CN117327024A - Compound, preparation method thereof and application of compound in polyurethane urea coating - Google Patents

Compound, preparation method thereof and application of compound in polyurethane urea coating Download PDF

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Publication number
CN117327024A
CN117327024A CN202311260424.7A CN202311260424A CN117327024A CN 117327024 A CN117327024 A CN 117327024A CN 202311260424 A CN202311260424 A CN 202311260424A CN 117327024 A CN117327024 A CN 117327024A
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groups
mass
slurry
secondary amine
prepolymer
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Inventor
滕向
刘大伟
牟昌盛
刘赵兴
尚永华
孙立冬
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Wanhua Chemical Group Co Ltd
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Wanhua Chemical Group Co Ltd
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Priority to CN202311260424.7A priority Critical patent/CN117327024A/en
Publication of CN117327024A publication Critical patent/CN117327024A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/30—Only oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
    • C08G18/3842—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
    • C08G18/3851—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing three nitrogen atoms in the ring
    • C08G18/3853—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing three nitrogen atoms in the ring containing cyanurate and/or isocyanurate groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/02—Polyureas
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate

Abstract

The invention relates to a compound, a preparation method thereof and application thereof in polyurethane urea coating, wherein the compound has the following structure; wherein R is 11 、R 21 、R 31 Identical or different and independently of one another selected from sec-butyl or (CH) 3 CH 2 OOCCH 2 )(CH 3 CH 2 OOC)CH‑；R 12 、R 22 、R 32 Are identical or different and are selected independently of one another from methylenediphenyl or methylenedicyclohexyl. The compound of one embodiment of the invention can be used as polyurethane urea paintThe cross-linking agent of (a) has the characteristics of prolonging the applicable period of the mixed construction of a formula system (a slurry system and a prepolymer system), enhancing the storage stability of the slurry system and improving the strength, elongation at break and thermal property of a final coating product.

Description

Compound, preparation method thereof and application of compound in polyurethane urea coating
Technical Field
The invention relates to a secondary amine cross-linking agent, in particular to a secondary amine cross-linking agent for polyurethane urea coating.
Background
HDI trimer (hexamethylene diisocyanate trimer) is often used in combination with flexible polyether modified isocyanate prepolymers to produce elastomeric polyurethaneurea materials, but the resulting material system has a short pot life; meanwhile, if amine compounds in the system are more, HDI trimer has ase:Sub>A high probability of forming ase:Sub>A polymer substance with more than an A-B-A structure, and the polymer substance contains more urease:Sub>A bonds and is often separated out in the curing process of the system, so that the chain growth and chain distribution in the material are affected, and the material performance is reduced. In addition, when the HDI trimer and the isocyanate prepolymer are subjected to physical cold splicing, an incompatibility phenomenon is easy to occur, and two groups of originally clear and transparent liquids are milky white after being mixed, so that the appearance of an isocyanate component is influenced, the downstream customer is not accepted, and meanwhile, the storage stability of the component is also influenced.
On the other hand, in the production of polyurethane urea materials, secondary amine chain extenders are common amine terminated compounds, but most common secondary amine compounds have linear structures, have low crosslinking degree and have certain influence on the strength and heat resistance of polyurethane chain segments. Meanwhile, in a slurry system containing plasticizer liquid filler, calcium carbonate and talcum powder solid filler, the amine chain extender can reduce the storage stability of the system, so that the sedimentation of the filler is more likely to occur.
For example, one prior art discloses an HDI trimer-type urethane component that can be added to an asparate polyurea formulation to prepare a polyurea coating. The HDI trimer-type urethane component is the product of an end-capping reaction of an HDI trimer with a monofunctional alcohol such as methanol or the like. However, the terminal groups of the HDI trimeric urethane component do not contain isocyanate groups nor active hydrogen groups, and do not participate in subsequent chemical reactions in the disclosed asparaguse polyurea formulation system, but rather are present as organic fillers. Thus, the above components do not solve the problems such as extending the pot life of the system, enhancing the storage stability of the slurry system, improving the strength and thermal properties of the linear difunctional secondary amine chain extender, and the like.
For another example, another prior art discloses a polyaspartic acid amide ester which is a difunctional secondary amine compound generated by the reaction of an unsaturated dibasic acid ester and a dibasic primary amine, and the problem of lower strength and thermal performance of a linear difunctional secondary amine chain extender is also present.
Disclosure of Invention
To overcome at least one of the above-described drawbacks of the prior art, in a first aspect, an embodiment of the present invention provides a compound having the structure:
wherein R is 11 、R 21 、R 31 Identical or different and independently of one another selected from sec-butyl or (CH) 3 CH 2 OOCCH 2 )(CH 3 CH 2 OOC)CH-；R 12 、R 22 、R 32 The same or different and are selected independently of one another from the following methylenediphenyl or methylenedicyclohexyl radicals:
in a second aspect, one embodiment of the present invention provides the use of the above-described compounds as cross-linking agents in polyurethane urea coatings.
In a third aspect, one embodiment of the present invention provides a process for the preparation of a secondary amine crosslinker comprising reacting a hexamethylene diisocyanate trimer with a bis-secondary amine compound to produce the secondary amine crosslinker; wherein the bis-secondary amine compound is selected from one or more of 4,4' -bis-secondary butylaminodiphenyl methane, 4' -bis-secondary butylaminodicyclohexyl methane and N, N ' - (methylenedi-4, 1-cyclohexanediyl) diethyl aspartate.
In a fourth aspect, one embodiment of the present invention provides a polyurethaneurea coating composition comprising a prepolymer component and a slurry component; the prepolymer component comprises polyether polyol and polyisocyanate, and the slurry component comprises a crosslinking agent comprising the compound described above or a secondary amine crosslinking agent prepared by the preparation method described above.
In a fifth aspect, one embodiment of the present invention provides a polyurethaneurea coating prepared from the above-described polyurethaneurea coating composition, wherein the polyurethaneurea coating comprises a prepolymer and a slurry; the prepolymer is made from the prepolymer component and the slurry is made from the slurry component.
In a sixth aspect, one embodiment of the present invention provides a coating made from the polyurethaneurea coating composition described above.
The compound of one embodiment of the invention can be used as a cross-linking agent of polyurethane urea paint, and has the characteristics of prolonging the applicable period of the AB material (slurry system and prepolymer system) of a formula system in mixed construction, enhancing the storage stability of the slurry system and improving the strength, elongation at break and thermal performance of a final coating product.
Drawings
The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention. Wherein:
FIG. 1 is an infrared spectrum of a secondary amine crosslinking agent # 1 prepared in example 1 of the present invention;
FIG. 2 is an infrared spectrum of the secondary amine crosslinking agent # 2 prepared in example 2 of the present invention;
FIG. 3 is an infrared spectrum of a secondary amine crosslinking agent # 3 prepared in example 3 of the present invention.
Detailed Description
Exemplary embodiments that embody features and advantages of the present invention will be described in detail in the following description. It will be understood that the invention is capable of various modifications in various embodiments, all without departing from the scope of the invention, and that the description is intended to be illustrative in nature and not to be limiting.
An embodiment of the present invention provides a compound having the structure:
wherein R is 11 、R 21 、R 31 Identical or different and independently of one another selected from sec-butyl or (CH) 3 CH 2 OOCCH 2 )(CH 3 CH 2 OOC)CH-；R 12 、R 22 、R 32 The same or different and are selected independently of one another from the following methylenediphenyl or methylenedicyclohexyl radicals:
in one embodiment, the above compounds may be used as a crosslinker in polyurethaneurea coatings.
An embodiment of the present invention provides a secondary amine crosslinker useful in polyurethane urea coatings comprising one or more of the compounds described above.
One embodiment of the present invention provides a method for preparing a secondary amine crosslinking agent, comprising reacting hexamethylene diisocyanate trimer (HDI trimer) with a bis-secondary amine compound to prepare a secondary amine crosslinking agent; wherein the bis-secondary amine compound is selected from one or more of 4,4' -bis-secondary butylaminodiphenyl methane, 4' -bis-secondary butylaminodicyclohexyl methane and N, N ' - (methylenebis-4, 1-cyclohexanediyl) diethyl aspartate.
In one embodiment, the reaction formula of the HDI trimer with the bis-secondary amine compound is as follows:
wherein Rx is 1 -NH-Rx 2 -NH-Rx 1 As a bis-secondary amine compound, rx 1 May be R as described above 11 、R 21 Or R is 31 ，Rx 2 May be R as described above 12 、R 22 Or R is 32 。R 11 、R 21 、R 31 、R 12 、R 22 、R 32 With R in formula I 11 、R 21 、R 31 、R 12 、R 22 、R 32 The same applies. Further, in the preparation of the secondary amine crosslinking agent, a reaction is carried out using a bis-secondary amine compound, R in the above reaction formula 11 、R 21 、R 31 R is the same radical 12 、R 22 、R 32 Are the same groups; by reacting two or more kinds of secondary amine compounds, R in the above formula 11 、R 21 、R 31 Not all are identical, R 12 、R 22 、R 32 Nor is it identical.
In one embodiment, among the employed bis-secondary amine compounds, for example, tetraethyl N, N '- (methylenebis-4, 1-cyclohexanediyl) aspartate or 4,4' -bis-secondary butylaminodiphenyl methane may be used alone, or a plurality of bis-secondary amine compounds may be used in combination; for example, the molar ratio of N, N ' - (methylenebis-4, 1-cyclohexanediyl) diethyl aspartate, 4' -bis-secondary butylaminodiphenyl methane to 4,4' -bis-secondary butylaminodicyclohexyl methane may be 1 (0-10): (0-1), further may be 1 (0.1-10): (0.1-1), for example 1:1:0.5, 1:3:1, 1:5:1, 1:8:1; alternatively, the molar ratio of 4,4' -bis-secondary butylaminodiphenyl methane, N ' - (methylenebis-4, 1-cyclohexanediyl) tetraethyl di-aspartate to 4,4' -bis-secondary butylaminodicyclohexyl methane is 1 (0-10): (0-1), further 1 (0.1-10): (0.1-1), for example 1:1:0.5, 1:3:1, 1:5:1, 1:8:1.
In one embodiment, the HDI trimer may be one or more of HT-100, HT-300, HT-600 of Wanhua chemistry.
In one embodiment, the molar ratio of the bis-secondary amine compound to the HDI trimer may be 3 to 10:1, and further may be 4 to 7:1, such as 5:1, 6:1.
In one embodiment, the reaction of the HDI trimer with the bis-secondary amine compound is carried out in an inert gas atmosphere, such as a nitrogen atmosphere.
In one embodiment, the temperature of the reaction of the HDI trimer with the bis-secondary amine compound may be 20 to 80 ℃, further may be 30 to 50 ℃, such as 35 ℃, 40 ℃, 45 ℃, 60 ℃, 70 ℃; the reaction time may be 1 to 10 hours, further 2 to 8 hours, for example 3 hours, 4 hours, 5 hours, 6 hours, 7 hours.
In one embodiment, the method of preparing the secondary amine crosslinker comprises: under the nitrogen atmosphere, slowly dropwise adding HDI trimer into the di-secondary amine compound, and carrying out addition reaction under certain reaction temperature and normal pressure and stirring.
In one embodiment, the stirring speed of the reaction system of the HDI trimer and the bis-secondary amine compound may be 100 to 400rpm, and further may be 150 to 300rpm, for example, 200rpm, 250rpm.
One embodiment of the present invention provides a polyurethaneurea coating composition comprising a prepolymer component and a slurry component; the prepolymer component comprises a polyether polyol and a polyisocyanate, and the slurry component comprises a crosslinker comprising the compound described above or a secondary amine crosslinker described above. Further, the prepolymer component may include polyether polyols, polyisocyanates, and small molecule alcohols.
In one embodiment, a polyurethaneurea coating composition includes a prepolymer component, a slurry component, and a catalyst component.
In one embodiment, the prepolymer component comprises 30 to 85 parts by mass of polyether polyol and 10 to 50 parts by mass of polyisocyanate, and the slurry component comprises 15 to 80 parts by mass of crosslinker.
In one embodiment, the prepolymer component includes 40 to 80 parts by mass of polyether polyol and 10 to 25 parts by mass of polyisocyanate, and the slurry component includes 20 to 60 parts by mass of crosslinking agent.
In one embodiment, the prepolymer component comprises 30 to 85 parts by mass of polyether polyol, 10 to 50 parts by mass of polyisocyanate, 1 to 10 parts by mass of small molecule alcohol, and 0 to 20 parts by mass of first plasticizer and/or solvent; further, the prepolymer component includes 40 to 80 parts by mass of polyether polyol, 10 to 25 parts by mass of polyisocyanate, 2 to 5 parts by mass of small molecule alcohol, and 5 to 20 parts by mass of first plasticizer and/or solvent.
In one embodiment, the slurry component includes 15 to 80 parts by mass of a crosslinking agent, 5 to 20 parts by mass of a second plasticizer, 0 to 10 parts by mass of a co-chain extender (e.g., 1 part by mass), 0 to 10 parts by mass (e.g., 1 part by mass) of an auxiliary agent and/or a solvent, and 10 to 60 parts by mass of an inorganic filler; further, the slurry component comprises 30 to 60 parts by mass of a cross-linking agent, 10 to 15 parts by mass of a second plasticizer, 0 to 5 parts by mass of an auxiliary chain extender, 2 to 5 parts by mass of an auxiliary agent and/or a solvent, and 35 to 50 parts by mass of an inorganic filler.
In one embodiment, the polyurethaneurea coating composition has an isocyanate index of 1 to 1.5, and further 1.03 to 1.3.
In one embodiment, the mass of the catalyst component is 0.05 to 0.6%, such as 0.1%, 0.2%, 0.3%, 0.4%, 0.5% of the mass of the polyurethaneurea coating composition.
In one embodiment, the catalyst component comprises an organometallic catalyst, further an environmentally friendly organometallic catalyst. The catalyst component may include one or more of zinc neodecanoate, bismuth neodecanoate, dibutyltin dilaurate, such as BiCAT8018, biCAT Z, bi2010, zn1910, valikat14H2 of the Belgium family, dabco T-120 of the Ying-Critical chemistry, and the like, leading in the United states.
In one embodiment, the polyether polyol has an average functionality of 2 to 3 and a weight average molecular weight of 1000 to 6500. Further, the polyether polyol may be one or more of polyoxypropylene polyol, polyoxyethylene propylene copolyol, polytetrahydrofuran polyol.
In one embodiment, the polyether polyol may be one or more of C2010, C2020, C2040, C2140, F3135, F3056D of the Wanhua chemistry, or PTMEG1000, PTMEG2000, etc. of the Dacron chemistry.
In one embodiment, the polyisocyanate may be a diisocyanate and derivatives thereof.
In one embodiment, the polyisocyanate comprises one or more of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate; such as one or more of the chemical Wanhua MDI-50, MDI-100LL, TDI-80, TDI-100, TDI-60, IPDI, HMDI.
In one embodiment, the equivalent ratio of polyisocyanate TDI-80 to active hydrogen components (polyether polyol and small molecule alcohol) is no greater than 2.
In one embodiment, the small molecule alcohol may be one or more of Trimethylolpropane (TMP), 1, 4-Butanediol (BDO), ethylene Glycol (EG), propylene Glycol (PG), bisphenol A (BPA).
In one embodiment, the first plasticizer and the second plasticizer are each independently selected from one or more of an environmentally friendly long chain chlorinated paraffin (e.g., 52# chlorinated paraffin of shandong rock sea), triethylene glycol diisooctyl (3G 8), acetyl tributyl citrate (ATBC), dioctyl terephthalate (DOTP), methyl chloropalmitat and methyl epoxysoyate.
In one embodiment, the co-chain extender may be a liquid amine-based chain extender, such as one or more selected from the group consisting of dimethyl thiodiaminotoluene (DMTDA), 3, 5-diethyltoluenediamine (DETDA), 4' -bis-secondary butylaminodiphenyl Methane (MDBA), 1, 4-bis-secondary butylaminophenyl, isophorone diamine, diamino dicyclohexyl methane, aspartic acid resins. For example, the auxiliary chain extender may be E300, E100, wanalink6200, wanalink1104, wanamine IPDA, wanamine H of the Yabao company 12 MDA, shenzhen fly F420, F520,One or more of F220.
In one embodiment, the inorganic filler is selected from one or more of calcium carbonate, talc, kaolin, white carbon black and magnesium oxide, for example 800 mesh calcium carbonate (Yangshan calcium carbonate works), 1250 mesh talc (Yongfeng chemical industry).
In one embodiment, the adjuvant includes one or more of an antifoaming agent, a dispersant, and an anti-settling agent.
In one embodiment, the solvent is selected from one or more of dimethyl carbonate, ethyl acetate, butyl acetate, propylene carbonate.
An embodiment of the present invention provides a polyurethaneurea coating prepared from the above-described polyurethaneurea coating composition, wherein the polyurethaneurea coating comprises a prepolymer system and a slurry system; the prepolymer is made by a prepolymer component and the slurry is made by the slurry component.
In one embodiment, the polyurethaneurea coating comprises the catalyst component described above.
In one embodiment, the materials of the prepolymer component may be mixed and reacted to produce a prepolymer system; the materials of the slurry components can be physically mixed to prepare a slurry system; the preparation of the prepolymer system and the slurry system can be carried out according to the existing preparation method.
An embodiment of the invention provides a preparation method of a polyurethane urea coating, which comprises the following steps: adding the prepolymer system, the slurry system and the catalyst components into a stirrer to disperse for 1-2 min, then pouring the uniformly dispersed materials into a mold, and standing for curing.
An embodiment of the present invention provides a coating made from the polyurethaneurea coating composition described above.
The compound of one embodiment of the invention can be used as a cross-linking agent of polyurethane urea coating, and has the characteristics of prolonging the pot life of the system, enhancing the storage stability of the slurry system and improving the strength and the thermal property of the coating.
The compound of one embodiment of the invention can be used as a cross-linking agent of polyurethane urea coating, can improve the pot life of HDI trimer and avoid the incompatibility phenomenon of the HDI trimer and isocyanate prepolymer in the prior art during cold splicing to a certain extent.
The compound of one embodiment of the invention can be used as a cross-linking agent of polyurethane urea paint, can reduce the catalytic effect of water on an asparagus polyurea system in the existing polyurethane urea paint material, and prolongs the pot life of the system.
The secondary amine crosslinking agent and the polyurethaneurea coating according to one embodiment of the present invention will be further described below with reference to the accompanying drawings and specific examples.
Example 1
Preparation of secondary amine crosslinking agent # 1
(1) Preparing raw materials according to the molar ratio of N, N '- (methylenebis-4, 1-cyclohexanediyl) diethyl aspartate (Shenzhen fly Co F420) to 4,4' -bis-secondary butylaminodiphenyl methane (MDBA, wanalink 6200) =2:1 to obtain a secondary amine composition A; the starting materials were formulated at a molar ratio of f420:6200:4,4' -bis-secondary butylaminodicyclohexyl methane (indian DK company Cl 1000) =0.1:1.8:0.1 to give secondary amine composition B.
(2) 142.6g of secondary amine composition A was charged into a 500ml four-necked flask, and 67.5g of HT-100 was added into the four-necked flask using a constant pressure dropping funnel; the flask was purged with nitrogen and the reaction temperature was set at 30℃and the stirring speed was 200rpm. HT-100 is controlled to be added dropwise within 0.5h, the reaction is carried out for 1h, then 64.6g of secondary amine composition B is added into a four-neck flask, the temperature is raised to 50 ℃ after the reaction is continued for 1h, and the material is discharged after the reaction for 1h, so as to obtain the 1# secondary amine cross-linking agent. The secondary amine crosslinking agent # 1 was tested using a Nicolet iS5 Fourier transform infrared spectrometer (Thermo fisher brand, U.S.A.), the infrared spectrum of which iS shown in FIG. 1.
2230cm as shown in FIG. 1 -1 The position has no absorption peak, which indicates that the isocyanate group (-NCO) has reacted completely; 1686cm -1 An absorption peak exists at the position, which indicates that the product contains isocyanurate heterocyclic structure; 2853-2963cm -1 An absorption peak exists at the position, which indicates that the product contains a methylene structure; 3340. 3649cm -1 The presence of an absorption peak at the position indicates that the product contains-NHSecondary amine structure.
Application example 1
Preparation of prepolymer A1
Polyether polyols C2010, C2020, F3135 and 1, 4-butanediol were added to the flask according to the formulation of application example 1 in table 1 below, and dehydrated in vacuo at 95 ℃ for 2 hours; cooling the system to 70 ℃, adding TDI-80, reacting for 1h, and then heating to 90 ℃ for reacting for 4h; then, plasticizer 3G8 is added into the flask, the temperature is reduced to 50 ℃ and the material is discharged, and the prepolymer A1 is obtained.
Preparation of slurry B1
The slurry B1 was obtained by mixing the various materials of the slurry components according to the formulation of application example 1 in Table 2, dispersing at a high speed of 1500rpm for 1 hour, and discharging.
Preparation of film (coupon)
Respectively weighing 87g of prepolymer A1 and 113g of slurry B1, adding 200g in total, weighing 0.1g of organic zinc catalyst Zn1910 (manufacturer's grace department), placing into a 300ml stirring cup, and adding 10g of additional dimethyl carbonate for dilution during configuration for convenient observation and sample preparation; the stirring cup is placed under a high-speed dispersing machine for dispersing for 2min, the rotating speed of the dispersing machine is 1000rpm, the mixed sample liquid is poured into a tetrafluoro mould after standing for 1min, and the film thickness is controlled to be about 1.5 mm.
Comparative example 1
Preparation of prepolymer A2
Polyether polyols C2010, C2020, F3135 and 1, 4-butanediol were added to the flask according to the formulation of comparative example 1 in table 1 below, and dehydrated in vacuo at 95 ℃ for 2 hours; cooling the system to 70 ℃, adding TDI-80, reacting for 1h, and then heating to 90 ℃ for reacting for 4h; then, plasticizer 3G8 and HT-100 are added into the flask, the temperature is reduced to 50 ℃ and the material is discharged, and the prepolymer A2 is obtained.
Preparation of slurry B2
According to the formulation of comparative example 1 in Table 2, the various materials of the slurry components were mixed and then dispersed at a high speed of 1500rpm, and after 1 hour of dispersion, the slurry B2 was obtained by discharging.
Preparation of film (coupon)
92.6g of prepolymer A2 and 107.4g of slurry B2 are respectively weighed, 200g of the total is weighed, then 0.1g of organozinc catalyst Zn1910 (the manufacturer of the beauty) is weighed and placed in a 300ml stirring cup, and 10g of dimethyl carbonate is additionally added for dilution during configuration for facilitating observation and sample preparation; the stirring cup is placed under a high-speed dispersing machine for dispersing for 2min, the rotating speed of the dispersing machine is 1000rpm, the mixed sample liquid is poured into a tetrafluoro mould after standing for 1min, and the film thickness is controlled to be about 1.5 mm.
TABLE 1 application example 1 and comparative example 1 prepolymer composition formulation
Table 2 slurry composition formulation of application example 1 and comparative example 1
Performance testing
(1-1) observation of the status of the prepolymer
The prepolymer prepared in application example 1 and comparative example 1 was placed in a constant temperature and humidity room for 24 hours, and the state was observed by sampling, and the results are shown in Table 3:
TABLE 3 prepolymer state
Application example 1 Comparative example 1
Appearance state of prepolymer Colorless and transparent Opaque liquid in milky white
As can be seen from table 1, the prepolymer components of application example 1 and comparative example 1 differ only in that: the prepolymer component of application example 1 was free of HT-100 and the prepolymer component of comparative example 1 also contained HT-100. As can be seen from the results of Table 3, the addition of HT-100 resulted in the pre-polymer of comparative example 1 being in a milky opaque state, affecting the appearance of the pre-polymer product, making it unacceptable to downstream customers, and also affecting the storage stability of the pre-polymer.
(2-1) slurry storage stability test
200g of each of the slurries prepared in application example 1 and comparative example 1 was placed in an oven at 50℃and after standing for 24 hours, the storage stability of the slurries was observed, and the results are shown in Table 4:
TABLE 4 results of storage stability test of slurries
As can be seen from table 2, the slurry components of application example 1 and comparative example 1 differ only in that: application example 1 uses a secondary amine crosslinking agent 1# instead of a secondary amine chain extender such as asparagus F420 of comparative example 1. From the results in Table 4, it can be seen that the secondary amine crosslinking agent # 1 is capable of significantly improving the storage stability of the slurry as compared to the secondary amine chain extender.
The slurries prepared in application example 1 and comparative example 1 were left to stand in an open place between constant temperature and humidity for 7 days, and then dispersed again uniformly for use.
(3-1) pot life test
In the preparation process of the sample wafer of application example 1 and comparative example 1, the mixture timing is started from the prepolymer and the slurry, after the mixed sample liquid is poured into a tetrafluoro mould, a scraper is used for scraping long scratches of 10cm vertically at a uniform speed, whether obvious scratches exist or not is observed after 30 seconds, and if no obvious scratches exist, the sample liquid is considered to be still in the pot life. The results are shown in Table 5:
table 5 pot life test results of the films of application example 1 and comparative example 1
From the results of Table 5, it can be seen that the pot life of the system can be significantly prolonged by adding the secondary amine crosslinking agent # 1 to the coating system of example 1 instead of the secondary bis-amine chain extender and HT-100 of comparative example 1.
(4-1) mechanical Property test
After the sample sheet of application example 1 and the sample sheet of comparative example 1 were placed in a constant temperature and humidity room for 7 days, tensile property evaluation was performed in accordance with GB/T19250-2013 polyurethane waterproof paint, and the results are shown in Table 6:
TABLE 6 tensile Property test results of films of application example 1 and comparative example 1
Application example 1 Comparative example 1
Tensile Strength/MPa 5.6 4.2
Elongation at break/% 405 320
From the results of Table 6, it is seen that the tensile strength and elongation at break of the article can be improved by 33% and 26%, respectively, by adding the secondary amine crosslinking agent # 1 to the coating system of example 1 instead of the secondary amine chain extender and HT100 of comparative example 1.
(5-1) Performance test after Heat treatment
The sample of application example 1 and the sample of comparative example 1 were placed in a constant temperature and humidity room for 7 days, and then the sample was placed in an oven at80℃for 7 days according to the heat treatment requirements in the "GB/T19250-2013 polyurethane waterproof paint", and the tensile properties were tested after being placed in the constant temperature and humidity room for 4 hours, and the results are shown in Table 7:
TABLE 7 tensile Property test results after heat treatment of films of application example 1 and comparative example 1
Application example 1 Comparative example 1
Tensile Strength/MPa before Heat treatment 5.6 4.2
Tensile Strength/MPa after Heat treatment 6.3 4.4
Tensile strength increase rate/% 13 5
Elongation at break/% 405 320
Elongation at break/% 393 266
Elongation at break loss rate/% 3 17
As can be seen from Table 7, the coating system of application example 1 has significantly increased strength improvement after heat treatment and significantly reduced elongation at break loss by adding a # 1 secondary amine crosslinker in place of the secondary bis-amine chain extender of comparative example 1 and HT 100.
Example 2
Preparation of secondary amine 2 crosslinker
196.8g of a secondary amine compound 6200 was charged into a 500ml four-necked flask, and 80g of HT-600 was added thereto using a constant pressure dropping funnel; the flask was purged with nitrogen and the reaction temperature was set at 35℃and the stirring speed was 260rpm. And controlling HT-600 to be added dropwise within 0.5h, continuously reacting for 1h, heating to 55 ℃, reacting for 1h, and discharging to obtain the 2# secondary amine crosslinking agent. The 2# secondary amine crosslinker was tested using a Nicolet iS5 fourier transform infrared spectrometer (Thermo fisher brand in the united states) and the infrared spectrum iS shown in figure 2.
2230cm as shown in FIG. 2 -1 The position has no absorption peak, which indicates that the isocyanate group (-NCO) has reacted completely; 1683cm -1 An absorption peak exists at the position, which indicates that the product contains isocyanurate heterocyclic structure; 2872-2960cm -1 An absorption peak exists at the position, which indicates that the product contains a methylene structure; 3343cm -1 An absorption peak was present at the position indicating that the product contained a-NH-secondary amine structure.
Example 3
Preparation of secondary amine 3 crosslinker
221.5g of tetraethyl (F420) of a secondary amine compound N, N' - (methylenedi-4, 1-cyclohexanediyl) di-aspartic acid was added to a 500ml four-necked flask, and 50-gHT-600 was added thereto using a constant pressure dropping funnel; the flask was purged with nitrogen and the reaction temperature was set at 40℃and the stirring speed was 300rpm. And controlling HT-600 to be added dropwise within 0.5h, continuously reacting for 1h, heating to 45 ℃, reacting for 1h, and discharging to obtain the 3# secondary amine crosslinking agent. The 3# secondary amine crosslinker was tested using a Nicolet iS5 fourier transform infrared spectrometer (Thermo fisher brand in the united states) and the infrared spectrum iS shown in figure 3.
As shown in FIG. 3, 2230cm -1 The position has no absorption peak, which indicates that the isocyanate group (-NCO) has reacted completely; 1708cm -1 An absorption peak exists at the position, which indicates that the product contains isocyanurate heterocyclic structure; 2850-2979cm -1 An absorption peak exists at the position, which indicates that the product contains a methylene structure; 3650cm -1 An absorption peak was present at the position indicating that the product contained a-NH-secondary amine structure.
Application example 2
Preparation of prepolymer A3
Polyether polyol C2010, PTMEG2000 and BPA were charged into a flask according to the formulation of application example 2 in Table 8 below, heated to 95℃and dehydrated in vacuo for 2 hours; after the system is cooled to 70 ℃, TDI-80 is added for reaction for 1h, and then the temperature is raised to 90 ℃ for reaction for 3h; and cooling the system to 50 ℃, adding dimethyl carbonate, stirring for 0.5h, and discharging to obtain a prepolymer A3.
Preparation of slurry B3
The slurry B3 was obtained by mixing the various materials of the slurry components according to the formulation of application example 2 in Table 9, dispersing at a high speed of 1500rpm for 1 hour, and discharging.
Preparation of film (coupon)
Separately weighing 135.5g of prepolymer A3 and 64.5g of slurry B3, adding up to 200g, weighing 0.4g of organozinc bismuth catalyst Valikat14H2 (manufacturer's grace department), and placing in a 300ml stirring cup; the stirring cup is placed under a high-speed dispersing machine for dispersing for 2min, the rotating speed of the dispersing machine is 1000rpm, the mixed sample liquid is poured into a tetrafluoro mould after standing for 1min, and the film thickness is controlled to be about 1.5 mm.
Comparative example 2
Preparation of prepolymer A4
Polyether polyol C2010, PTMEG2000 and BPA were added to the flask according to the formulation of comparative example 2 in table 8 below, heated to 95 ℃ and then vacuum dehydrated for 2 hours; after the system is cooled to 70 ℃, TDI-80 is added for reaction for 1h, and then the temperature is raised to 90 ℃ for reaction for 3h; and cooling the system to 70 ℃, adding HT-600, reacting for 1h, cooling the system to 50 ℃, adding dimethyl carbonate, stirring for 0.5h, and discharging to obtain the prepolymer A4.
Preparation of slurry B4
The various materials of the slurry components were mixed and then dispersed at a high speed of 1500rpm according to the formulation of comparative example 2 in table 9, and after 1 hour of dispersion, the slurry B4 was obtained by discharging.
Preparation of film (coupon)
147.4g of prepolymer A4 and 52.6g of slurry B4 are weighed respectively, 200g of the total is added, and then 0.4g of organozinc bismuth catalyst Valikat14H2 (of the manufacturer of the beauty) is weighed and placed in a 300ml stirring cup; the stirring cup is placed under a high-speed dispersing machine for dispersing for 2min, the rotating speed of the dispersing machine is 1000rpm, the mixed sample liquid is poured into a tetrafluoro mould after standing for 1min, and the film thickness is controlled to be about 1.5 mm.
Application example 3
The prepolymer A3 prepared in application example 2 was directly used for the subsequent film preparation.
Preparation of slurry B5
The slurry B5 was obtained by mixing the materials of the slurry components according to the formulation of application example 3 in Table 9, dispersing at a high speed of 1500rpm for 1 hour, and discharging.
Preparation of film (coupon)
120g of prepolymer A3 and 80g of slurry B5 are weighed respectively, 200g of the total is weighed, and then 0.4g of the organozinc bismuth catalyst Valikat14H2 (the manufacturer of the beauty) is placed in a 300ml stirring cup; the stirring cup is placed under a high-speed dispersing machine for dispersing for 2min, the rotating speed of the dispersing machine is 1000rpm, the mixed sample liquid is poured into a tetrafluoro mould after standing for 1min, and the film thickness is controlled to be about 1.5 mm.
Comparative example 3
The prepolymer A4 prepared in comparative example 2 was used directly for the subsequent film preparation.
Preparation of slurry B6
According to the formulation of comparative example 3 in Table 9, the various materials of each slurry component were mixed and then dispersed at a high speed of 1500rpm, and after 1 hour of dispersion, the slurry B6 was obtained by discharging.
Preparation of film (coupon)
128.6g of prepolymer A4 and 71.4g of slurry B6 are weighed respectively, 200g of the total is added, and then 0.4g of organozinc bismuth catalyst Valikat14H2 (of the manufacturer of the beauty) is weighed and placed in a 300ml stirring cup; the stirring cup is placed under a high-speed dispersing machine for dispersing for 2min, the rotating speed of the dispersing machine is 1000rpm, the mixed sample liquid is poured into a tetrafluoro mould after standing for 1min, and the film thickness is controlled to be about 1.5 mm.
TABLE 8 formulation of prepolymer composition for application example 2 and comparative example 2
Table 9 slurry composition formulations of application examples 2 to 3 and comparative examples 2 to 3
Performance testing
(1-2) observation of the status of the prepolymer
The prepolymer A3 of application examples 2 and 3 and the prepolymer A4 of comparative examples 2 and 3 were placed in a constant temperature and humidity room for 24 hours, and the observation state was sampled, and the results are shown in table 10:
table 10 application examples 2 to 3, comparative examples 2 to 3, prepolymer state
Application example 2/application example 3 Comparative example 2/comparative example 3
Appearance state of prepolymer Colorless and transparent Opaque liquid in milky white
As can be seen from table 10, the prepolymers of application examples 2 and 3 differ from those of comparative examples 2 and 3 only in that: the prepolymer A3 of application examples 2, 3 was free of HT-600, and the prepolymer A4 of comparative examples 2, 3 also contained HT-600. As can be seen from the results of Table 10, the addition of HT-600 resulted in the pre-polymer A4 of comparative examples 2 and 3 being milky opaque, which affected the appearance of the pre-polymer product, making it unacceptable to downstream customers, and also affecting the storage stability of the pre-polymer.
(2-2) storage stability test of slurry
200g of each of the slurries prepared in application examples 2 and 3 and comparative examples 2 and 3 was placed in an oven at 50℃and after standing for 24 hours, the storage stability of the slurries was observed, and the results are shown in Table 4:
table 11 the results of the slurry storage stability test of examples 2 to 3 and comparative examples 2 to 3 were applied
As can be seen from table 9, the slurry components of application example 2 differ from those of comparative example 2 only in that: application example 2 replaced the 6200 bis-secondary amine chain extender of comparative example 2 with a # 2 secondary amine crosslinker; application example 3 differs from comparative example 3 only in the slurry components: application example 3 the F420 secondary amine chain extender of comparative example 3 was replaced with a 3# secondary amine crosslinker. From the results in table 11, it can be seen that the secondary amine 2# crosslinking agent is capable of significantly improving the storage stability of the slurry compared to the 6200 secondary amine chain extender; the 3# secondary amine crosslinker can significantly improve the storage stability of the slurry compared to the F420 secondary amine chain extender.
(3-2) pot life test
In the preparation process of the sample sheets of application examples 2 to 3 and comparative examples 2 to 3, the mixture of the prepolymer and the slurry is started, after the mixed sample liquid is poured into a tetrafluoro mold, a scraper is used for scraping long scratches of 10cm at a constant speed vertically, whether obvious scratches exist or not is observed after 30 seconds, and if no obvious scratches exist, the sample liquid is considered to be still in the applicable period. The results are shown in Table 12:
table 12 pot life test results using the films of examples 2 to 3, comparative examples 2 to 3
Application example 2 Comparative example 2 Application example 3 Comparative example 3
Pot life evaluation Pot life of 50min 26min pot life 56min pot life 21min pot life
From the results in Table 12, it can be seen that the pot life of the system can be significantly prolonged by adding a secondary 2 amine crosslinker instead of the secondary bis-amine chain extender 6200 and HT-600 of comparative example 2 to the coating system of example 2; application example 2 has a 92.3% longer pot life than comparative example 2. Similarly, the pot life of the coating system of application example 3 can be significantly extended by adding a 3# secondary amine crosslinker in place of the di-secondary amine chain extender of comparative example 3, f$20 and HT-600; application example 3 showed a 166% longer pot life than comparative example 3.
(4-2) mechanical Property test
After the sample sheets of application examples 2 to 3 and the sample sheets of comparative examples 2 to 3 were placed between constant temperature and constant humidity for 7 days, tensile property evaluation was performed in accordance with GB/T19250-2013 polyurethane waterproof paint, and the results are shown in Table 13:
table 13 tensile property test results of films of application examples 2 to 3, comparative examples 2 to 3
Application example 2 Comparative example 2 Application example 3 Comparative example 3
Tensile Strength/MPa 12.8 9.2 14.1 10.5
Breaking extensionLong rate/% 601 450 540 397
From the results of Table 13, it can be seen that the tensile strength and elongation at break of the article can be improved by 39% and 34%, respectively, by adding a secondary 2 amine crosslinker instead of the secondary bis-amine chain extender 6200 and HT600 of comparative example 2 to the coating system of example 2. Similarly, the coating system of application example 3 can provide 34% and 36% improvement in tensile strength and elongation at break, respectively, of the article by adding a 3# secondary amine crosslinker in place of the secondary amine chain extenders F420 and HT600 of comparative example 3.
(5-2) Performance test after Heat treatment
The test pieces of application examples 2 to 3 and the test pieces of comparative examples 2 to 3 were placed in a constant temperature and humidity room for 7 days, and then the test pieces were placed in an oven at80℃for 7 days according to the heat treatment requirements in the "GB/T19250-2013 polyurethane waterproof paint", and the test pieces were taken out and placed in the constant temperature and humidity room for 4 hours, and the tensile properties were tested as shown in Table 14:
table 14 results of tensile property test after heat treatment using the films of examples 2 to 3, comparative examples 2 to 3
As can be seen from Table 14, the coating system of application example 2 significantly increased the strength improvement after heat treatment of the article and significantly reduced the elongation at break loss by adding a 2# secondary amine crosslinker in place of the bis-secondary amine chain extender 6200 and HT600 of comparative example 2. Similarly, the coating system of application example 3 significantly increased the strength improvement after heat treatment of the article and significantly reduced the loss of elongation at break by adding a 3# secondary amine crosslinker in place of the di-secondary amine chain extenders F420 and HT600 of comparative example 3.
Application example 2-1
Preparation of prepolymer A5
Polyether polyol C2010, PTMEG1000 and 1, 4-butanediol were added to the flask according to the formulation of application example 2-1 in Table 15 below, heated to 95℃and dehydrated in vacuo for 2 hours; cooling the system to 70 ℃, adding IPDI, reacting for 1h, and then heating to 100 ℃ to react for 6h; and cooling the system to 50 ℃ and discharging to obtain a prepolymer A5.
Table 15 prepolymer composition formulation of application example 2-1
Component (A) Manufacturing factories Dosage (parts by mass)
Polyether polyol C2010 Wanhua chemistry 100
PTMEG1000 Large continuous chemical industry 100
1, 4-butanediol Alatine 8
Polyisocyanate IPDI Wanhua chemistry 130
Total amount of 338
Preparation of slurry B3-1
300g of B3 was weighed into a stirring cup, 9g of titanium pigment (brand R706, yingchuang Co.) was added thereto, stirred for 30 minutes at 1000rpm using a high-speed disperser, and discharged to obtain slurry B3-1.
Preparation of film (coupon)
108.3g of prepolymer A5 and 91.7g of slurry B3-1 are weighed respectively, 200g are added up, and then 0.4g of organometallic catalyst BiCAT8018 (leading in the United states of America of manufacturer) is weighed and placed in a 300ml stirring cup; the stirring cup is placed under a high-speed dispersing machine for dispersing for 2min, the rotating speed of the dispersing machine is 1000rpm, the mixed sample liquid is poured into a tetrafluoro mould after standing for 1min, and the film thickness is controlled to be about 1.5 mm.
Application example 3-1
The prepolymer A5 prepared in application example 2-1 was directly used for the subsequent film preparation.
Preparation of slurry B5-1
300g of B5 was weighed into a stirring cup, 7.5g of titanium pigment (brand R706, yingchuang Co.) was further added, and stirred at 1000rpm for 30 minutes using a high-speed disperser, and discharged to obtain slurry B5-1.
Preparation of film (coupon)
90.7g of prepolymer A5 and 109.3g of slurry B5-1 are weighed respectively, 200g are added up, and then 0.4g of organometallic catalyst BiCAT8018 (leading in the United states of America of manufacturer) is weighed and placed in a 300ml stirring cup; the stirring cup is placed under a high-speed dispersing machine for dispersing for 2min, the rotating speed of the dispersing machine is 1000rpm, the mixed sample liquid is poured into a tetrafluoro mould after standing for 1min, and the film thickness is controlled to be about 1.5 mm.
(6) Yellowing resistance test
The samples of application example 2-1 and the samples of application example 3-1 were first placed in a constant temperature and humidity room and treated for 7 days, and then Lab values of the samples were measured using a color meter (CR-10, ke Sheng Jib Co., ltd.). Then, the sample was placed in an ultraviolet aging oven (GT-7035-UB, high-speed rail equipment Co., ltd.) to be aged, and the irradiation power was 30w for 72 hours. After irradiation, the sample was taken out, and the Lab value of the sample was measured again using a color meter.
Lab values represent luminance (L), red-green shade (a), and yellow-blue shade (b), respectively. Δb+ is the post-irradiation b value minus the pre-irradiation b value, and is used to indicate the degree of yellowing. The Lab and Deltab+ values of the two groups of samples before and after irradiation are shown in Table 16:
TABLE 16 yellowing resistance test data for samples of application example 2-1 and application example 3-1
Application example 2-1 Application example 3-1
Lab value before irradiation L 93.5，a-9.2，b+4.9 L 97.0，a-9.5，b+3.7
Lab value after irradiation L 90.3，a-8.4，b+29.4 L 95.6，a-9.6，b+5.3
Δb+ before and after irradiation 24.5 1.6
As can be seen from Table 16, the 3# secondary amine crosslinking agent used in application example 3-1 has good yellowing resistance and can be applied to top coating; the secondary amine crosslinking agent # 2 used in application example 2-1 is not yellowing resistant and is suitable for coating applications that are not exposed or have no yellowing resistance requirements.
Unless otherwise defined, all terms used herein are intended to have the meanings commonly understood by those skilled in the art.
The described embodiments of the present invention are intended to be illustrative only and not to limit the scope of the invention, and various other alternatives, modifications, and improvements may be made by those skilled in the art within the scope of the invention, and therefore the invention is not limited to the above embodiments but only by the claims.

Claims (10)

1. A compound having the structure:
wherein R is 11 、R 21 、R 31 Identical or different and independently of one another selected from sec-butyl or (CH) 3 CH 2 OOCCH 2 )(CH 3 CH 2 OOC)CH-；R 12 、R 22 、R 32 Identical or different and are selected, independently of one another, from the following structures:
2. use of a compound according to claim 1 as a cross-linking agent in polyurethane urea coatings.
3. A preparation method of a secondary amine cross-linking agent comprises the steps of reacting hexamethylene diisocyanate trimer with a bis-secondary amine compound to prepare the secondary amine cross-linking agent; wherein the bis-secondary amine compound is selected from one or more of 4,4' -bis-secondary butylaminodiphenyl methane, 4' -bis-secondary butylaminodicyclohexyl methane and N, N ' - (methylenedi-4, 1-cyclohexanediyl) diethyl aspartate.
4. The production process according to claim 3, wherein the molar ratio of N, N ' - (methylenebis-4, 1-cyclohexanediyl) diethyl aspartate, 4' -bis-secondary butylaminodiphenyl methane to 4,4' -bis-secondary butylaminodicyclohexyl methane in the bis-secondary amine compound is 1 (0 to 10): 0 to 1; or,
the molar ratio of the 4,4' -di-sec-butylaminodiphenyl methane, N ' - (methylenedi-4, 1-cyclohexanediyl) diethyl aspartate to the 4,4' -di-sec-butylaminodicyclohexyl methane is 1 (0-10) (0-1).
5. The production method according to claim 3, wherein the reaction temperature of the reaction is 20 to 80 ℃, further 30 to 50 ℃; and/or the number of the groups of groups,
the reaction time of the reaction is 1-10 h, and further 2-8 h; and/or the number of the groups of groups,
the molar ratio of the bis-secondary amine compound to the hexamethylene diisocyanate trimer is 3-10:1.
6. A polyurethaneurea coating composition comprising a prepolymer component and a slurry component; the prepolymer component comprises a polyether polyol and a polyisocyanate, and the slurry component comprises a crosslinker comprising the compound of claim 1 or the secondary amine crosslinker produced by the production process of any one of claims 3 to 5.
7. The composition according to claim 6, wherein the prepolymer component comprises 30 to 85 parts by mass of the polyether polyol and 10 to 50 parts by mass of the polyisocyanate, and the slurry component comprises 15 to 80 parts by mass of the crosslinking agent; and/or the number of the groups of groups,
the composition includes a catalyst component including an organometallic catalyst; or,
the prepolymer component comprises 30-85 parts by mass of polyether polyol, 10-50 parts by mass of polyisocyanate, 1-10 parts by mass of small molecular alcohol and 0-20 parts by mass of first plasticizer and/or solvent; and/or the number of the groups of groups,
the slurry comprises 15 to 80 parts by mass of the cross-linking agent, 5 to 20 parts by mass of the second plasticizer, 0 to 10 parts by mass of the auxiliary chain extender, 0 to 10 parts by mass of the auxiliary agent and/or the solvent and 10 to 60 parts by mass of the inorganic filler.
8. The composition according to claim 7, wherein the mass of the catalyst component is 0.05 to 0.6% of the mass of the composition; and/or the number of the groups of groups,
the catalyst component comprises one or more of zinc neodecanoate, bismuth neodecanoate and dibutyltin dilauryl sulfide; and/or the number of the groups of groups,
the average functionality of the polyether polyol is 2-3, and the weight average molecular weight is 1000-6500; and/or the number of the groups of groups,
the polyisocyanate comprises one or more of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate and dicyclohexylmethane diisocyanate; and/or the number of the groups of groups,
the small molecular alcohol is selected from one or more of trimethylolpropane, 1, 4-butanediol, ethylene glycol, propylene glycol and bisphenol A; and/or the number of the groups of groups,
the first plasticizer and the second plasticizer are respectively and independently selected from one or more of long-chain chlorinated paraffin, triethylene glycol diisooctyl ester, acetyl tributyl citrate, dioctyl terephthalate, methyl chloropalmitoleate and methyl epoxidized soyate; and/or the number of the groups of groups,
the auxiliary chain extender is selected from one or more of dimethyl sulfide diamino toluene, 3, 5-diethyl toluene diamine, 4' -di-sec-butylamino diphenyl methane, 1, 4-di-sec-butylamino benzene, isophorone diamine, diamino dicyclohexylmethane and aspartic acid resin; and/or the number of the groups of groups,
the inorganic filler is one or more selected from calcium carbonate, talcum powder, kaolin, white carbon black and magnesium oxide; and/or the number of the groups of groups,
the auxiliary agent comprises one or more of a defoaming agent, a dispersing agent and an anti-settling agent; and/or the number of the groups of groups,
the solvent is selected from one or more of dimethyl carbonate, ethyl acetate, butyl acetate and propylene carbonate.
9. A polyurethaneurea coating prepared from the polyurethaneurea coating composition of any one of claims 6 to 8, wherein the polyurethaneurea coating comprises a prepolymer and a slurry; the prepolymer is made from the prepolymer component and the slurry is made from the slurry component.
10. A coating formed by the polyurethaneurea coating of claim 9.
CN202311260424.7A 2023-09-27 2023-09-27 Compound, preparation method thereof and application of compound in polyurethane urea coating Pending CN117327024A (en)

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