Composition comprising compounds with functional mercaptopropyl
The present invention relates to coating or adhesive composition consisting of (a) compounds comprising two or more olefinic unsaturated group containing at least one electron-withdrawing functionality linked to a carbon atom bonds; (C) compounds containing at least two functional mercaptopropyl, and a catalyst comprising at least one, optionally blocked NH-group, as well as to the method of applying a coating or adhesive composition by spraying the spray nozzle liquid composition consisting of compounds (a) and (b), moreover, a small quantity of a liquid composition of a catalyst containing at least one, optionally blocked NH-group, spray in an aerosol spray composition. 2 N. and 6 C.p. f-crystals, 9 PL.
The present invention relates to compositions containing
connection comprising two or more olefinic unsaturated group containing at least one electron-withdrawing functionality linked to a carbon atom unsaturated linkages;
connection, comprising at least two functional margravate connections, containing active hydrogen. It is believed that such reactions include the accession of the anion derived from nucleophilic containing active hydrogen compounds, acting as a donor, to an activated unsaturated group, which acts as an acceptor. When the data containing the active hydrogen compounds are C-H compounds such as ester of malonic acid or acetoacetate, the reaction is known as the reaction joining Michael (Michael reaction). It is also known that S connection can act as containing active hydrogen compounds in the reaction mechanism similar to the mechanism of the reaction of Michael. In future, the same reaction mechanism with S connections called thio-Michael reaction.
Compositions, such as those described in the first paragraph, curing by means of such thio-Michael's reaction, known from European patent application EP-A 0160824. Listed in this description, the catalysts are Quaternary ammonium compounds, tetramethylguanidine, databaseconnect, diazabicyclo. Thio-Michael's reaction catalyzed by strong data bases, it is difficult to control. Such reactions or proccacia amines may be present, but, according to this publication, they are not reactive at ambient temperatures. Moreover, base catalyzed reactions can experience acid inhibition. Present in the air, carbon dioxide or acid substrate can be very slow or even stop the stitching.
US 2759913 describes how copolymerization of unsaturated monomers containing functional mercaptopropyl compounds with a basic catalyst, such as a hydroxide of trimethylantimony. As mentioned above, the reaction with this catalyst, it is difficult to control.
British patent application SV-AND 2166749 describes curable at room temperature coverts composition consisting of unsaturated complex polyester compounds, including at least three tirinya group and the catalyst is a tertiary amine, such as triethylamine. However, as you can see from the examples of GB-AND 2166749, this reaction requires about 16 hours of curing at ambient temperatures. The faster the reaction will take place only at high temperatures.
European patent application EP-A-0284374 describes polymerizable vinyl is vinovich unsaturated groups, including at least one electron-withdrawing functionality linked to a carbon atom unsaturated communication connection, comprising at least two functional mercaptopropyl, and a catalyst, such as diethylamine. The fact that these reagents, as such, can be used in coating or adhesive compositions is not described.
U.S. patent US-A-5840823 describes an adhesive composition, comprising a compound consisting of two or more olefinic unsaturated groups containing at least one electron-withdrawing functionality linked to a carbon atom unsaturated connection, and the connection involving many groups, selected from tylnej groups, primary amino groups or secondary amino groups. However, in US-A-5840823 not described and not assume the use of compounds with primary or secondary amino groups in combination with the connection involving tirinya group.
The purpose of the invention is to propose a composition that overcomes the disadvantages indicated above.
The purpose of the invention is achieved by using the composition of this type, which is described in the first paragraph that includes a catalyst containing at least one will neovastat, what is needed is strongly basic catalysts, however, compositions curable by thio-Michael's reaction involving the catalyst according to the invention, show a rapid curing at ambient temperatures. This has the obvious advantage that any a short time of manufacture. You can save energy, because the curing occurs at ambient temperatures. Moreover, compared to the Michael reaction and thio-Michael reaction catalyzed by strong bases, reaction time is much less depends on the amount of catalyst. This is an advantage for easy cooking recipe. It was also found that the method can be carried out with the oligomers with low viscosity. This has the advantage that it is possible to prepare compositions which contain small amounts of solvents or do not contain, but are still sprayed. Reactive groups involved in the curing reaction, are considerably less toxic than most are capable of crosslinking of the reactive groups in other or opaque adhesive compositions, such as isocyanates. After curing Nanase and is high.
In connection comprising two or more olefinic unsaturated groups, olefinic unsaturated groups contain at least one electron-withdrawing functionality linked to a carbon atom bonds. Olefinic unsaturated bond may be a double or triple bond. Preferably olefinic unsaturated group of compounds comprising two or more olefinic unsaturated group, have a structure corresponding to the following formula I:
where at least one of R1, R2, R3and R4contains electron-withdrawing functionality linked to a carbon atom bonds and at least one of R1, R2, R3and R4associated with polyvalent group containing at least two valence.
Examples of electron-withdrawing functionality include carbonyl, carboxyl, ester, thiocarbonyl, dicarboxyl, complex thioethers, sulfoxide, sulfonyl, alphagroup, phosphate, postit, phosphonic, phosphinic, a nitrogroup, nitrile and amide.
In the case when R1, R2, R3and/or R4are monovalent, electron-withdrawing functionality can be connected is cycloalkenyl and aryl, which optionally can be substituted by various other functionalities, such as carboxylic acid or hydroxide. If they do not include electron-withdrawing functionality, R1, R2, R3and/or R4can be independently selected from a hydrogen atom, a linear or branched alkyl, cycloalkyl, alkenyl, cycloalkenyl, quinil, cycloalkenyl and aryl, which optionally can be substituted for different functionalities, such as carboxylic acid or hydroxide. When at least one of R1, R2, R3and R4associated with polyvalent group and is not electron-withdrawing functionality, it can be a simple link. Polyvalent group binds at least two groups of formula 1. Polyvalent group can be selected from a simple link, substituted or unsubstituted alkylene, cycloalkyl, Alcanena, cycloalkenyl, akinlana, cycloalkenyl, arylene or combinations thereof. Polyvalent group optionally may contain heteroatoms such as-O-, -S-, -Si - I-R-, and groups such as amide group, urea group, and a complex ester.
Preferably the group of formula I is obtained from unsaturated carbon - or polyunsaturated and can be a monocarboxylic or polycarboxylic acid. Examples of suitable monocarboxylic acids are acrylic acid, methacrylic acid, cinnamic acid, propargilovyh acid and dehydroretinol acid. Examples of suitable polycarboxylic acids are Tarakanova acid, maleic acid, taconova acid or their anhydrides, as well as musicanova acid and fumaric acid. You can also use complex monetary mono - and polycarboxylic acids and complex diesters polycarboxylic acids, such as esters of acrylic acid, mononitro-monetary maleic acid, diethylmaleate, esters cyanacrylate acids and esters alcaligenaceae acid, described in WO 98/41561. Preferred are acrylic acid or its ester, maleic acid, its ester or anhydride.
When a group of the formula I derived from acrylic acid or its ether complex, a suitable example compounds containing two or more olefinic unsaturated group is triacrylate of trimethylolpropane.
When a group of formula I is obtained from maleic acid, its complex ether(s) or anhydride, suitable examples of compounds containing two or more olefinic unsaturated groups include someonethere reacted with polyisocyanates; the reaction product of the compound with an epoxy functional group, such as rdur® E10 (aliphatic epoxysilane sold by Shell chemical company) and isobutylphthalate, further reacted with a trimer of isophorondiisocyanate, for example with Vstanat® T E, produced by the firm; the reaction product of maleic anhydride, dipentaerythritol and butanol.
An alternative group of the formula I can be obtained from unsaturated aldehyde.
Finally, the connection comprising two or more olefinic unsaturated group containing at least one electron-withdrawing functionality linked to a carbon atom unsaturated communication can be an unsaturated ketone, such as Divinington or dibenzalacetone.
The connection comprising at least two functional mercaptopropyl, can be prepared by direct esterification of organic acids containing functional mercaptopropyl, with a polyol. Examples of organic acids containing functional mercaptopropyl include 3-mercaptopropionic acid, 2-mercaptopropionic acid, thiosalicylic acid, mercaptoethanol acid, mercaptohexanol acid or cysteine. Examples of compounds, Polychaeta), trimethylolpropane-Tris-(3-mercaptopropionate), trimethylolpropane-Tris-(2-mercaptopropionate) and trimethylolpropane-Tris-(2-mercaptoacetate). The following example compounds obtained in this way is the connection, which includes the core of hyperbranched macromolecular polyol based on the original polyol, such as trimethylolpropane, and dimethylolpropionic acid. This polyol then atrificial 3-mercaptopropionic acid and isononanoic acid. These methods are described in European patent application EP-A 0448224 and international patent application WO 93/17060. Another example of compounds comprising at least two functional mercaptopropyl, is a polyurethane resin with a functional mercaptopropanol. In the first stage, preparing a polyurethane with isocyanate functional groups of the diols, diisocyanates and structure elements containing groups, which facilitate the stabilization of the resin in water dispersion. Such groups are, for example, derivatives of polyethylene oxide, groups, sulfonate sodium and other ionic stabilizing groups. In the second stage polyurethane with isocyanate functional groups is reacted with di-, tri - or tetrafunctional ntoe attitude tylnej groups to isocyanate groups in this stage is between (2-5):1. This resin is suitable for covering the composition is water-based.
The alternate connection, comprising at least two functional mercaptopropyl, may, for example, have a structure according to the following formula: T[(C3H6O)nCH2SNONCE2S]3and T is a triol, such as trimethylolpropane or glycerol, and n is an integer from 0 to 20. This compound is sold by Henkel under the trade name of Henkel Capcure® 3/800.
Other methods of synthesis with the aim of producing compounds containing at least two functional mercaptopropyl include
- the reaction of aryl - or alkylhalogenide with NaHS to introduce side mercaptopropyl in alkyl or aryl compounds, respectively;
reaction of Grignard reagent with sulfur for the introduction of side mercaptopropyl structure;
response of polymercaptan with the polyolefin in nucleophilic reactions, such as reaction joining Michael on the electrophilic reaction or a radical reaction;
- restoration of disulfides and
- other routes reaction, as described in Advanced Organic hmistry, Jerry rch, 4thedition, 1992, R. 1298.
It is preferable, when NGF is to between 1:2 and 2:1, preferably about 1:1.
In alternative implementations of the present invention, the compound comprising two or more olefinic unsaturated group containing at least one electron-withdrawing functionality linked to a carbon atom unsaturated communication and connection, comprising at least two functional mercaptopropyl may constitute one and the same connection. This option leads to smossyvesa composition in the presence of a catalyst comprising at least one, optionally blocked NH-group.
The composition according to the present invention includes a catalyst containing at least one NH-group, which optionally can be blocked. Catalysts comprising at least one NH-group are, for example, primary and secondary amines. Catalysts comprising at least one blocked NH-group are, for example, aldimine, ketimine, enamines and oxazolidine. Also included catalysts, where NH-group receive as a result of sunlight or UV exposure.
Examples of primary amines include ISOPHORONEDIAMINE, butylamine, n-octylamine, n-nonylamine, N,N-dieta mixture. Also included polyoxyalkylene, such as mono-, di - or triamine of polyoxyethylene/polyoxypropylene. They are sold by the company untsman under the trade name Jeffamine®, for example Jeffamine® T-403.
Suitable secondary amine is, for example, dioctylamine.
Other suitable catalysts are catimini, i.e., the condensation products of primary amino groups with ketones or aldimine, i.e., the condensation products of primary amino groups with aldehydes. In these condensation reactions are formed group with the following formula:
where R5represents an alkyl group, a cyclic group or an aromatic group, and R6represents hydrogen in the case aldimine or alkyl group, cyclic group, or an aromatic group in the case ketimine. Preferably R5and/or R6represent alkyl groups. More preferably 5and/or R6represent alkyl groups containing 1-10 carbon atoms.
Examples of aldimines include condensation products of monofunctional amines, similar n-octyl - or n-nonylamine, and polyfunctional amines, similar to isophorondiamine, acetaldehyde, Propionaldehyde the fact is, for example, Vestamine® A, isophorone-bis-isobutyramide from the company . You can also use aromatic aldehydes and dialdehyde, heterocyclic aldehydes and dialdehyde and mixtures thereof. Examples of aromatic aldehydes include 4-acetamidobenzaldehyde, anthracene-9-carboxaldehyde, 3-benzyloxybenzaldehyde, 4-benzyloxybenzaldehyde, 3-benzyloxy-4-methoxybenzaldehyde, 3,5-bis(trifluoromethyl)benzaldehyde, 3-bromo-4-methoxybenzaldehyde, 5-bromo-2-methoxybenzaldehyde, 2-bromobenzaldehyde, 3-bromobenzaldehyde, 4-bromobenzaldehyde-bromocinnamaldehyde, 3-bromo-4-fermentology, 4-bromo-2-fermentology, 5-bromo-2-fermentology, 5-bromo-2-hydroxybenzaldehyde, 2-chlorobenzaldehyde, 3-chlorobenzaldehyde, 4-chlorobenzaldehyde and other halogen-substituted aromatic aldehydes, 4-butoxybenzaldehyde, 2,3-dihydroxybenzaldehyde and other isomers, 2,3-dimethoxybenzaldehyde and other isomers of 3,4-dimethoxy-6-nitrobenzaldehyde, 4-dimethylaminobenzaldehyde, 2,5-dimethyl-p-anisaldehyde, 2,4-dinitrobenzaldehyde, 4-phenoxybenzaldehyde, 3-phenoxybenzaldehyde, 4-phenylbenzene, p-toluene aldehyde, o-toluene aldehyde and m-toluene aldehyde, 2,4,6-trimethylbenzaldehyde and other alkyl substituted benzaldehyde. Examples aromatically thiophene-2-carboxaldehyde, thiophene-3-carboxaldehyde, 5-acetoxymethyl-2-furaldehyde, 4-bromo-2-thiophenecarboxaldehyde, 3,5-dimethyl-1-phenylpyrazol-4-carboxaldehyde, 3-phenyl-1H-Piramal-4-carboxaldehyde, picolinamides, 4-pyridinecarboxamide, 3-pyridinecarboxamide and 4-chinainternational. Example heterocyclic dialdehyde includes 2.5-thiophencarboxylic.
Suitable kamiminami are condensation products of mono - and polyfunctional amines, for example, acetone, methyl ethyl ketone, isobutyl ketone, methylisobutylketone, ethylaminoethanol, cyclohexanone, acetophenone, hydroxyacetophenone or acetylbiphenyl. One example is the reaction product of 3 moles of ethylmercaptan and 4-(aminomethyl)-1.8-octanediamine.
An example of a suitable oxazolidine is Incozol® LV, selling Industrial lymers Ltd., i.e. the reaction product of 1 mole of diallylmalonate and 2 moles of oxazolidine derived from diethanolamine and Isobutyraldehyde.
An example of a suitable enamine is 1-pyrrolidinyloxyl.
Catalysts, where NH-group is formed by UV-irradiation, describes J. F. Samego et al., J. Org. hm., 1990, 55, PP. 5919-5922. Examples of catalysts, where NH-group is formed by UV-irradiation,toxi]carbonyl]hexane-1,6-diamine, N-[[1-(3,5-acid)-1-methylethoxy]carbonyl]piperidine, [[1-(3,5-acid)-1-methylethoxy]carbonyl]Amin, [[2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, 4,4’-[bis-[[(2-nitrobenzyl)oxy]carbonyl]trimethylene]dipiperidino, 3,3’,5,5’-tetraethoxyorthosilicate and mixtures thereof.
Catalysts with NH-functional groups, optionally blocked, can be used alone, as mixtures of catalysts of the same nature or as mixtures of catalysts of different nature. In particular, if the composition according to the invention is used as a primer, it is preferable to use as catalyst a mixture of aldimines and ketimines. When mixing, you can use the mass ratio (0.1 to 10:1, preferably (2-6):1. It was found that this leads to better adhesion to the substrate.
Because the reaction time is only slightly depends on the amount of catalyst, it is possible to use a high concentration of catalyst without giving the response of the uncontrolled nature. It was found that the sensitivity of the soil or the top layer to acid base or primer and, therefore, the curing time is lower when using higher concentrations katerega layer or soil type tertiary amines, because they are believed to stick to the used acid primer or acid base and neutralize its acidity. Then use the full amount of the catalyst to catalyze the reaction. Suitable tertiary amine is N,N-dimethylethanolamine.
Preferably the catalyst is used in an amount of 0.01-10 equivalents. % nitrogen groups, based on the total amount of unsaturated and tylnej groups. More preferred is an amount equal to 0.1 to 6 EQ. %.
The composition according to the present invention can provide a composition for water-based composition based on the solvent or composition without solvent. Since the composition may consist of oligomers with a low viscosity, it is particularly convenient to use in the form of a coating with a high dry matter content or coating without solvent. Preferably theoretical content of volatile organic part (V) of the composition is less than 450 g/l, more preferably less than 350 g/l, most preferably less than 250 g/L.
To further reduce the content of volatile organic part, it is possible to use reactive diluents, such as diethylmaleate, methoxypropylacetate the functional performance communications connection, such as dodecylmercaptan and silanes with functional mercaptopropyl-mercaptopropionylglycine. Functional mercaptopropyl and olefinic unsaturated group of the reactive diluents also take into consideration when talking about above is equivalent to the relation.
The present invention is of particular interest for covering compositions or adhesives. Preferably use two-component composition. Preferably the first component of a two component coating or adhesive includes a compound containing two or more olefinic unsaturated group, and a compound comprising at least two functional mercaptopropyl at that time, as the second component of the composition includes a small amount of a solution of the catalyst. However, if this is desirable, the second component may include, after the catalyst part or all of the amount or compounds containing olefinic unsaturated groups, or compounds comprising functional mercaptopropyl.
Formulations may contain pigments, which create additional effects, pigments, such as aluminum particles, absorbers, UV-light, amplifiers adhesion, such as aoaci, increase fluidity, and other additives.
The composition of the present invention can be applied by conventional means, including spraying, painting brush, a coating roller or dipping. However, the composition of the present invention is particularly suitable for application using a device with external mixing, where the liquid composition, including
connection comprising two or more olefinic unsaturated group containing at least one electron-withdrawing functionality linked to a carbon atom bonds, and
connection, comprising at least two functional mercaptopropyl,
sprayed through the spray nozzle with a small amount of a liquid composition of a catalyst consisting of at least one catalyst comprising at least one optionally blocked NH-group, which inject into a sprayable composition. Such apparatus is described, for example, in WO 98/41316. Thanks to a very efficient use of the catalyst compositions of the present invention have a very short curing times, which makes this method particularly suitable for the compositions.
Coalescency grounds such as aluminum, steel or galvanized steel, for industrial use of any type. The composition can be used, for example, as an adhesive or coating, for example, as a filler, primer, filler primer, the top layer or the transparent cover. The composition is especially advantageous to use as cover for car repair, because it is easily sprayed and it can be applied at ambient temperature. Typically when repairing cars, you need to apply multiple layers such as a primer, primer, and clear coating. Due to the short time of drying the next layer can be applied after a short period of time after the first coat.
Further, the invention is illustrated by the following examples.
Table I lists the compounds that are being sold these companies.
In the examples for connections use the following abbreviations.
DU - diazabicyclo,
D - N,N-dimethylethanolamine,
ID - isophorondiamine,
RTMR - pentaerythritol-tetrakis-(3-mercaptopropionate),
TAP-JAC is the reaction product of 3 moles of ethylmercaptan and 4-(aminomethyl)-1.8-octanediamine,
TSR(2MA)3 - timeoptions),
TMRCA - trimethylolpropane
In the examples of the functional mercaptopropyl and olefinic unsaturated groups present in opaque compositions in an equivalent ratio of 1:1.
The time of curing is measured using drying recorder VK. The curing time is the time between sample application and the phase when the pencil drying recorder VK already does not damage the floor in a downward direction to the base (phase III).
With cover can freely turn when mark energetic pressing your finger disappears after 1 or 2 minutes.
The viscosity is measured pan slot viscometer type of ATS 2000.
The adhesion test, using the so-called test on the breakaway, which with the help of cutter lf make cross-cut at an angle of 45, after which the paint stick sticky tape standard type and again gently yank it off. Values 1-10 represent the scale for the assessment of adhesion being in the range from very poor adhesion (1) to excellent adhesion (10).
Adhesion on Gitterschnitt measured in accordance with ISO 2409. Adhesion is determined visually on a scale from 0 (no separation) to 5 (complete separation). the operating conditions: 10 days at 100% relative humidity at 42S.
Resistance to splitting is measured by the standard Frd-test Frd 57-4. Values 0-7 represent the scale for assessment of resistance to splitting in the range from very poor (7) to excellent (0).
Accelerated test weather is conducted according to the international standard ISO 2810.
The presence of swellings in the hardened layers have S-0714. The results of the determined values in the range from 1 (largest swelling) to 10 (no warping), with additional codes for the density of swellings, and F means “minor” M “average” and D “dense”.
Obtaining complex functional polyester with maleate groups
Two-liter 4-necked flask equipped with a stirrer with adjustable speed, thermocouples in combination with a regulator, distillation column, condenser, device for ozonation of nitrogen and shirt with heating. In the flask is charged 1240 grams of diethylmaleate, 235 grams of 1,5-pentanediol, 360 grams of 2-butyl-2-ethylpropane, 3.7 grams of a catalyst comprising an oxide dibutylamine, and 5 wt.% xylene. Start barbthroat nitrogen and agitate. Set these temperatures shirts Dagda speed of distillation will decrease, add another 5 wt.% xylene for about 60 minutes, followed by reaction under reduced pressure. At the end of xylene together with the remainder of the ethanol is distilled off. The degree of conversion in the reaction, calculated from the amount of ethanol that is more than 98%. The dry matter content in the final product is equal to 99.6%. Viscosity at 23 ° C is equal to 1 Pas. Maleate number is 278 mg KOH/g of dry matter.
Getting oligourethane with maleate functional groups
Two-liter 4-necked flask equipped with a stirrer with adjustable speed, thermocouples in combination with a regulator, partial condenser hot irrigation device for ozonation of nitrogen and shirt with heating. In the flask is charged with 375 grams rdura® E10. Include bubbling nitrogen and a stirrer, and a portion of the load is heated to a temperature of 100C. Then add 260 grams of isobutylphthalate and 0.64 grams of 2-ethylhexanoate chromium(III), while the temperature of the load support at 120C (exothermic reaction). The reaction is carried out at 120C until the degree of conversion of COOH will not be, at least 98%, followed by cooling to 80C. Then add 0.5 grams of the catalyst of dilaurate dibutylamine, then SL is eraut at 90 ° C, when the degree of transformation JI equal to at least 98%. The product is cooled, diluted with n-butyl acetate to a dry matter content of 70 wt.%. The measured dry matter content in the resulting product is equal to 72.4%. Viscosity at 23 ° C is equal to 1.9 Fold. Maleate number is 84 mg KOH/g of dry matter.
Obtaining complex Mediafire with functional mercaptopropyl
Two-liter 5-necked flask equipped with a stirrer with adjustable speed, thermocouples in combination with a controller, a column in the Game, condenser, device for ozonation of nitrogen and shirt with heating. In the flask is charged with 48 grams of trimethylolpropane, 763 grams dimethylolpropionic acid and, as a catalyst, 20.5 grams of para-toluenesulfonic acid. Start barbthroat nitrogen and turn up the heat shirt. When a portion of the load melted, turn the mixer. Spend the first stage of esterification at 140 C, until it reaches an acid number of less than 10 mg KOH/g of dry matter. Then add 108 grams of isononanoic acid, followed by rinsing for about 5 wt.% xylene. During this time the solution download cooled to 120C. Then add 582 grams of 3-mercaptopropionic acid temperature load is increased to 140 ° C. The second stage of esterification is conducted CIP 140 C with an additional 10 grams of para-toluenesulfonic acid, with delegacia xylene under reduced pressure, until it reaches an acid number of less than 15 mg KOH/g of dry matter. Then add 6 grams of lithium carbonate, followed by cooling and dilution of n-butyl acetate to the solids content of 81 wt.%. Obtaining complete filtration at about 70C, using a filter, working under pressure, with a catalyst filter that gives pure resin. Total IT - and S-value obtained is equal to 254 mg KOH/g of dry matter. The dry matter content is 81.8 percent. Viscosity at 23 ° C equal to 1.3 Fold.
Examples 4-11. The comparison examples a and B.
The following examples 4 to 11 and comparison examples a and b are prepared covering composition, comprising 40 g RTMR and 36 g TMRCA. Use a variety of catalysts, as shown in table II. In examples 4-11 using the catalyst according to the invention. In comparison examples a and b using the catalysts of the prior art. All of the examples 4 to 11 and comparison examples a and b using 0.5 equiv. % of catalyst. Prepare composition and then applied to a glass plate using a 200-micron blade. Samples of the CTE is 5 g/L.
The comparison examples a and b show that the catalysts, which represents a tertiary amine and ethanolic sodium, are not highly effective at room temperature, compared with the catalysts according to the invention at equal concentrations. Examples 4-11 shows the relative efficiency of different catalysts according to the invention. The curing time is much shorter than the time of curing in comparison examples a and B.
Repeat example 10 except that they use different amounts of catalyst, i.e., Vestamine® A. Equimolar amount of catalyst in example 10 corresponds to 2 wt.%. The corresponding test results are shown in table III, demonstrate the sensitivity of the system to the amount of the used catalyst.
In these examples, theoretical V equal to 165 g/l
The comparison examples C and D
Repeat example comparison And except that they use a different catalyst, i.e., DU in two different quantities. The test results shown in table IV, demonstrate that the use as a catalyst DU either leads to an extremely fast response with a relatively small concentration katalysatoren basic catalysts.
In these examples, the comparison of theoretical V equal to 165 g/l
Covering composition includes 40 g RTMR and to 64.8 g of complex functional polyester with maleate groups in example 1. The catalyst is 2 wt.% Vestamine® A (2,3 EQ. %). Theoretical V equal to 400 g/l of the Drawing is conducted according to example 4. The curing time is 22 minutes at S.
Example 16 and example comparison E
In example 16 and the corresponding example comparison E use of 31.2 g RTMS combined with 50 g of a complex of the polyester with maleate functional groups prepared in example 1. In example 16 as a catalyst using a 1.5 wt.% Vestamine® A (1.7 EQ. %). In the example of comparison of E as the catalyst used D in a quantity equimolar to the amount of catalyst in example 16. Theoretical V equal to 250 g/l, as for example 16, and example comparison, that is, the Composition is applied to the base in the same manner as in example 4. The curing time for example 16 is 20 minutes, while the curing time, for example, comparison of E is more than 24 hours at S.
Examples 17, 18, 19 and example comparison E
Prepare the following recipe primer/filler, gram:
Complex is 6,26
Calcium carbonate 14,20
Magnesium silicate 5,70
Titanium dioxide 14,00
The zinc phosphate 6,30
Furnace carbon black with a low
the colour intensity of 0.04
groups example 1 13,80
To get the composition the desired viscosity suitable for spraying, add 10,00 grams of butyl acetate.
This primer/filler is applied by spraying using a device with external mixing, as described on pages 16-17 of the present description, using various catalysts, steel base, and the coating layer is 80 μm after curing at S. In example 17 use of 2.5 equiv. % TAN-JAC. The filler is suitable for grinding after 5 minutes. In example 18 use of 2.5 equiv. % ACCESSORIES>. The filler is suitable for grinding after 30 minutes.
In example 17, example 18, theoretical VOC is 290 g/l
Prepared in example 18 composition is applied by spraying using a device with an external mixing on steel base. In the example of comparison of F on steel base put filler Autocryl® 3110. Then all primed base is treated with a protective layer of Autocryl® LV. Curing occurs when those who esecutore cut assess the adhesion of the primer to the steel base. The results are given in table V.
To prepared in example 18 composition add adhesion promoters, namely 4% by weight of solid binder, representing epoxysilane (example 19). Conduct the same test as above. The results are also given in table V.
For the following tests using samples of the compositions according to example 18 and example comparison F. these samples primer to be applied on the grounds that pre-treated using a wash primer® CR. Then a primer is applied a protective layer Autocryl® LV. Curing occurs at a temperature T. The results are given in the following table VI.
In this example, prepare the soil according to the present invention, grams:
Complex polyester with maleate
functional groups in example 1 97,41
Sparkle Silver® E 5000 AR 48,43
Butyl acetate 69,58
Theoretical V equal to 165 g/L. This formulation of the primer is applied by spraying to steel base, pre-coated filler utocryl® 3110. The ground put the device with external mixture described above using 2.5 equiv. % TAP-JAC. On the resulting film can re-apply treatment includes the following compounds, grams:
Butyl acetate 36,00
Wook® 306 0,85
inuvin® 292 1,08
inuvin ® 1130 2,17
Theoretical V equal to 435 g/L. This formulation is sprayed device with external mixing with 5 EQ. % solution of catalyst TAP-JAC. The layer thickness after drying of 50 μm. With it you can freely go through 10 minutes after curing at room temperature when spraying on various commercial soils such as Autobase® and Autowave®.
Cook another transparent coating with the following formula, grams:
Oligourethane with maleate
groups example 2 100,00
Butyl acetate 44,94
inuvin® 123 0,48
inuvin® 1130 0,48
Wook® 333 0,27
This recipe sew 5 EQ. % solution of catalyst Vestamine® A and applied, utverjdayut and test as in example 21. This recipe transparent cover can be freely accessed through 20 minutes after curing at room temperature.
Form the putty recipe, which includes pasta with maleate functional groups, pasta with functional mercaptopropyl and kata is"ptx2">Barium sulfate 12,1
The magnesium silicate and 82.2
Complex polyester with maleate
groups example 1 100,0
Pasta with functional mercaptopropyl includes gram:
Titanium dioxide 2,8
Barium sulfate 6,1
Magnesium silicate 41,1
The used catalyst is a 1.8 grams of TAP-JAC (2,75 EQ. %). When mixing the two pastes and catalyst to get the putty over time machinability 3.5 minutes, which becomes solid after 4.5 minutes and are suitable for grinding after 10 minutes after application on steel base and curing at S.
Make same composition as in example 23, except that the catalyst was replaced Vestamine® A (2,75 EQ. %). Get the putty over time machinability 5.5 minutes, which is solid through 41 minute and is suitable for grinding after more than one hour after coating on a steel substrate and curing at S.
Examples 25 and 26
In examples 25 and 26 serves two transparent coating water-based according to the invention.
Acryloyl-functional polyurethane emulsion (43% dry. prophetic. in water, 454 C=C equivalent for Mac is versaut using ID (5 EQ. %), whereas in example 26 composition utverjdayut using Jeffamine® T 403 (2.7 EQ. %).
Transparent coating applied to a glass base using 100-micron blade, and utverjdayut when S (see table VII).
The following examples 27-35 prepare opaque composition comprising a complex of the polyester with maleate functional groups in example 1 and various compounds with functional mercaptopropyl equivalent ratio of functional mercaptopropyl and olefinic unsaturated groups is 1:1. Use different catalysts in the amount of 0.75 EQ. %. The composition is applied onto a glass plate using a 200-micron blade. Samples utverjdayut at a temperature T. In table VIII lists the curing time in minutes.
This example describes the adhesive composition according to the invention.
Complex polyester with maleate functional groups were obtained from 237 g of 1,4-dimethylcyclohexylamine, 175 grams of neopentyl glycol, 181 grams of Isobutanol and 403 g of maleic anhydride. Obtaining carried out as described in example 1. The obtained complex polyester has a viscosity of 31.6 Pas at 23 ° C and maleate a number equal to 251 mg KOH/g ve innymi functional groups; 135 grams RTMR; 300 grams of caso3; 0.7 gram of water and 3.3 grams Incozol® LV.
Thus obtained adhesive is applied by brush to the surface of two samples, each of which is made of polyvinyl chloride (PVC), Acrylonitrile-butadiene-styrene azopolymer (ABS), reinforced with glass complex of the polyester (GRP) and aluminum (A1). The amount of the applied composition is about 40 to 50 grams per square meter of surface. Samples of the same materials compress together at ambient temperature for 30 minutes. After 24 hours, determine the tensile strength of the obtained adhesive joints. Get the results, shown in table IX.
The results show that the composition is suitable as an adhesive (adhesive composition) for different materials.
1. Coating or adhesive composition comprising a compound comprising two or more olefinic unsaturated group containing at least one electron-withdrawing functionality linked to a carbon atom unsaturated connection; the connection comprising at least two functional mercaptopropyl; and a catalyst comprising at least one optional blocking the primary or secondary amines, aldimines, ketimines, enamines, oxazolidines or mixtures thereof.
3. Coating or adhesive composition according to any one of the preceding paragraphs, characterized in that the catalyst is used in an amount of 0.01-10% EQ. the nitrogen groups of the total number of unsaturated and tylnej groups.
4. Coating or adhesive composition according to any one of the preceding paragraphs, characterized in that the olefinic unsaturated groups, compounds containing two or more olefinic unsaturated group, have a structure of the following formula I:
where at least one of R1, R2, R3and R4includes electron-withdrawing functionality linked to a carbon atom bonds, and at least one of R1, R2, R3and R4associated with polyvalent group containing at least two valence.
5. Coating or adhesive composition on p. 4, characterized in that the electron-withdrawing functionality selected from carbonyl, carboxyl, complex ether, thiocarbonyl, dicarboxyl, complex thioesters, sulfoxide, sulfonyl, sulfopropyl, phosphate, phosphite, phosphonite, phosphinite, nitro, nitrile and amide.
6. Coating or adhesive composition on p. 5 the holding from 2 to 10 carbon atoms.
7. Coating or adhesive composition according to any one of the preceding paragraphs, characterized in that the functional mercaptopropyl and olefinic unsaturated groups are present in an equivalent ratio of between 1:2 and 2:1.
8. The method of applying a coating or adhesive composition according to any one of the preceding paragraphs, characterized in that the liquid composition consisting of compounds comprising two or more olefinic unsaturated group containing at least one electron-withdrawing functionality linked to a carbon atom bonds, and compounds comprising at least two functional mercaptopropyl, spray the spray nozzle, and that a small amount of a liquid composition of a catalyst consisting of at least one catalyst containing at least one optional blocked NH-group, spray in an aerosol spray composition.
FIELD: polymer materials.
SUBSTANCE: invention relates to polymer composition based on binder, namely unsaturated polyether resin or oligoether acrylates, and may be used in medicine, in production of paint and lacquer materials, etc. Composition comprises, wt parts: unsaturated polyether resin or oligoether acrylates or mixtures thereof, 100; polymerization promoter, in particular complex compound prepared by reaction of vanadium derivatives (vanadium pentoxide, ammonium methavanadate, of methavanadic acid) with orthophosphoric acid/water/butanol mixture, 0.3-0.88; polymerization initiator: cumene hydroperoxide, 0.3-0.44; and modifying additives, 0-20.
EFFECT: optimized makeup involving inexpensive, easily available, and highly efficient promoter.
1 tbl, 6 ex
FIELD: building industry and materials.
SUBSTANCE: invention proposes a polymeric composition comprising the following components, mas. p. p.: polysulfide oligomer, 100; unsaturated polyester resin PN-1, 90-100; aerosil, 5-20; organic peroxide, 3-20; cobalt naphthenate 10% solution in styrene, 2-4, and 2,4,6-tris-(dimethylaminomethyl)-phenol, 0.5-1. The composition provides preparing covers with enhanced strength properties, adhesion to substrates and showing hydroinsulating properties, resistance against effect of acid and alkali solutions and improved technological procedure for their applying. Invention can be used in preparing hydroinsulting, sealing and anti-corrosive compositions processed by pouring and spraying method.
EFFECT: improved and valuable properties of composition.
FIELD: polymeric materials.
SUBSTANCE: invention relates to polymeric protective materials and can be used for creature of anticorrosive covers. Photohardening composition for cover comprises the following components, mas. p. p.: polysulfide oligomer, 5-10, unsaturated polyester resin, 100-105, and a photoinitiating agent, 3-6. Resin of sort PN-9119 is used as unsaturated polyester resin that represents products of polycondensation of propylene glycol with dimethylterephthalate and maleic anhydride dissolved in styrene (the styrene concentration is 35-45%). Proposed composition provides the high hardening rate to obtain materials showing the high cross-linking frequency and regularity of structure that enhance bending and stretching strength, resistance against corrosion and adhesion properties of the cover.
EFFECT: improved and valuable properties of composition.
2 tbl, 10 ex