KR100192201B1 - Moisture curing one component polyurethane composition and preparation method thereof - Google Patents

Abstract

A moisture curable one-component polyurethane composition and a method for producing the same are disclosed which can be applied even under adverse conditions of high temperature and humidity, such as in summer. The polyurethane composition is obtained by mixing 30-70% of the amine in the equivalence ratio of a ketone monomer to a divalent or trivalent primary amine to obtain a semiketamine compound, and adding the aldehyde monomer to the semiketamine compound in an equivalent ratio of 30 -70% mixed reaction to obtain a latent curing agent polyadimine-ketamine, and mixed the isocyanate compound composed of the polyadimine-ketamine and a polyisocyanate, a polyurethane prepolymer having two or more isocyanate groups, or a mixture thereof To prepare. In particular, when the polyurethane waterproofing material is manufactured by applying the above composition, there is no swelling under the conditions of humidity of 80% RH or higher and surface temperature of 50 ° C or higher, and tensile strength of 35kgf / cm 2, tear strength of 30kg / cm, elongation of 500% or more. It can be secured.

Description

Moisture curable one-component polyurethane composition and preparation method thereof

The present invention relates to a moisture-curable one-component polyurethane composition comprising a Sheiff's base, which is a latent curing agent in which aldehydes and ketones are present in one chain by reacting aldehydes and ketones with diamines, and a method for preparing the same.

The present invention also relates to the use of such moisture-curable one-component polyurethane compositions for building materials, in particular for waterproofing materials, flooring materials, sealants, coatings and adhesives in civil engineering and buildings.

Polyurethane materials for civil and building use were introduced in the early 1980s. Polyurethane material is capable of seamless construction, which is a characteristic of the material itself, and conforms well to constructional structures, chemical properties such as adhesion to the surface, chemical resistance, durability, sound absorption, dimensional stability, The same physical properties are excellent, and in particular, due to the great advantage that the elongation is excellent, it is excellent in tracking the cracks of the ground, and the demand for building interior, exterior walls and floor waterproofing of the building is increasing.

However, at present, polyurethane materials having such excellent characteristics for construction are produced by isocyanate prepolymer and polyol mixture in the production plant, and they must be constructed through several steps of weighing, blending, stirring, and construction according to the mixing ratio determined at the construction site. Since defects in the tops are likely to occur and skilled professionals are required, it is a cause of increase in labor costs, which in turn increases the construction cost and reduces the construction efficiency.

In general, two-component polyurethane materials have to use both agitated waterproofing materials within a limited pot life, so the time interval between agitation and construction must be well controlled, and if the time is not correct, the amount of material loss increases.

Therefore, in order to maintain the excellent physical and chemical properties of these polyurethane materials and to compensate for the shortcomings of the two-component type, one-component formulations of polyurethane building materials have been studied. For example, an NCO wt% content of 1-5% isocyanate prepolymer is studied. It synthesize | combines, and adds a filler, stabilizer, a coloring agent, etc., and uses the method of one-component polyurethane material.

However, this method has a disadvantage in that the curing time is slow at room temperature and only a little moisture is present, and storage stability is deteriorated, and swelling defects of the coating film are easily generated by carbon dioxide generated by the reaction of water and isocyanate. To compensate for this disadvantage, Japanese Patent Publication No. 5-75035 discloses a method of improving storage stability and curing rate by using a catalyst of morpholino diethyl ether. However, this method did not solve the occurrence of defects caused by swelling of the coating film caused by carbon dioxide. Therefore, in order to solve this problem, US Patent No. 4720535 or Japanese Patent Laid-Open Publication No. 4-226522 discloses a method using a Shif's base, which is a latent curing agent. In other words, aldehyde is reacted with primary di or tri amine to make poly aldimine, which is mixed with an isocyanate prepolymer and used as a one-component material.

However, when the poly-aldimine is mixed with an isocyanate and used as a one-component urethane material, the reactivity is fast in a high temperature and high humidity environment, and thus there is an inadequate problem in waterproofing the roof of a building in summer. That is, the hardening of the surface and the bottom of the coating proceeds easily, but the inside of the coating is difficult to penetrate moisture from the hardened coating surface, so that the progress of curing is slow and swelling defects are frequently caused by aldehydes dissociated during curing.

In addition, another method using latent hardeners is described in British Patent No. 1575666, wherein a secondary amine is reacted with a ketone or an aldehyde to form a polyenamine which is then mixed with an isocyanate prepolymer to form a one part solution. In this case, however, the isocyanate of the prepolymer must be masked or an isocyanate having a very low reactivity should be used, and it is difficult to use as a building material because of low storage stability.

Therefore, in the present invention, the cure rate can be controlled when aldimine and ketamine are simultaneously present in the latent curing agent chain while seeking a method that is excellent in storage stability and low construction failure rate even under such high temperature and high humidity conditions. It has been found that the defect rate is low and that the present invention can be applied even under adverse environmental conditions such as high temperature and high humidity, and has completed the present invention.

The moisture-curable one-component polyurethane composition according to the present invention is a semiketimine compound obtained by mixing and reacting a ketone monomer with an equivalent ratio of 30-70% of an amine in a divalent or trivalent primary amine. Latent curing agents polyadimine-ketimine and polyisocyanate, polyurethane prepolymers having two or more isocyanate groups, obtained by mixing an aldehyde monomer in an equivalent ratio of 30-70% of the amine It consists of an isocyanate compound composed of a mixture of these.

The polyurethane composition yields a semi-ketamine compound obtained by mixing 30-70% of an amine in an equivalent ratio with a ketone monomer in an equivalent ratio of a divalent or trivalent primary amine, and an aldehyde monomer in an equivalent ratio of the amine in an equivalent ratio of the amine. 30-70% mixed reaction to obtain a latent curing agent polyadimine-ketamine, and mixed the isocyanate compound composed of the polyadimine-ketimine and a polyisocyanate, a polyurethane prepolymer having two or more isocyanate groups, or a mixture thereof To prepare.

When the latent curing agent according to the present invention is prepared by applying an isocyanate prepolymer, a filler, and other additives to prepare a one-component urethane waterproofing material, there is no swelling under a humidity of 80% RH or higher and a surface temperature of 50 ° C or higher and a tensile strength of 35kgf / 2 cm, tear strength 30kg / cm, elongation has a great advantage to secure the physical properties of more than 500% and these methods will be described in more detail below.

1. Synthesis of latent hardener

The polyaldimine-ketamine, a latent curing agent of the moisture-curable polyurethane composition according to the present invention, first reacts a ketone monomer with an equivalent ratio of 30-70% of the amine in a divalent or trivalent primary amine and adds an aldehyde monomer thereto. Polyalmine-Keti, a latent curing agent in which aldimine and ketamine are present simultaneously in a chain by removing 30% to 70% of the amine in an equivalence ratio and removing unreacted material, a small amount of water, and impurities through filtration and vacuum. Make a min.

As the amine used here, isophorone diamine, polyoxypropylene diamine, polyoxypropylene triamine, methanediamine, ethylenediamine, propylenediamine, metha xylenediamine, etc. are preferable, and isophorone diamine or polyoxypropylenediamine of Caldex company is especially preferable. Phosphorus D-230, D-400 (trade name) and the like are particularly preferable.

As the ketone monomer, it is preferable to use methyl isobutyl ketone, diisobutyl ketone, methyl ethyl ketone, acetone, methyl-n-propyl ketone, methyl-n-butyl ketone, ethyl butyl ketone and the like.

Moreover, as an aldehyde monomer, it is preferable to use acetaldehyde, propionaldehyde, benzaldehyde, butyl aldehyde, isobutyl aldehyde, etc.

Moisture scavengers may be used to promote the reaction in the ketimine reaction, for example, desiccants such as calcium chloride, magnesium sulfate, titanium tetrachloride, potassium carbonate, barium oxide, zinc chloride, zeolite, and the like, and particularly titanium tetrachloride. And zeolites are more preferred.

2. Preparation of Polyurethane Prepolymer

The urethane prepolymers for preparing moisture-curable one-component polyurethanes are alone or in combination of aliphatic or aromatic diisocyanates, modified isocyanates, or polymeric isocyanates with diols or triols of polyetherpolyols, polyester polyols, hydroxylpolycarbonates, and the like. A chain extender or the like is reacted with a mixture of to prepare a prepolymer (isocyanate compound) having an isocyanate content of 2-10 based on the prepolymer weight%.

The aromatic diisocyanate used here is preferably 2.4 / 2.6 toluene diisocyanate (TDI 80/20), 2,4 toluene diisocyanate (TDI 100), 4,4'-diphenylmethane diisocyanate (Monomeric MDI), and the like. As the aliphatic diisocyanate, isophorone diisocyanate, cyclohexane diisocyanate, hydrogenated diphenylmethane diisocyanate and 1,6 hexamethylene diisocyanate are preferable. As the modified isocyanate, trade names COMONATE LL, COSMONATE LK, COSMONATE LT, etc., produced by Kumho Mitsui Toatsu Co., Ltd. are preferred, and M-100, M-200, produced by Kumho Mitsui Toatsu Co., Ltd. , M-300, M-400 and the like are preferable.

The polyether polyol is preferably a diol or triol having a molecular weight of 400 to 6000, and in particular, PP-1000, PP-2000, PP-3000, GP-3000, GP-4000 produced by Korea Polyol Co., Ltd. And molecular weight 1000 to 4000, such as), are more preferable.

The polyester polyol preferably has an average molecular weight of 500-6000 by condensation of polycarboxylic acid and polyhydric alcohol by condensation reaction, especially SE-1714, SE-1541, SE-2014 produced by Samsung Polymer. As for molecular weight 1000-3000, etc. are more preferable.

Other polycarbonates having two or more active hydrogens in one molecule, polytetramethylene ether polyols, polycaprolactone polyols, polybutadiene polyols, polyether polyols, or polymer polyols obtained by grafting vinyl monomers to polyester polyols alone or the like It can be mixed and used.

Chain extenders for increasing the hardness and physical properties of urethanes include ethylene glycol, diethylene glycol, 1,3 propylene glycol, 1,4 butanediol, 1,3 butanediol, tripropylene glycol, trimetholpropane, glycerin, etc. can do. These chain extenders are limited in the range of 1-10% by weight of polyols because they are more reactive than polyols and increase the viscosity of the final urethane prepolymer.

3. Moisture curable 1-component polyurethane

The moisture-curable one-component polyurethane of the present invention is prepared by mixing the polyadimine-ketimine and the polyisocyanate and / or polyurethane prepolymer with various fillers, colorants, plasticizers, other additives, and the like, as necessary.

The number of amino groups resulting from the hydrolysis of polyadimine-ketimine in the presence of a suitable catalyst is suitably 1.0-1.5 times the number of isocyanate groups of the isocyanate compound, and particularly preferably 1.05-1.2 times.

As the filler, it is preferable to use calcium carbonate, talc, silica, barium sulfate, kaolin, clay and the like in the range of 30-50% in the total blend. It is also possible to use flow preventing fillers for wall or sealing purposes, for example aliphatic amide waxes, fume-silica, surface treated bentonite, etc. within the range of 1-20% by weight of the total formulation. Do.

Plasticizers include general plasticizers such as dioctyl phthalate, dibutyl phthalate, dioctyl adipate, diisodecyl phthalate and diisononyl phthalate and flame retardant plasticizers such as triphenyl phosphate, tricresyl phosphate and trisisopropyl phenyl phosphate. Accordingly used alone or in combination in the range of 5-20% by weight of the total formulation.

Solvents used for viscosity adjustment range from 5 to 20% by weight of ketones such as methyl ethyl ketone and acetone, aromatic hydrocarbons such as toluene and xylene, petroleum solvents such as mineral spirits, or cellulose acetate, butyl cellulsolve, etc. It can be used within and is most preferably used in the range of 10 to 15% by weight. Other colorants such as carbon black, titanium dioxide, chromium oxide green and the like can be used within the range of 2-10 wt%.

The above fillers, additives, colorants, and other preparations are introduced into a dissolvable reactor capable of vacuum dehydration, followed by sufficient mixing and stirring. At this time, when the water content of the various additives is high, the storage stability of the final product is lowered, so it is necessary to dehydrate or lower the water content by adding zeolite or the like as a moisture absorbent. When the mixture is sufficiently mixed and stirred, the mixture is stirred by adding isocyanate or isocyanate prepolymer, and then mixed with the above-mentioned polyaldimine-ketamine. The mixture is mixed with vacuum, degassed, and packed in a container filled with dry nitrogen to be completely sealed. Let's do it.

The moisture-curable one-component polyurethane composition prepared in this way has a storage stability of more than 6 months in an airtight container and there is no phenomenon such as swelling of the coating film even under a high temperature and high humidity environment, and the coating film cured by moisture has mechanical and chemical properties. It can be used as a waterproof, flooring, sealant, coating or adhesive.

Examples of the moisture-curable one-component polyurethane composition according to the present invention are described below, but the present invention is not limited thereto.

Synthesis Example 1

Preparation of Polyaldimine-Ketamine

Into a four-necked flask equipped with a stirrer, thermometer, dropping funnel, vacuum connector and reflux tube, add 100 g of methyl isobutyl ketone, 400 g of xylene, 300 g of molecular sieve (zeolite) and add 170 g of isophorone diamine in 30 minutes with stirring funnel. It is dripped over. The temperature was raised to 80 ° C. and reacted for 8 hours to synthesize ketamine. Final confirmation of the reaction at this time was confirmed by FT-IR. That is, it was confirmed by confirming that the carbonyl peak of methyl isobutyl ketone near 1650 cm ^-1 before the reaction disappeared as the reaction proceeded and the -C = N- peak of ketamine produced by the reaction appeared near 1760 cm ^-1 . Finally, the reaction was stopped after confirming that the carbonyl peak of the isobutyl ketone disappeared. After the ketamine reaction was completed, the temperature was lowered to 30 ° C., and then 107 g of benzaldehyde was added dropwise over 30 minutes through a dropping funnel. After completion of the dropwise addition, the temperature was raised to 100 ° C. over 30 minutes, and the water produced during the reaction was removed by azeotropic xylene. After 4 hours of azeotropy, the outflowed water was 10g and 8g, theoretically different from the outflow of 18g, was assumed to be adsorbed on the molecular sieve (zeolite). Final reaction confirmation at this time was confirmed by FT-IR. That is, the C = O peak of benzaldehyde was confirmed to disappear as the reaction proceeded, and the reaction was stopped after completely disappearing.

The reaction product was filtered to remove molecular sieves, and vacuum was applied at 100 ° C. to remove xylene and small amounts of water to synthesize polyadimine-ketamine.

Synthesis Example 2-12

Preparation of Polyaldimine-Ketamine

Synthesis Example 2-12 was the same method as in Synthesis Example 1 using diethyl triamine containing D-230 and secondary amine of Caldex Co., Ltd. of polyoxy alkylenediamine as the amine. Methyl isobutyl ketone and methyl ethyl ketone were used, and aldehyde was synthesized using acetaldehyde in addition to the benzaldehyde used in Example 1. Also at this time, final confirmation of the reaction was performed by FT-IR.

The contents of the raw materials and contents used in Synthesis Examples 1 to 12 are shown in Table 1 below.

Synthesis Example 13

Synthesis of Polyurethane Prepolymer

A four-necked flask was equipped with a stirrer, a nitrogen inlet tube, a thermometer, and a dropping funnel, followed by 91.6 g of dioctylphthalate and 735.4 g of a polyether polyol (GP-3000, Korea Polyol Co., Ltd.). 173 g of -toluene diisocyanate, TDL80 / 20) was added dropwise with stirring. After dropping, the temperature was raised to 80 ° C. over 30 minutes to react for about 5 hours to synthesize a polyurethane prepolymer having an isocyanate at the end. At this time, the progress of the reaction was confirmed by obtaining the content of isocyanate by using the reverse titration method using standard dibutylamine.

Synthesis Example 14-20

Synthesis of Polyurethane Prepolymer

Synthesis Examples 14-29 synthesize a polyurethane prepolymer in the same manner as in Synthesis Example 13, wherein polyether polyol is used while changing diol and triol, and 1,3 butanediol is used as a chain extender. Prepared. In this case as well, the reaction progress was performed by reverse titration using standard dibutyl amine.

Table 2 below shows the raw material name and content used at this time.

Example 1-8

Calcium carbonate, a solvent, a plasticizer, a stabilizer, etc. were put together in a beaker type flask equipped with a nitrogen injection tube, a stirrer, a thermometer, and a vacuum connection tube, followed by stirring for 30 minutes at room temperature while flowing dry nitrogen. Next, the polyurethane prepolymer of Synthesis Example 13, 16, 18, or 20 was added, followed by stirring and mixing at room temperature for about 15 minutes, and the mixture was mixed for about 15 minutes by addition of the polyadimine-ketamine of Synthesis Example 1 or 5, and then at room temperature. Vacuum was applied at to remove bubbles to prepare the moisture curable one-component polyurethane composition of the present invention.

The raw materials and contents used in Table 3 below are shown.

Comparative Example 1

In the same manner as in Synthesis example 1, polyaldimine was prepared using benzaldehyde, instead of methyl isobutyl ketone, in isophoronediamine which is an alicyclic amine. A moisture curable one-component polyurethane composition was prepared in the same manner as in Example 5 using the raw materials as shown in Table 3 below.

Comparative Example 2

In the same manner as in Synthesis Example 5 to prepare a poly aldimine in the aliphatic polyamine D-230 using benzalaldehyde instead of methyl isobutyl ketone, in the same manner as in Example 6 using a raw material as shown in Table 3 below A moisture curable one-component polyurethane composition was prepared.

Property experiment

Measurement of the physical properties of the moisture-curable one-component polyurethane composition obtained in Examples 1-8 and Comparative Examples 1 and 2 were prepared in accordance with the KSF-3211 and KSM-6518 method to prepare tensile strength, tear strength, elongation, tensile strength, etc. The tag free time was measured according to the KSF-4910 method. The results are shown in Table 4 below.

In addition, as a test for checking whether swelling occurred, the cement brick prepared by the method specified in KSF-4004 was precipitated in water for 3 hours, and then left in a thermostat at 60 ° C for 80% RH for 1 hour. The moisture-curable one-component polyurethane composition was applied to a thickness of 3 mm, and swelling was observed while curing in a thermostatic chamber at 60 ° C. and 80% RH. The results are shown in Table 4 below.

From the above results, it can be seen that the difference between the compositions of the present invention and the compositions of the comparative example is not significantly different in physical properties, but the compositions of the present invention are very excellent in the occurrence of swelling phenomenon. That is, the compositions of the present invention were not at all in the swelling phenomenon, Comparative Examples 1, 2 was confirmed that the swelling phenomenon occurs after 4 hours.

Claims (13)

A latent curing agent poly aldimine-ketamine obtained by mixing an aldehyde monomer with an equivalent ratio of 30-70% of an amine in a ketimine compound comprising a ketone monomer in an equivalent ratio of 30-70% of an amine in a divalent or trivalent primary amine; And an isocyanate compound composed of a polyisocyanate, a polyurethane prepolymer having two or more isocyanate groups, or a mixture thereof, wherein a mixing ratio of the poly aldimine-ketimine and the isocyanate is in the presence of a catalyst of the poly aldimine-ketimine. A moisture-curable one-component polyurethane composition characterized by mixing so that the number of amino groups produced by hydrolysis is 1.0-1.5 times the number of isocyanate groups of the isocyanate compound. 2. The isophorone diamine, polyoxypropylenediamine, polyoxypropylenetriamine and derivatives thereof composed of aliphatic primary amines and secondary amines having a molecular weight of 200-1000 as the amines, methanediamine, ethylenediamine. Moisture-curable one-component polyurethane composition, characterized in that at least one selected from the group consisting of, propylene diamine, metha xylene diamine. The method of claim 1, wherein at least one selected from the group consisting of methyl isobutyl ketone, diisobutyl ketone, methyl ethyl ketone, acetone, methyl-n-propyl ketone, methyl-n-butyl ketone, and ethyl butyl ketone as the ketone monomer Moisture-curable one-component polyurethane composition, characterized in that any one is used. The moisture-curable one-component polyurethane composition according to claim 1, wherein at least one selected from the group consisting of acetaldehyde, propionaldehyde, benzaldehyde, butylaldehyde, and isobutylaldehyde is used as the aldehyde monomer. The polyisocyanate of claim 1, wherein the isocyanate compound is an aliphatic or aromatic diisocyanate, a modified isocyanate, a polymeric isocyanate, or a polyether polyol of a diol or a triol, a polyester polyol, a hydroxyl polycarbonate, or the like. A moisture-curable one-component polyurethane composition, wherein the content of isocyanate groups is 2-10% by weight based on 100% by weight of the prepolymer as a prepolymer obtained by reaction with a mixture of these alone or a mixture thereof. Obtaining a ketimine compound consisting of 30 to 70% of an amine in an equivalent ratio of a ketone monomer to a divalent or trivalent primary amine; Mixing a aldehyde monomer with an equivalent ratio of 30-70% of the amine in an equivalent ratio to obtain a latent curing agent poly aldimine-ketamine; And mixing the isocyanate compound composed of the poly aldimine-ketimine and a polyisocyanate, a polyurethane prepolymer having two or more isocyanate groups, or a mixture thereof. The method according to claim 6, wherein at least one moisture absorbent selected from the group consisting of calcium chloride, magnesium sulfate, titanium tetrachloride, potassium carbonate, barium oxide, zinc chloride and zeolite is used as an accelerator in the reaction of the ketimine compound. A method for producing a moisture-curable one-component polyurethane composition characterized by the above-mentioned. The method of claim 6, wherein the isocyanate compound is selected from aliphatic or aromatic diisocyanates, modified isocyanates, polymeric isocyanates, or polyether polyols of diols or triols, polyester polyols, hydroxyl polycarbonates, etc. selected from them. A process for producing a moisture-curable one-part polyurethane composition, which is obtained by reacting alone or a mixture thereof with a chain extender. A latent curing agent poly aldimine-ketamine and a poly urea obtained by mixing an aldehyde monomer with an equivalent ratio of 30-70% of an amine in an equivalent ratio of a ketone monomer with an equivalent ratio of a ketone monomer to a divalent or trivalent primary amine. An isocyanate compound composed of an isocyanate, a polyurethane prepolymer having two or more isocyanate groups, or a mixture thereof; and at least one selected from calcium carbonate, talc, silica, barium sulfate, kaolin, clay as a filler, A moisture-curable one-component polyurethane waterproofing agent comprising in a range of 50% by weight and comprising a colorant, a plasticizer and an additive. A latent curing agent poly aldimine-ketamine and a poly urea obtained by mixing an aldehyde monomer with an equivalent ratio of 30-70% of an amine in an equivalent ratio of a ketone monomer with an equivalent ratio of a ketone monomer to a divalent or trivalent primary amine. An isocyanate compound composed of an isocyanate, a polyurethane prepolymer having two or more isocyanate groups, or a mixture thereof; and at least one selected from calcium carbonate, talc, silica, barium sulfate, kaolin, clay as a filler, A moisture-curable one-component polyurethane flooring agent comprising in a range of 50% by weight and comprising a colorant, a plasticizer and an additive. A latent curing agent poly aldimine-ketamine and a poly urea obtained by mixing an aldehyde monomer with an equivalent ratio of 30-70% of an amine in an equivalent ratio of a ketone monomer with an equivalent ratio of a ketone monomer to a divalent or trivalent primary amine. A moisture-curable one-component polyurethane sealing agent comprising an isocyanate compound composed of an isocyanate, a polyurethane prepolymer having two or more isocyanate groups, or a mixture thereof, comprising a flow preventing filler, a colorant, a plasticizer and an additive. A latent curing agent poly aldimine-ketamine and a poly urea obtained by mixing an aldehyde monomer with an equivalent ratio of 30-70% of an amine in an equivalent ratio of a ketone monomer with an equivalent ratio of a ketone monomer to a divalent or trivalent primary amine. A moisture-curable one-component polyurethane adhesive comprising an isocyanate compound, an isocyanate compound composed of an isocyanate, a polyurethane prepolymer having two or more isocyanate groups, or a mixture thereof, and comprising a filler, a colorant, a plasticizer, and an additive. The latent curing agent poly-dimine-ketimine obtained by mixing an aldehyde monomer with an equivalent ratio of 30-70% of an amine in an equivalent ratio of a ketone monomer with an equivalent ratio of a ketone monomer to a divalent or trivalent primary amine. A moisture-curable one-component polyurethane coating agent comprising an isocyanate compound composed of a polyisocyanate, a polyurethane prepolymer having two or more isocyanate groups, or a mixture thereof, and comprising a filler, a colorant, a plasticizer, and an additive.