DE1200988B - Adhesive based on solutions of homo- and / or copolymers of 2-chlorobutadiene in organic solvents - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CI .:

C 09 j

German class: 22 i - 2

Number: 1 200 988

File number: F 32196IV c / 22 i

Filing date: September 24, 1960

Opening day: September 16, 1965

It is known to use solutions of polychlorobutadiene, which usually contain auxiliaries and fillers, for Use for bonding leather, rubber, plastics, wood, metals and other materials.

However, it has been shown that adhesives based on polychlorobutadiene, which are both resins, in particular terpene resins or modified terpene-phenolic resins as well as condensation resins made from phenols and aldehydes, often behave in an unstable manner on storage. Mostly can in storage Such adhesive combinations result in a flaky agglomeration of the auxiliaries they contain, which eventually settle on the bottom of the storage vessel can be observed. To avoid this disadvantage is therefore mostly used in practice adhesive solutions based on Polychlorobutadiene, which contain tetraalkylthiuram disulfide in addition to other auxiliaries, these adhesives Type do not show the above-mentioned flocculation or settling phenomena or in comparison to adhesives, which do not contain tetraalkylthiuram disulfide, only after a considerably longer storage time. Also will the compatibility of such polychlorobutadiene solutions with certain resins is improved.

On the other hand, however, polychlorobutadiene adhesives containing tetraalkylthiuram have serious disadvantages. In contact with other materials, for example when stored in vessels made of iron or copper or alloys of these metals, adhesives based on solutions occur
from homo- and / or copolymers of
2-chlorobutadiene in organic solvents

Applicant:

Paint factories Bayer Aktiengesellschaft,

Leverkusen

Named as inventor:

Eugen Bock,

Dr. Dietrich Rosahl, Leverkusen;

Dr. Manfred Dollhausen, Hitdorf / Rhine;

Dr. Anton Heinz, Cologne-Flittard;

Dr. Fritz Schmidt, Dabringhausen

or polysulfides or mixtures of both from the aliphatic or cycloaliphatic series and the correspond to the following general formula:

R ₁ - S _x - R ₂

wherein χ is an integer from 1 to 5, R _{1 is} both a lower and a higher alkyl or cycloalkyl radical and R _{2 is} hydrogen, a lower or higher one

very often already after a short period of time means considerable, un- 30 alkyl or cycloalkyl radical,
wanted discoloration. Furthermore, suitable compounds of this type, which often come from adhesions, for example of objects of the present invention, especially in Beaus leather, even when using Polyclohr- costume, are tert-dodecyl mercaptan, n-dobutadiene solutions, which to the exclusion of the above decyl mercaptan , n-octyl mercaptan and n-decyl mer-mentioned metals were stored, considerable amounts of captan and didodecyl di- or polysulfide were stored. The coloring phenomena. Auxiliaries to be used according to the invention should

It is already known that thiuram- dene solutions of 2-chlorobutadiene homo- or Co-containing Polychlorobutadiene-based adhesives, the polymerizate in amounts of 0.1 to 8 percent by weight, Prepared in vessels made of iron or brass or preferably stored in quantities of 0.5 to 2 percent by weight are, for example, based on the content of solid 2-chlorine, by adding certain substances, such as 40 cents Zinc oxide or calcium silicate, back-butadiene polymer can be incorporated. The best

to push. However, the incorporation of effective amounts of these materials is at a loss of valuable adhesive engineering Properties associated, for example with a loss of what is often required in practice Stickiness of the adhesive spreads.

There were now adhesives based on solutions of homo- and / or copolymers of the solid 2-chlorobutadiene found, which are free of results with a content of long-chain, d. H. Mercaptans containing 10 to 14 carbon atoms in amounts of about 1.5 percent by weight achieved.

The additives to be used according to the invention are suitable both for stabilizing adhesive solutions from homopolymers of 2-chlorobutadiene with different degrees of polymerization as well

the disadvantages of adhesive copolymers of chloroprene with copolymers similar to those mentioned above are. These adhesives according to the invention are labeled with sizable monomers, such as, for example, 2,3-dichloro due to a content of mercaptans butadiene. These polymers can after per se

509 687/431

3 4

known methods can be obtained. If necessary, known anti-aging agents, such as polymers of 2-chlorobutadiene in combination, for example phenols and amines, can also be added,
cut with other copolymers, for example The adhesive solutions according to the invention are based on butadiene-acrylonitrile. The adhesives according to the invention can display solutions 5 storage stability and at the same time show in contact with the 2-chlorobutadiene polymers in various with certain metals, such as iron or copper or solvents, the solid alloys thereof showing no discoloration. With the help of the content of these solutions according to the adhesives of this type used, the discoloration-free gluing, solvent or solvent mixture is aimed and especially of leather types, also according to on the other hand, should be dimensioned so that these adhesive solutions in iron or copper can be deleted , sprayable or containing containers for roller application possible. Discoloration-free approved solution is obtained. It goes without saying that adhesives, especially leather, are also possible, especially with 2-chlorobutadiene polymer adhesives, which are of practically interesting dark storage. Kind to use in the form of kitten. These adhesive The parts of the substance solutions mentioned in the examples below usually have a solids content of between 10 and 30 percent by weight, unless otherwise stated
Cherishes. example 1

As a solvent for the 2-chlorobutadiene polymer

mostly known organic sol- To produce an adhesive according to the invention

ventien, such as B. aromatic hydrocarbons 20 are substance

(Benzene and its homologues toluene, xylene), cyclo- _{m Teüe} PoiycMorbutadiene rubber from
aliphatic hydrocarbons e.g. B. Cyclohexane, _{Defo 1000 (DIN 53 514 frd of}
chlorinated aromatic or aliphatic carbon thiuram derivatives),
Hydrogen, (chlorobenzene, chloroethylene or ethy- 4 parts zinc oxide
lendichlorid), esters such as methyl acetate, ethyl acetate 25 and 4 parts magnesium oxide
as well as those of higher organic acids and 2 parts of tert-dodecyl mercaptan
Alcohols, ketones, such as methyl ethyl ketone or mixtures of these solvents with one another. Aliphatic hydrocarbons, which are inert on a roller mixer of a suitable size, are usually processed in a mixture for half a period of 5 to 15 minutes to form a uniform sheet with one or more of the aforementioned solutions. The rolled head obtained is used medium. together with 40 parts of terpene phenol resin in

The additives according to the invention can be homogeneous to 360 parts of a solvent mixture

term homo- or copolymer dispersed in the production, the out

be added to the solution or the finished solution. _{40 parts of} methyl acetate

However, it is on the other hand the incorporation of 35 40 parts gasoline with boiling range 65 and according to the invention to use additions m to 95 ⁰ C and
polychloride-20 parts of toluene used to prepare the solution
butadiene rubber possible. Furthermore, the incorporation of the additives can also already be mixed together in the poly.

merisatlatex, which is used to produce chlorobutadiene 40 The adhesive produced in this way with a viscosity

rubber is used. of 1000 cP is stable for more than 130 days while a

For the production of adhesives based on comparative adhesive prepared in the same way without

2-chlorobutadiene polymer solutions of the above additive according to the invention clearly after 10 days

mentioned type, the most diverse known perceptible flocculation and separation

Auxiliary materials are used. 45 examples are shown.

called: means for increasing the adhesive properties, one with the adhesive according to the invention on one such as B. natural or synthetic resins, phenolic glass plate glued, synthetically tanned white leather modified Coumarone resins, unmodified coumarone strips indicate after storage in the dark for more than resins, alkylphenol-formaldehyde resins or resins do not discolour for 6 months. At settlement sale Base modified or unmodified Colopho- 50 look with an adhesive made from thiuram-containing nium ester. Polychlorobutadiene, but otherwise in the same way as

Furthermore, known thermosetting additives, such as that produced according to the invention, can already be used

aromatic di- and / or polyisocyanates, such as. B. after 10 days on the white leather surface

Triphenylmethane 4,4 ', 4 "-triisocyanate, 4,4'-Diphenyl- borrowed yellow discolorations are observed,

methane diisocyanate or the reaction product of 55. Further examples of the invention follow

3 mol of toluene diisocyanate and 1 mol of trimethylol adhesive combinations:
propane, come into use. Furthermore, in

Vulcanization accelerator in this context, Example 2
niger, such as B. bifunctional strongly basic mono-

or polyamines, preferably primary or secondary, 60 _{100 Teüß} p _oly chi _{orbutadienkautS} chuk vom

such as B. Polyalkylenpolyamm called. £ j _e j? _o ^ qq

It is also possible to use known acid acceptors g j _& ^ _& zinc oxide

add, for which the metal oxides and 3 _{parts of Ma} g _nes i _um o _X yd,

Carbonates of metals of main group II of 1.5 parts tert. Dodecyl mercaptan and

Periodic Table. 65 20 parts of a terpene-phenol resin

Finally, there are the usual filling and reinforcement '

substances such as carbon blacks, silicic acid or their dissolved to form an adhesive with a viscosity of 1000 cP

Salts and dye pigments into consideration. the solvent mixture given in Example 1.

Example 3

Parts of polychlorobutadiene rubber from

Defo 1000,

5 parts magnesium oxide,
3 parts of n-dodecyl mercaptan and 40 parts of a terpene phenol resin,

dissolved to form an adhesive with a viscosity of 1000 cP with the solvent mixture given in Example 1.

IO

Example 4

Parts of polychlorobutadiene rubber from Defo 500,

3 parts zinc oxide,

4 parts magnesium oxide, 10 parts precipitated silica (small amount

Containing calcium silicate),

2 parts of n-decyl mercaptan and

30 parts of a terpene-phenol resin,

ao

dissolved to form an adhesive with a viscosity of 1000 cP with the solvent mixture given in Example 1.

Example 5

Parts of polychlorobutadiene rubber from ^a5

Defo 1000,

3 parts magnesium oxide,

5 parts of zinc carbonate,

1 part of n-octyl mercaptan and 20 parts of a terpene phenol resin,

dissolved to form an adhesive with a viscosity of 1000 cP with the solvent mixture given in Example 1. In the above examples 2 to 5, the processing method and testing proceed in a manner analogous to that in Example 1. It is found that all the adhesives mentioned above Compositions have an increased storage stability compared to unmodified adhesives of this type, but in particular neither when stored in vessels made of iron or copper or their alloys nor discolour if leather is glued.

Claims (2)

Patent claims: 1. Adhesive based on solutions of homo- and / or copolymers of 2-chlorobutadiene in organic solvents, characterized in that these Adhesive solutions 0.1 to 8 percent by weight, based on the content of solid 2-chlorobutadiene polymer, Mercaptans or polysulfides of the general formula or mixtures thereof, in which χ denotes an integer from 1 to 5, R ₁ denotes both a lower and a higher alkyl or cycloalkyl radical and R ₂ denotes hydrogen, a lower or higher alkyl or cycloalkyl radical. 2. Adhesive according to claim 1, characterized in that the same long-chain aliphatic Mercaptans with 8 to 14 carbon atoms in amounts of the order of 1.5 percent by weight contains. Considered publications:
U.S. Patent No. 2,838,463;
French Patent No. 1,097,360;
Luttgen, "The Technology of Adhesives", 1959, Part 1, pp. 320/321. 509 687/431 9.65 © Bundesdruckerei Berlin