JPH05503549A - Polyurea gel compositions and articles obtained therefrom - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] TECHNICAL FIELD OF THE INVENTION Polyurea gel compositions and articles obtained therefrom The present invention relates to cured gels and curable compositions for providing gels.

background Cured gels, including polyurethane gels, seal electrical components and metal structures, e.g. For example, it has long been used to protect against corrosion caused by seawater. For example, polyurethane The gel is made from the ingredients that make up the gel (silicone or polyisonoanaates and hydroxyl). (terminated polybutadiene or polyester neck) and diluent, then by pouring the mixture around the joint and curing it in place. Cast in place around the multi-core cable joint. polyisocyanate Curing of /diol mixtures is relatively slow at room temperature (eg, several days even with addition of catalyst).

In recent years, U.S. Patent Nos. 4,600,261 and 4,634,207 (Debout) As specifically disclosed, the disclosure of which is incorporated by reference herein for all purposes. Articles comprising precured gels may be used to protect electrical contacts and other substrates. It is used to protect.

[Other known uses for gels include Noricon gels and non-Soricon gels, especially European Patent No. 174165 (1986) by Chunk and Toy No. 229102 (1987) by Toy and using butyl gel. and other electrical components, and those patents cover high voltage terminals and connectors. The use of such gels as insulation and stress grading compositions in specifically mentions the use of The disclosure of each of these applications is incorporated herein by reference. Configure.

Although the polyurethanes used according to the prior art have excellent short-term physical properties, , its anti-acid properties are poor. i.e. they are within the expected service range. hydrolytic and thermal stability, moisture resistance, and resistance to compression set, especially at high temperatures. Poor long-term chemical and physical properties, such as resistance. More polyurethane Tanger extracts plasticizers from poly(vinyl chloride) insulation under certain circumstances and Otherwise, the function of the poly(vinyl chloride) insulation will be impaired.

Disclosure of invention We have developed a new package that is useful for sealing and environmentally protecting substrates, especially electrical connections. discovered a new composition. The novel composition has improved tensile strength, elongation, toughness, and Unexpected compatibility with substrates containing compositions containing poly(vinyl chloride) It is a valuable combination as a gel sealant composition. Accepts high levels of dilution without significant syneresis while retaining good tack. In one aspect, the present invention provides compositions comprising crosslinked polyureas.

The crosslinked polyurea is preferably present as a gel. Its composition and preferences or the polyurea gel also has a Boland hardness of 1 to 5009 and at least 50% It has an ultimate elongation of . Preferably the polyurea gel contains at least 25% to 95% by weight % diluent (based on the combined weight of polyurea and diluent). more preferable A polyurea containing at least 25% to 95% by weight of a diluent is a polyurea. It has a gel fraction of 5% to 75% by weight of the total weight of diluent. preferably The diluent is compatible with (e.g. swells) the cross-linked polyurea and It is preferably a liquid that is chemically unaffected by the conditions used in its manufacture.

In another aspect of the invention, the average molecular weight between the urea groups in the polyurea is 5009 g per mole of polymer, for example not more than 250 g per mole of polymer. , that's it Gels with a high density of urea groups are particularly useful when high dielectric constants are required. stomach( For some applications an average molecular weight between urea groups of 500 or more is preferred, e.g. per mole of polymer (both 10009 or at least 2 per mole of polymer) 000g is desirable, for example, if a low dielectric constant gel is required.

In this specification, the term crosslinking refers to a structure in which a total of three or more molecular segments are suspended. a covalent bond formed by a chemical reaction between two or more crosslinking sites, or Formed by a chemical reaction between a crosslinking moiety and an intermediate molecule, the remainder of that molecule sag. at least two covalent bonds having at least three molecular segments descending It means the combination. Typically the intermediate compound has at least three crosslinking sites It is a low molecular weight compound or low molecular weight oligomeric substance. The crosslinking is trifunctional (T- link, i.e. a bridge with three molecular segments depending on it), or is tetrafunctional (H-link, i.e., has four molecular segments depending on it) crosslinks) or have greater functionality.

In another aspect, the present invention has a polish hardness of 1 to 500 g when fully cured. providing a crosslinkable composition having an ultimate elongation of at least 50%; is a first organic compound containing an amine group, an isocyanate group or an isonoanate a second organic compound containing a precursor group, and a first organic compound and a second organic compound; compound, and a diluent in an amount of 25% to 95% by weight of the total weight of the diluent. It becomes. In a preferred embodiment, the first organic compound has an average of n amine groups per molecule. the second organic compound has an average of m isocyanates per molecule. or polyisocyanates or polyisocyanates containing isocyanate precursor groups. It is a cyanate precursor. where each of n and m is at least 2 and the sum of n and m is at least 4.1, and the composition is free from added catalyst. have a gel time (defined below) of 600 seconds or less at 25°C.

In another aspect, the invention provides a kit comprising at least two containers. , the container is as follows.

(1) a first organic compound having an amine group; (2) an isocyanate group or an isocyanate group; Second organic compound having a cyanate precursor group (3) inert to the reaction with the first organic compound and inert to the reaction with the second organic compound; A diluent that is inert (the total amount of diluent in the container is equal to the amount of diluent in the container) 25% to 95% by weight of the total weight of organic compound and diluent) The distribution of the substance between the containers comprises at least one substance selected from: When the container was kept at room temperature (25°C) under dry conditions for 6 months, the first organic compound and and the second organic compound is stable.

When mixed and fully cured, the contents of the container should have a Borland hardness of 1 to 500 g and a A crosslinked polyurea having an ultimate elongation of at least 50% is provided.

Preferably in this aspect of the invention, the first organic compound has an average of n molecules per molecule. The second organic compound is a polyamine containing an amine group, and the second organic compound has an average of m isocarbons per molecule. Polyisocyanate or polyisocyanate with cyanate or isocyanate precursor is a polyisocyanate precursor, and each of n and m is at least 2 and the sum of n and m is at least 4.1.

Another aspect of the invention is a polishing hardness of 1 to 500 g and an ultimate elongation of at least 50%. Provided is a method for producing a polyurea gel having a (1) a first organic compound having an amine group, and (2) an isocyanate group or is a second organic compound having an isocyanate precursor group, is inert towards the first organic compound and inert towards the second organic compound. of the total weight of the first organic compound, second organic compound, and diluent of the diluent The reaction is carried out in the presence of at least 25% to 95% by weight. This essential point of the invention Preferably, the first organic compound has an average of n amine groups per molecule. The second organic compound has an average of m isocyanate groups per molecule. or polyisocyanate or polyimide having an isocyanate precursor group. a socyanate precursor, and each of n and m is at least 2; , n and m are at least 4.1.

In another aspect, the invention comprises a polyurea gel containing 1 to 5009 borons. for protection of substrates, comprising a composition having a hardness of at least 50% and an ultimate elongation of at least 50%. provide goods for Preferably the article includes a cured gel in contact with the substrate. means for deforming, more preferably the cured gel, into intimate and conformable contact with the substrate; including means for causing

In another aspect, the invention provides 1 to 500 g of polyurea comprising a cured polyurea. at least partially by a composition having a hardness and an ultimate elongation of at least 50%. to provide a protectively encased substrate.

In another aspect, the present invention provides: (1) a first organic compound having an amine group; compound, (2) a compound having an isonoanate group or an isocyanate precursor group; two organic compounds, and (3) chemically affected by the reaction between the first organic compound and the second organic compound; diluent (the diluent comprises a first organic compound, a second organic compound and a diluent) present at least 25% to 95% by weight of the total weight) surrounding the substrate with a mixture comprising; and having the mixture in contact with the substrate. A method of wrapping a substrate is provided, the method comprising curing a substrate. This summary of the invention Preferably, the first organic compound has an average of n amine groups per molecule. is a polyamine, and the second organic compound has an average of m isocyanates or is a polyisocyanate or polyisocyanate having an isonanoate precursor group. an anate precursor, each of n and m being at least 2; The sum of n and m is at least 4.1.

A further gist of the invention is: (1) providing a cured polyurea gel; (2) providing at least a portion of the substrate with the composition; applying the cured gel to the substrate so as to substantially enclose the Provided is a method for protecting a substrate comprising:

Another gist of the invention is: (1) Providing a composition comprising a crosslinked polyurea (the composition has a (Boland hardness of 0g and ultimate elongation of at least 50%) (2) applying the composition to the substrate such that the composition surrounds at least a portion of the substrate; and Provided is a method for protecting a substrate comprising:

Another gist of the invention is: (A) Each of the diluents has a dielectric constant different from any other diluent selected. Select a diluent blend, indicating that the diluent weight ratio is such that the blend has the desired dielectric constant. (B) selecting the blend to have a first organic compound having an amine group; a second organic compound having an isonanoate group or an isocyanate precursor group adding the compound into a composition comprising the compound, and curing and crosslinking the composition. (The proportion and amount of the blend is determined so that the composition has a given dielectric constant.) Provided is a method for producing a composition having a predetermined dielectric constant, which comprises: do.

In many of these aspects of the invention, the diluent comprises a mixture of components; At least one of the ingredients is liquid at room temperature and is different from at least one of the other ingredients. It is preferable that the dielectric constant is as follows.

Brief description of the drawing Figure 1 shows that the hardness of the cured polyurea gel of the present invention depends on the polyurea concentration or crosslink density ( How it changes depending on the triamine content (triamine content of triamine/diamine blends) explain.

Figure 2 illustrates how gel time varies with polymer concentration.

Figure 3 shows that the strength exhibited by the cured polyurea gel of one embodiment of the present invention is - concentration and crosslinking density (triamine content of triamine/cyamine blends). Explain how it changes.

Figures 4 and 5 show the effect of various ketones on the gel time of the gels of the invention. vinegar.

Figures 6 and 7 show the effects of ketone pro- and y-king agents on gel time and gel hardness. Showing the effect of quantity. Figure 8 shows the effect of aldehyde block on gel time and gel hardness. The effect of the amount of kinging agent is shown.

Figure 9 shows the effect of water addition on gel time.

detailed description of the invention The average molecular weight (MC) during crosslinking of the cured polyurea gel in the present invention is preferably or at least 2,000°, preferably less than 4,000°. at least 7.500°, such as at least 10.000°, and in some embodiments at least 20° ,000. The Poland hardness of the composition is preferably between 2 and 375 g, especially between 2 and 1. 25g, specifically 2-409. The ultimate elongation of the composition is preferably at least 250%, in particular at least 650%, for example at least 700%, especially less At least 800%.

The first (amine-containing) compound used to prepare these novel gels is a single compound or mixture of compounds, e.g. at least 3 amine groups per molecule and/or at least two amine groups per molecule. one or more compounds that

The second (isonoanate or isocyanate precursor containing) compound is similar may be a single compound or a mixture of compounds, e.g. at least 3 per molecule. one or more compounds with reactive groups and/or at least two reactive groups per molecule One or more compounds having of the first compound or combination of compounds; The molar equivalent ratio for a compound or combination of compounds is preferably based on the size of the reactant molecules. The moiety is linked to one or more other molecules by at least two bridges (at least (forms a closed loop that includes some 3D networks) be. More preferably at least 50%, such as 65%, preferably 75% A bridge forms such a closed loop. For this purpose the second of the first compound The molar equivalent ratio of ．． 8 to about 1 to 125 to 1, more preferably 0. The ratio is 9:1 to 1.11:1.

Polyurea gels may be precured (i.e., cured before contact with the substrate). Alternatively, it may be cured after contacting the base material. If you pre-cure the gel, use the cured poly Means for deforming the urea gel into contact with the substrate and/or cured polyurea A means of keeping the raw gel in contact with the substrate, preferably by compression, is preferably involved.

Preferably, the cured polyurea gels and gel compositions of the invention are gels or gel compositions. It has a bonding strength greater than the adhesive strength of objects.

The compositions of the invention preferably contain at least 25%, such as at least 30%. More preferably it contains at least 45% diluent, such as at least 60%. par Cent is the weight of the total weight of crosslinked polyurea and diluent. these The amount of diluent corresponding to the range is preferred for preparing the gel and/or gel composition. Preferably use it.

Preferably the first organic compound has the following formula: Q i [, A EhD), -+, A Q, and the second organic compound has the following formula, P f [-A-] 7 Elk-+, A P (where h, j, i and and k are integers that are the same or different and have a value of 1, and h, j , the sum of i and k is at least 20 and not more than 200, Each of the Q groups is the same or different, is directly bonded to the carbon atom of the A group, and is primary or is a secondary amine group, each of the P groups is the same or different, and the carbon atom of the A group is an isocyanate or isocyanate precursor group, and A Each of the groups may be the same or different and have the following formula % formula % 2- or -〇-3i(R')2　R- (in the formula, each of the R groups is the same or different , alkylene, substituted alkylene, alkenylene, substituted alkenylene, ary lene or a substituted arylene group, each of the R' groups being the same or different, alkyl, substituted alkyl, aryl or substituted aryl group), Each of the D groups may be the same or different and may represent a valence bond or a secondary amine group or Alkylene, substituted alkylene, alkenylene, substituted alkenylene, arylene, or a substituted arylene group, and each of the E groups is the same or different and the atoms valence bond or alkylene, substituted alkylene, alkenylene, substituted alkenylene, arylene or substituted arylene group).

The term valence bond refers to a bond that directly connects two atoms in the backbone of a first compound and a second compound. means a single covalent bond that binds

The isocyanate bridger group is dependent on the reaction conditions used to prepare the polyurea gel. A group capable of forming an isocyanate group under , that is, compounds with active hydrogen atoms (substituted or unsubstituted phenols, or alkyl-substituted malonates) and are relatively non-reactive. make a chemical compound, and then heat it (e.g. up to 150°C) to quickly produce insia. - is the group to be regenerated.

Examples of such relatively non-reactive compounds include isonatrifluoride and alkyl moiety. Carbamates are produced by reaction with phenols or aromatic ocytum. Ru. The blocking group can be removed by heat alone or by blocking the Containing active hydrogen atoms such as aliphatic or aromatic amines or alcohols It is removed by reacting with a monomer or polymer compound.

Suitable amines include alpha-amino- Propyl, omega-amino-terminated polypropylene oxides, 200-20.0 Alpha-amino-ethyl, omega-amino-terminated polyethylene with a molecular weight of 0.00 alpha aminoethyl having a molecular weight of 250 to 25,000, Omega-amino-terminated polytetramethylene oxides, etc.: The following approximate structure Dimercyamine, which has the following approximate structure, and dimer diacid, which has the following approximate structure: or an excess of substituted or unsubstituted alkylene or arylene ranges of dicarboxylic acids. Amine-rich polyamide resins such as reaction products with amines: bisphenols A reaction product of epoxy resin with diamine such as ethylenetriamine amine-terminated amine-epoxy adduct; 4,4'-diamino-3,3°-dimethylene lucinchlorohexylmethane, noaminodiphenylsulfone, ethylene bisary methylenenoaniline, noethyltolueneamine, 3,5-dimethylthio 2.4- Aromatic amines such as toluenoamine: amine-terminated polybutadiene enes, amine-terminated butadiene-acrylonitrile copolymers, and aminopropylene Pyldimethyl-terminated polydimethylsiloxanes, aminobutyldimethyl-terminated porins There are amine-terminated polyorganosiloxanes such as methylcyclohexanes, etc. but is not limited to this. Suitable amine-rich polyamides include the trademark FELSUAMI do 100, fersamide 115, fersamide 125 and aelsamide 140 is available from Henkel. to the appropriate epoxy amine adduct. is available from Henkel under the trademark Felsamine, such as Felsamine C30. There are things to do.

Suitable polyisocyanates or their precursors contain at least 2 polyisocyanates per molecule. There is an organic isocyanate order with isocyanate groups. polyisocyanate The compounds may have small, large, or intermediate molecular weights, and ethylenediyne anate, trimethylene diisocyanate, dodecamethylene diisocyanate , hexamethylene diisocyanate, hexamethylene diisonoanate trimer , tetraethylene diisocyanate, pentamethylene diisocyanate, propylene diisocyanate, Ren-1,2-diisocyanate, 2,3-dimethyltetramethylene diisocyanate nate, 1,4-shiisonanatocyclohexane, methyl-hexamethylene di Isocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohe xyl isocyanate, cyclobentene-1,3-diincyanate, p-phini Nishin diisocyanate, naphthalene diisocyanate, 4.4゛-diphenylene 4,4'-diphenylenepropane diisocyanate, 4,4'-diphenylenepropane diisocyanate , tetramethylxylylene diisocyanate (TMXDI), 1.2.3.4- Tetraisocyanate butane, butane-1゜2.3-h diisocyanate, to polyether and polyester prepolymers such as polyisocyanates isocyanate-containing linear or branched aromatic isocyanate order Contains a wide range of organic polyisocyanates, including: The cost of such prepolymers Typical examples include the trademarks Desmocap IIA and Desmocanop 1 by Mobay. It is sold at 2.

The diluent is any organic liquid that has the desired compatibility with the polyurea. wide range Crosslinked gels of the invention can be produced having solubility parameters of . Especially the present invention provides larger solubility parameters than previously expected for applications such as those listed above. It is possible to provide a gel composition having a tar. Therefore, the preferred dilution for The agent has a Hildebrand concentration of at least 7.6 degrees, more preferably at least 8 degrees of humidity. Ludebrand, and most preferably at least 9 degrees of Hildebrand dissolution. Indicates the degree parameter. Suitable diluents include mineral oil, sold under the trademark “permethyl” has the general formula H[-C(CH3)2]nH (in the formula, n is 10 or more), and has about 35 Aliphatic hydrocarbon oils such as those having a viscosity of ~5 Qcps; partially hydrogenated carbonization of at least partially aromatic, preferably polynuclear, such as terphenyl Hydrogen oils, aliphatic, aromatic and inorganic acid esters (such esters include diethyl Luheki/luphthalate, citrideneluphthalate, triethylhexyl trimeri Tate, dibutyl phthalate, butyl benzyl phthalate, diethyl phthalate , ethyl hequinyl diphenyl phosphate, tricresol phthalate, stone and t -butylphenyl diphenyl phthalate), N-ethyl-〇, p-sulfonate sulfonamide M, such as Namamide, having a viscosity of about 1 to about 106 centipoise silicone fluids such as dimethyl silicones (published International Application No. 90/100) 35 (1990) by Dubrow. Its disclosure is for all eyes to see. Incorporated herein for purpose. ) etc., as well as mixtures of any two or more of the above. There are things. Preferably the solubility parameters of the gel and the solubility parameters of the diluent. (or the average solubility parameter of the diluent if more than - liquid diluent is present) is less than or equal to 2 Hildebrands, more preferably less than or equal to 1 Hildebrand, and most preferably differ by less than 0.5 Hildebrand.

Optionally, the reactants also include one or more hydroxy compounds as diluents. Amin is Much more than soocyanates or isocyanate precursors and hydroxy compounds Since it reacts quickly, the latter acts as an essentially inert diluent.

The crosslinkable compositions of the present invention and compositions made according to the present invention contain flame retardants, corrosion inhibitors, inhibitors, antioxidants, UV stabilizers, fungicides and other bio-killing substances, pigments, fillers that increase and decrease thermal or electrical conductivity, and density or other physical Various additional ingredients may be included, such as fillers to adjust properties. So Additives or fillers such as to influence these and the overall cost of the final composition. May be used. A particularly useful ingredient for inclusion in the Kel of the present invention is U.S. Pat. ．． 852.646 (1989) by Dittmer and Dubrow, and Holland and Rost in European Patent No. 0,324.255, published in is described.

The disclosure thereof constitutes a part of this specification for all purposes.

Advantageously, the polyurea gels of the invention contain stabilizers and antioxidants, such as - ．． 6-Hexamethylenebis(3,5-not-tert-butyl-4-hydroxyhydrogen) doronnamate), tetrakis[methylene 3-(3', 5'-notert -Butyl-4'-hydroxyphenyl)propionate comethane, oftadenol 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propyl onate, N, N'-bis[3-(3', 5°-tert-butyl-4' -Hydroxyphenyl)propionate comethane, thione ethylene bis(3, 5-7-tert-methyl-4-hydroxyhydronnamate), triethylene Glycol His (3(3'-tert-butyl-4°-hydroxy-5°-methyl) tylphenyl) propionate, octadecyl-3-(3',5'-diter t-4'-hydroxyphenyl)-propione-h,N,N'-hexamethylene (3,5-not-tert-butyl-4-hydroxy-hydrocinnamamide) 2-methyl-4,6-bis[(octylthio)methyllaphenol, 4. 4″-thiobis-5-tert-butyl (1r cresol), 2,2′-methylene Bis(4-methyl-5-tert-butylphenol), 4.4°-methylene bis (2,6-tert-butylphenol), di-tert-butylphenol Nor, 2,2'-methylenebis(4-ethyl-5-tert-butyl)pheno of synclopentadiene and ortho-tert-butylhydroxytoluene. Reaction product, 2(2°-hydroxy-5′-methylphenyl)benzotriazo 2(2'-hydroxy-3',5'-di-tert-amylphenyl)base ndzotriazole, 2(2′-hydroxy-3′,5′-tert-butyl Luphenyllolobenzotriazole, bis(1,2.2,6.6-bentamethyl -4-piperinyl) sebacate, dimethylsacunnate and 4-hydroxo-2 ．． 2, 6. 6-tetramethyl-1-piperidine ethanol condensation product, Bis(2, 2. 6. 6-tetramethyl-4-piperidyl) sebacate, ( [3,5-bis(1,1-dimethylethyl)-4-human hepquinphenyl]methyl ) Butyl-bis(1. 2. 2. 6. 6-bentamethyl-4-piperidini ) ester, nickel bis[0-ethyl(3,5-di-tert-butyl-4 -Hydroxypendylcophosphinate, 4,4°-bis(α.α-methylbenzene) ndinoridiphenylamine, the product of the condensation reaction of diphenylamine and acetone, Arylated phenylamine, octylated diphenylamine, poly((6-(( 1. 1. 3. 3-tetramethylbutyl (2, 2. 6. 6-tetramethyl-4-piperidyl)imino)hexamethyl Ren ((2.2.6.6-tetramethyl-4-piperidyl)imino)), zinc dialkyl dithiocarbamate, dialkyl dithiophosphate, dial Chyl thiodipropionate, distearyl pentaerythritol diphosphite trisnonylphenylphosphite, dilaurylhytronenephosphine tris(3,5-di-tert-butylphenyl)phosphite, tetra (3.5-tert-butylphenyl)-4. 4'-biphenylene diphos Contains phytophytes, polycarbodiimides, etc.

The polyurea gel of the present invention is “amine rich” for greater oxidative stability is preferred. That is, the ionicity of the amine in the starting material used to produce the polyurea is The ratio to socyanate is 1 or more, for example 1,02 or more to 1, more preferably 1.05 or more to 1, for example 1, 1 or more to 1.

As used herein, the term "gel time" refers to isocyanates, amines, and other components. between when it is first mixed and when the mixture stops flowing under its own weight. means the elapsed time. At this moment, the container containing the reaction components is tilted to cause flow. It is quite easy to check by observing whether it is true or not. , a reproducibility of 25% was obtained. Ru. For some applications, the gel time at 25°C is less than 900 seconds, preferably less than 600 seconds. lower, more preferably 600 seconds or less, such as 200 seconds or less, most preferably 100 seconds It is less than 50 seconds, especially less than 50 seconds. In other applications, transfers from one container to another are If you prefer to have more free time to work with uncured gels, such as Long gel times of tens of minutes or even hours are preferred. Those skilled in the art will understand their specific One will readily determine what gel time is most desirable for a given application. Benefits of the present invention The points can be varied by selecting the appropriate combination of isocyanate and amine components. This means that it is possible to formulate compositions that have a curing time of approximately 100%.

If long curing times are desired, as is done with epoxy resin coatings, Increase gel time by blocking amine groups with ketones or aldehydes. can be done. Carbonyl groups of ketones and aldehydes react with amine groups. It creates an imine group, and the imine group is non-reactive with the iso/anate group. water exists and (e.g. atmospheric humidity) the imine group can be hydrolyzed to regenerate the amine group. is reactive. Mixing the iso/anate component with the amine component with blocked amine groups. By combining gels, the gel time can be increased from, for example, 2 minutes to over 24 hours. Wear.

Figure 4 shows that before mixing with the iso/anate component (dimer diisocyanate), The amine component of the formulation (Chefamine T5000) was mixed with different amounts of acetone. The effect of reacting for different times is shown.

Increasing the amount of acetone increases the gel time from about 2 minutes to more than 60 minutes, which increases the amount of amine. Indicates activation. Greater effect compared to 30-40 min reaction time 40-50 min The inactivation reaction (reaction of amine and ketone) is observed after a reaction time of 30 to It shows that it is still incomplete after 40 minutes.

Figure 5 shows dimer diisocyanate, Shefamine T-5000 and Thermino Three differences in increasing the gel time of gels based on Rule 66 ketones, acetone, 2-butanoni and methyl isobutyl ketone (MrBK ) to compare the effectiveness of 7-tyl isobutyl ketone is the more effective of the three. Figure 6 shows dimer diisocyanate/Chefamine T-5000 Kel. The effect of increasing the stoichiometric ratio of MIBK on the gel time of Therefore, MIBK was reacted with the amine at 60° C. for 3 hours and then at room temperature for the next 21 hours. expensive There is a plateau at the MIBK level, indicating complete reaction with the amine groups.

Figure 7 shows that the Kel time is affected by the addition of a ketone (in this case 2-decanone) However, the physical properties (measured by hardness) are hardly affected. Figure 8 is , Desmoda-N-330 after a reaction time of 16 hours at 60°C and 1 hour at room temperature. A similar effect was observed in gels made from 0 and Shefamine D-4000 when aldehydes ( dodecanal).

Various ketones and aldehydes act as blocking agents for amines. It can be used as Suitable ketones and aldehydes include acetate.　, 2-b Thanone (methyl ethyl ketone), methyl isobutyl ketone, 17″2-decanone , 2-undecanone, 3-tridecanone, 3-decane and non, 10-nonadeca Non, 4-hydronkey 4-methylpentanone, acetophenone, decaner undecanal, dodecanal, [benzaldehyde, and ethoxy] Examples include, but are not limited to, benzaldehyde. For some reason volatile block For applications where no kinging agent is desired, 2-decanone and 2-undecanone are recommended. UnaL A blocking agent with high molecular weight and low volatility is preferred.

Imine on one side and ketone (or aldehyde) 1 and acetic acid on the other side The equilibrium between the two is influenced by the amount of atmospheric moisture present. atmosphere water Increasing the amount will push the equilibrium towards ketones (or aldohytones) and amines. and, as a result, reduce gel time. Dimer diisocyanate and 2- Chefamine T-5000 blocked with undecanone (19.5 hours at 60°C) This effect is illustrated graphically in Figure 9 for gels from (reacted for 2.5 hours at room temperature) I will clarify. Dry “one-part” gel with a very long shelf life Made from dried blocked amine, isocyanate and extender fluids Can be done. To cure the gel, simply expose the uncured gel to atmospheric moisture. water or preferably add water to the gel.

The invention is illustrated in the following examples.

Example 1 Production of polyurea using isocyanates This method uses the following formulations 1-1 to 1. The method 6 used to produce -15 will be generally described. Each gel has three basic ingredients, i.e. 1) The following structure: Tetramethylquinrene isocyanate (TMIDI, American Sci. (commercially available from Anamide) and the following approximate structure: of dimer diisocyanate (DD11410, commercially available from Henkel) having 2) amine-terminated polypropylene ether (min. Chefamine D-40 having a molecular weight of 4,000 and approximately 2 amine groups per molecule 00, or similar molecules having a molecular weight of 5.000 and about 3 amine groups per molecule. Chefamine T-5000), 3) Prepared using the inert diluent shown in Table 1 below.

1 f no Sensuiser 141 Ethylheto/Lunophenyl Monosunoto Chemicals 1i f Futisizer 160 Butyl Hennorphthalate Mongo Ntochemica Luz 1□ l　DEP　Noethylphthalate　Yeastmanokodafuku　(JHB40　i min. Terphenyl that has been commercialized as a commercial product Mono No. 11 PPG-1022 5-propylene glycol Reaction of unionocarbide toisonoanate and amine is fast even when highly diluted with an extender, so two masterbatches are required. , one for isocyanate (part A) and one for amine (part B) are very I found it desirable. These masterbatches are generally of equal volume or etc. Contains a large amount of material and very quickly (mixes to start the reaction. Part A container contains isocyanate. nates, some diluents, stabilizers, and fillers. 8 part container contains amine, diluted Contains the remainder of the diluent, stabilizers, etc.

In preparing the gels for all of the following examples, the exact amounts of ingredients were measured on an analytical balance ( (accuracy: 0.01 g) and mixed to make Part A and Part B.

Parts A and B were then quickly mixed and gel times as fast as 10 seconds were observed). B cast on a car or flat sheet. Typically the gel is 6” x 6”xo, Quickly cast to 125" (15,24X15.24X0.3175cm), Cured at room temperature. Gel properties were measured after the gel was cured for 24 hours at room temperature. . Elongation was measured by punching from a molded slab using the method described in ASTM D419. It was measured using a tensile test piece. 609 mixed formulation for hardness measurement. It was placed in a 00ffll beaker and cured. Hardness: Volando Steve Systex 1i4 inch (0,635c m) 5g of bird with pole probe measured at -.

The probe was advanced at a speed of 0.2 mm/sec to a depth of 4 mm into the kel.

Stress relaxation is determined by holding the probe at a constant depth and measuring the hardness 1 minute after the initial hardness measurement. The hardness was measured as the percentage decrease in hardness when measured again.

The tank value is the maximum value observed when pulling the probe out of the gel after measuring hardness. Measured as force. Obtained for gels prepared using DBP as diluent The results are shown in Table 2.

! 2-2 20.002.7910.326.89 13 33 36 35 '12-1532.001.15 1,375.48 47 4 2.0 55 1□ Table 3 shows polyetheramine (amine-terminated polypropylene oxide), Texaco, with a molecular weight of 2000 and an average of two terminal amino groups per molecule. Chefamine D-2000) and T-5000 (commercially available from Chemical Co., Ltd.) with a diluent. dibutyl phthalate (DBP) or Phosflex 362 at various concentrations as (diphenyloctyl/triphenylphosphate mixture) in the presence of various mixtures. Figure 2 shows the physical properties of gels prepared using the method of Example 1 from compounds.

Manufacture of polyurea using blocked isocyanates This method is described in detail below. Examples 4-1 to 4-19 used to make formulations comprising gels of the invention Describe the law generally. Each gel is prepared from four basic ingredients: Ru.

1) Blocked isocyanates: Desmocap 11A and Desmocap 1 2 (both commercially available from Mobay). Desmocap IIA (equivalent weight approximately 1750) is 3 Desmocup 12 (equivalent weight approximately 2470) is a difunctional, polypropylene Made from glycol, toluene diisocyanate and alkylphenol , a blocked isocyanate oligomer.

2) Curing agent: Amine-terminated polypropylene oxide (Chefamine D-400 or Shefamine D-2000, commercially available from Texaco) or 4.4°-dia Mino-3,3'-dimethyldicyclohexylmethane (DDD, commercially available from BASF) sales). Chefamine D-400 (molecular weight approximately 400) and D-2000 (molecular weight (approximately 2000) is a difunctional amine-terminated polypropylene ether oligomer. .

3) Antioxidant: Irganox 1034, commercially available from Ciba Geigy) Diluent: Phthalate ester, dioctyl phthalate (D.

P1 (commercially available from Aldrich Chemical Co.) or dioctyl phthalate (DTDP) (commercially available from Exxon Chemical Company).

Component 3 was used at a concentration of 1% of the mixture for all formulations.

Weigh the ingredients on a weighing scale (accuracy 0.019) and then weigh the ingredients on a weighing scale with a propeller blade. Mixed with a head stirrer. The blended mixture is 6” x 6”Xo, 125 ( 15,24X15.24X0.3175cm), and air circulation Cured in an oven for 17 hours at 120°C.

Elongation is measured by drawing strength punched from a slab formed using the method described in ASTM 0419. It was measured using a tension test piece. Three 201111 scintillation vials Fill with each mixture of 129 and incubate at 120 °C for 17 hours in an air circulation oven. hardened with. Three 20 x 1 scintillation vials for hardness measurements. Fill with 12 g of each mixed formulation and heat in an air circulation oven for 17 hours. Cured at 20°C. Hardness was measured using a volant chisture analyzer as described above. Measurements were made on each formulation sample. The results are shown in Table 4.

Using the method of Example 3, the difunctional amine, 4,4'-diamino-3°3'-dimethyl Tyldicyclohexylmethane (DDD, equivalent weight 119) and approximately 2.4% block A branched isocyanate powder containing a branched isocyanate group and having an equivalent weight of about 1750. Edge urethane polymer (Desmocap IIA, commercially available from Mobay) and approximately 1.7% containing an ether group having an equivalent weight of about 2470. A linear aromatic urethane polymer (Desmocup 12, commercially available from Mobay) ) gels were made from various mixtures of These gels contain various concentrations of dioctyl fluoride. Prepared in the presence of tallate. The results are shown in Table 5.

Example 5 Using the general method of Example 1, various noaminos and/or triamines were prepared. I made a gel from the seeds. The formulations used and the evaluation results are explained in Tables 6.7 and 8. Ru. In Table 6, gel samples 6-1 to 6-12 use Therminol 66 as a diluent. We will explain the properties of gels obtained by using different polyurea concentrations. Gel sample 6-13 is Fefamine D2000 was omitted, but otherwise similar. In Table 7, the gel test Materials 7-1 and 7-2 contain Shelfflex 371 and Santicizer as diluents. -141 or DED is shown. Gel samples 7-3 to 7 ~7 shows how the properties of the gel change with polyurea concentration. In table 8 made gels using various diluents. Kell samples 8-5 to 8-8 had 20% of the Gel properties at reamer content were determined using HB-40 as diluent and various cyamines. /triamine ratio. Gel samples 8-9 were Polyol (PPG-1025) to obtain polyurea gel in Lyol diluent and amine. Sample 8-14 contained a stabilizer (Irganot from Ciba Geigy). (2009) was added to the composition used to prepare the gel. Gel samples 8-20 to 8- 23 how to change the diluent mixture to change the solubility parameters of the gel. E17-5 1.20 7.04 46.75 15.00 75 46 o, o117-6 1.01 5.874g, 12 12.50 95 21 0. 01 Near-70,814,7049,5010,00180141,01 Table 7 Note: b) Nelflex 371; d) Sanchisizer 141゜e) DEP; * Concentration of Polyurea in Gel Composition Table 8 Notes: C) Santisizer-154: d) Santisizer 141: e) DEP; f) HB -40; g) DBP: h) Sanchisizer 160:1) D4000; j) PPG-1025: k) Phosflex 362; 1) Shelfflex DTD P; a) Antioxidant: n) Ketodiene Flex 8: p) TOTM; *6ma Example 6 with + depression Using the method of Example 1, HB-4Q, Santicizer-154, and A gel was prepared using the mixture. The formulation contains 1.5g DDI and lo g of Shefamine T-5000 was used, and the diluent was used at the concentration shown in Table 9. that Table 9 also shows the electrical properties of the gel produced by

19-2 95 to 5 2.78 3,75 3.0X10” i Method of Example 1 using a polyfunctional polyisocyanate (a device supplied by Mobay Chemicals). A gel was prepared from Smoda-N-3300). This polyisocyanate is By reaction of hexamethylene diisocyanate with a mixture of di- and triamines, It is understood that it is manufactured by A gel was prepared using the ingredients listed in Table 10.

The properties of these gels are shown in Table 11.

Notes to Table 10: a) Therminol 60; b) Shelfflex 371; C) Sanchi Sizer 154; r) Compared to a polyurethane gel similar to Therminol 66 in an experiment to demonstrate improved thermal knee-song behavior of some polyurea gels. The gel is prepared using a diluent to have a polymer network and crosslink density of the same order. A compound was prepared. Two polyurea gels are examples of the present invention. compared with two polyurethane gels without. The formulation used as well as the as-cured and bottles of samples of each formulation after 7 days in an oven maintained at 100°C. Table 12 shows the land hardness. Table 12 shows that polyurethane gel after 7 days at 100°C hardness decreases by more than 75 and 85% respectively, while polyurea gel It shows that the hardness decreases by only 39% and 11% after aging.

In a separate experiment, stoichiometrically isocyanate-rich and amine-rich Stabilized gels of the present invention were prepared that were identical but otherwise identical. 2 gels Expose to oxygen in DSC at 25°C and measure the time elapsed before rapid uptake of oxygen. and <14.5, 16.1 and 19.6 minutes, respectively. Thus amine Rich gels exhibit much greater oxidative stability than other gels.

Notes to Table 12: *These are not examples of the invention.

Example 9 A kit for the preparation of urea gel was prepared from the ingredients listed in Table 13 (all amounts are parts by weight). Parts A and B are placed in disposable cartridges for each application. connection is made through a static mixer/dispenser, e.g. water block by curing was formed.

The gel time of the first formulation is approximately 3 minutes, the gel has a hardness of 35q and a 1,5% The force relief had a tack of about 4-5 g. The gel time for the second formulation was also around 3 minutes; The sample had a hardness of 29g, a tack of 7.5g, and a stress relaxation of 85%.

The third formulation had a gel time of about 2.5 minutes, a hardness of 289, a tank of 259; It showed 70% stress relaxation. This last formulation was published in U.S. Patent No. 4.600.26. No. 1, No. 4.634.207, No. 4.864.725, No. 4.865゜ No. 905, No. 4.610.738, and No. 4.622.692. as a filler in protective articles such as, and U.S. Pat. No. 4.846.72. No. 1, No. 4.859.809, and No. 4.880.676 and published European Patent Application No. 0.298.71=3 and International Application No. 8910833 Telephone F terminal block and wires and cables as described in No. 8 Particularly suitable for use as a filler in sealing. All disclosures of the above patents The entirety is incorporated into this specification for all purposes.

i: Tetrakis [methylene 3-(3', 5'-]] tert-butyl-4-hydride Roxyphenylpropionate comethane zero: 4,4'-bis(α,α-dimethyl benzyl)nphenylaminoki, bis(1,2,2,6,6-pentamethifle) -4-piperidinyl)se This example is a diluent with a softkel of the present invention of 40% or less. A gel was prepared using the method of Example 1, which shows that the content can be adjusted.

The formulations used and the properties of the gels obtained are shown in Table 14. These kels are especially large. Has a high tack value.

*Example 1 cured at room temperature for 2 hours after 87 hours at 60℃ The polyurea gel of the present invention contains about 22% dioctyl phthalate as a plasticizer. To evaluate the compatibility with plasticized polyvinyl chloride, polyurethanes other than those of the present invention were tested. compared to Ngel. The formulations of polyurea and polyurethane (in parts by weight) are shown in the table below. 15.

A flat PvC sheet with a thickness of 23 to 30 mls (0.63 to 0.76 mm) is For opening 0.25 inch (6.3 am) thick sheets! and heat the aggregate to 80℃ It was maintained for 7 days. Changes in weight, tensile strength and elongation at break of PvC sheets was then measured. Ensure that the PVC sheet placed in contact with the polyurea gel has a weight of 3%. However, its tensile strength remained almost unchanged (increased by 1.5%), and its fracture elongation degree decreased by 20%. PVC/-1- placed in contact with polyurethane gel is 1 The weight decreased by 3.6% while its tensile strength increased by 18.8% and its elongation at break increased by 4. It decreased by 6%.

1 Shiefamine D2000 2.00 around 1 1 Stabilizer 0.3 0.04j (: Denor trimellitate in I n-octyl 50: Using the method of Example 1, the following A polyurea gel was prepared from the ingredients below.

Part A/Part by weight Part B 2 Part by weight DDT 2.90 Norbamide 125 2.00 Therminol 60 11.25 Therminol 60 11.25 Ketonoe 77 and 7x8 11.25 Ketonoe Enofrefux 8 11.25 Norbamide 125 is commercially available from Silvachem. It is an amide-rich polyamide. Kel has a hardness of 349 and a stress of 14.5%. Relaxation, and 1g tack was applied overnight.

Figure 1 shows the hardness of the cured polyurea gel of Example 1 depending on the polymer concentration and diluent. Show how it changes depending on the level. Figure 2 shows that the hardness of these cured gels is Figure 3 shows how the gel time varies with the ratio of triamine to triamine. It shows how it changes depending on the remer concentration and the ratio of diamine to triamine.

Example 13 This example demonstrates the high polymer content of the present invention made from ketone-blocked amines. The production of this gel will be explained.

Chefamine T-5000, 2-decanone, and Therminol 66 Exten Part B (amine) polyurea gel masterbatch containing the dermal liquid is mixed with those materials. Prepared by measuring into a plastic beaker. Mix these solutions and Cover with aluminum foil and place in an oven at 60°C for 16 hours to generate ketimine. I set it. After removing from the oven, the solution was allowed to cool to room temperature for 2 hours. A section square Weigh out the components of Terahatsuchi (dimer isocyanate), mix them, and separate them. (same part A was used for all formulations). there was). Part A was then mixed with part B. Leave the mixture to come to room temperature and stir periodically. I checked the conversion.

Measure the hardness of the gel using a 1/4” ball probe using a Volando Surface Analyzer. The measurement was carried out by inserting 4 mm at 0.2 mm/sec. The results are shown in Table 16.

N, D, - not measured Example 14 This example illustrates the blocking of amines by aldehydes in the gel of the present invention. I will clarify.

Part B (amine) masterbatch and Part A masterbatch were mixed with Desmoda-N-33. 00, Chefamine D-4000, Dodecyl Aldehyde, and Therminol 6 Extender liquid was prepared generally by the method of the immediately preceding example. 20% A series of gels containing the polymer were prepared and analyzed in a similar manner. The results are shown in Table 17.

Part 18 i Diniphamine D-400010,0010,0010,0010,0010 ,001o,oB1 Sa-Minor 60 20.56 20.56 20.56 20.56 20.56 20.5Ei: 110 days curing 158 135 112 87 64 48 jIG 7 FIG.2 Triamine concentration in triamine/diamine mixture %IG 3 Effect of acetone on gel time Added acetone (%) Various ketone pros, Tsukifugu effect Ketone/amine reaction time (hours) Effect of stoichiometry on curing time Stoichiometric ratio MIBK Effect of stoichiometry on Kel time and gel hardness Fig, 7 Effect of dodecanal on gel time and gel hardness Effect of water on gel time influence Moisture content (stoichiometric %) Summary book Rapid curing, excellent combination of chemical and physical properties, and anti-aging properties , for example a Boland hardness of 1 to 5009 and an ultimate elongation of at least 50%. A crosslinkable gel composition that provides a polyurea gel composition. These compositions , especially for the environmental protection of electrical conductors, connectors, splices, and , for example, by tightly surrounding the sheathed cable where it enters the splice case. Particularly useful for sealing.

,-,,,-,A,,,,,,,,,H,PCT/US 91101266

Claims (1)

[Claims] 1. A composition comprising a crosslinked polyurea and having a Borland hardness of 1 to 500 g and an ultimate elongation of at least 50%. 2. 2. The composition of claim 1 further comprising a diluent from 25% to 95% by weight of the total weight of crosslinked polyurea and diluent. 3. 2. The composition of claim 1, wherein the average molecular weight between urea groups in the polyurea is less than or equal to 250 g per mole of polymer. 4. A composition according to claim 1, wherein the average molecular weight between urea groups in the polyurea is at least 500 g per mole of polymer. 5. The average molecular weight between the crosslinks in the polyurea is at least 2000 g per mole. The composition according to claim 1. 6. The polyurea gel contains between 5% and 75% by weight of the total weight of polyurea and diluent. 3. The composition according to claim 2, which has a reflux fraction. 7. 3. The composition of claim 2, wherein the diluent comprises two diluents having different dielectric constants. 8. Cross-linked with a Borland hardness of 1 to 500 g and an ultimate elongation of at least 50% A method for producing a polyurea composition comprising: (1) a first organic compound having an amine group; and (2) an isocyanate group or is a diluent that is inert to reaction with the first organic compound and is inert to reaction with the second organic compound. , a second organic compound, and a diluent. A method comprising the step of reacting in the presence of at least 25% to 95% by weight of the measured weight. 9. The first organic compound contains an average of n amine groups per molecule, where n is at least 2, and the second organic compound contains an average of m isocyanate groups or isocyanate groups per molecule. topricase group (m is at least 2), and the sum of n and m is small 9. The method according to claim 8, wherein the method is at least 4.1. 10. The first organic compound has the following formula: Q-{[-A-]h-D)i-1-A-Q, and the second organic compound has the following formula: P-1{[-A -]j-E}k-1-A-P (where h, j, i and k are are the same or different integers having a value of at least 1, and h, j, i and and k is at least 20 and not more than 200, each of the Q groups is the same or different, is directly bonded to the carbon atom of the A group, and is a primary or are secondary amine groups, each of the P groups is the same or different, is directly bonded to the carbon atom of the A group, and is an isocyanate or isocyanate precursor group, and each of the A groups is the same or different, and is an isocyanate or isocyanate precursor group, Formula, -R-, -R-O-R-, -R-CO2-R-, -R-NH-CO-R-, -R-NH-CO2-R-, -R-S-R-, -O-Si(R')2- or -O-Si(R')2-R- (wherein each R group is the same or different, alkylene, substituted alkylene, alkylene nylene, substituted alkenylene, arylene, or substituted arylene group, each of the R' groups being the same or different and being an alkyl, substituted alkyl, aryl, or substituted aryl group, and each of the D groups being the same or different; and each of the E groups may be the same or different, a valence bond, a secondary amine group, an alkylene, a substituted alkylene, an alkenylene, a substituted alkenylene, an arylene, or a substituted arylene group; Kylene, substituted alkylene, alkenylene, substituted alkenylene, arylene, and is a substituted arylene group. 11. The first organic compound is an alpha-aminopropyl, omega-amino-terminated polypropylene oxide having a molecular weight of 200 to 20,000; Ethylene oxide; alpha-amino-ethyl, omega-amino-terminated polytetramethylene oxide with molecular weight of 250-25,000: 4,4'-dia Mino-3,3'-dimethyldicyclohexylmethane; diethyltoluenediacone, 3,5-dimethylthio-2,4-toluenediamine; aminopropyldimethyl-terminated polydimethylsiloxane having a molecular weight of 2,000 to 30,000; Aminobutyldimethyl-terminated polydimethyl siloxanes having a molecular weight of 2,000 to 30,000; dimer diamines; amine-rich polyamide resins; amine-terminated polyamide resins; amine-epoxy adduct; diaminodiphenylsulfone; ethylene bisaniline; methylene dianiline; diethyltoluene diamine; 3,5-dimethylthio-2,4-toluene diamine; amine-terminated polybutadiene; Acrylonitrile copolymer; or a mixture of two or more of these 9. The method according to claim 8. 12. The second organic compound is ethylene diisocyanate; trimethylene diisocyanate; Anate; dodecamethylene diisocyanate; hexamethylene diisocyanate; hexamethylene diisocyanate trimer; tetraethylene diisocyanate; pentamethylene diisocyanate; propylene-1,2-diisocyanate; 2,3-dimethyltetramethylene diisocyanate; 1,4-diisocyanate cyclohexane; methyl -Hexamethylene diisocyanate; 3-isocyaner tomethyl-3,5,5-trimethylcyclohexyl isocyanate; cyclopene Chin-1,3-diisocyanate; p-phenylene diisocyanate; naphthalene 4,4'-diphenylenemethane diisocyanate; 4,4'-diphenylenepropane diisocyanate; tetramethylxylylene diisocyanate Anate; 1,2,3,4-tetraisocyanatebutane; Butane-1,2,3-triisocyanate; Isocyanate-containing straight-chain and branched aliphatic and aromatic polyether or isocyanate-containing straight-chain and branched aliphatic and aromatic poly 9. The method according to claim 8, wherein the ester is an ester. 13. 9. The method of claim 8, wherein the amine groups in the first organic compound are blocked by imine formation with aldehydes or ketones. 14. Aldehydes or ketones can be converted into acetone, 2-butanone, methylisobutyl ketone, 2-decanone, 2-undecanone, 3-tridecanone, 3-decanone, 10-nonadecanone, 4-hydroxy-4-methylpentanone, acetophenone, decanal, undecanone, canal, dodecanal, benzaldehyde, and etho 14. The method according to claim 13, wherein the method is selected from the group consisting of xybenzaldehyde. 15. The steps of: (1) providing a composition comprising a crosslinked polyurea having a Borland hardness of 1 to 500 g and an ultimate elongation of at least 50%; and (2) applying the composition to a substrate. A method of protecting a substrate comprising: 16. 16. The method of claim 15, wherein the composition further comprises a diluent, from 25% to 95% by weight of the total weight of crosslinked polyurea and diluent. 17. 16. The method of claim 15, wherein the average molecular weight between urea groups in the crosslinked polyurea is 250 g or less per mole of polymer. 18. 16. The method of claim 15, wherein the average molecular weight between urea groups in the crosslinked polyurea is at least 500 g per mole of polymer. 19. 16. The method of claim 15, wherein the average molecular weight between crosslinks in the crosslinked polyurea is at least 2000 g per mole. 20. 17. The method of claim 16, wherein the crosslinked polyurea has a gel fraction of 5% to 75% by weight of the combined weight of crosslinked polyurea and diluent. 21. A kit comprising at least two containers, each container containing: (1) a first organic compound having an amine group; (2) an isocyanate group or an isocyanate group; a second organic compound having an anate precursor group; and (3) a diluent (in a diluent container) that is inert to the reaction with the first organic compound and inert to the second organic compound. The total amount of the agent is the first and second organic compound and 25% to 95% by weight of the total weight of the diluent), and the distribution of the substance between the containers is achieved by drying the containers at room temperature (25°C). The conditions are such that the first organic compound and the second organic compound are stable when kept for 6 months, and when mixed and completely cured, the contents of the container have a Borland hardness of 1 to 500 gσ and a A kit providing a crosslinked polyurea gel having an ultimate elongation of at least 50%. 22. The first organic compound has an average of n amine groups per molecule (n is at least 2) and the second organic compound has an average of m isocyanate groups or isocyanate groups per molecule. (m is at least 2), and the sum of n and m is at least 22. The kit according to claim 21, wherein also 4.1. 23. The first organic compound has the following formula: Q-{[-A-]h-D}i-1-A-Q, and the second organic compound has the following formula: P-{[-A- ]j-E}k-1-A-P (wherein, those of h, j, i and k h, j, i and and the sum of are secondary amine groups, each of the P groups is the same or different, is directly bonded to a carbon atom of the A group, is an isocyanate or isocyanate precursor group, and each of the A groups is the same or different, and is an isocyanate or isocyanate precursor group, Formula, -R-, -R-O-R-, -R-CO2-R-, -R-NH-CO-R-, -R-NH-CO2-R-, -R-S-R-, -O-Si(R')2- or -O-Si(R')2-R- (wherein each R group is the same or different, alkylene, substituted alkylene, alkylene nylene, substituted alkenylene, arylene, or substituted arylene group, each of the R' groups being the same or different and being an alkyl, substituted alkyl, aryl, or substituted aryl group, and each of the D groups being the same or different; and each of the E groups may be the same or different, a valence bond, a secondary amine group, an alkylene, a substituted alkylene, an alkenylene, a substituted alkenylene, an arylene, or a substituted arylene group; Kylene, substituted alkylene, alkenylene, substituted alkenylene, arylene, and is a substituted arylene group) The kit according to claim 21. 24. The first organic compound is an alpha-aminopropyl, omega-amino-terminated polypropylene oxide having a molecular weight of 200 to 20,000; Ethylene oxide; alpha-amino-ethyl, omega-amino-terminated polytetramethylene oxide with molecular weight from 250 to 25,000; 4,4'-dia Mino-3,3'-dimethyldicyclohexylmethane; diethyltoluenediamine, 3,5-dimethylthio-2,4-toluenediamine; aminopropyldimethyl-terminated polydimethylsiloxane with a molecular weight of 2,000 to 30,000: 2, Aminobutyldimethyl-terminated polydimethyl siloxanes having a molecular weight of 000 to 30,000; dimer diamine; amine-rich polyamide resin; amine-epoxy adduct; diaminodiphenylsulfone; ethylene bisaniline; methylene dianiline; diethyltoluene diamine; 3,5-dimethylthio-2,4-toluene diamine; amine-terminated polybutadiene; Acrylonitrile copolymer; or a mixture of two or more of these 22. The kit according to claim 21. 25. The second organic compound is ethylene diisocyanate; trimethylene diisocyanate; Anate; dodecamethylene diisocyanate; hexamethylene diisocyanate; hexamethylene diisocyanate trimer; tetraethylene diisocyanate; pentamethylene diisocyanate; propylene-1,2-diisocyanate; 2,3-dimethyltetramethylene diisocyanate; 1,4-diisocyanate cyclohexane; methyl -Hexamethylene diisocyanate; 3-isocyaner Tomethyl-3,5,5-trimethylcyclohexyl isocyanate; cycloben Thene-1,3-diisocyanate; p-phenylene diisocyanate; naphthalene 4,4'-diphenylenemethane diisocyanate; 4,4'-diphenylenepropane diisocyanate; tetramethylxylylene diisocyanate Anate; 1,2,3,4-tetraisocyanatebutane; Butane-1,2,3-triisocyanate; Isocyanate-containing straight-chain and branched aliphatic and aromatic polyether or isocyanate-containing straight-chain and branched aliphatic and aromatic poly The kit according to claim 21, which is an ester. 26. 22. The kit of claim 21, wherein the amine group in the first organic compound is blocked by imine formation with an aldehyde or ketone. 27. Aldehydes or ketones can be converted into acetone, 2-butanone, methylisobutyl ketone, 2-decanone, 2-undecanone, 3-tridecanone, 3-decanone, 10-nonadecanone, 4-hydroxy-4-methylpentanone, acetophenone, decanal, undecanone, canal, dodecanal, benzaldehyde, and etho The kit according to claim 26 selected from the group consisting of xypennaldehyde. to. 28. a first organic compound, isocyanate or polymer having an amine group, having a borland hardness of 1 to 500 g and an ultimate elongation of at least 50% when fully cured; A crosslinkable composition comprising a second compound having a isocyanate precursor group, and a diluent in an amount of 25% to 95% by weight of the total weight of the first organic compound, the second organic compound, and the diluent. . 29. the first organic compound has an average of n amine groups per molecule; the product has m isocyanate or isocyanate precursor groups per molecule, each of n and m is at least 2, and the sum of n and m is at least 4. 1, and the composition has a gel time of 600 seconds or less at 25°C. 30. The first organic compound has the formula: Q-{[-A-]h-D}i-1-A-Q, and the second organic compound has the formula: P-{[-A- ]j-E}k-1-A-P (wherein, those of h, j, i and k h, j, i and and the sum of are secondary amine groups, each of the P groups is the same or different, is directly bonded to a carbon atom of the A group, is an isocyanate or isocyanate precursor group, and each of the A groups is the same or different, and is an isocyanate or isocyanate precursor group, Formula, -R-, -R-O-R-, -R-CO2-R-, -R-NH-CO-R-, -R-NH-CO2-R-, -R-S-R-, -O-Si(R')2- or -O-Si(R')2-R- (wherein each R group is the same or different, alkylene, substituted alkylene, alkylene nylene, substituted alkenylene, arylene, or substituted arylene group, each of the R' groups being the same or different and being an alkyl, substituted alkyl, aryl, or substituted aryl group, and each of the D groups being the same or different; and each of the E groups may be the same or different, a valence bond, a secondary amine group, an alkylene, a substituted alkylene, an alkenylene, a substituted alkenylene, an arylene, or a substituted arylene group; Kylene, substituted alkylene, alkenylene, substituted alkenylene, arylene, and is a substituted arylene group). 31. 29. The crosslinkable composition of claim 28, wherein the amine groups in the first organic compound are blocked by imine formation with an aldehyde or ketone. 32. Aldehydes or ketones can be converted into acetone, 2-butanone, methylisobutyl ketone, 2-decanone, 2-undecanone, 3-tridecanone, 3-decanone, 10-nonadecanone, 4-hydroxy-4-methylpentanone, acetophenone, decanal, undecanone, canal, dodecanal, benzaldehyde, and etho 32. The crosslinkable composition according to claim 31, which is selected from the group consisting of xybenzaldehyde. 33. The following: (1) a first organic compound having an amine group; (2) an isocyanate group or an isocyanate group; a second organic compound having a cyanate precursor group, and (3) at least 25 polymers that are inert to the first organic compound and the second organic compound. % to 95% by weight of diluent is placed on the substrate and the mixture A method of protecting a substrate comprising curing the material. 34. The first organic compound has an average of n amine groups per molecule (n is at least 2). ), the second organic compound has an average of m isocyanate groups or a precursor group (m is at least 2), and the sum of n and m is small. 34. The method of claim 33, wherein the method is at least 4.1. 35. The first organic compound has the formula: Q-{[-A-]h-D}i-1-A-Q, and the second organic compound has the formula: P-{[-A- ]j-E}k-1-A-P (wherein, those of h, j, i and k each is the same or different and is an integer having a value of at least 1, the sum of h, j, i and k is at least 20 and not more than 200, and each of the Q groups is the same or different and the carbon of the A group Bonds directly to atoms, primary or are secondary amine groups, each of the P groups is the same or different, directly bonded to a carbon atom of the A group, is an isocyanate or isocyanate precursor group, each of the A groups is the same or different, Formula, -R-, -R-O-R-, -R-CO2-R-, -R-NH-CO-R-, -R-NH-CO2-R-, -R -S-R- , -O-Si(R')2- or -O-Si(R')2-R- (wherein each R group is the same or different, alkylene, substituted alkylene, alkylene nylene, substituted alkenylene, arylene, or substituted arylene group, each of the R' groups being the same or different and being an alkyl, substituted alkyl, aryl, or substituted aryl group, and each of the D groups being the same or different; and each of the E groups may be the same or different, a valence bond, a secondary amine group, an alkylene, a substituted alkylene, an alkenylene, a substituted alkenylene, an arylene, or a substituted arylene group; Kylene, substituted alkylene, alkenylene, substituted alkenylene, arylene, and is a substituted arylene group). 36. The first organic compound is an alpha-aminopropyl, omega-amino-terminated polypropylene oxide having a molecular weight of 200 to 20,000; Ethylene oxide; alpha-amino-ethyl, omega-amino-terminated polytetramethylene oxide with molecular weight from 250 to 25,000; 4,4'-dia Mino-3,3'-dimethyldicyclohexylmethane; diethyltoluenediamine, 3,5-dimethylthio-2,4-toluenediamine; aminopropyldimethyl-terminated polydimethylsiloxane having a molecular weight of 2,000 to 30,000; 2, Aminobutyldimethyl-terminated polydimethyl siloxanes having a molecular weight of 000 to 30,000; dimer diamine; amine-rich polyamide resin; amine-epoxy adduct; diaminodiphenylsulfone; ethylene bisaniline; methylene dianiline; diethyltoluenediamine; 3,5-dimethylthio-2,4-toluenediamine; amine-terminated polybutadiene; Acrylonitrile copolymer; or a mixture of two or more of these 34. The method according to claim 33. 37. The second organic compound is ethylene diisocyanate; trimethylene diisocyanate; Anate; dodecamethylene diisocyanate; hexamethylene diisocyanate; hexamethylene diisocyanate trimer; tetraethylene diisocyanate; pentamethylene diisocyanate; propylene-1,2-diisocyanate; 2,3-dimethyltetramethylene diisocyanate; 1,4-diisocyanate cyclohexane; methyl -Hexamethylene diisocyanate; 3-isocyaner tomethyl-3,5,5-trimethylcyclohexyl isocyanate; cyclopene Chin-1,3-diisocyanate; p-phenylene diisocyanate; naphthalene 4,4'-diphenylenemethane diisocyanate; 4,4'-diphenylenepropane diisocyanate; tetramethylxylylene diisocyanate 1,2,3,4-tetraisocyanate butane; butane-1,2,3-triisocyanate; isocyanate-containing linear and branched aliphatic and aromatic polymers Linear and branched aliphatic and aromatic polyesters containing riethers or isocyanates 34. The method of claim 33, wherein the method is stell. 38. 34. The method of claim 33, wherein the amine groups in the first organic compound are blocked by imine formation with aldehydes or ketones. 39. Aldehydes or ketones can be converted into acetone, 2-butanone, methylisobutyl ketone, 2-decanone, 2-undecanone, 3-tridecanone, 3-decanone, 10-nonadecanone, 4-hydroxy-4-methylpentanone, acetophenone, decanal, undecanone, canal, dodecanal, benzaldehyde, and etho 39. The method of claim 38, wherein the method is selected from the group consisting of xypennaldehyde. 40. (A) Each of the diluents has a different inducer than any other diluent selected. (B) selecting a blend of diluents that exhibits a dielectric constant; the weight ratio of the diluents is selected such that the blend has a desired dielectric constant; and (B) incorporating the blend into a composition comprising a crosslinked polyurea gel. , in an amount such that the composition exhibits a desired dielectric constant.