As
| Publication number | Publication date |
|---|---|
| BE649045A (en) | 1964-10-01 |
| GB1025719A (en) | 1966-04-14 |
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