Method of preparing accelerator, curing agent and diluent and applying the same to eliminate amine blushing and amine blooming

Abstract

Disclosed is an extension of a partial application of the previous invention (P.R.C. Pat. Application No. 201110357015.X) that overcomes the issues of the previous invention requiring a too long curing time of the accelerator, curing agent and diluent after they are mixed with epoxy resin, polyurethane resin, polyurea resin and polyisocyanate resin at the conditions of low temperature and high humidity and producing amine blushing, amine blooming or treaded surface phenomenon. The present invention reduces the curing time and overcomes the aforementioned drawbacks of the resins effectively.

Claims

1. A first curing agent for eliminating amine blushing and amine blooming, consisting of six compounds represented by the following structural Formulas (8), (9), (10), (11), (12) and (13) respectively: ##STR00010## wherein, R is H, C.sub.4H.sub.9, C.sub.9H.sub.19 or C.sub.15H.sub.2X+1, and X is any integer from 12 to 15; R, R.sub.1, R.sub.2 and R.sub.3 are polyamine radicals; R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are CH.sub.3, C.sub.2H.sub.5, C.sub.3H.sub.7 or C.sub.4H.sub.9; Z is H or OH; is a radical moiety of formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde or benzaldehyde and their mixtures produced in Mannich condensation reaction; the compounds of Formulas (8), (9) and (10) have a total weight percentage from 40% to 95% with respect to the total weight of the compounds of Formulas (8)-(13); and the compounds of Formulas (11), (12) and (13) have a total weight percentage from 5% to 60% with respect to the total weight of the compounds of Formulas (8)-(13).

2. The first curing agent for eliminating amine blushing and amine blooming according to claim 1, wherein is a radical moiety of benzaldehyde produced in Mannich condensation reaction.

Description

DESCRIPTION OF THE PREFERRED EMBODIMENTS

(1) The technical characteristics, contents, advantages and effects of the present invention will be apparent with the detailed description of a preferred embodiment accompanied with related drawings as follows.

(2) To overcome the problems and drawbacks of the prior art, the present invention provides a solution by modifying the chemical structure of the original coating and adjust the recipe and proportion appropriately, and also reduces the manufacturing cost to offer a price close to the price of the conventional curing agent. In addition, the curing agent manufactured by Air-Products and Chemicals, Inc., USA requires hydrogen gas and a high-pressure reactor for the operation and uses high-priced noble metal, so that the price of products of the present invention is lower than the price of products manufactured by Air-Products and Chemicals, Inc., USA.

(3) The inventor of the present invention, who is also the inventor of the previous invention (P.R.C. Pat. No. 103102506) provides an accelerator for eliminating amine blushing and amine blooming, consisting of seven compounds represented by the following structural Formulas (1), (2), (3), (4), (5), (6) and (7) respectively:

(4) ##STR00006##

(5) Wherein, R is C.sub.4H.sub.9, C.sub.9H.sub.19 or C.sub.15H.sub.2X+1, and X is any integer from 12 and 15; R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are CH.sub.3, C.sub.2H.sub.5, C.sub.3H.sub.7 or C.sub.4H.sub.9; Z is H or OH; is a radical moiety of formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde or benzaldehyde and their mixture produced in Mannich condensation reaction; the compound of Formula (1) has a weight percentage from 40% to 95%; the compounds of Formulas (2), (3) and (4) have a total weight percentage from 2.5% to 30%; and the compounds of Formulas (5), (6) and (7) have a total weight percentage from 2.5% to 30%.

(6) In a preferred embodiment, is a radical moiety of benzaldehyde produced in Mannich condensation reaction.

(7) In another preferred embodiment, the accelerator may be a diluent of a curing agent.

(8) In an embodiment, the present invention further provides a first curing agent for eliminating amine blushing and amine blooming, consisting of six compounds represented by the following structural Formulas (8), (9), (10), (11), (12) and (13) respectively:

(9) ##STR00007##

(10) Wherein, R is H, C.sub.4H.sub.9, C.sub.9H.sub.19 or C.sub.15H.sub.2X+1, and X is any integer from 12 to 15; R, R.sub.1, R.sub.2 and R.sub.3 are polyamines radicals; R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are CH.sub.3, C.sub.2H.sub.5, C.sub.3H.sub.7 or C.sub.4H.sub.9; Z is H or OH; is a radical moiety of formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde or benzaldehyde and their mixtures produced in Mannich condensation reaction; the compounds of Formulas (8), (9) and (10) have a total weight percentage from 40% to 95%; and the compounds of Formulas (11), (12) and (13) have a total weight percentage from 5% to 60%.

(11) In a preferred embodiment, is a radical moiety of benzaldehyde produced in Mannich condensation reaction.

(12) In an embodiment, the present invention further provides a diluent of an accelerator or a curing agent for eliminating amine blushing and amine blooming, consisting of seven compounds represented by the following structural Formulas (14), (15), (16), (17), (18), (19) and (20) respectively:

(13) ##STR00008##

(14) Wherein, R is C.sub.4H.sub.9, C.sub.9H.sub.19 or C.sub.15H.sub.2X+1, and X is any integer from 12 to 15; R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are CH.sub.3, C.sub.2H.sub.5, C.sub.3H.sub.7 or C.sub.4H.sub.9; Z is H or OH; is benzene ring; the compound of Formula (14) has a weight percentage from 40% to 95%; the compounds of Formulas (15), (16) and (17) have a total weight percentage from 2.5% to 30%; and the compounds of Formulas (18), (19) and (20) have a total weight percentage from 2.5% to 30%.

(15) In an embodiment, the present invention further provides a second curing agent for eliminating amine blushing and amine blooming, consisting of fix compounds represented by the following structural Formulas (21), (22), (23), (24), (25) and (26) respectively:

(16) ##STR00009##

(17) Wherein, R is H, C.sub.4H.sub.9, C.sub.9H.sub.19 or C.sub.15H.sub.2X+1, and X is any integer from 12 to 15; R is a polyamine radical; R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are CH.sub.3, C.sub.2H.sub.5, C.sub.3H.sub.7 or C.sub.4H.sub.9; Z is H or OH; is benzene ring; the compounds of Formulas (21), (22) and (23) have a total weight percentage from 40% to 95%; and the compounds of Formulas (24), (25) and (26) have a total weight percentage from 5% to 60%.

(18) In an embodiment, the present invention further provides a third curing agent for eliminating amine blushing and amine blooming, consisting of six compounds represented by the following structural Formulas (8), (9), (10), (11), (12) and (13) of the first curing agent respectively and six compounds represented by the following structural Formulas (21), (22), (23), (24), (25) and (26) of the second curing agent respectively, wherein, R is H, C.sub.4H.sub.9, C.sub.9H.sub.19 or C.sub.15H.sub.2X+1, and X is any integer from 12 to 15; R, R.sub.1, R.sub.2 and R.sub.3 are polyamine radicals; R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are CH.sub.3, C.sub.2H.sub.5, C.sub.3H.sub.7 or C.sub.4H.sub.9; Z is H or OH; is a radical moiety of formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde or benzaldehyde and their mixtures produced in Mannich condensation reaction; is benzene ring; the compounds of Formulas (8), (9) and (10) in the first curing agent have a total weight percentage from 40% to 95%; the compounds of Formulas (11), (12) and (13) have a total weight percentage from 5% to 60%; the compounds of Formulas (21), (22) and (23) in the second curing agent have a total weight percentage from 40% to 95%; the compounds of Formulas (24), (25) and (26) have a total weight percentage from 5% to 60%; the first curing agent in the third curing agent has a weight percentage from 5% to 95%; and the second curing agent has a weight percentage from 5% to 95%.

(19) In a preferred embodiment, R is a polyamine selected from the group consisting of aliphatic polyamine, araliphaticpolyamine, aromatic polyamine, cycloaliphatic polyamine, heterocyclic polyamine, poly(alkylene oxide) and polyaminoamide.

(20) In another preferred embodiment, R is a polyamine selected from the group consisting of aldimine or ketimine of aminoethylpiperazine (AEP) or aminoethylpiperazine (AEP), aldimine or ketimine containing at least one secondary amine, and aldimine or ketimine containing silicon.

(21) Preferably, the polyamine represented by R includes but not limited to aliphatic polyamine, araliphatic polyamine, aromatic polyamine, cycloaliphatic polyamine, heterocyclic polyamine, poly(alkylene oxide), polyaminoamide or their mixtures, or any other polyamine well known to persons having ordinary skill in the art.

(22) The aliphatic polyamine of the present invention includes but not limited to polyethylene polyamine, wherein the polyethylene polyamine is one selected from the group consisting of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, propylenediamine, dimethylaminopropylamine, 1,4-butanediamine, 1,3-pentanediamine, 1,6-hexamethylenediamine or their mixtures, or any aliphatic polyamine well known to persons having ordinary skill in the art.

(23) The poly(alkylene oxide) of the present invention includes but not limited to poly(oxypropylene)diamine, triamine or their mixture, or any other poly(alkylene oxide) well known to persons having ordinary skill in the art. Wherein, triamine may be purchased from Huntsman Corporation, and the Product Nos. are Jeffamine D230, D400, D2000, D5000, and T403.

(24) The cycloaliphatic polyamine of the present invention includes but not limited to isophorone diamine, diaminocyclohexane or their mixture, or any other cycloaliphatic polyamine well known to persons having ordinary skill in the art.

(25) The aromatic polyamine of the present invention includes but not limited to toluene diamine, or any other aromatic polyamine well known to persons having ordinary skill in the art.

(26) The heterocyclic polyamine of the present invention includes but not limited to aldimine or ketimine of aminoethylpiperazine (AEP) or aminoethylpiperazine (AEP), or any other polyamine including aldimine and ketimine of at least one secondary amine, or aldimine and ketimine containing silicon, or aldimine or ketimine of any other heterocyclic polyamine well known to persons having ordinary skill in the art.

(27) In the present invention, cardanol or cardol is used as a starting material to manufacture an accelerator, a curing agent and a diluent, and they are highly hydrophobic and environmentally friendly natural products. Wherein, the accelerator or diluent is manufactured by cardanol and cardol through Mannich condensation reaction, and the curing agent is a product obtained by performing a Mannich condensation reaction of cardanol and cardol and then a transamination of the polyamine, or a curing agent obtained by reacting phenol with formaldehyde and other aldehyde (such as benzaldehyde) and polyamine. The present invention uses cardanol and cardol as a highly hydrophobic curing agent obtained from a raw material which is contributed by the long-chain structure (as indicated by R in the structural formulas of the present invention) and the 15-carbon long-chain structure provides a highly lipophilic curing agent of the present invention.

(28) Since the curing agent of the present invention has a dimethylamino group and a hydroxyl group also having some hydrophilicity, therefore the curing agent of the present invention can be reacted in water at a temperature lower than room temperature and has an effective effect of resisting amine blushing and amine blooming.

(29) In an embodiment of the present invention, the use of epoxy resin further illustrates the technical measure of the present invention. However, it is noteworthy that polyurethane resin, polyurea resin or polyisocyanate resin in addition to epoxy resin are considered to be covered by the scope of the present invention.

(30) In this embodiment, the present invention is mixed with epoxy resin BE188 (provided by Chang Chun Plastic Co., Ltd., Taiwan) in the ratio of 1:1, and the coating film completely hardened for approximately 12 hours is observed and determined whether or not amine blushing or amine blooming is produced, and the coating film is cleaned and dried, and then gently touched by a right index finger to check if there is any oily substance on the surface. If no oil substance is on the surface, then the film surface is touched with force again. If there is no oil substance found, then the first testing stage passes. The process is waited for another 12 hours (It is now 24 hours after hardening), and then the same test is taken again. If no spots such as amine blushing and amine blooming are produced, then the whole test is passed.

(31) In the first embodiment of the present invention, the first curing agent is formed by six compounds represented by Formulas (8), (9), (10), (11), (12) and (13) respectively, wherein the total weight percentage of the compounds represented by Formulas (8), (9) and (10) is equal to 80%; the total weight percentage of the compounds represented by Formulas (11), (12) and (13) compound is equal to 20%, and R is C.sub.15H.sub.2+1, X is any integer from 12 to 15; R, R.sub.1, R.sub.2 and R.sub.3 are diethylenetriamine (DETA); R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are CH.sub.3; Z is H; and after the test, no amine blushing, amine blooming or any other spot is produced, so that the first embodiment passes the test.

(32) In the second embodiment of the present invention, the second curing agent is formed by six compounds represented by Formulas (21), (22), (23), (24), (25) and (26) respectively, wherein the total weight percentage of the compounds represented by Formulas (21), (22) and (23) is equal to 80%; the total weight percentage of the compounds represented by Formulas (24), (25) and (26) is equal to 20%; R is C.sub.15H.sub.2X+1, and X is any integer from 12 to 15; R is diethylenetriamine (DETA); Z is H; and after test, no amine blushing, amine blooming or other spots is found, so that the second embodiment also passes the test.

(33) In summation of the description above, the present invention has better price, environmental protection and effects than the products manufactured by Air-Products and Chemicals, Inc., USA.