DE1900467A1 - Stabilization of oligomers of allyl chloride - Google Patents
Stabilization of oligomers of allyl chlorideInfo
- Publication number
- DE1900467A1 DE1900467A1 DE19691900467 DE1900467A DE1900467A1 DE 1900467 A1 DE1900467 A1 DE 1900467A1 DE 19691900467 DE19691900467 DE 19691900467 DE 1900467 A DE1900467 A DE 1900467A DE 1900467 A1 DE1900467 A1 DE 1900467A1
- Authority
- DE
- Germany
- Prior art keywords
- oligomers
- allyl chloride
- epoxy
- stabilized
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
- C07C17/278—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of only halogenated hydrocarbons
- C07C17/281—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of only halogenated hydrocarbons of only one compound
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/42—Use of additives, e.g. for stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C21/00—Acyclic unsaturated compounds containing halogen atoms
- C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
- C07C21/04—Chloro-alkenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
- C08K5/57—Organo-tin compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
- C08K5/57—Organo-tin compounds
- C08K5/58—Organo-tin compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or 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; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L43/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or 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; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
■:·· . V■: ··. V
S 67/37S 67/37
Solvay & Oie.Solvay & Oie.
33 Rue du Prince Albert, Brüssel/Belgien33 Rue du Prince Albert, Brussels / Belgium
Stabilisierung von Oligdmeren des Ällylchlorids.Stabilization of oligomers of allyl chloride.
Priorität! Belgische Patentanmeldung Nr. 53 099 vom 9»Januar 1968Priority! Belgian patent application no. 53 099 dated January 9, 1968
stabilisierten · Me Erfindung betriff 1|die Gewinnung von/Oligomeren des Ällylchlorids , welche sich insbesondere gut für die Weichmachung der Vinylpolymeren, insbesondere des Polyvinylchlorids eignen.stabilized · Me invention concerns 1 | the production of / oligomers of allyl chloride, which is particularly good for softening vinyl polymers, especially polyvinyl chloride suitable.
Wenn auch das Polyvinylchlorid ein sehr geschätztes Material ist, besitzt es doch gewisse Mangel, welche seine Verwendung auf besonderen Gebieten erschweren.Even if the polyvinyl chloride is a very valued material, it has certain shortcomings, which are its Difficult use in special areas.
So ist bekannt, Weichmacher in Polyvinylchlorid einzuverleiben, um seinen Einsatz zu erleichtern.It is known to incorporate plasticizers into polyvinyl chloride, to facilitate its use.
Es wurde festgestellt, daß die Oligomeren des Ällylchlorids ausgezeichnete Weichmaoher für die Polymeren des Vinylchlorids sind, aber daß sie schlechte Eigenschaften hinsichtlich der Alterung aufweisen.It was found that the oligomers of allyl chloride are excellent softeners for the polymers of vinyl chloride, but that they have poor properties with regard to aging.
Die durch die Oligomerisation des Allylohloride in Gegenwart von kationischen Katalysatoren erhaltenen Produkte schwärzen sich bei der Lagerung , und ihre Verwendung als solche zum Weichmachen der Polymeren des Vinylchlorids führt zum Erhalten von Gegenständen, deren Transparenz zu wünschen übrig lässt· The products obtained by the oligomerization of allylo chloride in the presence of cationic catalysts blacken on storage, and their use as such to soften the polymers of vinyl chloride leads to objects whose transparency leaves something to be desired.
909848/1379909848/1379
ORIGINAL-ORIGINAL-
Es wurden nun Stabilisierungsansätze mit einem oder mehreren Bestandteilen eingesetzt, welche sich als sehr wirksam für die Stabilisierung der Oligomeren auf der Grundlage von Allylchlorid erwiesen und deren Einverleibung in Polyvinylchlorid ermöglichen.There have now been used stabilization approaches with one or more ingredients, which are very Proven effective for the stabilization of oligomers based on allyl chloride and their incorporation enable in polyvinyl chloride.
Die Erfindung betrifft daher Oligomere auf der Grundlage von Allylchlorid, welche eine verbesserte Stabilität besitzen. Sie werden duroh Polymerisation des Allylchlorids in Gegenwart eines Aluminiumhalogenide oder eines Alkylaluminiumhalogenids als Katalysator mit anschließender Wiedergewinnung durch Destillation unter verringertem Druck des nicht umgesetzten Monomers und Waschung des Oligomers mittels Wasser erhalten, wobei die Oligomeren durch Einverleibung von 0,1 bis 5 Gew.# an Verbindungen stabilisiert werden, ausgewählt unter der Gruppe, welche Epoxyderivate, die Organozinnderivate und das Morpholin enthält·The invention therefore relates to oligomers based on allyl chloride, which have improved stability own. They become through the polymerization of the allyl chloride in the presence of an aluminum halide or an alkyl aluminum halide as a catalyst then recovering the unreacted monomer by distillation under reduced pressure and Washing of the oligomer obtained by means of water, the oligomers being obtained by incorporation of 0.1 to 5 wt. are stabilized on compounds, selected from the group which epoxy derivatives, the organotin derivatives and which contains morpholine
Sleicnfalls zum Ziel die Stabilisierung der/Oligomeren des Allylchloride, worin das Monomer ein Olefin, z.B. Äthylen, Propylen, die Butene usw., oder ein Vinylmonomer, z.B. das Vinylchlorid, das Styrol usw. sein kann. The aim is also to stabilize the oligomers of allyl chloride, in which the monomer can be an olefin, for example ethylene, propylene, butenes, etc., or a vinyl monomer, for example vinyl chloride, styrene, etc. can be.
Die Polymerisationsreaktion des Allylchlorids wird bei einer Temperatur zwischen -600C und +400C in Gegenwart von einem oder mehreren Aluminiumhaiogeniden als Katalysatoren JranrtTirtx ausgeführt.The polymerization reaction of the allyl chloride is carried out at a temperature between -60 0 C and +40 0 C in the presence of one or more Aluminiumhaiogeniden as catalysts JranrtTirtx.
Die für die Erfindung benutzten Aluminiumhalogenide sind vorzugsweise AlCl, und die Alkylaluminiumhalogenide () und ^The aluminum halides used for the invention are preferably AlCl, and the alkyl aluminum halides () and ^
Gemäß einer bevorzugten Ausführungsform der Erfindung setzt man den Katalysator in mehreren Bruchteilen während der Polymerisationereaktion hinsu.According to a preferred embodiment of the invention, several fractions of the catalyst are added during the polymerization reaction.
909848/1379909848/1379
Am Ende der Reaktion wird das nichtumgewandelte Monomer durch Destillation unter verringertem Druck wiedergewonnen. At the end of the reaction, the unconverted monomer becomes recovered by distillation under reduced pressure.
Das wiedergewonnene Allylchlorid kann in den Reaktor ohne Vorbehandlung zurückgeführt werden.The recovered allyl chloride can be returned to the reactor without pretreatment.
Nach dem Waschen mit Wasser wird das Oligomör des Allyl-After washing with water, the oligomer of the allyl
chlorids, welches ein mittleres Molekulargewicht zwischen 500 und 500 besitzt, durch einfachen Zusatz von 0,1 bis 5 Gew.% eines oder mehrerer Stabilisatoren, ausgewählt aus der Gruppe, welche die Epoxyderivate, die Organozinnderivate und das Morpholin enthält, stabilisiert.chloride, which has an average molecular weight between 500 and 500, simply by adding 0.1 to 5% by weight of one or more stabilizers, selected from the group which contains the epoxy derivatives, the organotin derivatives and the morpholine stabilizes.
Unter diesen Stabilisatoren kann man als bevorzugt die Monoepoxyde mit niedrigem Molekulargewicht, die epoxydierten öle, gegebenenfalls in Kombination mit Metallseifen, die Polyepoxyde, wie die Epoxyharze, Alkylzinncarboxylate, Alkylzinnmerkaptide und insbesondere Alkylzinnthioglycolate*-erwähnen. Preferred among these stabilizers are the low molecular weight monoepoxides, the epoxidized oils, optionally in combination with metal soaps, the polyepoxides, such as the epoxy resins, alkyltin carboxylates, Mention alkyl tin mercaptides and especially alkyl tin thioglycolates *.
Die verschiedenen Stabilisatoren können getrennt oeter in Mischung angewendet werden.The different stabilizers can be separated in Mixture can be applied.
Die Oligomeren des Allylchlorids, welche mittels der oben erwähnten Stabilisatoren stabilisiert sind, schwärzen sich nicht mehr bei der Lagerung und erweisen sich als ausgezeichnete primäre Weichmacher der Polymeren des Vinylchlorids.The oligomers of allyl chloride, which by means of the above stabilizers mentioned are stabilized, no longer blacken on storage and turn out to be excellent primary plasticizers for vinyl chloride polymers.
Überdies besitzen die Gegenstände, hergestellt aus einem Polymer des Vinylchlorids und Oligomeren des Allylchlorids, welche wie oben beschrieben erhalten sind, ausgezeichnete Tranzparenz und Einsatzfähigkeit und weisen gute mechanische Eigenschaften auf, welche denjenigen überlegen sind, die erhalten werden, wenn man übliche Weichmacher verwe'pt. Sie besitzen insbesondere eine ausgezeichnete Zugfestigkeit.Moreover, the items made from one have Vinyl chloride polymer and allyl chloride oligomers obtained as described above are excellent Transparency and usability and have good mechanical properties that are superior to those which are obtained when conventional plasticizers are used. In particular, they have excellent tensile strength.
8/13798/1379
ORIGINAL INSPECTEDORIGINAL INSPECTED
% f « I I · % f «II ·
• t· t »• t · t »
—JL- - JL-
Außerdem beobaohtet man beim Einsatz durch Verkneten auf Walzen eines Polymers des VinylChlorids, weichgemacht mittels der erfindungsgemäß stabilisierten Oligomeren des Allyl chi or i ds, daß die G-elierung sich rascher vollzieht, als wenn man einen Weichmacher vom Estertyp, w-ie Dioctylphtalat verwendet.In addition, one observes the use by kneading on rolls of a polymer of vinyl chloride, plasticized by means of the oligomers of allyl chi or i ds stabilized according to the invention that gelation occurs more rapidly as if using an ester-type plasticizer, w-ie dioctyl phthalate used.
In einen Kolben von 5 1 führt man unter einem Strom trockenen Stickstoffs und unter Ausschluß von Luft und Feuchtigkeit 2000 g Allylchlorid ein. Man kühlt auf -200C mittels eines Bades aus Methanol und Kohlendioxydeie ab· Man setzt während 2 Stunden 1,8 g AlCl^ alle 15 Minuten zu, dann destilliert man unter verringertem Druck das nicht umgewandelte Allylchlorid ab· Man wäscht darauf das Oligomer bis zum Verschwinden der Asidität. Man gewinnt 634 g an dem Oligomer des AlIyI-chlorids mit einem mittleren Molekulargewicht von 410.2000 g of allyl chloride are introduced into a flask of 5 liters under a stream of dry nitrogen and with exclusion of air and moisture. The mixture is cooled to -20 0 C. by means of a bath of methanol and Kohlendioxydeie · is reacted for 2 hours 1.8 g AlCl ^ every 15 minutes, then distilled under reduced pressure of allyl chloride from the unconverted · it is washed until the oligomer to the disappearance of asidity. 634 g of the oligomer of aluminum chloride with an average molecular weight of 410 are obtained.
Man setzt darauf zu dem Oligomer 9,5 g der verschiedenen in der !Tabelle I angegebenen Verbindungen zu.9.5 g of the various compounds given in Table I are then added to the oligomer.
Die Oligomeren werden darauf in einen belüfteten Trockenschrank von 500C gebracht und man beobachtet ihre Verfärbung nach 40-stündiger Verweilzeit·The oligomers are then placed in a ventilated drying cabinet at 50 ° C. and their discoloration is observed after a residence time of 40 hours.
Die Ergebnisse dieser Feststellungen folgen in Tabelle I.The results of these findings are shown in Table I.
909848/13 7909848/13 7
ORIGINAL INSPECTEDORIGINAL INSPECTED
t . . I'll I ιt. . I'll I ι
R2 R 1
R 2
octylzinn + 25$ epoxydiertes
Sojaöl75j6! Dhioglycolate of Di-n-
octyl tin + 25 $ epoxidized
Soybean oil
707PerroclSre
707
Tabelle I-5-
Table I.
D 671organic thiocin compound Advastab
D 671
760 fferroclare
760
+ ungesättigte Barium-Cad- 10
mium-Seile + EpoxyverbindungOrganotin compound StanolSre
+ unsaturated barium cad- 10
mium ropes + epoxy compound
Oligomers nachAppearance of the
Oligomers
Zink-SeifeEpoxy compound + cadmium
Zinc soap
Zink-SeifeEpoxy compound + caloium-
Zinc soap
Aufenthalt bei
500C40 hours
Stay at
50 0 C
dunkelbrauns black
dark brown
CZ 11Advastab
CZ 11
55Stanoldre
55
E 98Advastab
E 98
DibutylzinnDiisooctyl thioglycolate of
Dibutyltin
E 49 Advastab
E 49
DibutylzinnDinonyl thioglycolate of
Dibutyltin
90'98A8/137990'98A8 / 1379
ORIGINAL INSPECTEDORIGINAL INSPECTED
- 6 -.
Beispiele 2-5- 6 -.
Examples 2-5
Gemäß der Arbeitsweise des Beispiels 1 wurden drei Oligomere des Allylchlorids hergestellt, denen Molekulargewichte 310, 350 und 460 sind. Diese Oligomeren werden durch eine der erfindungsgemäßen Verbindungen stabilisiert.Following the procedure of Example 1, three oligomers of allyl chloride were prepared having molecular weights 310, 350 and 460 are. These oligomers are stabilized by one of the compounds according to the invention.
Man stellt dann durch Verkneten auf Walzen homogene Mischungen von Polyvinylchlorid und den stabilisierten Oligomeren des Allylchlorids her. Die Mischung, die bei einer Temperatur von 1500C leicht geliert, wird durch Pressen in Platten übergeführt. Dann werden die folgenden mechanischen Eigenschaften gemessen:Homogeneous mixtures of polyvinyl chloride and the stabilized oligomers of allyl chloride are then produced by kneading on rollers. The mixture, which gels slightly at a temperature of 150 ° C., is converted into plates by pressing. Then the following mechanical properties are measured:
Torsionsmodul G gemäß der Norm ASTM D 1043/51 Reißfestigkeit und Bruchdehnung bei Raumtemperatur gemäß der Norm ASTM D 412 iPyp D.Torsional modulus G according to the ASTM D 1043/51 standard, tear strength and elongation at break at room temperature according to the ASTM D 412 iPyp D.
Die Ergebnisse dieser Versuche folgen in Tabelle II und zeigen, daß die Platten aus Polyvinylchlorid, welches mittels der erfindungsgemäß stabilisierten Oligomeren des Allylchlorids weichgemacht wurden (Beispiel 3-5 )9 bessere mechanische Eigenschaften besitzen als die Platten aus mittels Dioctylphtalat weichgemachtem Polyvinylchlorid (Beispiel R2)The results of these tests are shown in Table II and show that the plates made of polyvinyl chloride plasticized by means of the oligomers of allyl chloride stabilized according to the invention (Example 3-5) 9 have better mechanical properties than the plates made of polyvinyl chloride plasticized by means of dioctyl phthalate (Example R2)
Außerdem besitzen die erfindungsgemäß erhaltenen Platten Transparenz.In addition, the plates obtained according to the invention have transparency.
909848/1379 original inspected909848/1379 originally inspected
to S to S
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O)O)
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ο α)ο α)
•Η Ο• Η Ο
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-7--7-
BeipieleExamples
Polyvinylchlorid 100Polyvinyl chloride 100
Dioctylphtalat(Molekulargewicht 390 40Dioctyl phthalate (molecular weight 390 40
Oligomer des Allylchlorids (mittleres Molekulargewicht 310 Allyl chloride oligomer (average molecular weight 310
Oligomer des Allylchlorids (mittleres Molekulargewicht 350)Allyl chloride oligomer (average molecular weight 350)
Oligomer des Allylchlorids (mittleres Molekulargewicht 460)Allyl chloride oligomer (average molecular weight 460)
Torsionsmodul Gr kg/cm*Torsional modulus Gr kg / cm *
bei 10 C 300at 10 C 300
bei 20uC bei 30°Cat 20 C and at 30 ° C
Reißfestikkeit(20°C) kg/om2 Tear strength (20 ° C) kg / om 2
Bruchdehnung(20°C)Elongation at break (20 ° C)
100100
4040
700700
185185
4545
215215
316316
100100
300300
3434
197197
282282
100100
6767
500500
120120
3131
191191
273273
909848/ 1379 ORIGINAL INSPECTED909848/1379 ORIGINAL INSPECTED
Claims (11)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BE53099 | 1968-01-09 | ||
| BE709095 | 1968-01-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1900467A1 true DE1900467A1 (en) | 1969-11-27 |
Family
ID=25647372
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19691900467 Pending DE1900467A1 (en) | 1968-01-09 | 1969-01-07 | Stabilization of oligomers of allyl chloride |
Country Status (5)
| Country | Link |
|---|---|
| BE (1) | BE709095A (en) |
| DE (1) | DE1900467A1 (en) |
| FR (1) | FR1602440A (en) |
| GB (1) | GB1221250A (en) |
| NL (1) | NL6900333A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180244593A1 (en) * | 2015-09-18 | 2018-08-30 | Kuraray Co., Ltd. | Homoallyl halide composition and method for storing homoallyl halide |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2964092D1 (en) * | 1978-07-27 | 1982-12-30 | Ici Plc | Stabilisation of chlorinated aliphatic hydrocarbons |
-
1968
- 1968-01-09 BE BE709095D patent/BE709095A/xx unknown
- 1968-12-20 FR FR1602440D patent/FR1602440A/fr not_active Expired
- 1968-12-31 GB GB61960/68A patent/GB1221250A/en not_active Expired
-
1969
- 1969-01-07 DE DE19691900467 patent/DE1900467A1/en active Pending
- 1969-01-09 NL NL6900333A patent/NL6900333A/xx unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180244593A1 (en) * | 2015-09-18 | 2018-08-30 | Kuraray Co., Ltd. | Homoallyl halide composition and method for storing homoallyl halide |
| US10618860B2 (en) * | 2015-09-18 | 2020-04-14 | Kuraray Co., Ltd | Homoallyl halide composition and method for storing homoallyl halide |
Also Published As
| Publication number | Publication date |
|---|---|
| GB1221250A (en) | 1971-02-03 |
| BE709095A (en) | 1968-07-09 |
| NL6900333A (en) | 1969-07-11 |
| FR1602440A (en) | 1970-11-23 |
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