DE2237525A1 - FORMED COPOLYMERS AND METHODS FOR THE PRODUCTION OF CYCLIC COMPOUNDS, CONJUGATED DOUBLE BONDING SYSTEMS, AND VINYL COMPOUNDS, CONTAINING AN ACTIVATING GROUP - Google Patents

Description

2 «* ° J f * l 2 *} F- 4, -J S v '

Dr. P Dosage. - Dr. E. Aeemann Dr.fcKoenigsberger - Dip ». Phys. R. Hol «b. _U .r

Dr. F. Zumstein | un.
Patent attorneys

8 Möneh.n 2, Μι * ««. «* · 4/1»

Case 486
12/10 / ka

SHJiM ΡΕΟ & ΕΙΪΙ S, p.Α., Milan / Italy

Made of cyclic compounds that form a system of conjugated

Contain double bonds and vinyl compounds that contain an activating group _? formed copolymers and processes

their manufacture.

The present invention relates to new copolymers starting from of cyclic compounds, which contain a system of conjugated double bonds, and of vinyl compounds, which have an activating Group in α-position with respect to the carbon-carbon -Double bond are obtained and the process for their production. In particular, the present invention relates a new class of alternating copolymers, that of cyclic polyene compounds that have 2 conjugated double bonds and of vinyl compounds with functional groups in the α-position with respect to the carbon-carbon double bond- ' gen, are formed.

There are known processes for the preparation of copolymers which

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alternating units formed by vinyl compounds with functional Groups, included.

The known processes are generally carried out by polymerization reactions carried out, always in Gegenv / art special Catalysts are installed, which can negatively affect the end product by giving rise to impurities, which often require the use of complex and very expensive cleaning methods.

It is now in accordance with an aspect of the present invention possible to obtain alternating copolymers and sometimes small percentages of randomly oriented copolymers derived from Vinyl compounds with activating groups in the α-position with respect to the carbon-carbon double bond, derived EIn- ^ units contain, the above polymers by reaction of the compounds mentioned with monomers with at least 2 conjugated Double bonds are retained v / ground. The polymerization reaction is carried out in the presence of a solvent by contacting a Monomers of the type of substituted vinyl compounds with a monomer having at least 2 conjugated double bonds, the give the products obtained a high degree of usability, carried out.

The vinyl monomers which contain an activating group in the α-position with respect to the carbon-carbon double bond are selected from the following class of compounds: maleic anhydride, acrylonitrile, methacrylonitrile, puma nitrile, acrylic acids, methacrylic acids, acrylates, methacrylates, fumaric acids and maleic acids, fumaric acid - and maleic acid esters, thioacrylates, dithioacrylates, acrylamide, thioacrylamide, N-substituted acrylamide, N-substituted thioacrylamide, N, N ^f -disubstituted acrylamide, Ν, ΐί'-disubstituted thioacrylamide, acrylic acid halides, thioacrylic acid halides, methyl vinyl sulfketones, vinyl vinyl, acrolein , Sodium amyl sulfonate, etc. The polyene compounds which contain at least 2 conjugated double bonds in their molecule are those as they are in various

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Property rights; - are listed by the same applicant, - for example, the following:

I) i-Isopropylidene-dicyclopentadiene
II) 1-Isopropylidene-5,6-dihydro-dicyclopentadiene III) 1-Isopropylidene-2 (or 3) -methyl-dicyclopentadiene IY) i-Isopropylidene-5,6-dihydro-2 (or 3 -) - methyl-dicyclopentadiene

V) 1-Isopropylidene ~ 3a, 4,7,7a-tetrahydroindene

VI) 1-Isopropylidene-2 (or 3) -methyl-3a, 4,7,7a-tetrahydroindene VII) 2-ITorborn-5-eny 1-4 '(or 5 ^f ) ~ cyclopentadienyl-methane V 11.1) dehydrodicyclopentadiene
IX) 2-Horborn-5-enyl-4 '(or 5 *) ~ (2 or 3'-methyl) -cyclopenta-

di eny 1-methane-X) (2-uroborn-5-eiiyl) -4 '(or 5 ") - (i ^l , 2' or 3 ^l -dimethyl) -

cyclopentadieny1-methane
XI) 2-ITor'born-5-enyl-4 '(or 5 ^l ) - (1 ^!, 2' or 3 ^! -Methyl-isopropyl) ~ cyclopentadienyl-methane

XII) 1- or 2-methyl-dehydrodicyclopentadiene XIH) isodicyclo-3,7a-pentadiene
XIV) 2-lior "bornanyl-4 ^r (or 5 ') - (2' or 3'-methyl) -cyclopenta-

dienyl methane
XV) 2 (2 ^l , 4 ^f -I> imethyl-penta-1 '^' - dienyli-norhor-S-en

XVI) 2- (2 ^l -methylene-4 ^l -methylpent-3'-enyl) -norlDor-5-en,

XVII) 2- (Horborn-5-en) .- 1 «- (3 ', 5 ·, 5 · -trimethyl-cyclohex ^ · -enylidene-1') - methane

XVIO) 2-XTorl) orn-5-enyl-1 '- (3 ^!, 5', 5 ^! -Trimethyl) -dicyclohexa- (2 ^t , 6?) -

di eny1-methane
IXX) 2- (2 ·, 4 ^! -Dimethyl-penta-1 ·, 3'-dienyl) -nor "bornen-XX) 2-isopropenylnor" bornadiene

XXI) 2,3-dimethylene-nort) orn-5-en.

XXII) Inden.

The formation of the copolymers can take place spontaneously afterwards to the simple contact of the two monomers or can be started by suitable initiators of the radical type. the Implementation of the latter method is preferred "when the reaction rate should be increased or if the acceptance

309807/1209.

Tor- and donor power of the two monomers are such that they do not allow the reaction itself to start.

Free radical initiators, which are advantageous according to the invention Methods used can be chosen from a large class of compounds: specially used can azoisobutyronitrile, benzoyl peroxide, t-buty! hydroperoxide, Cumene hydroperoxide, di-t-butyl peroxide, t-butyl peracetate, phenyl percarbonate, Diisopropyl percarbamate, etc.

They are in the reaction vessel at a concentration in the range from 0 to 10 wt. ^, Based on the weight of the introduced Monomers, introduced. As mentioned above, the reaction is carried out in the presence of a solvent which formed by an unsubstituted or substituted aliphatic, cycloaliphatic or aromatic hydrocarbon can be.

Aromatic hydrocarbons are preferably used. The temperature is in a wide range from -150 to +150 ⁰ G and preferably between + 20 ° and 80 ⁰ C.

The copolymers obtained by the process according to the invention, which represent a further feature of the invention, can be used as Thickeners in aqueous or organic solvents, used as dispersants, stabilizers and protective colloids will. Some other typical applications are in the field of pressure sensitive adhesives, adhesives for metals, Detergents, foam suppressants, paper additives, antistatic agents and the like.

The following examples serve to explain the invention more clearly, without restricting them.

example 1

In a 50 cm glass flask from which the air had been removed,

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• 12 cnr toluene, 20 mmol of the compound I, 60 mmoles acrylonitrile (ACLT) un O S ₁ mmol of azoisobutyronitrile (AIBN) were charged. The flask was sealed and placed in a thermostatic bath kept ^{at 60 ° G.} The reaction was carried out for 5 hours, after which it was terminated by coagulating the polymer in methyl alcohol. The amount of the copolymer was vacuum getrocknetj 14 hours at 50 ⁰ G it was 1.03 g and had a ¥ for ert [^] in toluene at 3O ⁰ O of 0.08 dl / g. The product was "completely soluble in toluene and chloroform, and elemental analysis for nitrogen ($ 7.71) indicated that the copolymer had a structure approximately close to that of an alternating copolymer.

Example 2

The previous example was repeated, but 40 mmol of compound I and 40 ml of ACH were introduced . 1.32 g of the copolymer were obtained with a value for ['I] in toluene at 30 ^° C. of 0.12 dl / g.

Elemental analysis for nitrogen ($ 6.3) showed that the copolymer of a completely alternating nature.

Example 3

Example 1 was repeated, except that 60 mmol of compound I and 20 mmol of ACF were fed in. 0.83 g of copolymer were obtained, with a value of [^] in toluene at 30 ⁰ C of 0.082 dl / g. Elemental analysis for nitrogen ($ 6) showed an alternating copolymer »

Example 4

In the above procedure, 20 mmoles of Compound II and 20 mmoles of ACN were copolymerized _{using a catalyst formed from 0.4 mmoles of AIBIi 9.} The copolymerization was carried out for 4 hours at -6Q ° C, to give 0.48 g of the copolymer that was soluble in toluene and chloroform / g had a value for H] in CHCl ₃ l> ei 30 ⁰ C of 0.136 dl, , The elementary

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Analysis for nitrogen (6.4 fo) showed that it was an alternating copolymer.

Example 5

The same test, ^{carried out at 80 °} C. for 1 hour, gave -0.67 g
of a copolymer with a value of [^] in CHCl, of 0.097. the
Elementary analysis for nitrogen (6.7 ° / °) showed that it was an approximately alternating copolymer.

Example 6

According to the above procedure, 5 mmol (II) and 15 mmol
Maleic anhydride (MA) is copolymerized in 12 cm of toluene using an initiator consisting of 0.2 mmol of AIBN. To
6 hours at 60 ° C., 1.36 g of a copolymer with a value for [^] in chloroform at 30 ^° C. of 0.32 dl / g were obtained.

Elemental analysis for C and H (C = 76.6 #, H = 7.5 $) confirmed with great certainty the formation of an alternating copolymer.

This result also showed that the comonomers with the structures I - IV under the claimed conditions over the
The conjugated double bond system they contain reacted.

Example 7

The above test was repeated except that 10 mmoles (II) and 10 mmoles of maleic anhydride (MA) were fed. 2.62 g of the copolymer were obtained with a value for [^] in chloroform at 30 ^° C. of 0.70 dl / g. The elemental analysis on C and H
(C = 75.3 fo, H = 7.4 fo) corresponded very well with the formation of an alternating copolymer.

Example 8

Example 6 was repeated, but 15 mmol II and 5 mmol MA were fed. 1.15 g of the copolymer having a value for [ ¹ ^] in

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CHO1, "at 30 ⁰ O of 0.27 dl / g were isolated. In this case, too, the elemental analysis for C and H (C = 76.2%, H = 7.5 ° C, agreed very well with the formation of an alternating one Copolymers.

Example 9

40 mmoles of indene (XXII) and 40 mmoles of MA were ^{copolymerized in 12 cm 5 of} toluene without the use of an initiator. Was obtained Ifaeh 22 hours at 60 ⁰ C. 0.87 g of a copolymer with a value of ^[1 ^] in dimethyl sulfoxide hei 30 ⁰ C of 0.34 dl / g. Elemental analysis (C = 72.1 ^ and H = 4 ₅ 85 "/ <>) showed that it was" an alternating copolymer.

Example 10

20 mmol (V) and 20 mmol maleic anhydride (M, A.) Were copolymerized in 12 cm toluene using an initiator formed from 0.4 mmol AIBU. After 6 hours at 60 ^° C., 1.78 g of the copolymer with an alternating structure were isolated.

Example 11

Twenty millimoles of a mixture of XV and XVI were copolymerized with 20 millimoles of MA in 12 cubic centimeters of toluene using an initiator consisting of 0.4 millimoles of AIBN. After 5 hours at 60 ^° C., 2.06 g of a copolymer with an alternating structure were obtained.

Example 12

20 mmol II was polymerized with 20 mmol MA in 12 cnr toluene without the use of an initiator. Hach 20 hours at 60 ° C to give 0.42 g "of a copolymer with a value for \\] in CHCl * at 30 ⁰ C of 0.60 dl / g. The elemental analysis for C and H (C = 75.2 io and H = 7.3 ° / °) agreed very well with a copolymer with an alternating structure.

Example 13

20 mmoles of a mixture of isomers XVII and XVIII were mixed with 20 mmoles of MA in 12 cm ^{5 of} toluene using one of 0.4 mmoles

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AIBN existing initiator copolymerized. After 7 hours, JO minutes at 60 ⁰ O 0.22 g of a copolymer were isolated, whose elemental analysis corresponded very well with a copolymer of alternating structure.

Example 14

According to the above procedure, 20 mmoles of VIII were made with 20 mmoles "5

MA copolymerized in 12 cm of toluene using an initiator consisting of 0.4 mmol of benzoyl peroxide. After 6 hours at 60 ^° C., 0.95 g of a copolymer was isolated which, in agreement with the elemental analysis, had an alternating structure.

Example 15

20 mmol IX was copolymerized with 20 mmol MA in 12 cnr toluene using an initiator of 0.4 mmol cumene hydroperoxide. After 8 hours at 80 ⁰ C. 1.6 g of a copolymer were isolated, whose elemental analysis indicated that it was an alternating copolymer.

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(π)

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CH CH

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309807/1209

Claims (1)

Claims 1. Copolymers formed from alternating or alternating Units derived from vinyl compounds with a functional group in the α-position with respect to the carbon-carbon double bond and of cyclic polyene compounds containing at least 2 conjugated double bonds. 2. Copolymers according to claim 1, characterized in that the vinyl compound is selected from the compounds maleic anhydride, Acrylonitrile, methacrylonitrile, fumaric acid dinitrile, acrylic acids, methacrylic acids, Acrylates, methacrylates, furaar acids and maleic acids, fumaric acid and maleic acid esters, thioaerylates, ■ Dithioacrylates, acrylamide, thioaerylamide, U-substituted acrylamide, N, N'-disubstituted thioacrylamide, acrylic acid halides, Ihioaerylsäurehalogen.iden, acrolein, Viny! Ketonen, Methylvinylsulfon, Methyl vinyl sulfoxide and sodium vinyl sulfonate. 3. Copolymers according to claim 1 or 2, characterized in that the cyclic polyene compound is selected from I) 1-isopropylidene-dicyclopentadiene
II) i-isopropylidene-S ^ -dihydro-dicyclopentadiene III) 1-isopropylidene-2 (or 3) -methy1-dicyclopentadiene IV) 1-isopropylidene-5,6-dihydro-2 (or 3) -methyl-dicyclopentadiene V) 1-isopropylidene-3a, 4,7,7a-tetrahydroindene VI) 1-Isopropylidene-2 (or 3) -methyl-3a, 4,7,7a-tetrahydroindene VII) 2-liorborn-5-enyl-4 '(or 5') -cyclopentadienyl-methane VIII) dehydrodicyclopentadiene IX) 2-Norborn-5-enyl-4 '(or 5 ^f ) - (2' or 3'-methyl) -cyclopen- tadieny1 methane
X) (2-norborn-5-enyl) -4 '(or 5') - (ΐ ', 2' or 3'-dimethyl) -cyclopentadiene-eny1-methane XI) 2-Norbom-5-eny1-4 '(or 5') - (i ', 2' or 3 ^! -Methyl-isopropyI) -cyclopentadieny1-methane 309 807/1209 XII) 1 or 2-methyl-dehydrodicyclopentadiene. XIV) 2-Norbornanyl- (4 'or 5 *) - (2' or 3'-methyl) -cyclopentadienyl-methane XV) 2 (2 ', 4' ^ dimethyl-penta-1 ', 3'-dienyl) -norborn-5-en XVI) 2- (2'-methylene-4 • -methylpent-3'-enyl) -norborn -5-en XVII) 2- (Norborn-5-en) -1 ^l - (3 ', 5 ^I , 5 ^l -trimethyl-cyclohex-2 ^l - enylidene-1 ') methane
XVIII) 2-Norborn-5-enyl-1 '- (3', 5 ', 5 ^f -trimethyl) -dicyclohexa- (2', 6 ¹ ) -dienyl-methane
XIX) 2- (2'4'-dimethyl-penta-1 ', 3'-dienyl) -norbornen- XX) 2-isopropenylnorbornadiene
XXI) 2,3-dimethylene-norborn-5-en
XXII) Inden. 4. Process for the production of copolymers, which consist of alternating, or alternating units are formed, which differ from vinyl compounds with a functional group in the α-position with respect to the carbon-carbon double bond and of cyclic polyene compounds which have at least two conjugated Have double bonds, derive, characterized in that a vinyl monomer according to claim 2 with a cyclic Bringing polyene monomers according to claim 3 in contact. 5. The method according to claim 4, characterized in that the polymerization reaction in the presence of radical initiators from the group azoisobutyronitrile, benzoyl peroxide, t-butyl hydroperoxide, Cumene hydroperoxide, di-t * butyl peroxide, t-butyl peracetate, Phenyl percarbonate and diisopropyl percarbamate is carried out. 6. The method according to claim 5, characterized in that the initiators in the reaction vessel in a concentration range from 0 to 10 wt. 5 ^, based on the weight of the introduced Monomers, are introduced. 7. The method according to any one of the preceding claims, characterized in that that the reaction in the presence of a solvent consisting of a substituted or unsubstituted aliphatic 309807/1209 see, cycloaliphatic or aromatic hydrocarbon "consists, is carried out. 8. The method according to claim 7, characterized in that the Reaction in the presence of an aromatic hydrocarbon solvent is carried out. 9. The method according to any one of the preceding claims, characterized in that the reaction is carried out at temperatures in the range of -150 ° and +150 ⁰ O and preferably between + 20 ° and +80 ⁰ C. 30 9 8 07/1 209