KR100246009B1 - Spray polyurea elastomer containing alkylolamine - Google Patents

Abstract

FIELD OF THE INVENTION The present invention relates to aliphatic and aromatic spray polyurea elastomers, wherein the first component and the at least one amine resin produced by the addition of alkylene carbonate to the pseudo-prepolymer obtained by reacting an isocyanate with an active hydrogen-containing material are alkylolamine It is characterized in that it is obtained by reacting the added and produced second component through a spray gun. According to the present invention, by adhering to the surface by using the hydrophobicity and low surface tension of the alkyl group of the alkylolamine and the excellent adhesion of the amine group to glass, metal, etc., the adhesion to the wet surface can be improved. There are advantages to it.

Description

Spray Polyurea Elastomers Containing Alkylolamines

The present invention relates to aliphatic and aromatic spray polyurea elastomers and, in particular, to spray polyurea elastomers containing alkylolamines.

Aliphatic and aromatic spray spray elastomers are known as useful coatings. Spray polyurea elastomers consist of two components, the first component being an isocyanate pseudo-prepolymer and the second component being an amine resin, the preparation method of which is described in US Pat. No. 5,442,034.

Spray polyurea elastomers described in US Pat. No. 5,442,034 reduce the viscosity of the first component to improve the surface properties of the spray polyurea elastomer used as a coating and to improve the mixing uniformity of the two components. It is characterized by adding an organic alkylene carbonate to a component.

However, the spray polyurea elastomer according to the prior art has a disadvantage in that the applicability to the wet surface is significantly lowered because the adhesion to the wet surface is inferior.

The present invention is to solve the disadvantages of the prior art as described above, an object of the present invention to provide a spray polyurea elastomer with improved adhesion to the wet surface.

In order to achieve the object as described above, the present invention is a spray polyurea elastomer, the first component and at least one amine produced by the addition of alkylene carbonate to the pseudo-prepolymer obtained by reacting isocyanate with active hydrogen-containing material It is characterized in that it is obtained by reacting the second component generated by adding alkylolamine to the resin through a spray gun.

In the above spray polyurea elastomer according to the present invention, the amine resin of the second component is an amine-terminated polyoxyalkylene polyol.

The alkylolamine added to the second component in the above spray polyurea elastomer according to the present invention is selected from methanolamine, dimethanolamine, trimethanolamine, dimethanoldiamine, trimethanoldiamine, dietinoldiamine and triethanoldiamine. It is characterized by losing.

Hereinafter, the spray polyurea elastomer according to the present invention will be described in detail.

The spray polyurea elastomer according to the present invention is largely composed of two components, a first component and a second component. The first component is produced by the addition of alkylene carbonate to the quasi-prepolymer obtained by reacting aliphatic, aromatic, or aliphatic / aromatic isocyanates with active hydrogen-containing materials.

Suitable aromatic polyisocyanates used in the first component of the sprayed polyurea elastomers according to the invention include m-phenylenediisocyanate, p-phenylenediisocyanate, polymethylenepolyphenyldiisocyanate, 2,4-toluene diisocyanate, 2,6 -Toluene diisocyanate, dianisidine diisocyanate, bitoylene diisocyanate, naphthalene-1,4-diisocyanate, bis (4-isocyanatophenyl) methane, bis (3-methyl-3-isocyanatophenyl) Methane, bis (3-methyl-4-isocyanatophenyl) methane, diphenylene-4,4'-diisocyanate and the like.

Other aromatic isocyanates used in the present invention include methylene-bridged polyphenylpolyisocyanate mixtures having about 2 to about 4 functional groups. Such isocyanate compounds are generally produced by phosgenation of the corresponding methylene-bridged polyphenylpolyamines. Methylene bridged polyphenylpolyamines are typically produced by the reaction of primary aromatic amines such as formaldehyde and aniline in the presence of hydrochloric acid and / or other acid catalysts. Processes for preparing polyamines and the corresponding methylene-bridged polyphenylpolyisocyanates resulting therefrom are known.

Typically, the methylene-bridged polyphenylpolyisocyanate mixture contains about 20 to 100% by weight of methylenediphenyldiisocyanate isomers, the remainder being high functional and high molecular weight polymethylenepolyphenyldiisocyanates. Such typical polyphenylpolyisocyanate mixtures comprise about 20 to 100% by weight of diphenyl diisocyanate isomers (of which 20 to 95% by weight are 4,4'-isomers) and the remainder of the polymer having an average functionality of about 2.1 to 3.5 and High functional polyphenylpolyisocyanates. Such isocyanate mixtures can be purchased or prepared.

Most preferred aromatic polyisocyanates are called MDI as methylenebis (4-phenylisocyanate). Pure MDIs, pseudo-prepolymers of MDIs, modified pure MDIs, and the like are useful. Since pure MDI is a solid and often inconvenient to use, liquid products based on MDI, ie methylenebis (4-phenylisocyanate), are used in the present invention.

Commercial examples of these materials are Dow's ISONATE 125M (pure MDI) and ISONATE 143L (liquid MDI). The amount of isocyanate used is preferably more than the chemical quantity, or chemical quantity based on all components of the formula.

Aliphatic isocyanates are typical aliphatic diisocyanates as described in US Pat. No. 4,748,192, and more particularly are trimer or biuretic forms of aliphatic diisocyanates such as hexamethylene diisocyanate, such as tetramethylxylene diisocyanate. Difunctional units of tetraalkylxylene diisocyanate. Cyclohexane diisocyanates can also be considered as preferred aliphatic isocyanates. Other aliphatic polyisocyanates useful are described in US Pat. No. 4,705,8 14. They include aliphatic diisocyanates such as alkylene diisocyanates having 4 to 12 carbon atoms in the alkylene radical, such as 1,12-dodecane diisocyanate and 1,4-tetramethylene diisocyanate. 1,3- and 1,4-cyclohexanediisocyanate and any desired mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophoronedi Isocyanates); cycloaliphatic diisocyanates such as 4,4'-2,2'- and 2,4'-dicyclohexylmethane diisocyanate and mixtures of the corresponding isomers are also described.

Aliphatic / aromatic diisocyanates include xylene-1,3-diisocyanate; Bis (4-isocyanatophenyl) methane; Bis (3-methyl-4-isocyanatophenyl) methane; And 4,4'-diphenylpropane diisocyanate. The above isocyanates may be used alone or in combination.

Active hydrogen-containing materials that react with the isocyanates of the first component described above include, but are not limited to, polyols or polymeric polyoxyalkyleneamines or combinations thereof.

Polyols include polyetherpolyols, polyesterdiols, triols, tetrols and the like having at least about 500, preferably at least about 1000 to up to about 3000 equivalents. Particular preference is given to such polyetherpolyols and the foregoing based on trihydric initiators of about 4,000 molecular weight. The polyethers may be prepared from ethylene oxide, propylene oxide, butylene oxide or mixtures of propylene oxide, butylene oxide and / or ethylene oxide. Other polymeric polyols useful in the present invention are polyesters of hydroxyl-terminated rubbers such as hydroxy-terminated polybutadiene. Hydroxy-terminated quasi-prepolymers of polyols and isocyanates are useful in the present invention.

As active hydrogen-containing materials, particular preference is given to primary and secondary amine terminators having about 2 to 6 functional groups, preferably about 2 to 3 functional groups and having an average molecular weight of at least 1,500 and an amine equivalent of about 750 to 4,000. Amine-terminated polyetherpolyols, including polyetherpolyols. Mixtures of amine-terminator polyethers can be used. Preferred amine-terminator polyethers have an average molecular weight of at least about 2,500. Such materials can be made by a variety of known techniques.

Amine-terminated polyether resins useful in the present invention are the resulting hydrides as polyether resins made from initiators suitable for lower alkylene oxides, such as, for example, ethylene oxide, propylene oxide, butylene oxide or mixtures thereof. It is added with the siloxane-terminator polyols and then aminated. When two or more oxides are used, they may be present as arbitrary mixtures or as blocks of one or other polyethers. In the amination step, the terminating hydroxyl groups in the polyol are essentially all secondary hydroxy groups in order to facilitate amination. Usually, the amination step does not completely replace all hydroxyl groups. However, most hydroxyl groups are replaced by amine groups. Therefore, amine-terminated polyether resins useful in the present invention preferably have at least 50% of their active hydrogens in the form of amine hydrogens. If ethylene oxide is used, it is necessary to cover the hydroxyl-terminated polyol with a small amount of higher alkylene oxide in order to make the terminator hydroxyl groups essentially all secondary hydroxyl groups. The polyols so prepared are then reductively aminated by known techniques.

In the present invention, polymer amine-terminated polyethers or simply polyether amines are also included within the scope of active hydrogen-containing materials of the first component of the invention and may be used alone or in combination with the above-mentioned polyols. The term "polymer" is meant to include polyetheramines having a molecular weight of at least about 2000. Especially preferred is JEFFAMINE as a series of polyether amines available from Huntsman. They are JEFFAMINE D-2000, an amine-terminated polyoxypropylenediol with a molecular weight of 2000, JEFFAMINE D-4000, an amine-terminator polyoxypropylenediol with a molecular weight of 4000, and T-, an amine-terminator polyoxypropylene triol, with an molecular weight of 3000. JEFFAMINE T-5000, an amine-terminated polyoxypropylenetriol of 3000 and molecular weight 5000.

Alkylene carbonates in the first component of the present invention are useful for lowering the relatively high viscosity of quasi-prepolymers produced by isocyanates and active hydrogen-containing materials. Alkylene carbonate used in the present invention has the structure shown in the following formula (1).

Wherein R ¹ and R ² are independently hydrogen or lower alkyl groups of 1 to 4 carbon atoms. Preferred examples of the alkylene carbonate of the present invention include ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate and the like.

The second component of the spray polyurea elastomer according to the invention consists of an amine terminator polyoxyalkylenepolyol and alkylolamine as amine resin.

The amine terminator polyoxyalkylenepolyols are preferably selected from diols or triols and most preferably comprise a mixture of diols and / or triols. The polyols in the second component, ie diols and / or triols, are the same as those described above in connection with the active hydrogen-containing material for producing the quasi-prepolymer of the first component.

Examples of the alkylolamine of the second component of the present invention include mecanolamine, dimethanolamine, trimethanolamine, ethanolamine, diethanolamine, triethanolamine, dimethanoldiamine, trimethanoldiamine, diethanoldiamine, and triethanoldiamine. . In such alkylolamines, the adhesion to the wet surface is improved by increasing the resistance to water when adhering to the surface by using the hydrophobicity and low surface tension of the alkyl group and the excellent adhesion of the amine group to glass, metal, and the like.

Chain extenders may be used in the present invention, preferably included in the second component and generally described as alkylsubstituted piperazines. Such chain extenders are prepared, for example, by reacting ammonia with a 2-amino-2-alkyl-1-alkanolalkyleneoxide adduct in the presence of a dehydrogenation-hydrogenation catalyst under appropriate reaction conditions. . More specifically, alkyl is selected from C1 to C4 alkyl and alkanols are selected from C3 to C10 alkanols. More preferably, the alkyl used is a methyl group and the alkanol is propanol. The alkylene oxide can be selected from C3 or higher alkylene oxides, most preferably from C3 to C4 alkylene oxides. Thus, for example, the most preferred alkylsubstituted piperazine is 2,2-dimethyl-5-alkylpiperazine as the 2-amino-2-methyl-1-propanol, 1,2-alkylene oxide adduct and ammonia. Prepared by reaction.

Alkyl-substituted piperazine used as chain extender in the second component of the present invention can be represented by the following formula (2).

Wherein R is a C1-C10 alkyl radical and R 'and R "are typically separate alkyl or inert-substituted alkyl radicals. More specifically, R' and R" are C1-C10, most preferably Is C1-C4 alkyl or inert-substituted alkyl radicals.

Advantageously the first and second components described above react to produce the spray polyurea elastomer according to the invention without the aid of a catalyst. However, catalysts can be used if desired.

Catalysts used include nickel in combination with one or more transition metals. Transition metals used with nickel include manganese, iron, zinc, copper and chromium. Preferably, the catalyst comprises nickel in combination with copper and / or chromium, and most preferably the catalyst comprises nickel in combination with both copper and chromium. The amounts of nickel, copper and chromium used in the catalyst vary. The reaction proceeds when about 50% nickel, 0% copper and 0% chromium of the total mass of the catalyst is used. The weight percentages of copper and chromium should be about 2-30%. About 70% to about 80% nickel and about 20 to 30% by weight copper and chromium are generally preferred.

Catalysts such as tertiary amines or organic tin compounds may be used, and may be suitable tin compounds such as tin salts of carboxylic acids, trialkyltin oxides, dialkyltin dihalides, dialkyltin oxides and the like. Wherein the organic groups of the organic part of the tin compound are hydrocarbon groups containing 1 to 8 carbon atoms. For example, dibutyl tin dilaurate, dibutyl tin diacetate, diethyl tin diacetate, dihexyl tin diacetate, di-2-ethylhexyl tin oxide, dioctyl tin dioxide, tin octoate, tin oleate, and the like, or mixtures thereof. This can be used.

Tertiary amine catalysts include trialkylamines (eg trimethylamine, triethylamine); Heterocyclic amines, such as N-alkylmorpholines (eg N-methylmorpholine, N-ethylmorpholine, dimethyldiaminodiethylether grade), 1,4-dimethylpiperazine, triethylenediamine And aliphatic polyamines, such as N, N, N'N'tetramethyl-1,3-butadiamine.

Other conventional chemical additives can be included in the first component or the second component, for example, foam stabilizers known as silicone oils or emulsifiers can be used. Foam stabilizers can be organosilanes or siloxanes. For example, compounds having a formula such as the following Formula 3 may be used.

RS ₁ [O- (R ₂ SiO) _n- (oxyalkylene) _m R] ₃

Wherein R is an alkyl group having from 1 to 4 carbon atoms, n is an integer from 4 to 8, m is an integer from 20 to 40, and can be obtained from oxyalkylene groups propylene oxide and ethylene oxide.

Pigments, such as titanium oxide, may be added to color the elastomer, preferably for the second component.

The volume ratio of the first component and the second component is generally 30 to 70 to 70 to 30, and preferably, the first component and the second component are used in a volume ratio of 1: 1.

The first component and the second component of the spray polyurea elastomer of the present invention are ejected directly from the high pressure equipment and impingement mixed. To this end, in the embodiments of the invention described below, a GUSMER VR-H-3000 proportioner unit equipped with a GUSMER GX-7-400 spray gun is used. The first component and the second component are each stored in separate high pressure chambers of the proportioner and then ejected at high speed by spray to impinge and mix with each other to produce a spray polyurea elastomer according to the present invention.

The pressure of the chamber of the first component is 2500-2700 psig and the temperature is 160 ° F. The pressure of the chamber of the second component is 2000 to 2200 psig and the temperature is 150 ° F. The hose temperature was 160 ° F, the spray jet pressure was 1500 to 2500 psi for both the first component and the second component, and the production rate of the polyurea elastomer according to the invention by spraying was 22.5 lbs / min.

[First Embodiment]

The 1st component is ISONATE 143L 54 piece which is liquid methylenebis (4-phenylisocyanate) as an isocyanate; 36 pieces of PP-2000 (manufactured by Korean Polyol), which is polypropylene glycol as active hydrogen-containing material; As alkylene carbonate, it consists of ten pieces of JEFFSOLPC (product of Husman) which is propylene carbonate.

As the amine resin, the second component is 48 pieces of JEFFAMINE D-2000 (manufactured by Husman), which is an amine-terminated polyoxypropylene diol having a molecular weight of 2000, and JEFFAMINE T-5000 (Husman, which is an amine-terminated polyoxypropylene triol having a molecular weight of 5000. 16 products); 19 pieces of ETHACURE 100 (produced by Ethyl), which is diethyltoluenediamine, and 12 pieces of UNLINK 4200 (produced by UOP), which are dialkyl-substituted methylene dianilines as chain extenders; As alkylolamine, it consists of five pieces of triethanolamine.

The first component and the second component are mixed in a volume ratio of 1: 1 by impingement mixing by spray equipment under high temperature and high pressure. The processability and physical properties of the resulting polyurea elastomers are indicated in Tables 1 and 2, respectively. In addition, the adhesion test results of the resulting polyurea elastomer are indicated in Table 3 below.

Second Embodiment

The first component is the same as in the first embodiment described above. That is, ISONATE 143L 54 piece which is liquid methylenebis (4-phenylisocyanate) as an isocyanate; 36 pieces of PP-2000 (manufactured by Korean Polyol) which are polypropylene glycol as active hydrogen-containing materials; The alkylene carbonate is composed of 10 pieces of JEFFSOL PC (manufactured by Husman) which is a propylene carbonate.

The second component is 46 pieces of JEFFAMINE D-2000 (manufactured by Husman), which is an amine-terminated polyoxypropylenediol having a molecular weight of 2000 as an amine resin, and JEFFAMINE T-5000 (Husman, which is an amine-terminated polyoxypropylene triol having a molecular weight of 5000. 4 products); 18 pieces of ETHACURE 100 (produced by Ethyl), which is diethyltoluenediamine, and 11 pieces of UNLINK 4200 (produced by UOP), which are dialkyl-substituted methylene dianilines as chain extenders; As alkylolamine, it consists of ten triethanolamine.

The first component and the second component are mixed in a volume ratio of 1: 1 by impingement mixing by spray equipment under high temperature and high pressure. The processability and physical properties of the resulting polyurea elastomers are indicated in Tables 1 and 2, respectively. In addition, the adhesion test results of the resulting polyurea elastomer are indicated in Table 3 below.

Third Embodiment

The first component is the same as the first and second embodiments described above. That is, ISONATE 143L 54 piece which is liquid methylenebis (4-phenylisocyanate) as an isocyanate; 36 pieces of PP-2000 (manufactured by Korean Polyol) which are polypropylene glycol as active hydrogen-containing materials; The alkylene carbonate is composed of 10 pieces of JEFFSOL PC (manufactured by Husman) which is a propylene carbonate.

The second component is 45 pieces of JEFFAMINE D-2000 (manufactured by Husman), which is an amine-terminated polyoxypropylene diol having a molecular weight of 2,000, and JEFFAMINE T-5000 (Husman, which is an amine-terminated polyoxypropylene triol having a molecular weight of 5000 as an amine resin. 4 products); 17 pieces of ETHACURE 100 (produced by Ethyl), which is diethyltoluenediamine, and 12 pieces of UNLINK 4200 (produced by UOP), which are dialkyl-substituted methylene dianilines as chain extenders; As alkylolamine, it consists of 15 pieces of triethanolamine.

The first component and the second component are mixed in a volume ratio of 1: 1 by impingement mixing by spray equipment under high temperature and high pressure. The processability and physical properties of the resulting polyurea elastomers are indicated in Tables 1 and 2, respectively. In addition, the adhesion test results of the resulting polyurea elastomer are indicated in Table 3 below.

Fourth Embodiment (Comparative Example)

The first component is the same as in the first embodiment described above. That is, ISONATE 143L 54 piece which is liquid methylenebis (4-phenylisocyanate) as an isocyanate; 36 pieces of PP-2000 (manufactured by Korean Polyol) which are polypropylene glycol as active hydrogen-containing materials; The alkylene carbonate is composed of 10 pieces of JEFFSOL PC (manufactured by Husman) which is a propylene carbonate.

The second component is JEFFAMINE D-2000 (manufactured by Husman), which is an amine-terminated polyoxypropylenediol having a molecular weight of 2000 as an amine resin, and JEFFAMINE T-5000 (Husman, which is an amine-terminated polyoxypropylene triol having a molecular weight of 5000. 16 products); It consists of 20 pieces of ETHACURE 100 (made by Ethyl) which is a diethyl toluenediamine, and 14 pieces of UNLINK 4200 (made by UOP) which is a dialkyl substituted methylene dianiline as a chain extender, and no alkylolamine is added.

The first component and the second component are mixed in a volume ratio of 1: 1 by impingement mixing by spray equipment under high temperature and high pressure. The processability and physical properties of the resulting polyurea elastomers are indicated in Tables 1 and 2, respectively. In addition, the adhesion test results of the resulting polyurea elastomer are indicated in Table 3 below.

Referring to Table 3, in the case of dry concrete and primed concrete, alkylolamine is added to the second component in the first, second and third examples in which alkylolamine is added to the second component. It can be seen that the adhesive strength is superior to that of the fourth embodiment (comparative example), which is not. In addition, in the case of the first, second and third examples in which the alkylolamine is added to the second component, it can be observed that the greater the amount of the added alkylolamine, the greater the adhesion. The adhesion test above is according to ASTM D4541 standard. The adhesion test on the wet surface cannot provide the data based on the standard because no international standard is established, but the surface using the hydrophobicity and low surface tension of the alkyl group of the alkylolamine and the excellent adhesion of the amine group to glass, metal, etc. The adhesion to the wet surface was also improved by increasing the resistance to water when adhering to.

Claims (2)

In sprayed polyurea elastomers, methanolamine, dimethanolamine and trimethanol are added to the first component and at least one amine resin produced by the addition of alkylene carbonate to the pseudo-prepolymer obtained by reacting isocyanate with active hydrogen-containing material. A spray polyurea elastomer, which is obtained by reacting a second component containing 5 to 30% by weight of an alkylolamine selected from amine, dimethanoldiamine, trimethanoldiamine, dietinoldiamine and triethanoldiamine through a spray gun. The spray polyurea elastomer according to claim 1, wherein the amine resin of the second component is an amine-terminated polyoxyalkylene polyol.