DE1283513B - Process for changing the mechanical properties of molded polyvinyl chloride articles - Google Patents

Process for changing the mechanical properties of molded polyvinyl chloride articles

Info

Publication number
DE1283513B
DE1283513B DED28690A DED0028690A DE1283513B DE 1283513 B DE1283513 B DE 1283513B DE D28690 A DED28690 A DE D28690A DE D0028690 A DED0028690 A DE D0028690A DE 1283513 B DE1283513 B DE 1283513B
Authority
DE
Germany
Prior art keywords
polyvinyl chloride
sulfur
solution
mechanical properties
changing
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
Application number
DED28690A
Other languages
German (de)
Inventor
Dipl-Ing Max Goecke
Rudolf Nagelschmidt
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
Degussa GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority to BE581278D priority Critical patent/BE581278A/fr
Priority to NL241962D priority patent/NL241962A/xx
Application filed by Degussa GmbH filed Critical Degussa GmbH
Priority to DED28690A priority patent/DE1283513B/en
Priority to DED28974A priority patent/DE1283514B/en
Priority to CH242062A priority patent/CH456139A/en
Priority to FR802084A priority patent/FR1239481A/en
Publication of DE1283513B publication Critical patent/DE1283513B/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
    • 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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/06—Sulfur
    • 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
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • 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
    • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
    • C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use 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; Derivatives of such polymers
    • C08J2327/02—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/04—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2327/06—Homopolymers or copolymers of vinyl chloride

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Description

BUNDESREPUBLIK DEUTSCHLAND DEUTSCHES 4B7WW PATENTAMTFEDERAL REPUBLIC OF GERMANY GERMAN 4B7WW PATENT OFFICE

AUSLEGESCHRIFTEDITORIAL

Int. CL:Int. CL:

Deutsche Kl.:German class:

Nummer: Aktenzeichen: Anmeldetag: Auslegetag:Number: File number: Filing date: Display date:

C08fC08f

39 M- 29/1839 M- 29/18

45/72, 47/2245/72, 47/22

P 12 83 513.1-43 (D 28690)P 12 83 513.1-43 (D 28690)

5. August 19585th August 1958

21. November 1968November 21, 1968

Es ist bekannt, aus thermoplastischen Polyvinylverbindungen, wie beispielsweise Polyvinylchlorid, Polyvinylacetat und Polyvinylidenchlorid, Formkörper herzustellen, die sich durch gute mechanische Eigenschaften und chemische Beständigkeit auszeichnen. Es war bisher jedoch nicht gelungen, derartigen Formkörpern, z. B. Folien, Rohren, Fäden und Kunstleder, kautschukelastische Eigenschaften zu verleihen.It is known from thermoplastic polyvinyl compounds, such as polyvinyl chloride, polyvinyl acetate and polyvinylidene chloride, molded articles that are characterized by good mechanical properties and chemical resistance. So far, however, it has not been possible to produce such shaped bodies, e.g. B. foils, pipes, threads and artificial leather to impart rubber elastic properties.

Weiterhin ist bekannt, Mischpolymerisate des Vinylchlorids mit anderen zur Vernetzung reaktiven Mischpolymerisatkomponenten mit Hilfe von Schwefel oder organischen Schwefelverbindungen und Vulkanisationsbeschleunigern unter Mitwirkung von Metalloxyden zu vernetzen.It is also known that copolymers of vinyl chloride with others reactive for crosslinking Mixed polymer components with the help of sulfur or organic sulfur compounds and vulcanization accelerators to crosslink with the help of metal oxides.

Es wurde nun überraschenderweise gefunden, daß es auch möglich ist, Polyvinylchlorid zu Formkörpern mit kautschukelastischen Eigenschaften zu verarbeiten, wenn man Polyvinylchlorid oder Formkörper aus Polyvinylchlorid in der Wärme mit ao elementarem Schwefel oder mit einer organischen Schwefelverbindung in Kombination mit primären Di- oder Polyaminen behandelt.It has now been found, surprisingly, that it is also possible to form polyvinyl chloride into molded articles with rubber-elastic properties to process when using polyvinyl chloride or moldings from polyvinyl chloride in the heat with ao elemental sulfur or with an organic Sulfur compound treated in combination with primary diamines or polyamines.

Als organische Schwefelverbindungen kommen Schwefelkohlenstoff oder Derivate des Schwefelkohlenstoffs in Betracht. Bewährt haben sich Xanthogenate^-Pentamethylen-Ammonium-Pentamethylen-Dithiocarbamat, Tetramethylthiuramdisulfid, 2-Mercaptobenzothiazol. The organic sulfur compounds are carbon disulfide or derivatives of carbon disulfide into consideration. Xanthates ^ -pentamethylene-ammonium-pentamethylene-dithiocarbamate have proven themselves, Tetramethylthiuram disulfide, 2-mercaptobenzothiazole.

An Stelle der Kombination aus Schwefelverbindüngen und Di- oder Polyamin kann man die Behandlung auch mit solchen Verbindungen vornehmen, die im Molekül gleichzeitig organisch gebundenen Schwefel und eine oder mehrere Aminogruppen enthalten.Instead of the combination of sulfur compounds and diamine or polyamine, one can use the Make treatment with compounds that are organically bound in the molecule at the same time Contain sulfur and one or more amino groups.

Die Behandlung des Polyvinylchlorids kann so vorgenommen werden, daß man den Schwefel oder die organische Schwefelverbindung und Di- oder Polyamin gleichzeitig oder nacheinander mechanisch in das Polyvinylchlorid einarbeitet, z. B. durch Einwalzen bei erhöhter Temperatur. Man kann aber auch so vorgehen, daß man diese Verbindungen in gelöster Form auf Polyvinylchlorid einwirken läßt, wobei es zweckmäßig ist, zunächst eine Behandlung mit einer Lösung des Schwefels oder der organischen Schwefelverbindung und anschließend eine Behandlung mit einer Lösung des Di- oder Polyamine vorzunehmen. Hierbei ist es zweckmäßig, als Lösungsmittel für das Di- bzw. Polyamin ein solches zu verwenden, das Polyvinylchlorid löst oder anquillt.The treatment of the polyvinyl chloride can be carried out so that the sulfur or the organic sulfur compound and di- or polyamine simultaneously or one after the other mechanically in incorporates the polyvinyl chloride, e.g. B. by rolling in at elevated temperature. But you can also proceed in such a way that these compounds are allowed to act in dissolved form on polyvinyl chloride, it is expedient to first treat with a solution of sulfur or the organic Sulfur compound and then to undertake a treatment with a solution of the di- or polyamine. It is advisable to use a solvent for the diamine or polyamine, the polyvinyl chloride dissolves or swells.

Nach dieser Behandlung wird der Formkörper zweckmäßig in der Wärme nachbehandelt, z. B.After this treatment, the shaped body is expediently aftertreated in the heat, e.g. B.

Verfahren zur Änderung der mechanischen
Eigenschaften von Polyvinylchlorid-FormkörpernMethod of changing the mechanical
Properties of molded polyvinyl chloride articles

Anmelder:Applicant:

Deutsche Gold- u. Silber-Scheideanstalt,German gold and silver refinery,

vormals Roessler, 6000 Frankfurtformerly Roessler, 6000 Frankfurt

Als Erfinder benannt:Named as inventor:

Dipl.-Ing. Max Goecke, 6380 Bad Homburg;Dipl.-Ing. Max Goecke, 6380 Bad Homburg;

Rudolf Nagelschmidt, 6450 HanauRudolf Nagelschmidt, 6450 Hanau

durch Lagern bei Temperaturen von etwa 60° C oder darüber.by storage at temperatures of about 60 ° C or above.

Das Polyvinylchlorid kann für sich aber auch Gemische mit Weichmacher, Pigment, Farbstoff, Stabilisatoren oder Füllstoffen verarbeitet werden. Besonders bewährt haben sich sogenannte aktive Füllstoffe, wie Ruß oder Oxyde von Metallen oder Metalloide. Das erfindungsgemäß behandelte Polyvinylchlorid läßt sich in üblicher Weise weiterverarbeiten, ζ. Β. zu Folien, Kunstleder, Rohren, Fäden und Platten. Die hergestellten Formkörper lassen sich überraschenderweise auch verschweißen.However, the polyvinyl chloride itself can also contain mixtures with plasticizers, pigments, dyes and stabilizers or fillers are processed. So-called active fillers have proven particularly useful, like soot or oxides of metals or metalloids. The polyvinyl chloride treated according to the invention can be further processed in the usual way, ζ. Β. to foils, artificial leather, pipes, threads and panels. Surprisingly, the molded bodies produced can also be welded.

Ob und welche chemischen Umsätze dabei auftreten, ist im einzelnen noch nicht geklärt worden.Whether and which chemical conversions occur, has not yet been clarified in detail.

Beispiel 1example 1

Eine Folie aus Polyvinylchlorid mit einem Gehalt von 30% Dioctylphthalat als Weichmacher, 10 % Farbpigment und 1% Bleistearat wird bei 60° C kontinuierlich während 5 Minuten durch Schwefelkohlenstoff hindurchgezogen. Die Folie wird dann oberflächlich getrocknet und durch ein zweites Bad geleitet, das aus einer Lösung von 20% Hexamethylendiamin in einem Gemisch aus Aceton und Cyclohexanon besteht. Darauf wird die Folie oberflächlich getrocknet und 5 Stunden lang auf 60% C erwärmt. Die so behandelte Folie hat eine gummiartige Elastizität erhalten.A film made of polyvinyl chloride with a content of 30% dioctyl phthalate as plasticizer, 10% Color pigment and 1% lead stearate is continuously passed through carbon disulfide at 60 ° C for 5 minutes pulled through. The surface of the film is then dried and passed through a second bath passed that from a solution of 20% hexamethylenediamine in a mixture of acetone and Cyclohexanone consists. The surface of the film is then dried and heated to 60% C for 5 hours warmed up. The film treated in this way has acquired a rubber-like elasticity.

Beispiel 2Example 2

Man verfährt wie im Beispiel 1, nur mit dem Unterschied, daß als erste Behandlungsflüssigkeit eine 20%ige Lösung von Kaliumxanthogenat in Aceton mit einem geringen Zusatz von Wasser verwendet wird. Als zweite Behandlungsflüssigkeit wird eine 20%ige Lösung von Äthylendiamin in Aceton und Essigester verwendet.The procedure is as in Example 1, only with the difference that the first treatment liquid a 20% solution of potassium xanthate in acetone with a small addition of water is used will. A 20% solution of ethylenediamine in acetone is used as the second treatment liquid and ethyl acetate are used.

809 638/1632809 638/1632

Beispiel 3Example 3

Eine Folie, wie sie im Beispiel 1 und 2 beschrieben ist, wird bei 60° C 5 Minuten lang in einem Bad behandelt, das aus einer 15%igen Lösung von 2-Mercapto-Bezimidazol in Methyläthylketon besteht. Nach dieser Einbadbehandlung hat die Folie gute elastische Eigenschaften erhalten.A film as described in Examples 1 and 2 is in a bath at 60 ° C. for 5 minutes treated that from a 15% solution of 2-mercapto-bezimidazole consists in methyl ethyl ketone. After this single bath treatment, the film has good elasticity Properties preserved.

Claims (5)

Patentansprüche:Patent claims: 1. Verfahren zur Änderung der mechanischen Eigenschaften von Polyvinylchlorid-Formkörpern, dadurch gekennzeichnet, daß man Polyvinylchlorid oder Formkörper aus Polyvinylchlorid in der Wärme mit Schwefel und/oder organischen Schwefelverbindungen in Kombination mit primären Di- oder Polyaminen behandelt.1. Process for changing the mechanical properties of molded polyvinyl chloride articles, characterized in that one has polyvinyl chloride or molded articles made of polyvinyl chloride in the heat with sulfur and / or organic sulfur compounds in combination treated with primary diamines or polyamines. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man die Behandlung des Polyvinylchlorids mit einer Verbindung durchführt, die gleichzeitig organisch gebundenen Schwefel und eine oder mehrere Aminogruppen enthält.2. The method according to claim 1, characterized in that that the treatment of the polyvinyl chloride is carried out with a compound which is organically bound at the same time Contains sulfur and one or more amino groups. 3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man den Schwefel oder die organische Schwefelverbindung und das primäre Di- oder Polyamin in Form einer Lösung verwendet. 3. The method according to claim 1, characterized in that that the sulfur or the organic sulfur compound and the primary di- or polyamine are used in the form of a solution. 4. Verfahren nach Anspruch 1 oder 3, dadurch gekennzeichnet, daß man einen Formkörper aus dem Polyvinylchlorid zunächst mit einer Lösung von Schwefel und/oder einer organischen Schwefelverbindung und dann anschließend mit einer Lösung des primären Di- oder Polyamine behandelt. 4. The method according to claim 1 or 3, characterized in that a molded body is made the polyvinyl chloride first with a solution of sulfur and / or an organic sulfur compound and then subsequently treated with a solution of the primary di- or polyamine. 5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß man die Lösung des primären Di- oder Polyamine in einem Lösungs- oder Quellungsmittel für das Polyvinylchlorid verwendet. 5. The method according to claim 4, characterized in that the solution of the primary Di- or polyamines used in a solvent or swelling agent for the polyvinyl chloride. In Betracht gezogene Druckschriften:
USA.-Patentschriften Nr. 2416 874, 2416 878,
600 414.Considered publications:
U.S. Patents Nos. 2416 874, 2416 878,
600 414.
DED28690A 1958-08-05 1958-08-05 Process for changing the mechanical properties of molded polyvinyl chloride articles Pending DE1283513B (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
BE581278D BE581278A (en) 1958-08-05
NL241962D NL241962A (en) 1958-08-05
DED28690A DE1283513B (en) 1958-08-05 1958-08-05 Process for changing the mechanical properties of molded polyvinyl chloride articles
DED28974A DE1283514B (en) 1958-08-05 1958-09-17 Process for changing the mechanical properties of molded vinyl chloride polymer bodies
CH242062A CH456139A (en) 1958-08-05 1959-07-31 Process for the production of molded articles of a non-textile type, starting from halogen-containing polyvinyl compounds
FR802084A FR1239481A (en) 1958-08-05 1959-08-05 Process for modifying the mechanical properties of polyvinyl compounds

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DED28690A DE1283513B (en) 1958-08-05 1958-08-05 Process for changing the mechanical properties of molded polyvinyl chloride articles

Publications (1)

Publication Number Publication Date
DE1283513B true DE1283513B (en) 1968-11-21

Family

ID=7039780

Family Applications (1)

Application Number Title Priority Date Filing Date
DED28690A Pending DE1283513B (en) 1958-08-05 1958-08-05 Process for changing the mechanical properties of molded polyvinyl chloride articles

Country Status (4)

Country Link
BE (1) BE581278A (en)
DE (1) DE1283513B (en)
FR (1) FR1239481A (en)
NL (1) NL241962A (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL270478A (en) * 1960-10-21

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2416878A (en) * 1943-08-20 1947-03-04 Du Pont Curing halogen containing linear polymers
US2416874A (en) * 1943-08-20 1947-03-04 Du Pont Treatment of interpolymers of vinyl chloride and esters of ethylenedicarboxylic acids
US2600414A (en) * 1947-08-22 1952-06-17 William C Mast Vulcanization of acrylic resins

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2416878A (en) * 1943-08-20 1947-03-04 Du Pont Curing halogen containing linear polymers
US2416874A (en) * 1943-08-20 1947-03-04 Du Pont Treatment of interpolymers of vinyl chloride and esters of ethylenedicarboxylic acids
US2600414A (en) * 1947-08-22 1952-06-17 William C Mast Vulcanization of acrylic resins

Also Published As

Publication number Publication date
BE581278A (en)
FR1239481A (en) 1960-08-26
NL241962A (en)

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