DE2200268A1 - Sealing compositions - Google Patents

Description

Dr. F. Zumsteln sen. - Dr. E. Assmann 2200268 Dr. R. Koenigsberger - Dlpl.-Phys. R. Holzbauer - Dr. F. Zumsteln Jun.

PATENT LAWYERS

TELEPHONE: COLLECTIVE NO. 225341

TELEX 529979

TELEGRAMS: ZUMPAT CHECK ACCOUNT: MUNICH 91139

BANK ACCOUNT: BANK H. HOUSES

8 MUNICH 2,

BRÄUHAUSSTRASSE 4 / HI

Case 3-7331 / GC 501

CIBA-GEIGY A.G., Basel / Switzerland Sealing compositions

The present invention relates to resin compositions which can be converted to elastomers at room temperature or below cure and products with exceptionally good physical properties, in particular for use as sealants or protective coatings are suitable. The resin compositions described below can be premixed and packed in suitable moisture-proof containers. During use or application, the harden Resins similar to elastomers with superior physical properties Properties. When using these compositions as a sealant or surface treatment agents must be used they are no longer premixed, whereby reliable and reproducible elastomers can be obtained.

It is already known to use sealing compositions of resins containing unsaturation in the form of vinyl groups or double bonds. These well-known Compositions generally have certain undesirable properties in that they are effective only at high temperatures.

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Temperatures can be cured and by air and moisture are adversely affected. They are commonly available in dual pack systems that contain the resin and the Contain crosslinking agents that must be mixed just before use. They are also sealing compositions known which contain vinylic unsaturation and which are crosslinked by using nitrile-N-oxides (See U.S. Patents 3,390,204 and 3,503,906). The sealants of the latter composition have drawbacks in that they have higher water absorption properties and inferiority compared to the compositions of the present invention have elastic properties (creep).

The compositions of the present invention which cure in contact with moisture comprise a resin of a plurality of acetylenic groups contains a polyhydroxamoyl halide and a latent base which is inert in the absence of water or heat. The term "a plurality of acetylenic Groups "means that there are at least two acetylene groups per polymer chain in the resin.

The present invention relates more particularly to moisture curable sealing compositions which

a) an acetylenically unsaturated resin,

b) a polyhydroxamoyl halide and

c) a latent base, such as a metal oxide which can react with water, or a molecular sieve which contains an alkaline substance such as ammonia or an organic amine which can be absorbed in the molecular sieve and which can be displaced from the molecular sieve by moisture.

Any resin that has acetylenic unsaturation and too Elastomers with favorable sealant properties can be cured in the manufacture of the invention Compositions are used.

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Examples of such resins are given below:

Polyether urethanes with a terminal triple bond, see by reacting a polyether polyol with a diisocyanate followed by treatment with an acetylene! Alcohol, such as propargyl alcohol, methylbutynol or ethynylcyclohexanol, were manufactured. A typical resin is a material made by reacting a polypropylene ether triol with tolylene diisocyanate followed by treatment with Propargyl alcohol.

Poly (thioether oxyether) urethanes with a terminal triple bond can by reacting a mercapto alcohol with a bis (2,2'-dihydroxyalkyl) sulfide and then a Treatment with a diisocyanate and an acetylenic alcohol were obtained. A typical resin is a material that by polymerizing mercaptopropanol and bis (2,2'-dihydroxypropyl) sulfide by acid-catalyzed condensation and treatment of this prepolymer with tolylene diisocyanate and propargyl alcohol was obtained.

Poly (ester-co-thioether) urethanes that form unsaturations Contained by triple bonds and those by repositioning a Dihydroxyalkyl sulfide, an aliphatic triol and thiodipropionic acid ester, followed by treatment with a diisocyanate and an acetylenic alcohol. A typical material of this type is a resin obtained by reacting thiodiethylene glycol, trimethylolpropane and dimethyl-3,3'-thiodipropionate and treating with tolylene diisocyanate and propargyl alcohol.

Poly- (ester-co-thioether), which has an unsaturation in the form of Have triple bonds and the reaction of a dihydroxyalkyl sulfide, an aliphatic triol and an aliphatic dibasic acid or a mixture thereof Acids and an acetylenic alcohol can be obtained. A typical material of this type is the reaction of thio-

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diethylene glycol, trimethylolpropane, propargyl alcohol, adipic acid and azelaic acid obtained resin.

The acetylenic unsaturation can also be found in the structure of the poly (ester-co-thioether) by adding butynediol to the starting reactants. A typical one The material is a resin that is obtained by reacting adipic acid, 2,2,4 - trimethyladipic acid, thiodiethylene glycol, propargyl alcohol and 2-butyne-1,4-diol is obtained.

If one uses a polymer with a relatively short chain (a liquid resin) of known molecular weight with known chemical structure, rubbers with good elongation and constant crosslinking density, in which the hardening points are located at the chain ends of the polymer molecule, are obtained. Elastomers with a higher modulus and lower elongation are obtained from resins whose hardening points are statistically over the Polymer structure are distributed.

After the resin has been formulated in a suitable manner with a hardener, a latent base or other chemically inert materials such as plasticizers, fillers or pigments and is packaged in moisture-proof containers, it is only necessary to produce the elastomeric products according to the invention with superior properties that Exposure to atmospheric moisture composition. The time required for the composition to fully cure depends on the type and relative amounts of resin, hardener, and latent base, as well as the relative humidity, temperature, and thickness of the layer applied. The use of a metal oxide, such as barium oxide or calcium oxide, as the latent base is particularly advantageous because the water acts as a catalyst in that it is formed again in the reaction of the hydrated metal oxide with the polyhydroxyamoyl halide hardener. This catalytic effect of water allows thick applied layers to harden in a relatively short time under unfavorable humidity conditions.

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The polyfunctional hydroxamoyl halides according to the invention can be used as hardening agents are represented by the following general formula

(HO-N = C) R
η

wherein R is an organic radical which is inert during the curing reaction or a carbon-carbon bond, X is a halogen atom and η is an integer greater than 1. R can thus be an alkylene, cycloalkylene, arylene, aralkylene, alkarylene, Alkylenediarylene, cycloalkylene-dialkylene, arylene-dialkylene radical etc., a methylene, ethylene, triirethylene, tetramethylene, Pentamethylene, hexamethylene, octamethylene, cyclohexylene, Cyclopentylene, xylylene, phenylethylene, phenylene dimethylene, Phenylene-diethylene-, methylenediphenylene-, ethylenediphenylene-, Cyclohexylenedimethylene, cyclopentylenedimethylene radical, etc. or an alkylene-oxyalkylene, arylene-oxyalkylene, Aralkylene-oxyaralkylene-, methylene-oxymethylene-, ethylene-oxyethylene-, Phenylene-oxyphenylene, methylenephenylene-oxyphenylenemethylene, Phenylenmethylene-oxymethylene phenylene radical or a corresponding thio radical, such as an ethylene-thioethylene, phenylene thiophenylene, Phenylenmethylene-thiomethylene phenylene residue etc. or a sulfone radical, such as an ethylene-sulfonylethylene- m-bis (methylensulfonyl) phenylene radical, etc. be. The maximum value of η depends of course on the number of carbon atoms present in the group R, since the value of η the value of R cannot exceed. The halogen atom X is a chlorine, bromine or iodine atom. X preferably represents a chlorine or bromine atom and most preferably represents a chlorine atom. The value of η is an integer from 2 to 10, preferably from 2 to 4. It is also possible to use polyfunctional nitroic acids.

Examples of polyfunctional hydroxamoyl chlorides suitable according to the invention are terephthal-bis (hydroxamoyl chloride), 2,3,5,6-tetramethylterephthal-bis (hydroxamoyl chloride), isophthal-bis (hydroxamoyl chloride), Malonyl bis (hydroxamoyl

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Chloride), succinyl bis (hydroxamoyl chloride), glutaryl bis (hydroxamoyl chloride), 1,4-cyclohexanebis (carbohydroxamoyl chloride), Methylene-ρ, ρ'-bis-ibenzhydroxamoylchloride), methyl en-m, m -bis (benzhydroxamoyl chloride), p-pheny1en-bi s- (acetohydroxamoyl chloride), 4,4'-diphenylene-bis- (carbohydric xamoyl chloride), Oxalyl bis (hydroxamoyl chloride) and 1,5-naphthalene bis (carbohydroxamoyl chloride); polyfunctional hydroxamoyl chlorides that contain more than two hydroxamoyl chloride groups have, such as 1,3,5-benzene-tris- (carbohydroxamoyl chloride), 1,5, V-naphthalene-tris-Ccarbhydroxamoylchlorid), 1,3,5-benzene-tris- (glyoxylhydroxamoyl chloride), penta- (acrylic hydroxamoyl chloride), Deca- (crotonylhydroxamoyl chloride), as well as polyfunctional hydroxamoyl chlorides, such as 2,2'-oxy-bis- (ethylcarbohydroxamoyl chloride), i.e. 2,2'-bis (carbohydroxamoyl chloride) diethyl ether, 4,4'-oxy-bis-ibenzhydroxamoyl chloride), i.e. 4,4'-bis (carbohydroxamoyl chloride) diphenyl ether, 2,2'-thia-bis-iäthylcarbohydroxamoylchlorid), 4,4'-thia-bis (benzhydroxamoylchloride), Oxal-bis (hydroxamoyl chloride) etc. If desired, mixtures of two or more polyfunctional hydroxamoyl chlorides can be used.

Another group of polyfunctional hydroxamoyl halides which can be used in accordance with the invention are polyfunctional ones Carbonyl hydroxamoyl chlorides of the general formula

R- (CC = NOH)
X

where R, X and η have the meanings given above, such as oxalyl bis (N-hydroxyformimidoyl chloride), malonyl bis (N-hydroxyformimidoyl chloride), Succinyl bis (N-hydroxyformimidoyl chloride), adipyl bis (N-hydroxyformimidoyl chloride), Sebacyl bis (N-hydroxyformimidoyl chloride), 1,2,3- (propane-tris- (glyoxylhydroxamoyl chloride), 1,2,4-pentane-tris- (glyoxylhydroxamöylchlorid), 1,4-cyclohexanebis (glyoxylhydroxamoyl chloride), p-xylylene bis (glyoxylhydroxamoyl chloride), 1,1 · thiodimethyl bis (glyoxylhydroxamoyl chloride) ether, 2,2'-thio-

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diethyl bis (glyoxylhydroxamoyl chloride) ether, isophthalyl bis (N-hydroxyformimidoyl chloride), Terephthalyl bis (N-hydroxyformimidoyl chloride), 4,4'-bis (phenylglyoxylhydroxamoyl chloride), 4,4'-methylenebis-phenylglyoxylhydroxamoylchloride), 4,4'-oxy-bis-phenylglyoxylhydroxamoyl chloride) and 4,4'-thiabis (phenylglyoxylhydroxamoyl chloride).

Polymers with pendant carbohydroxamoyl chloride groups, such as ethylene acrylic acid copolymers and partially hydrolyzed polyalkyl acrylates, in which two or more of the pendant carboxyl groups in carbon hydroxamoyl chloride groups transferred, etc., can also be used in the present invention.

Another group of polyfunctional hydroxamoyl halides that can be used as hardeners according to the invention, are polyfunctional carbonylhydroxamoyl chlorides of the general formula

R (OCC = N-OH)
ι '
X

where R, X and η have the meanings given above, such as ethylene glycol, resorcinol, 4,4'-dihydroxybiphenylene, Isopropylidene-4,4'-bisphenol etc. esters of carboxycarbonitrile chlorides Etc.

The above-described polyfunctional hydroxamoyl halides are the preferred hardeners. However, it is also possible to use polyfunctional carbonyl nitroic acids.

In one embodiment of the present invention, the latent base used for curing is an oxide of the alkali or alkaline earth metals. Typical compounds of this type include barium oxide, calcium oxide, lithium oxide, magnesium oxide, etc. The term "latent base" includes a metal oxide which remains inert to the hardener under anhydrous conditions,

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which, however, in the presence of moisture yields an alkaline material with polyfunctional hydroxamoyl halides reacts to form the hardener of the resin.

In a further embodiment, the latent base comprises a molecular sieve material containing an alkaline substance, which is displaced or driven out of the molecular sieve by water. The molecular sieve material, in general is available in the form of a free flowing powder a pored structure with a high degree of adsorptive affinity for polar molecules. Generally there is a molecular sieve material consisting essentially of crystalline aluminosilicate with a crystal structure of SiO.-tetrahedra and AlO. tetrahedra, which form a network with uniform spherical cavities which are connected to one another by uniform openings. Inside these cavities the alkaline substances are adsorbed.

Almost any alkaline material that is in the cavities of the molecular sieve adsorbed and displaced therefrom by moisture can be used according to the invention. Such materials are disclosed in U.S. Patents 2,882 and 2,882,244. Examples of preferred alkaline substances which according to the invention are in the molecular sieve material include ammonia as well as primary, secondary and tertiary organic amines. Preferred combinations of an alkaline substance with a molecular sieve material include ammonia and sodium zeolite A (in U.S. Pat 2 882 243), a primary amine (e.g. methylamine, Ethylamine, ethylenediamine and the like) and calcium-magnesium zeolite A (see US Pat. No. 2,882,243) and secondary and tertiary amines (e.g. dimethylamine, diethylamine, diethylenetriamine, Trimethylamine, triethylamine, piperazine and the like) and sodium zeolite X (see U.S. Patent 2,882,244).

A latent base of this type is obtained by adding anhydrous finely divided molecular sieve material at a temperature of

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preferably 0 to 25 ° C with an anhydrous alkaline Substance which, when normally liquid, is usually alone or when in gaseous form or as a solid is present, dissolved in a suitable anhydrous solvent, is used, brings into contact. The amount of alkaline substance, the molecular sieve material and the contact time are selected so that the target concentration of the adsorbed alkaline substance in the Molecular sieve material reached. Usually the preferred maximum concentration is the alkaline adsorbed Substance in the molecular sieve material about 15 to 20% by weight based on the molecular sieve material, although also higher and lower concentrations can be used. Subsequently, the excess and not adsorbed alkaline Substance, if any, removed from the molecular sieve material by washing the material.

The advantage of using a molecular sieve that is alkaline Contains substance, the latent base is that heat is used in addition to or instead of moisture can to get the hardening reaction going. Generally speaking, an alkaline substance is made with the help of Water is displaced from or driven out of a molecular sieve material, also displaced or driven out by heat. Thus, when it is desired to initiate the crosslinking reaction with heat, the crosslinkable one is treated Composition preferably only with a sufficient amount of heat to prevent the desired amount of alkaline from escaping To effect substance from the molecular sieve material.

The bis (hydroxamoyl chlorides) are easily obtained by reaction an aldehyde oxime with a chlorinating agent such as nitro sylchloride, chlorine, etc.

The Carbonylhydroxamoylchloride can be made from polyhaloacetyl compounds, like Bi s- (chloroacetyl), .Methylene-bis- (chloroacetyl), Ethylene-bis-chloroacetyl), o-, m- and p-bis-chloroacetyl) benzene, 4,4'-bis- (chloroacetyl) -biphenyl, bis- (4-chloroacetyl-

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phenyl) ether, by reacting the polyhaloacetyl compound with a nitrosating agent such as an alkyl nitrite, NpO. ,, Nitrosyl chloride etc. and hydrogen chloride under anhydrous Conditions are established.

The Carbonylhydroxamoylchloride can also be obtained by reacting an amino ester with sodium nitrite and hydrogen chloride Formation of a diazo ester followed by conversion of the diazo ester with nitrous acid and hydrogen chloride can be obtained into the hydroxamoyl chloride. Thus can from Glycine or one of its precursors, such as aminoacetonitrile, glycinate ester of diols, triols, etc., which are then converted into the polyfunctional carbonylhydroxamoyl chlorides can be transferred.

The polyfunctional nitrous acid of the following general formula

R (C = NOH)
η

in which R and η have the meanings given above can be obtained by mixing the corresponding polyfunctional hydroxamoyl halide, such as the hydroxamoyl chloride, with silver nitrate implements.

The polyfunctional carbonylnitrolic acids of the general formula

0 NO «

R- (CC = NOH) _n

wherein R and η have the meanings given above, is obtained by reacting a polyketone with NpO., whereby one the polycarbonylnitrolic acid is obtained directly.

The polyfunctional carbonylnitrolic acids of the general formula

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- li -

O NO ₂

R- (O-C-C = NOH)

wherein R and η have the meanings given above, is obtained one from ß-ketoesters. For example, acetoacetic acid esters can easily be obtained by reacting diketene with polyols and nitrosating the ß-keto esters can be prepared with aqueous nitrous acid to form the corresponding oximinoketo esters. Treatment of these compounds with concentrated nitric acid gives nitroic acid in excellent yield, and treatment of the nitroic acid with hydrogen halide results in the hydroxamoyl halide. The response can be in a single stage can be carried out by mixing the oximinoketoester with a mixture of nitric acid and hydrogen halide reacted so that the hydroxamoyl halide is obtained directly. Other methods of making those mentioned above However, nitro acids are familiar to the person skilled in the art.

The composition of the invention is anhydrous when under Conditions stored is stable for a long period of time. This should be done before adding a latent base the other ingredients are dried, which can be achieved by one of the following methods:

1.) vacuum distillation to remove water;

2.) Azeotropic water removal by adding a solvent, that forms an azeotropic solution such as toluene, xylene, ether, or the like;

3.) Adding a drying agent such as magnesium sulfate, a molecular sieve and the like.

According to the invention, the resins are cured at room temperature (about 25 ° C.). A stoichiometric curing rate is generally used for curing the resin Amount or a slight excess of a hydroxamoyl halide, preferably the hydroxamoyl chloride, with a latent base in the presence of moisture.

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22ÜÜ268

The amount of polyfunctional hydroxamoyl halide used (based on the weight of the polymer) is about 0.05 to about 50%, preferably about 3 to about 20%.

The latent base, which is present in the form of the above-mentioned oxides or the molecular sieves loaded with amines, should be present in at least a stoichiometric amount, based on the polyhydroxamoyl halide, preferably in an excess of about 10 to about 400 % over the stoichiometrically required amount.

The molecular weight of the resins used in the present invention ranges from about 1,000 to about 25,000. Most preferably, the molecular weight is from about 2,000 to about 10,000.

The compositions according to the invention can optionally Contain various additives that give the product specific desired properties. So can the compositions Fillers such as carbon black, silicon dioxide and the like, stabilizers such as UV stabilizers, antioxidants, pigments, such as titanium dioxide, plasticizers or materials that improve flexibility, hydrogenated terphenyl (HB 40 Monsanto) and the like and other suitable additives which make the compositions particularly suitable for particular uses make, included.

The following examples are intended to explain the invention further without, however, restricting it.

example 1

Manufacture of a liquid end-capped with acetylene groups Polyether urethane resin

1 equivalent weight (1 mol) of tolylene diisocyanate, based on the hydroxyl number, was added to a polyether polyol. The temperature was increased to 100 ⁰ C, and this temperature was held until the content of free isocyanate groups, determined by Stan-

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22ÜU268

dard titration method, had decreased to about half of the original amount. Propargyl alcohol (1 mole per free isocyanate group) and 0.25 g of dibutyltin dilaurate as a catalyst were then added while the resin was allowed to cool to room temperature. After all the isocyanate groups had been urngesetzt (determined by IR spectroscopy) were trace amounts of volatile material at a temperature of 100 ⁰ C and a pressure of 5 mm Hg from the H arζ ABG e tr t hen.

Using the procedure described above, trifunctional Polyether resins containing acetylene end groups with the molecular weights given below from tolylene diisocyanate, the appropriate polypropylene oxide and propargyl alcohol.

Table I.

EW ^{1 )} des
Polyol MW des
Polyol MW of the Har
zes (ber.) EW des Har
zes (ber.) Visco
sity of
Harzes, Cps. % ChC ²⁾ 525 1577 2267 756 62,000
(with 9%
Xylene) ber. 1600 4800 5490 1830 30,000 3.18 3.18 1.32 1.30

1) EW = equivalent weight obtained by dividing the

Molecular weight by the number of functional End groups.

2) Determined by titration with silver.

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_ ₁₄ _ 22UU268

Example 2

To 100 g of the resin prepared according to Example 1 (molecular weight 2267) 14.15 g of terephthaloyl bis (hydroxamoyl chloride) and 28 g of well-dried calcium oxide were added. That Material was hand mixed with a small amount of xylene and spread in the form of a thin layer on a glass plate and brought into contact with the atmosphere. That Material was no longer tacky after 45 minutes.

Example 3

A 3 l flask was filled with 87.08 g of tolylene diisocyanate (0.5 mol), 42.05 g of methylbutynol (0.5 mole) and 0.16 ml of dibutyltin dilaurate were charged. An exothermic reaction set in, and the reaction mixture became very viscous. After 5 hours the amine equivalent was 256 (theoretical 268). Then were 792.5 g (EW 1585) of trifunctional polypropylene oxide and then 0.1 ml of dibutyltin dilaurate added as a catalyst, whereupon the mixture was stirred at 50 ° C. for a further 3 days. Then 5 ml of methanol was added to destroy the remaining isocyanate. A very pale, free-flowing resin was obtained.

Example 4

The resin prepared according to Example 3 (the methylbutynol end groups had) was with 6.35 parts of terephthal-bis (hydroxamoyl chloride) mixed per 100 parts of resin until a clear solution was obtained. Then 100 parts of USP talc and 6.50 parts of commercial calcium oxide per 100 parts of resin are well mixed with the resin and the formulated material at room temperature placed in a chamber with 50% relative humidity. After 3.5 hours, the Resin formed a thin skin. A solid formed non-sticky skin within a few hours.

Example 5

A trifunctional resin with a calculated molecular weight of 5646 was prepared as described in Example 1,

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The resin was divided into six equal parts, and the im The following amounts of hardeners were dissolved in the resin, whereupon 50 parts of USP talc and 6 parts of commercially available Calcium oxide was added per 100 parts of resin to each formulation. The formulated resins were mixed well and placed in a 50% relative humidity chamber at room temperature. The resins cured as in the following table is specified, made of a non-adhesive material.

Table II

Harder Amount (phr) not adhesive Terephthal-bis- (hydrox
amoyl chloride) 6.2 Yes Oxalyl-bis (hydroxamoyl
chloride) 4.1 Yes Terephthalyl-bis- (N-hydroxy-
formimidoyl chloride) 7.7 Yes 1,3,5-benzene-tris (glyoxyl
hydroxamoyl chloride) 6.95 Yes 4,4'-Oxy-bis- (phenylglyoxyl-
hydroxamoyl chloride) 10.15 Yes 4,4'-methylenebis (phenyl-
glyoxylhydroxamoyl chloride) 10.1 Yes

phr = parts of hardener used per 100 parts of resin.

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- ie - 22UU268

Example 6

To 100 parts of the resin prepared according to Example 1 (molecular weight 5490) were added 60 g of fine, naturally occurring Silicon dioxide, which is commercially available under the name "Imid A-IO", and 6.34 grams of terephthaloyl bis (hydroxamoyl chloride). The ingredients were mixed well using a three-roll paint mill and the resulting one Mixture was divided into three equal parts. 10.6 g of calcium oxide were added to part 1, and 5.3 g to part 2 Calcium oxide, and part 3 was given 3 g of calcium oxide. The three mixtures were passed through the three-roll mill again and quickly applied to a galvanized metal plate to form a thin layer. The samples were in a A humidity chamber maintained at 23 to 24 C with a relative humidity of 50% was introduced. Over the course of a few hours, Parts 1 and 2 became non-sticky Surface on. Part 3 took a slightly longer time to form a non-stick surface.

Example 7

In a 5 l three-necked flask, which is equipped with a mechanical stirrer, a Barrett still connected to a reflux condenser and a nitrogen inlet tube was provided, 2097 g of a mixture of 1-mercapto-2-propanol were added (65 mol% or 54% by weight) and 35 mol% or 46% by weight bis (2,2'-dihydroxypropyl) sulfide, 42 g Trimethylolpropane, 1000 g of benzene and 20 g of technical grade p-toluene-'sulfonic acid. The reaction mixture quickly refluxed with stirring under a nitrogen atmosphere heated. Heating and stirring continued until the theoretical amount of water (340 ml) had been collected. the The reaction mixture was then cooled, and 14.8 g of potassium carbonate, dissolved in 100 ml of water were added. The reaction mixture was stirred for 30 minutes and then heated to reflux, until 100 ml of water had been collected by azeotropic distillation.

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- 17 - 22ÜU268

The reaction mixture was hot-filtered to separate the precipitated salts. The filtrate was in vacuo concentrated so that the prepolymer · in the form of a viscous pale yellow liquid received. The end group analysis showed 0.80% by weight of hydroxyl (OH) groups and 0.36% by weight Mercaptan (SH) groups. The yield of prepolymer was 1740 g.

In a 1 l three-necked flask, which is equipped with a mechanical stirrer, nitrogen inlet, calcium chloride drying tube, and heating mantle were added, 800 g of des was added Prepolymer, 80.7 g of tolylene diisocyanate and 5 drops of dibutyltin dilaurate. The hydroxyl end groups react among these Conditions faster than the mercaptan groups, and man allowed the reaction to proceed until an amine equivalent of 1600 was obtained (theoretical amine equivalent 1608, based on on OH). At this point 5 drops of triethylenediamine were added to prevent the reaction of the mercapto groups with the tolylenediisocyanate to catalyze, and the reaction was continued until an amine equivalent of 2020 (theoretically 1899, based on OH and SH). Then 27.6 g of propargyl alcohol were added and the reaction mixture was heated until the isocyanate band in the infrared region disappeared. The resin was cooled and then checked for terminal acetylene group content examined. Theory: 1.23, found 1.36.

A sealant formulation was prepared using this resin according to the following recipe:

resin

Talc TBHC ¹ ^ CaO
Ethyl acetate ²⁾

1) TBHC = terephthalic bis (hydroxamoyl chloride)

2) Solvent, used to dissolve the TBHC

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100 Parts 60 5, 96 2, 86 4, 5

- ^6pm - 10pm? 68

The formulation was ground on a three roll paint mill until homogeneous and then distributed into molds. the resulting composition cured to a non-adhesive material in a few hours.

Example 8 Poly- (ester-co-thioether) urethane with proparglene groups

1392 g (6.75 moles) dimethyl 3,3'-thiodipropionate, 849 g (6.95 moles) thiodigylcol and 26.8 g (0.2 moles) trimethylolpropane were placed in a 3 liter three-necked round bottom flask fitted with a A heating mantle, a stirrer, a thermometer, a nitrogen inlet and a condenser suitable for distillation are provided was introduced. Then 25 grams of tetraisopropyl titanate was added to the flask under nitrogen. The temperature of the Contents rose to 190 ° C, and the methanol distilled off. After 3 hours vacuum was applied and heating stopped continued for a further 3 hours.

Then 10 ml of HpO and 300 ml of benzene were added after cooling of the contents to about 60 C to destroy the catalyst. The water was then in the form of an azeotropic mixture distilled from the flask into a Dean-Stark trap. The flask was cooled and the polymer was dissolved in benzene dissolved and filtered using a filter aid made of diatomaceous earth (5% by weight of the polymer). The solution of the polymer in benzene was evaporated on a rotary evaporator, leaving 1600 g of a viscous amber resin obtained with the following analysis values: C 45.92% by weight, H 6.20% by weight, S 23.84% by weight.

The hydroxyl group determination with phenyl isocyanate gave a value of 1.1% by weight of hydroxyl groups (-OH).

13.1 g of tolylene diisocyanate were added to 116 g of the above resin, and the mixture was heated to 85 ° C. for 3 hours. Titration of an aliquot sample with di-n-butylamine indicated that the half of tolylene diisocyanate was reacted. the

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22ÜU268

The reaction mixture was cooled to 50 ° C., and 4.2 g of propargyl alcohol and 0.05 ml of dibutyltin dilaurate were added as a catalyst and the reaction mixture was stirred overnight at room temperature. An IR spectrum then showed that there were no isocyanate groups more were left.

3.6 g of this resin were intimately mixed with 0.24 g of terephthalic bis (hydroxamoyl chloride) and 0.11 g calcium chloride mixed. The resin cured over 6 hours in contact with from the atmosphere to a non-stick, highly elastomeric material that was insoluble in tetrahydrofuran.

Example 9

A branched poly (ester-co-thioether) with propargylic end groups was made from 61.1 g of thiodiglycol, 2 g of trimethylolpropane, 3.1 g of propargyl alcohol, 65.8 g of adipic acid and 9.4 g of azelaic acid prepared using 1 g of p-toluenesulfonic acid as a catalyst used. The reactants were placed in a 300 ml three-necked flask along with 100 ml of xylene, and the water of condensation was removed by azeotropic distillation. After collecting 18.5 ml of water, was the polymer by precipitating the reaction mixture in isopropanol isolated.

The polymer was dried and added by adding 0.72 g of terephthalic bis (hydroxamoyl chloride) and 0.35 g of calcium oxide a tough, elastomeric composition that was insoluble in benzene.

Example 10

Following the procedure described in Example 9 for making the uncured resin, the following materials were obtained a branched poly (ester-co-thioether) with an unsaturation formed by triple bonds in the skeleton:

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Adipic acid 2,2,4-trimethyladipic acid Thiodigylcol propargyl alcohol 2-butyne-1,4-diol p-toluenesulfonic acid Xylene

To 4.39 g of the polymer was added 0.64 g of terephthalic bis (hydroxamoyl chloride) and 0.31 g CaO and mixed the whole intimately. A non-adhesive elastomer was obtained, which in Toluene was insoluble.

100 2200268 G 68.3 G 9.8 G 54.4 G 4.2 G 3.2 G 1 ml

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Claims (12)

Claims 1.) Moisture curable sealing composition,
characterized in that they a) an acetylenically unsaturated resin, b) a polyhydroxamoyl halide and c) a latent base, such as a metal oxide, or an alkaline one Substance, such as ammonia or an organic amine, ■ that can be adsorbed in the molecular sieve, and the can be displaced from the molecular sieve by moisture, containing molecular sieve contains. 2.) Composition according to claim 1, characterized in that the polyfunctional hydroxamoyl halide is one of the
following formulas X OX OX R (C = NOH) _n , R (CC = NOH) _n or R (OCC = NOH) _n corresponds to where R is an organic radical which is inert during the crosslinking reaction or a carbon-carbon bond, X is a halogen atom and η is an integer from 2 to 10. 3.) Composition according to claim 2, characterized in that the polyfunctional hydroxamoyl halide terephthalbis (hydroxamoyl chloride) is. 4.) Composition according to claim 2, characterized in that the polyfunctional hydroxamoyl halide 1,3,5-phenyltris (glyoxylhydroxamoyl chloride) is. 5.) Composition according to claim 2, characterized in that the polyfunctional hydroxamoyl chloride 4,4'-oxy-bis (phenylglyoxylhydroxamoyl chloride) is. 209831/0981 6.) Composition according to claim 1, characterized in that the resin has an acetylenically unsaturated end group provided polyether urethane, poly (ester-co-thioether) urethane, Poly-Cester-co-thioether) or poly (thioetheroxyether) urethane is. 7.) Composition according to claim 2, characterized in that that the latent base is calcium oxide. 8.) Composition according to claim 2, characterized in that the latent base is barium oxide. 9.) Composition according to claim 2, characterized in that the displaceable by moisture from the molecular sieve alkaline substance is ethylenediamine. 10.) Composition according to claim 1, characterized in that it a) one provided with acetylenically unsaturated end groups Resin, b) terephthaloyl bis (hydroxamoyl chloride) and c) calcium oxide contains. 11.) Composition according to claim 10, characterized in that the provided with acetylenically unsaturated end groups Resin a poly (ester-co-thioether) urethane, a poly (ester-co-thioether) or a poly (thioether oxyether) urethane. 12.) Use of the moisture curable compositions according to one of the preceding claims for sealing materials and coatings. 209831/0981 ^ '