CH492744A - Ethylene-glycidyl acrylate copolymer useful for the - Google Patents
Ethylene-glycidyl acrylate copolymer useful for theInfo
- Publication number
- CH492744A CH492744A CH430868A CH430868A CH492744A CH 492744 A CH492744 A CH 492744A CH 430868 A CH430868 A CH 430868A CH 430868 A CH430868 A CH 430868A CH 492744 A CH492744 A CH 492744A
- Authority
- CH
- Switzerland
- Prior art keywords
- ethylene
- copolymer
- glycidyl
- copolymers
- glycidyl ester
- Prior art date
Links
- 229920001577 copolymer Polymers 0.000 title claims abstract description 25
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000005977 Ethylene Substances 0.000 claims abstract description 15
- -1 glycidyl ester Chemical class 0.000 claims abstract description 9
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical group CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 4
- 239000002685 polymerization catalyst Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000010526 radical polymerization reaction Methods 0.000 claims 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 239000000945 filler Substances 0.000 abstract description 2
- 239000011521 glass Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract description 2
- 239000000123 paper Substances 0.000 abstract description 2
- 239000004014 plasticizer Substances 0.000 abstract description 2
- 229920003002 synthetic resin Polymers 0.000 abstract description 2
- 239000000057 synthetic resin Substances 0.000 abstract description 2
- 239000002023 wood Substances 0.000 abstract description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract 1
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 abstract 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 abstract 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract 1
- 229910052783 alkali metal Inorganic materials 0.000 abstract 1
- 238000003475 lamination Methods 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- 150000003254 radicals Chemical class 0.000 abstract 1
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- RHMZKSWPMYAOAZ-UHFFFAOYSA-N diethyl peroxide Chemical compound CCOOCC RHMZKSWPMYAOAZ-UHFFFAOYSA-N 0.000 description 1
- BRDYCNFHFWUBCZ-UHFFFAOYSA-N dodecaneperoxoic acid Chemical compound CCCCCCCCCCCC(=O)OO BRDYCNFHFWUBCZ-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
-
- 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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- 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
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
- C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Copolymer consists of 50-97 wt.% ethylene and 3-50 wt.% of the glycidyl ester of acrylic, methacrylic or ethacrylic acid. The copolymer may be used alone or modified with a filler, synthetic resin and plasticiser as a moulding comp. for the manufacture of films and coatings. At above 200 deg.C., the copolymer is cross-linkable and is also highly useful as an adhesive e.g. in the lamination of metals, wood, paper and glass. The copolymer is produced at 100-300 deg.C. at a pressure above 500 atmos. e.g. at 10,000-50,000 psi., in the presence of a free radical generator, e.g. azobisisobutyronitrile EtOOEt, H2O2 and alkali metal persulphates, percarbonates. The pref. glycidyl ester is the methacrylate.
Description
Verfahren zur Herstellung von Copolymeren aus Äthylen und Glycidylestern
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung neuer Copolymere aus Athylen und Glycidylestern.
Das erfindungsgemässe Verfahren ist dadurch gekennzeichnet, dass man 50 bis 97 Gew. o/o Äthylen und 3 bis 50 Gew. O/o eines Glycidylesters der Formel
EMI1.1
worin R Wasserstoff oder eine Alkylgruppe mit 1 oder 2 Kohlenstoffatomen bedeutet, bei einem Druck oberhalb 500 Atmosphären und einer Temperatur im Bereich von 100 bis 3a01C C in Gegenwart eines freien Radikale bildenden Polymerisationskatalysators copolymerisiert.
Glycidylester, welche unter die oben angegebene Formel fallen, sind Glycidylacrylat, Glycidylmethacrylat und Glycidyläthacrylat.
Die Copolymere können nach bekannten Verfahrensweisen hergestellt werden, beispielsweise durch Polymerisation von Gemischen aus Athylen und Glycidylester entweder in einem Rohrreaktor oder in einem Autoclav beim angegebenen Druck, d. h. oberhalb 500 Atmosphären, beispielsweise zwischen 703 und 3515 kg/cm2 oder darüber, und bei Temperaturen zwischen 100 und 3000 C unter Verwendung freie Radikale bildenden Polymerisationskatalysatoren in kalytisch aktiven Mengen, wie Azokatalysatoren, z. B. a,a Azobisisobutyronitril, und Peroxyverbindungen, z. B.
Diäthylp eroxid, Wasserstoffperoxid, Di-tert.butylper- oxid, Perbernsteins äure, Lauroylhydroperoxid, Tetrahy dronaplithaiiinperoxid, sowie Alkali-, Erdalkali- oder Ammoniumpersulfaten, -perboraten und -percarbonaten. Derartige Katalysatoren wendet man gewöhnlich in Mengen von 0,01 ovo bis 0,2 0/o, bezogen auf das Monomerengewicht, an.
Die erfindungsgemäss herstellbaren Copolymeren finden entweder als solche oder nach Modifizierung mit Füllstoffen, synthetischen Harzen und/oder Weichmachern Verwendung als formbare Stoffe zur Herstel lung von nützlichen Filmen und Überzügen.
Bei Temperaturen oberhalb 2000 C sind die Co lymere vernetzbar und als Klebstoffe sehr nützlich und können als die harzartige Bindemittelkomponente bei der Herstellung von laminierten Gegenständen verwendet werden, beispielsweise als bindende Schicht für Metalle wie Aluminium und für Holz, Papier und Glas.
Zur Veranschaulichung des erfindungsgemässen Verfahrensablaufes dient das folgende Beispiel. Wenn nichts anderes angegeben ist, sind die Prozentwerte Gewichtsprozente.
Beispiel
Athylen und Glycidylmethacrylat (GMA) wurden in einer Versuchsserie, wiedergegeben in untenstehender Tabelle 1, copolymerisiert. Die Copolymerisation wurde kontinuierlich in einem 3-Liter-Druckautoclav durchgeführt, in dem ein Rührer mit 12WU/min umlief, und zwar bei einer Temperatur von 2000 C und einem Druck zwischen 1060 und 1480 kg/cm2, unter Verwendung von a,a-Azobisisobutyronitril als Katalysator bei einer Konzentration von 3 Gew. o/o. Tabelle 1 zeigt die mittlere Zufuhrgeschwindigkeit von Athylen in kg/h sowie die prozentuale Menge des Glycidylmetha crylat-comonomers, das vor der Zugabe des ethylens in den Autoclav mit diesem gemischt wurde.
Die Menge an Glycidylmethacrylat, die in jedem Copolymer gefunden wird, ist ebenfalls angegeben.
Tabelle 1 zeigt weiterhin die Eigenschaften der entstandenen Copolymere.
Der Schmelzindex wurde nach ASTM D-1238-57T gemessen.
Zugfestigkeit und Streckgrenze in kg/cm2 und Dehnung in O/o der ursprünglichen Länge bei der Bruchgrenze wurden nach ASTM D-638-S8T an Proben gemessen unter Verwendung der Apparatur B gemäss ASTM D-412-51T bei einer Beanspruchung von 25.4cm/min. Die Steifigkeit wurde nach ASTM D-747-58T gemessen.
Die Härte ist nach der Shore-Skala, Arbeitsverfahren C angegeben.
Tabelle I Versuch Nr. 1 2 3 4 5 6 Äthylenzufhr, kgQl 22,3 22,7 22,7 22,7 22,7 22,7 0/oGMAinZufuhr 1,17 0,75 1,6 2,0 2,8 3,38 fo GMA in Produkt 8,0 11,0 15,8 19,6 23,5 29,3 Schmelzindex 107,6 0,24 0,5 30,0 76,0 72,0 Zugfestigkeit, kg/cm2 106,5 129 111,6 79,2 55,9 42,7 Streckgrenze, kg/cm2 106,5 96,4 77,8 67,3 54,1 39,7 Dehnung % 73 490 505 515 428 500 Steifigkeit X 10-4 1,78 1,64 1,15 0,81 0,59 0,37 Härte, shore 75 75 71 63 59 51
Zum Vergleich hergestellte Copolymere aus Äthylen und anderen Acrylestermonomeren zeigen beträchtlich geringere Zugfestigkeitseigenschaften und Steifigkeiten verglichen mit den Glycidylmethycrylat-copolymeren, die erfindungsgemäss erhältlich sind.
Beispielsweise besitzt ein Copolymer und Äthylacrylat, welches 50 Gew. 0/o Äthylacrylat enthält, eine Zugfestigkeit von 60 kg/cm2 und eine Steifigkeit von 0,78. Zugfestigkeit und Steifigkeit eines Polymers bestimmen in grossem Masse die Verwendbarkeit des Polymeres beispielsweise in Filmen, Formartikeln und Beschichtungen.
Proben einiger der Copolymere gemäss Tabelle 1 wurden auf Aluminium beschichtet, indem man das betreffende Copolymer und ein Aluminiumblech zwei Minuten bei 1160 C und einem Druck von 2110kg/ cm2 zusammenpresste.
Die Bindungsfestigkeit der Copolymere zu Aluminium wurde folgendermassen bestimmt: Das beschichtete Blech wurde in Streifen von 2,54 cm Breite geschnitten, und die Beschichtung wurde vom Aluminiumblech auf einer Versuchsmaschine nach Tinius Olsen mit iner Abreissgeschwindigkeit von 5 cm/min abgerissen. Die zur Trennung der Copolymerschicht vom Aluminiumblech benötigte Kraft wurde in kg/cm gemessen. Die Bindungsfestigkeiten der Copolymerschichten sind in untenstehender Tabelle II angegeben.
Tabelle II Copolymere aus Äthylen/ Bindungsfestigkeit zu Al, Glycidylmethacrylat, hergestellt kgicm gemäss Versuch Nr.
1 0,53 2 0,79 5 3,35 6 9,29
Es wurde gefunden, dass die Äthylen/Glycidylme- thycrylatcopolymere bei Erhitzen auf erhöhte Temperaturen vernetzten, was durch den Anstieg des Schmelzindex der Copolymere beim Erhitzen angezeigt wurde. Zur Veranschaulichung dieser Eigenschaft ist der Schmelzindex des gemäss Versuch 5, Tabelle 1 hergestellten Copolymers beim Erhitzen auf 2700 C während verschiedener Zeiten in untenstehender Tabelle aufgeführt.
Tabelle 111 Erhitzungszeit Schmelzindex auf 2700 C (min) (ASTM D-1238-57T), g:10 min
5 130,5 10 61,6 15 24,4 25 1,0
Man erhält ähnliche Resultate wie vorstehend angegeben, wenn äquivalente Mengen an Glycidylacrylat oder Glycidyläthacrylat mit Äthylen an Stelle von Glycidylmethycrylat copolymerisiert werden.
Process for the production of copolymers from ethylene and glycidyl esters
The present invention relates to a process for the preparation of new copolymers from ethylene and glycidyl esters.
The process according to the invention is characterized in that 50 to 97% by weight of ethylene and 3 to 50% by weight of a glycidyl ester of the formula are used
EMI1.1
wherein R is hydrogen or an alkyl group having 1 or 2 carbon atoms, copolymerized at a pressure above 500 atmospheres and a temperature in the range from 100 to 3,000 ° C. in the presence of a free radical-forming polymerization catalyst.
Glycidyl esters which fall under the formula given above are glycidyl acrylate, glycidyl methacrylate and glycidyl ethacrylate.
The copolymers can be prepared by known procedures, for example by polymerizing mixtures of ethylene and glycidyl ester either in a tubular reactor or in an autoclave at the specified pressure, i. H. above 500 atmospheres, for example between 703 and 3515 kg / cm2 or above, and at temperatures between 100 and 3000 C using free radical-forming polymerization catalysts in catalytically active amounts, such as azo catalysts, e.g. B. a, a azobisisobutyronitrile, and peroxy compounds, e.g. B.
Diethyl peroxide, hydrogen peroxide, di-tert.butyl peroxide, pernstinic acid, lauroyl hydroperoxide, tetrahydronaplithaiiin peroxide, as well as alkali, alkaline earth or ammonium persulfates, perborates and percarbonates. Such catalysts are usually used in amounts of from 0.01 ovo to 0.2 o / o, based on the weight of the monomer.
The copolymers which can be prepared according to the invention are used either as such or after modification with fillers, synthetic resins and / or plasticizers as moldable substances for the production of useful films and coatings.
At temperatures above 2000 C the copolymers are crosslinkable and very useful as adhesives and can be used as the resinous binder component in the manufacture of laminated objects, for example as a binding layer for metals such as aluminum and for wood, paper and glass.
The following example serves to illustrate the process sequence according to the invention. Unless otherwise indicated, the percentages are percentages by weight.
example
Ethylene and glycidyl methacrylate (GMA) were copolymerized in a series of tests, shown in Table 1 below. The copolymerization was carried out continuously in a 3 liter pressure autoclave in which a stirrer was rotating at 12 WU / min, at a temperature of 2000 C and a pressure between 1060 and 1480 kg / cm 2, using α, α-azobisisobutyronitrile as a catalyst at a concentration of 3 wt. o / o. Table 1 shows the average feed rate of ethylene in kg / h and the percentage amount of the glycidyl methacrylate comonomer that was mixed with the autoclave before the ethylene was added.
The amount of glycidyl methacrylate found in each copolymer is also given.
Table 1 also shows the properties of the resulting copolymers.
The melt index was measured according to ASTM D-1238-57T.
Tensile strength and yield point in kg / cm2 and elongation in O / o of the original length at the breaking point were measured on samples in accordance with ASTM D-638-S8T using apparatus B in accordance with ASTM D-412-51T at a load of 25.4 cm / min . The stiffness was measured according to ASTM D-747-58T.
The hardness is given according to the Shore scale, working method C.
Table I Experiment No. 1 2 3 4 5 6 Ethylene feed, kgQl 22.3 22.7 22.7 22.7 22.7 22.7 0 / oGMAin feed 1.17 0.75 1.6 2.0 2.8 3.38 fo GMA in product 8.0 11.0 15.8 19.6 23.5 29.3 Melt index 107.6 0.24 0.5 30.0 76.0 72.0 Tensile strength, kg / cm2 106 , 5 129 111.6 79.2 55.9 42.7 Yield strength, kg / cm2 106.5 96.4 77.8 67.3 54.1 39.7 Elongation% 73 490 505 515 428 500 Stiffness X 10- 4 1.78 1.64 1.15 0.81 0.59 0.37 Hardness, shore 75 75 71 63 59 51
For comparison, copolymers prepared from ethylene and other acrylic ester monomers show considerably lower tensile strength properties and stiffnesses compared to the glycidyl methacrylate copolymers obtainable according to the invention.
For example, a copolymer and ethyl acrylate which contains 50% by weight of ethyl acrylate has a tensile strength of 60 kg / cm 2 and a stiffness of 0.78. The tensile strength and stiffness of a polymer determine to a large extent the usability of the polymer, for example in films, molded articles and coatings.
Samples of some of the copolymers according to Table 1 were coated on aluminum by pressing the relevant copolymer and an aluminum sheet together for two minutes at 1160 ° C. and a pressure of 2110 kg / cm 2.
The bond strength of the copolymers to aluminum was determined as follows: the coated sheet was cut into strips 2.54 cm wide, and the coating was torn from the aluminum sheet on a Tinius Olsen test machine at a tear-off speed of 5 cm / min. The force required to separate the copolymer layer from the aluminum sheet was measured in kg / cm. The bond strengths of the copolymer layers are given in Table II below.
Table II Copolymers of ethylene / bond strength to Al, glycidyl methacrylate, produced kgicm according to experiment no.
1 0.53 2 0.79 5 3.35 6 9.29
It was found that the ethylene / glycidyl methacrylate copolymers crosslink when heated to elevated temperatures, which was indicated by the increase in the melt index of the copolymers on heating. To illustrate this property, the melt index of the copolymer prepared according to Experiment 5, Table 1, when heated to 2700 ° C. for various times, is listed in the table below.
Table 111 Heating time melt index to 2700 C (min) (ASTM D-1238-57T), g: 10 min
5 130.5 10 61.6 15 24.4 25 1.0
Results similar to those given above are obtained when equivalent amounts of glycidyl acrylate or glycidyl ethacrylate are copolymerized with ethylene instead of glycidyl methacrylate.
Claims (1)
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH430868A CH492744A (en) | 1968-03-22 | 1968-03-22 | Ethylene-glycidyl acrylate copolymer useful for the |
| FR145164A FR1569004A (en) | 1968-03-22 | 1968-03-25 | |
| DE19681770051 DE1770051A1 (en) | 1968-03-22 | 1968-03-25 | Ethylene copolymers |
| GB14210/68A GB1146579A (en) | 1968-03-22 | 1968-03-25 | Ethylene copolymers |
| NL6804226A NL6804226A (en) | 1968-03-22 | 1968-03-26 |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH430868A CH492744A (en) | 1968-03-22 | 1968-03-22 | Ethylene-glycidyl acrylate copolymer useful for the |
| FR145164 | 1968-03-25 | ||
| DE19681770051 DE1770051A1 (en) | 1968-03-22 | 1968-03-25 | Ethylene copolymers |
| GB14210/68A GB1146579A (en) | 1968-03-22 | 1968-03-25 | Ethylene copolymers |
| NL6804226A NL6804226A (en) | 1968-03-22 | 1968-03-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH492744A true CH492744A (en) | 1970-06-30 |
Family
ID=27509190
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH430868A CH492744A (en) | 1968-03-22 | 1968-03-22 | Ethylene-glycidyl acrylate copolymer useful for the |
Country Status (5)
| Country | Link |
|---|---|
| CH (1) | CH492744A (en) |
| DE (1) | DE1770051A1 (en) |
| FR (1) | FR1569004A (en) |
| GB (1) | GB1146579A (en) |
| NL (1) | NL6804226A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA995122A (en) * | 1970-12-28 | 1976-08-17 | Kanji Yoshikawa | Multi-layer product of metal and resin, and its production |
| NL152272B (en) * | 1971-03-16 | 1977-02-15 | Sumitomo Chemical Co | PREPARATION OF ETHENIC COPOLYMERS. |
| US3849591A (en) * | 1972-03-03 | 1974-11-19 | Sumitomo Electric Industries | Laminate tape including an adhesive resin ternary copolymer of ethylene,vinyl acetate and glycidyl methacrylate or glycidyl acrylate and laminate sheath cable made therefrom |
| JPS636011A (en) * | 1986-06-25 | 1988-01-12 | Sumitomo Chem Co Ltd | Vinyl chloride-grafted ethylene copolymer and its production |
| US11046801B2 (en) | 2016-07-02 | 2021-06-29 | Rheomod de México, S.A.P.I. de C.V. | Grafted polymers |
-
1968
- 1968-03-22 CH CH430868A patent/CH492744A/en not_active IP Right Cessation
- 1968-03-25 GB GB14210/68A patent/GB1146579A/en not_active Expired
- 1968-03-25 DE DE19681770051 patent/DE1770051A1/en active Pending
- 1968-03-25 FR FR145164A patent/FR1569004A/fr not_active Expired
- 1968-03-26 NL NL6804226A patent/NL6804226A/xx unknown
Also Published As
| Publication number | Publication date |
|---|---|
| GB1146579A (en) | 1969-03-26 |
| NL6804226A (en) | 1969-09-30 |
| DE1770051A1 (en) | 1971-09-16 |
| FR1569004A (en) | 1969-05-30 |
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