DE1494431C3 - Use of terpolymers for the production of coatings - Google Patents

Description

3 4

The low molecular weights of these polymers are secured by a valve, a temperature measurement is not only sufficient for the achievement and three separate liquid metering devices of high degrees of hardness are important, but also for the gene is provided, 3 liters of freshly cleaned, production of sufficiently highly concentrated solutions. Distilled and dried over aluminum oxide For the production of lacquers and coating agents, 5 toluene is poured in and then heated to 50 ° C, because it is for technical and economic reasons. a gas mixture consisting of 2.5 1 ethytrated solutions in organic solvents or oils, 101 propylene and 0.251 hydrogen during so-called liquid polymers without solvents to be used for 25 minutes with simultaneous cooling of the toluene, but the solutions despite this io to 35 ⁰ C initiated. Under these conditions, high polymer concentrations (for example almost the total amount of the gas introduced - 50%) are still so viscous that they are easily processed, a mixture is absorbed by the solvent, for example painted on in a conventional manner. Now 60 ml of a 10% igen solution of the di-. or splashed. The lacquers and cyclopentadiene are added in toluene and then coating agents according to the invention are prepared in such a way that the polymerization is carried out with simultaneous introduction that initially by polymerization of the mono- a gas mixture consisting of 60 mol percent mers in suitable solvents with metal ethylene and 40 mol percent Propylene, solution drops diluted by inorganic complex catalysts in each case of a part of the catalyst grains of these described unsaturated olefin copolymers A and B are started. The catalyst components of low molecular weights are produced, ao component A consists of a solution of 5.7 millimoles.From these dilute solutions, the vanadium oxytrichloride (VOCl ₃ ) in 95 ml of toluene, the polymers after purification of the catalyst-catalyst component B from a solution 15 millimoles of ethylaluminum sesquichloride (Al ₂ Et ₃ Cl ₃ ) can next be isolated from constituents by removing the solvent. The polymer is used in 50 ml of toluene.

but preferably with such solvents, 25 After the start of the reaction, the metering devices are also usually suitable for producing the speeds of the catalyst components and lacquer and coating solutions. In this case, the gas mixture feed is regulated so that everything needs to be done, the solvent is then converted into non-conducted gas. In this case, it is necessary to be completely removed, but only to the extent that the pressure remains constant at constant temperature, as is the case for the polymer concentrations 30 in the reactor. Simultaneously with the start of polymerization is desired. If necessary, these solutions can be carried out, the continuous addition of further then still with other additives, such as. B. 540 ml of a 10% solution of dicyclopentadiene its solvents, air-drying oils and in toluene and the continuous supply of siccatives are added. If the polymers contain 0.8 l of hydrogen in the reaction mixture,
but after the catalyst has been completely freed from the polymerization solvents, while keeping the temperature constant at 35 ° C., the catalyst is used for the continuous additions. B. because the polymerization solvent as varnish components A and B, of 82 liters of the ethylene / and coating solution components undesirable propylene gas mixture, of 540 ml of 10% Dischein, these are again in suitable solution cyclopentadiene solution and from 0, 8 1 hydrogen gas: medium dissolved and, if necessary, with additives 40 2 hours required. Now there is no further provision. The additions made by both methods are stirred for a further 60 minutes and at the same time solutions can now be cooled to room temperature in closed vessels. Then it can be stored for as long as you like. To generate the catalyst by adding ethyl alcohol des- \) paint or the coatings, they are now activated on the.

surfaces to be treated in a suitable manner 45 To remove the catalyst residues applied and either at room temperature the clear, easily mobile solution ■ initially with or at an elevated temperature, preferably under the dilute aqueous hydrochloric acid and then with water Cured by the influence of air. washed.

For the state of the art, the following are two variants la) and Ib)

French patent 1413 234_hinzuzüge, the 50 described the further treatment. -

deal with the production of ethylene propylene

Terpolymers concerned, with alkyl la) as termonomers. The solvent is removed by norbornadienes and alkenylnorbornenes are used and distillation in vacuo at 50 ° C in a rotary

the crosslinking is achieved by vulcanization. tion evaporator. With complete distillation of the

The toluene according to this French patent specification 1 413 234 55 becomes 161 g of a tacky clear Manufactured products have received rubber-like residue from the desired

Character and are therefore to be used for terpolymer production with the following composition not suitable for coatings. stands:

The invention is illustrated by the following examples Propylene content: 30 mol percent (determined according to

explained: .60 the infrared method)

Iodine number: 44 (determined according to the iodine

A. Preparation of the polymer solutions - chloride method)

. . Weight percent

Terpolymers of ethylene, propylene and dicyclopentadiene

cyclopentadiene. In a 65 filled with inert gas in the polymer: 23

5 liter glass reactor with a stirrer, two ' \ rj] benzene, 32 ° C: 0.045 [l / g]

Gas inlet pipes, a gas outlet leading to the middle molecule

Completion of the reactor against the outside atmosphere lar weight: ~ 15000 (osmometric)

Ib) Since toluene is also a cheap solvent for the production of the lacquers and coating agents, it is expediently incomplete distilled off, but only to the extent that it is necessary to produce a desired polymer concentration is required. The solution freed from catalyst residues is then concentrated only until a residue of 362 g is preserved. This creates a spreadable 50% ethylene-propylene-dicyclopentadiene terpolymer solution received, which - as shown in the further examples - directly or continue after stirring in additives can be processed.

B. Manufacture of coating agents, as well as their application and curing

example 1

The unsaturated ethylene propylene terpolymer described under A, variant 1 a), which is polymer for short A should be mentioned, was made with solvents and drying agents according to the following recipe mixed:

Parts by weight

Polymer A 100

Toluene 200

Cobalt naphthenate solution, 1% 1

Zirconium naphthenate solution, 1% 30

Manganese naphthenate solution, 1% 1

The solution obtained in this way was applied to sheet steel, brass, glass and plywood with a brush and resulted in a layer thickness of 5 to 10 μ after the first application. The coating was already dust-dry after 5 minutes and handled after 2 ¹ I ₂ hours.

The determination of the pencil hardness initially resulted in degrees of hardness of 3 H; However, the incisions made in this way had completely disappeared after 20 to 30 minutes, which indicates a particular suppleness and considerable recovery capacity of the coatings obtained. · _T _

To determine the degree of crosslinking of the coatings, the samples were used for 4 hours Solvent extracted to determine the soluble fraction. This soluble portion was in the case of Exposure to light, both in a moist and in a dry state, could take place. As a result This test did not reveal any discoloration or other changes in the coatings.

The behavior towards "water, soda solution and sulfuric acid was determined according to the test specifications, as described in the aforementioned book by G. Z e i d 1 e r, "Lack- und Anstrichmittelindustrie", p. 226, determined. As a result of this test,

ίο under none of the named stresses any Detect changes in the coatings, while z. B. commercial, so-called AHwetter paints based on alkyd resin or synthetic paints based on polybutadiene under the same conditions showed significant changes.

Example2

The specified in Example 1. A mixture of PoIymer, solvents and dry materials was as described in the previous example, plated onto various surfaces and at higher temperatures, once ie at 8O ⁰ C and baked on the other at 150 ° C. There were obtained at 8O ⁰ C within 45 minutes and at 150 ⁰ C within 20 minutes griffeste coatings of good hardness and elasticity.

Example 3

In a hopper mill, polymer A was mixed with solvent, pigment and drying agents accordingly mixed with the following recipe:

Parts by weight

Polymer A 100

Toluene '300

Titanium dioxide (anatase) 40

Cobalt naphthenate solution, 1% 1

Zirconium naphthenate solution, 1% 30

Mangannaphthenatlösung, l ° / _o ig 1

This mixture was brushed onto the surface mentioned in Example 1; after 10 minutes, these coatings were touch-dry and dry to touch after 2 V ₂ hours. ■

Accelerated weathering tests with the Xenotest device, as described in Example 1,

Methyl ethyl ketone as a solvent at 7.2% and 5 ° gave no discoloration or other discoloration

in the case of n-heptane at 3.3%, i.e. H. in no case changes to the coatings.

over 10%. Since films with a soluble fraction of less than 10% are usually considered fully crosslinked are designated, this finding suggests a high degree of crosslinking of the coatings obtained

shut down.
Tests for resistance to weathering and chemicals were also carried out

accomplished.
To determine the weather resistance, based on the accelerated weathering test according to Z eid 1 he, such as z. B. in the book by G. Ze idler, "Lack- und Anstrichmittelindustrie", Wilhelm Knapp-Verlag, Dusseldorf, 2nd edition, p. 279, is selected an irradiation cycle of 3 · 9 hours, during which the paints in one Xenotestgerät were exposed. At certain intervals, the Ücr / .tigc were each immersed in water so that the

Example4

The polymer A was made with polymerizable monomers, peroxide and heavy metal salt accordingly mixed with the following recipe:

Parts by weight

¹ polymer A 100

Styrene 400

Divinylbenzene '. 22nd

Methyl ethyl ketone peroxide 2.2

Cobalt naphthenate solution, 1% 2.2

The mixture was brushed onto the surfaces mentioned in Example 1. The spreads were after Dust dry about 15 minutes and after 3 hours

grabbed. The pencil hardnesses are between 5 and 7 H.

Example 5

_{The 5O ° / O} ige polymer solution described under A, variant 1 b) was with

1 part by weight of cobalt naphthenate solution, l / o'g>

30 parts by weight Zirkonnaphthenatlösung, l% 'g> 1 part by weight Mangannaphthenatlösung, l ° / _o ig

mixed and with a brush on sheet steel, brass, glass and plywood in a 5 to 10 μ thickness Layer applied. After 5 minutes of storage at

Room temperature were dusty rock the coatings and handled after 2 ¹ J ₂ hours. After 24 hours * the hardness of the coating was 7 H. "

B e i s ρ i e 1 6

The polymer solution described under A, variant Ib) was applied without further additives to sheet steel, brass, glass and plywood. After 5 minutes storage time at room temperature; ίο all covers are dust-dry. Now the sample were: placed in a heated at 100 ⁰ C heating cabinet After 2 hours, the samples were dry to touch, NaCl 5 hours the hardness was 7 H.

Claims (1)

1 2 chain lying; in this case aging can occur Claim: not only networking, but also chain splitting genes, which then very quickly lead to a full The use of terpolymers leads to constant destruction of the coating,
Average molecular weight of at most 50,000 5 However, such disadvantages can be attributed not only to those based on ethylene, at least one hydrocarbon, but to a greater extent in the case of other α-olefins and at least one polyene which is multiply unsaturated by all natural and synthetic raw materials for lacquer, which may be in organic form. determine with appropriate functional groups; Niche solvents can be dissolved, for so it is only on the saponifiable ester groups in the production of coatings. io natural air-drying oils, with the alkyd resins and pointed out in the case of polyesters; it is the saponifiable urethane groups in polyurethane resins and finally the hydroxyl groups in the Epoxy resin paints mentioned, which under the influence of 15 corresponding aging conditions disadvantageous- The invention relates to the use of wise manifold reactions are accessible,
polymers with an average molecular weight In contrast, the inventive method leads of a maximum of 50,000 based on ethylene, turning the terpolymers into coatings that are at least one other -olefin and at least by being particularly resistant to aging polyunsaturated polyene, which characterize the given infuences. A to forfeit according to the invention can be dissolved in organic solvents, reversible terpolymer product is to be used in its Manufacture of coatings. most professional execution from three different building blocks Synthetic polymers are increasingly being built up. As base materials for varnishes and paints, bicyclic ones are used here turn. In so far as these are polymeric diene compounds, such as. B. dicyclopentadiene, nor-hydrocarbons acts, these consist of almost bornadiene, norbornadiene derivatives, norbornene derivatives exclusively from polymers of butadiene or from side double bonds, such as. B. Me copolymers of butadiene and styrene with entethylene norbornene, propenyl norbornene and isopropenyl corresponding low molecular weight or their norbornene. However, other non-conforming modification products can also be used, for example, by 3 ° jugated polyenes such. B. monocyclic and aliphatic maleic acid additive develop. ■. table connections are used. These synthetic polymers have another important prerequisite for the double bonds originating from butadiene have such polyunsaturated compound-drying properties and can either fertilize on their own is their good ability to copolymerize with, or in a blend with other air-drying oils, the ethylene and / or olefins used to produce the copolymers used in corresponding lacquer compositions. For a sufficient den. They also have the property of curing the coatings and lacquers with rapid air drying at elevated temperatures, so that or without siccatives at room temperature or they can be used as stoving lacquers. You at elevated temperature and for the achievement of can continue in a mixture with polymerizable 40 degrees of hardness are namely relatively high monomers such. B. styrene, diallyl phthalate or degrees of unsaturation are desirable.
Dicyclopentadiene with the catalytic participation of A preferred embodiment of this unsaturated Cure peroxides and metal salts as well; th copolymer paints and coating agents is finally they can be characterized by a low molecular weight with suitable crosslinking agents, such as. B. Sulfur and possibly carbon dioxide. It has been shown that not only high levels of unsaturation are baked out in order to achieve rapid, also too solid, insoluble superoptimal degrees of hardness. degrees of stability, but also low molecular weights. The polymers and copolymers mentioned are desirable. The molecular weights per se result in lacquers and paints with well-known olefin copolymers, such as. B. the MoIeseiten application possibilities and valuable 5 ° kulargewichte under the name of ethylene-propylene. technical characteristics. They can be used in copolymers or ethylene-propylene terpolymers - only - as is the case with most paints and known rubbers, are higher than 150,000, paints - to the extent that there are limits to what is usually not 150,000 to 500,000.
In contrast, as already indicated, the terpolymer chemicals to be used according to the invention are able to withstand the effects of aging, temperature and chemicals. average molecular weights of not more than 50,000, In such cases, polymers based on ■ are in particular from 3,000 to 30,000.
of conjugated diolefins such as polybutadiene or Butadiene copolymers, because of their highly unsaturated properties, these products have between 0.1 and 0.5 liters / character and because of the availability of a 60 grams (measured in the Oswald viscometer in benzene, large number of double bonds in the main chain at 32 ° C in 0.5 to 3 ° / _o by weight solutions),
limited in their use. The high unsaturation to achieve these low molecular weights namely represents a preferred point of attack for is expediently at elevated temperatures manifold effects of aging, as they are then used in aromatic solvents Embrittlement phenomena, in yellowing, but 65 from molecular weight regulators and increased Katalyauch Worked in a "softening of the coatings to the emitter concentrations. When using pressure is coming. Those of organometallic complex catalysts are particularly unfavorable Double bonds from when they are mainly hydrogen, for example, as a regulator.