DE1257429B - Process for the production of crosslinkable or crosslinked copolymers - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CL:

C08f

German class: 39 c - 25/01

Number: 1257 429

File number: B 78136IV d / 39c

Filing date: August 17, 1964

Open date: December 28, 1967

It is known to crosslink polymers made from ethylenically unsaturated compounds. So one has z. B. already polyethylene by high-energy rays and copolymers of ethylene and Propylene with peroxides, chlorinated and sulfochlorinated Ethylene and polypropylene cross-linked with metal oxides. Copolymers are also already available with polymerized functional groups such as epoxy, hydroxyl or N-methylolamide groups, and they are made by adding crosslinking agents such as polyvalent amines and isocyanates or amides. However, the results obtained are still unsatisfactory in some respects.

It has now been found that it is advantageous to use crosslinkable and / or crosslinked copolymers can be produced if you have 2,3-dihydrofurans with ethylenically unsaturated compounds in the presence of cationic and / or Ziegler-Natta catalysts at temperatures from -100 to + 60 ° C copolymerized and optionally the copolymers in the presence of cationic catalysts or networked with the help of peroxides.

The unsubstituted 2,3-dihydrofuran and the 2,3-dihydro-5-alkylfurans are used to produce the copolymers preferred. However, other substituted 2,3-dihydrofurans, the alkylene, alkylaryl or carry aryl residues, which can also be linked to the furan ring via an ether bridge, use.

Ethylenically unsaturated monomers are those with cationic or with Ziegler-Natta catalysts polymerizable monomers, optionally mixed with one another, in question. Exemplary be olefins such as ethylene, propylene, butene, isobutene, cyclic olefins such as cyclopentadiene, cyclooctadiene, Cyclooctatetraene, vinylcyclohexene, dienes such as butadiene or isoprene, and also vinyl alkyl ethers such as methyl, Ethyl, propyl, butyl and isobutyl vinyl ethers, called. It is also possible to use monoepoxides in the To use polymerization. Preferred comonomers are the aliphatic olefins. The quantity ratio the dihydrofurans mentioned to the comonomers can depending on the desired properties of the copolymers and according to the crosslinking density to be achieved of the crosslinked products in can be varied widely. However, it is advantageous if the compounds used as comonomers Do not exceed 90 percent by weight of the monomer mixture. Are preferred for Production of the copolymers from dihydrofurans and olefins 10 to 25 percent by weight dihydrofuran

Method of manufacture

crosslinkable or crosslinked copolymers

Applicant:

Aniline & Soda Factory in Baden

Aktiengesellschaft, Ludwigshafen / Rhein

Named as inventor:

Dr. Herbert Naarmann, Ludwigshafen / Rhine;

Dr. Kurt Schneider, Limburgerhof

and 90 to 75 percent by weight olefins, ζ. Β. Ethylene, used.
Catalysts for the copolymerization of the dihydrofurans with the comonomers mentioned are the customary cationic polymerization catalysts, in particular Friedel-Crafts catalysts, and the catalysts of the Ziegler-Natta type, as obtained by combining compounds of the transition elements of groups IV to VIII Periodic table of the elements with metals, metal hydrides or organometallic compounds from groups I to IV of the periodic table of the elements arise in question. Examples are:

Aluminum chloride, aluminum bromide, boron trifluoride and etherate of boron trifluoride, tin (IV) chloride, Iron (III) chloride, molybdenum (V) chloride, titanium (IV) chloride, optionally in the presence of metal alkyls, such as aluminum triethyl, aluminum triisobutyl, tin dibutyl dichloride, di-tert.-butylmagnesium, mercury diphenyl chloride, and optionally with the addition of metal halides, such as cobalt (III) chloride, Titanium (III) chloride or zinc (II) chloride. The ratio of the additives, such as the metal alkyls and / or the metal halides for the Friedel-Crafts catalyst is expediently between 0.1 and 10 percent by weight.

The catalysts are generally used in amounts of 0.1 to 5 percent by weight, based on the compounds to be polymerized. Larger amounts can of course also be used, but this generally has no particular advantages.
The polymerization temperatures depend on the type of compounds to be polymerized and on the type of catalysts used. You should expediently below + 6O ⁰ C, preferably between

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3 4

see -80 and +40 ⁰ C, lie. To maintain temperatures below and a high elastic percentage. It ^{is preferred to use 0} ° C. if it is also possible to use high levels which are otherwise difficult to dispense in polymerized cyclic enol ethers or want to copolymerize wetting polyisobutylenes without major degradation in vinyl ethers. For the copoly- crosslinked products to be transferred. In the case of suitable merization with isobutene, temperatures of about 5 are required. Selection of comonomers in solution through -30 to -50 ° C. The use of higher guided crosslinking also for the production of numerous temperatures, however, is z. B. serve in the Copolymeri- waterproof paints.

sation of dihydrofurans with olefins such as ethylene It is a particular advantage of the new copoly-

or propylene, or expedient with epoxides. merisate that they not only work with ionic catalysts,

The copolymerization can be crosslinked in bulk or in io but also with the aid of peroxides

Presence of solvents and diluents can. Examples of suitable peroxides are

like benzene, toluene, xylene, cyclohexane, isooctane, called :( «, oc-dialkylbenzyty-peroxide ^ is - ^^ - dichloro-

n-hexane or gasoline fractions. oc, «- dialkylbenzyl) peroxide, tert.-butyl-a-cumylper-

Since the polymerization proceeds very quickly, it is oxide, 2,5-dialkyl-2,5-bis- (tert-alkylperoxy) -hexane,

expedient, the catalyst or the catalyst 15 optionally also in a mixture with dicumyl peroxide.

to be presented in a mixture, if necessary to let it »mature«. The selection of the suitable peroxides is based

and the monomers gradually approximately in the range here according to the type and amount of comonomers,

The extent to which it is consumed during polymerization, which also determines the processing temperatures.

will admit. It is also possible over the course of the men. Particularly suitable peroxides are those whose

Adding new catalysts to polymerization. One 20 decomposition temperatures above the softening

can also make the process continuous, temperatures of the copolymers are,

by the copolymer formed, to the extent that, for. B. the crosslinking of the copolymers

as it arises, discharges from the reaction vessel. from 2,3-dihydrofuran and ethylene, butadiene or

By adding amines or amides to the butadiene and styrene at temperatures from 60 to

The remaining catalysts are used in polymerization batches, e.g. with HiKe of 0.2 percent by weight

inactivated quantities of carbon dioxide and the copoly- di-tert-butyl peroxide obtained is carried out,

meren isolated in a known manner. The networking speed in networking

The new copolymers are generally made with peroxides in a known manner

light colored products and can be used in the thermal addition of further crosslinking additives, such as di-

Plastics known type processed into moldings 3 ° and trivinyl or allyl compounds, by adding

will. Their solubility in the usual organic p-benzoquinone-dioxime, B3ei (IV) -oxide and 1,5-

Solvents and their softening range or 2,6-dichloro-p-benzoquinone, are accelerated,

depending on the type and amount of polymerized In some cases it is advantageous by adding

Comonomers. z. B. Sulfur degradation reactions in peroxidic

The special characteristic of the obtained copoly- 35 to prevent crosslinking.

merisate is their content of tetrahydrofuran grup- The crosslinking reactions that preceded or also

pings. Although substituted tetrahydrofurans simultaneously with the deformation of the copolymers

known to be difficult to make with ring opening poly, give products that

can be merized, it is surprisingly better mechanical compared to the uncrosslinked

possible, the copolymers according to the invention below 40 properties and increased swelling resistance

To convert ring opening into cross-linked polyethers. point. You will find in particular for the production of

The moldings and coatings in particular are used as ring-opening catalysts. very

by H. Meerwein (Angewandte Chemie, 24 they are suitable for the production of clear, water-resistant

[1960], p. 927) for the polymerization of tetrahydrofuran coatings, as adhesives and as quality-improving

proposed catalysts, such as trialkyloxonium 45 fillers for rubbers.

salts, dialkyl hydroxonium salts and acylium salts, The parts mentioned in the following examples

suitable. Surprisingly, the ring opening is parts by weight. The specified K values were

reaction also with other cationic catalysts, according to H. Fikentscher, Cellulosechemie, 13

z. B. Antimony trichloride, antimony pentachloride, Phos- (1932), p. 58, determined,
phosphorus oxychloride or mixtures of acetyl chloride 50

and aluminum chloride, possible. The networking of example 1
Copolymers takes place so easily that already one

Addition of alcohols or water to the still 50 parts of dried 2,3-dihydro-5-methylfuran

Polymerization catalyst-containing copolymers are treated with 50 parts of dried vinyl isobutyl ether

mixed during work-up at temperatures above 55 and 400 parts of η-hexane. Be at 0 ° C

about 50 ° C leads to crosslinked products. 0.05 part of boron trifluoride diethyl etherate has been added. Select

it thus in hand, optionally the uncrosslinked end of the exothermic polymerization reaction

To isolate copolymers and in a separate one the temperature in the reaction vessel is not over

To cross-link reaction, or rise ^{in a stage equal to 10 0 C.} After 2 hours the volatile

produce crosslinked polymers. So reaction products, such as the eastern monomers and

About the amount of polymerized Dihydro- the solvent, at 50 ⁰ C in a vacuum of 12 Torr

furans, which are then distilled off as tetrahydro- in the copolymer. 89 parts of a copolymer are obtained

furan groups are present, the crosslinking, which is soluble in methyl chloride, has a K value (1%

adjust density within wide limits. After solving) 53 and a softening point of

According to the method according to the invention, it is possible to have 65 about -5 ° C.

Copolymers composed predominantly of olefins 10 parts of the copolymer obtained are in

to crosslink according to a new principle and dissolved on this 40 parts of methylene chloride and after addition

Way elastomers with good temperature resistance of 0.1 part acetyl chloride on an iron sheet on

brings. A completely cross-linked, only swellable coating is obtained.

Example 2

A mixture of 0.5 parts of aluminum chloride, 0.5 part of triethylaluminum and 100 parts of toluene is stirred ^ hour at 10 ° C and then cooled to -25 ⁰ C. A solution of 70 parts of 2,3-dihydrofuran and 30 parts of cyclopentadiene in 200 parts of toluene is added to this mixture over the course of 2 hours. The temperature is not allowed to rise above ⁰ ° C. during the feed. After the feed, the reaction mixture is still ¹ Z stand for ₂ h at 2O ⁰ C and then the copolymer at temperatures below 20 ° C is isolated. The catalyst residues still contained in the polymer are inactivated by adding formamide.

The copolymer obtained is in mixtures of toluene and chlorobenzene (volume directory 1: 1) soluble and has a K value (l ° / _o solution) of 56. The softening point of the copolymer obtained is about 163 ⁰ C.

If the rest of the catalyst in the copolymer is not inactivated immediately, but the copolymer is When worked up in methanol at an elevated temperature, crosslinked products are already formed.

Example 3

40 parts of ethylene and 10 parts of dihydrofuran in 200 parts of petroleum ether are added separately to a mixture of 0.3 part of aluminum chloride, 0.5 part of aluminum diethyl chloride, 0.2 part of cobalt chloride and 100 parts of benzene over the course of 2 hours. The polymerization temperature is kept below 45 to 50 ° C. After working up, 28 parts of a copolymer are obtained which contains 27 percent by weight of dihydrofuran in copolymerized form and has a softening point of about 88.degree. The K value (0.5 ° / ₀ solution in decahydronaphthalene) is 84th

10 parts of the copolymer obtained, which still contains catalyst residues, are crosslinked ^{at temperatures above 60 ° C. by adding water.}

10 parts of the copolymer, in which the catalyst residues before working up by adding 0.5 parts of dibutylamine have been inactivated, on the other hand, by simply adding water or alcohol Cannot be crosslinked at higher temperatures. However, the isolated polymer is successfully crosslinked with the addition of 1 percent by weight of a mixture of acetyl chloride and zinc chloride (ratio 1: 1). The product is insoluble and is due to its high melt viscosity and its adhesiveness suitable as hot melt adhesive on wood, paper and metals.

10 parts of the copolymer are mixed with 3 parts of carbon black CK 3 and 0.2 part of di-tert-butyl peroxide and ^{heated to 110 °} C. for 3 hours. A completely insoluble, crosslinked product is obtained.

Example 4

The procedure is as in Example 3, but instead of aluminum chloride titanium (III) chloride and instead of ethylene propylene for the preparation of the copolymers. This gives 18 parts of a copolymer having a K value of (O, Z 5 ° _o solution in decahydronaphthalene) of 79 and having a softening point of about 183 ° C. The copolymer can be crosslinked in the above manner in Example 3.
5

Example5

90 parts of 2,3-dihydrofuran and 10 parts of cyclooctadiene (l, 5) will be within 5 hours

ίο a mixture of 1 part titanium tetrachloride and Given 100 parts of η-hexane. The polymerization temperature is -5 ° C. After the polymerization allowed to stand at 45 ° C. for 2 hours. Then the solvent and the unreacted Monomers distilled off. 74 parts of a copolymer are obtained, which according to its iodine number Contains 8.2 percent by weight of vinylcyclohexene polymerized. The K value of the copolymer (1% Solution in carbon tetrachloride) is 36.5, the softening point is around 144 ° C. The polymer is soluble in aromatic hydrocarbons at room temperature.

The copolymer obtained can be obtained by adding 0.1 part of aluminum chloride and 0.1 part of water and heating to 90 ° C converted into crosslinked products which are completely insoluble and provide clear waterproof films or metal coatings.

Example 6

100 parts of isobutylene and 10 parts of 2,3-dihydrofuran are added simultaneously, but separately, to a mixture of 1.2 parts of boron trifluoride in 125 parts of liquid dry ethylene. After the polymerization, the solvent and the unreacted monomers are distilled off. This gives 64 parts of a colorless Copolymeriates having a K value (l ° / _o solution in dichlorobenzene) 78. The product is z. B. soluble in boiling xylene, ethylbenzene or styrene. The solutions produce a tough, clear film when they dry out.

The copolymer can be added by adding 0.1 part of tin (IV) chloride and 0.1 part of hydrochloric acid Crosslink room temperature via the tetrahydrofuran rings contained in the copolymer. The product is no longer soluble in gel-free form in the solvents mentioned above, even at the boiling point. the Mooney viscosity ML 4 'at 100 ° C is e.g. 48 in contrast to 34.5 for the non-crosslinked product (determined according to ASTM 927-57 T).

Example 7

100 parts of butadiene and 25 parts of dihydrofuran are added in the course of 1 hour to a mixture of 300 parts of petroleum ether, 0.5 part of aluminum diethyl monochloride, 0.2 part of cobalt (II) acetylacetonate and 0.1 part of aluminum tribromide. The reaction temperature is -30 ° C. The reaction is allowed to continue at + 5 ° C. for a further hour. After drawing off the solvent, 78 parts of a polymer containing 12 weight percent dihydrofuran and the butadiene to 85 ° / ₀ in 1,4-cis-structure contains in copolymerized form.

After crosslinking 50 parts of the product with 0.5 part of cumene hydroperoxide in the presence 25 parts of carbon black CK 3 at 140 ° C. for one hour becomes a product with tear strength

Claims (1)

7 8 of 170 kg / cm ^a (DIN 53504). Uncrosslinked ethylenically unsaturated compounds have a tensile strength of 5 kg / cm ² . maintenance of cationic and / or Ziegler- Natta catalysts at temperatures of -100 Fatent claim: Feis ₊₆₀ ° _c copolymerized and possibly the Process for the preparation of crosslinkable or 5 copolymers in the presence of cationic cross-linked copolymers, thereby marked catalysts or with HiMe of peroxides draws that 2,3-dihydrofurans are also crosslinked. 709 710/600 12.67 © Bundesdruckerei Berlin