A compound, a method for preparing the same, and an application thereof in polyurethane urea coating

Abstract

The present application relates to a kind of compound, its preparation method and application in polyurethane urea coating, the compound has the following structure;Wherein, R 11 , R 21 , R 31 Same or different, and each other independently selected from sec-butyl or (CH3CH2OOCCH2) (CH3CH2OOC) CH-;R 12 , R 22 , R 32 Same or different, and each other independently selected from methylenediphenyl or methylenedicyclohexyl.The compound of one embodiment of the present application can be used as a crosslinking agent for polyurethane urea coating, with the characteristics of extending the pot life of the formulation system (slurry system and prepolymer system) mixed construction, enhancing the storage stability of slurry system and improving the strength, elongation at break and thermal properties of the final coating product.

Description

Technical Field

[0001] This invention relates to secondary amine crosslinking agents, and more particularly to a secondary amine crosslinking agent for use in polyurethane urea coatings. Background Technology

[0002] HDI trimer (hexamethylene diisocyanate trimer) is often used in combination with flexible polyether-modified isocyanate prepolymers to produce elastic polyurethane urea materials. However, the resulting material system has a short pot life. Furthermore, if the system contains a high concentration of terminal amine compounds, the HDI trimer has a high probability of forming polymers exceeding the "ABA" structure. These polymers contain more urea bonds and often precipitate during the system's maturation process, affecting chain growth and distribution within the material and leading to a decline in material performance. Additionally, when physically mixing HDI trimer and isocyanate prepolymers, incompatibility can easily occur. The two originally clear and transparent liquids become milky white after mixing, affecting the appearance of the isocyanate component and making it unacceptable to downstream customers. It also affects the storage stability of this component.

[0003] On the other hand, secondary amine chain extenders are commonly used terminal amine compounds in the production of polyurethane urea materials. However, most common secondary amine compounds have linear structures and low crosslinking degrees, which have a certain impact on the strength and heat resistance of polyurethane segments. Furthermore, in slurry systems containing plasticizer liquid fillers, calcium carbonate, and talc solid fillers, amine chain extenders can reduce the storage stability of the system, making it more prone to filler sedimentation.

[0004] For example, a prior art discloses an HDI trimer-type urethane component that can be added to an aspartic polyurea formulation to prepare polyurea coatings. This HDI trimer-type urethane component is a product of end-capping an HDI trimer with a monofunctional alcohol (such as methanol). However, the end groups of this HDI trimer-type urethane component do not contain isocyanate groups or active hydrogen groups, and therefore do not participate in subsequent chemical reactions in the disclosed aspartic polyurea formulation; instead, it exists as an organic filler. Therefore, this component cannot solve problems such as extending the pot life of the system, enhancing the storage stability of the slurry system, or improving the strength and thermal properties of linear difunctional secondary amine chain extenders.

[0005] For example, another prior art discloses a polyasparagine ester, which is a bifunctional secondary amine compound generated by the reaction of an unsaturated diester acid ester and a diamine. It also suffers from the problem of low strength and thermal properties of linear bifunctional secondary amine chain extenders. Summary of the Invention

[0006] To overcome at least one of the defects of the prior art, in a first aspect, one embodiment of the present invention provides a compound having the following structure:

[0007]

[0008] Among them, R 11 R 21 R 31 They may be the same or different, and are independently selected from sec-butyl or (CH3CH2OOCCH2)(CH3CH2OOC)CH-; R 12 R 22 R 32 The same or different, and independently selected from the following methylene diphenyl or methylene dicyclohexyl groups:

[0009]

[0010] Secondly, one embodiment of the present invention provides the application of the above-mentioned compound as a crosslinking agent in polyurethane urea coatings.

[0011] Thirdly, one embodiment of the present invention provides a method for preparing a secondary amine crosslinking agent, comprising reacting a hexamethylene diisocyanate trimer with a bis-secondary amine compound to obtain the secondary amine crosslinking agent; wherein the bis-secondary amine compound is selected from one or more of 4,4'-bis-sec-butylaminodiphenylmethane, 4,4'-bis-sec-butylaminodicyclohexylmethane, and N,N'-(methylenedi-4,1-cyclohexanediyl)diaspartic acid tetraethyl ester.

[0012] Fourthly, one embodiment of the present invention provides a polyurethane urea 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 crosslinking agent, wherein the crosslinking agent comprises the above-mentioned compound or a secondary amine crosslinking agent prepared by the above-mentioned preparation method.

[0013] Fifthly, one embodiment of the present invention provides a polyurethane urea coating, which is prepared from the above-described polyurethane urea coating composition, wherein the polyurethane urea coating comprises a prepolymer and a slurry; the prepolymer is prepared by the prepolymer component, and the slurry is prepared by the slurry component.

[0014] In a sixth aspect, one embodiment of the present invention provides a coating prepared from the above-described polyurethane urea coating composition.

[0015] The compound of one embodiment of the present invention can be used as a crosslinking agent for polyurethane urea coatings, and has the characteristics of extending the pot life of the AB component (slurry system and prepolymer system) of the formulation system during mixed construction, enhancing the storage stability of the slurry system, and improving the strength, elongation at break and thermal properties of the final coated product. Attached Figure Description

[0016] The accompanying drawings are for illustrative purposes only and are not intended to limit the scope of the invention. Wherein:

[0017] Figure 1 The infrared spectrum of the No. 1 secondary amine crosslinking agent prepared in Example 1 of this invention;

[0018] Figure 2 The infrared spectrum of the 2# secondary amine crosslinking agent prepared in Example 2 of this invention;

[0019] Figure 3 The infrared spectrum of the 3# secondary amine crosslinking agent prepared in Example 3 of this invention. Detailed Implementation

[0020] Typical embodiments embodying the features and advantages of the present invention will be described in detail in the following description. It should be understood that the present invention can have various variations in different embodiments without departing from the scope of the present invention, and the description herein is for illustrative purposes only and not intended to limit the present invention.

[0021] One embodiment of the present invention provides a compound having the following structure:

[0022]

[0023] Among them, R 11 R 21 R 31 They may be the same or different, and are independently selected from sec-butyl or (CH3CH2OOCCH2)(CH3CH2OOC)CH-; R 12 R 22 R 32 The same or different, and independently selected from the following methylene diphenyl or methylene dicyclohexyl groups:

[0024]

[0025] In one embodiment, the above-mentioned compound can be used as a crosslinking agent in polyurethane urea coatings.

[0026] One embodiment of the present invention provides a secondary amine crosslinking agent that can be used in polyurethane urea coatings, comprising one or more of the above-described compounds.

[0027] 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 obtain the secondary amine crosslinking agent; wherein the bis-secondary amine compound is selected from one or more of 4,4'-bis-sec-butylaminodiphenylmethane, 4,4'-bis-sec-butylaminodicyclohexylmethane, and N,N'-(methylenedi-4,1-cyclohexanediyl)diaspartic acid tetraethyl ester.

[0028] In one embodiment, the reaction formula between the HDI trimer and the diamine compound is as follows:

[0029]

[0030] Among them, Rx1-NH-Rx2-NH-Rx1 is a diamine compound, and Rx1 can be any of the above-mentioned R... 11 R 21 or R 31 Rx2 can be the R mentioned above. 12 R 22 or R 32 R 11 R 21 R 31 R 12 R 22 R 32 With R in Equation I 11 R 21 R 31 R 12 R 22 R 32 The same. Furthermore, in the preparation of the secondary amine crosslinking agent, a bis-secondary amine compound is used for the reaction, then R in the above reaction formula... 11 R 21 R 31 For the same group, R 12 R 22 R 32 If the same functional group is used, and two or more secondary amine compounds are used in the reaction, then R in the above reaction formula will be... 11 R 21 R 31 Not exactly the same, R 12 R 22 R 32 They are not exactly the same.

[0031] In one embodiment, the secondary diamine compound used may be, for example, N,N'-(methylenedi-4,1-cyclohexanediyl)diaspartic acid tetraethyl ester or 4,4'-bis-sec-butylaminodiphenylmethane, used alone, or a mixture of multiple secondary diamine compounds may be used; for example, the molar ratio of N,N'-(methylenedi-4,1-cyclohexanediyl)diaspartic acid tetraethyl ester, 4,4'-bis-sec-butylaminodiphenylmethane, and 4,4'-bis-sec-butylaminodicyclohexylmethane may be 1:(0-10):(0-1), and more preferably 1: (0.1~10):(0.1~1), for example 1:1:0.5, 1:3:1, 1:5:1, 1:8:1; or, the molar ratio of 4,4'-bis-sec-butylaminodiphenylmethane, N,N'-(methylenedi-4,1-cyclohexanediyl)diaspartic acid tetraethyl ester to 4,4'-bis-sec-butylaminodicyclohexylmethane is 1:(0~10):(0~1), and can further be 1:(0.1~10):(0.1~1), for example 1:1:0.5, 1:3:1, 1:5:1, 1:8:1.

[0032] In one embodiment, the HDI trimer may be one or more of Wanhua Chemical's HT-100, HT-300, and HT-600.

[0033] In one embodiment, the molar ratio of the di-secondary amine compound to the HDI trimer can be 3 to 10:1, and more preferably 4 to 7:1, such as 5:1 or 6:1.

[0034] In one embodiment, the reaction of the HDI trimer with the diamine compound is carried out in an inert gas atmosphere, such as a nitrogen atmosphere.

[0035] In one embodiment, the reaction temperature of the HDI trimer with the diamine compound can be 20–80°C, and more preferably 30–50°C, such as 35°C, 40°C, 45°C, 60°C, or 70°C; the reaction time can be 1–10 h, and more preferably 2–8 h, such as 3 h, 4 h, 5 h, 6 h, or 7 h.

[0036] In one embodiment, the preparation method of the secondary amine crosslinking agent includes: slowly adding HDI trimer dropwise to a bis-secondary amine compound under a nitrogen atmosphere, and carrying out an addition reaction under a certain reaction temperature, normal pressure, and stirring.

[0037] In one embodiment, the stirring speed of the reaction system of HDI trimer and diamine compound can be 100-400 rpm, or more specifically 150-300 rpm, such as 200 rpm or 250 rpm.

[0038] One embodiment of the present invention provides a polyurethane urea 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 crosslinking agent, which includes the aforementioned compound or the aforementioned secondary amine crosslinking agent. Further, the prepolymer component may include a polyether polyol, a polyisocyanate, and a small molecule alcohol.

[0039] In one embodiment, the polyurethane urea coating composition includes a prepolymer component, a slurry component, and a catalyst component.

[0040] In one embodiment, the prepolymer component includes 30 to 85 parts by weight of polyether polyol and 10 to 50 parts by weight of polyisocyanate, and the slurry component includes 15 to 80 parts by weight of crosslinking agent.

[0041] In one embodiment, the prepolymer component comprises 40 to 80 parts by weight of polyether polyol and 10 to 25 parts by weight of polyisocyanate, and the slurry component comprises 20 to 60 parts by weight of crosslinking agent.

[0042] In one embodiment, the prepolymer component comprises 30-85 parts by weight of polyether polyol, 10-50 parts by weight of polyisocyanate, 1-10 parts by weight of small molecule alcohol, and 0-20 parts by weight of first plasticizer and / or solvent; further, the prepolymer component comprises 40-80 parts by weight of polyether polyol, 10-25 parts by weight of polyisocyanate, 2-5 parts by weight of small molecule alcohol, and 5-20 parts by weight of first plasticizer and / or solvent.

[0043] In one embodiment, the slurry component includes 15-80 parts by weight of a crosslinking agent, 5-20 parts by weight of a second plasticizer, 0-10 parts by weight of a chain extender (e.g., 1 part by weight), 0-10 parts by weight of an additive and / or a solvent, and 10-60 parts by weight of an inorganic filler; further, the slurry component includes 30-60 parts by weight of a crosslinking agent, 10-15 parts by weight of a second plasticizer, 0-5 parts by weight of a chain extender, 2-5 parts by weight of an additive and / or a solvent, and 35-50 parts by weight of an inorganic filler.

[0044] In one embodiment, the isocyanate index of the polyurethane urea coating composition is 1 to 1.5, more specifically 1.03 to 1.3.

[0045] In one embodiment, the mass of the catalyst component is 0.05 to 0.6% of the mass of the polyurethane urea coating composition, for example, 0.1%, 0.2%, 0.3%, 0.4%, or 0.5%.

[0046] In one embodiment, the catalyst component includes an organometallic catalyst, further comprising an environmentally friendly organometallic catalyst. The catalyst component may include one or more of zinc neodecanoate, bismuth neodecanoate, and di(dodecyl sulfide)dibutyltin, such as leading US companies BiCAT8018 and BiCAT Z, Umicore Bi2010, Zn1910, and Valikat14H2, and Evonik Dabco T-120, etc.

[0047] 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, polyethylene oxide polyol, polyethylene oxide-propylene copolymer polyol, and polytetrahydrofuran polyol.

[0048] In one embodiment, the polyether polyol may be one or more of Wanhua Chemical's C2010, C2020, C2040, C2140, F3135, and F3056D, or Dalian Chemical's PTMEG1000, PTMEG2000, etc.

[0049] In one embodiment, the polyisocyanate may be a diisocyanate or its derivatives.

[0050] In one embodiment, the polyisocyanate includes one or more of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, and dicyclohexylmethane diisocyanate; for example, one or more of Wanhua Chemical's MDI-50, MDI-100, MDI-100LL, TDI-80, TDI-100, TDI-60, IPDI, and HMDI.

[0051] In one embodiment, the equivalent ratio of polyisocyanate TDI-80 to the active hydrogen component (polyether polyol and small molecule alcohol) is not greater than 2.

[0052] 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), and bisphenol A (BPA).

[0053] In one embodiment, the first plasticizer and the second plasticizer are each independently selected from one or more of environmentally friendly long-chain chlorinated paraffins (such as 52# chlorinated paraffin from Shandong Yanhai), triethylene glycol diisooctanoate (3G8), acetyl tributyl citrate (ATBC), dioctyl terephthalate (DOTP), chloropalmitoyl methyl ester and epoxidized soybean oleate methyl ester.

[0054] In one embodiment, the chain extender may be a liquid amine chain extender, such as one or more selected from dimethylthiodiaminotoluene (DMTDA), 3,5-diethyltoluenediamine (DETDA), 4,4'-bis(sec-butylamino)diphenylmethane (MDBA), 1,4-bis(sec-butylamino)benzene, isophorone diamine, diaminodicyclohexylmethane, and aspartic acid resin. For example, the chain extender may be Albemarle's E300 and E100, or Wanhua Chemical's Wanalink 6200, Wanalink 1104, Wanamine IPDA, and Wanamine H. 12 MDA refers to one or more of Shenzhen Feiyang's F420, F520, and F220.

[0055] In one embodiment, the inorganic filler is selected from one or more of calcium carbonate, talc, kaolin, silica, and magnesium oxide, such as 800 mesh calcium carbonate (Yangshan Calcium Carbonate Plant) and 1250 mesh talc (Yongfeng Chemical).

[0056] In one embodiment, the additives include one or more of defoamers, dispersants, and antisettling agents.

[0057] In one embodiment, the solvent is selected from one or more of dimethyl carbonate, ethyl acetate, butyl acetate, and propylene carbonate.

[0058] One embodiment of the present invention provides a polyurethane urea coating, which is prepared from the above-mentioned polyurethane urea coating composition, wherein the polyurethane urea coating includes a prepolymer system and a slurry system; the prepolymer is prepared by the prepolymer component, and the slurry is prepared by the slurry component.

[0059] In one embodiment, the polyurethane urea coating includes the catalyst components described above.

[0060] In one embodiment, the materials of the prepolymer component can be mixed and reacted to obtain a prepolymer system; the materials of the slurry component can be physically mixed to obtain a slurry system; the preparation of the prepolymer system and the slurry system can be carried out according to existing preparation methods.

[0061] One embodiment of the present invention provides a method for preparing a polyurethane urea coating, comprising the following steps: adding a prepolymer system, a slurry system and a catalyst component into a stirrer and dispersing for 1 to 2 minutes, then pouring the uniformly dispersed material into a mold and allowing it to mature.

[0062] One embodiment of the present invention provides a coating prepared from the above-described polyurethane urea coating composition.

[0063] The compound of one embodiment of the present invention can be used as a crosslinking agent for polyurethane urea coatings, and has the characteristics of extending the pot life of the system, enhancing the storage stability of the slurry system, and improving the strength and thermal properties of the coating.

[0064] The compound of one embodiment of the present invention can be used as a crosslinking agent for polyurethane urea coatings, which can improve the pot life of HDI trimer and, to a certain extent, avoid the incompatibility that occurs when HDI trimer and isocyanate prepolymer are cold-blended in the prior art.

[0065] The compound of one embodiment of the present invention can be used as a crosslinking agent for polyurethane urea coatings, which can reduce the catalytic effect of water on the aspartic polyurea system in existing polyurethane urea coating materials and extend the pot life of the system.

[0066] The secondary amine crosslinking agent and polyurethane urea coating of one embodiment of the present invention will be further described below with reference to the accompanying drawings and specific embodiments.

[0067] Example 1

[0068] Preparation of #1 secondary amine crosslinking agent

[0069] (1) The raw materials were prepared according to the molar ratio of N,N'-(methylene di-4,1-cyclohexanediyl) diaspartic acid tetraethyl ester (Shenzhen Feiyang Company F420): 4,4'-bis-sec-butylaminodiphenylmethane (MDBA, Wanhua Chemical Wanalink 6200) = 2:1 to obtain secondary amine composition A; the raw materials were prepared according to the molar ratio of F420:6200:4,4'-bis-sec-butylaminodicyclohexylmethane (India DK Company Cl1000) = 0.1:1.8:0.1 to obtain secondary amine composition B.

[0070] (2) Add 142.6g of secondary amine composition A to a 500ml four-necked flask. Add 67.5g of HT-100 to the flask using a constant-pressure dropping funnel. Purge the flask with nitrogen to replace the air. Set the reaction temperature to 30℃ and the stirring speed to 200rpm. Complete the addition of HT-100 within 0.5h, and react for another 1h. Then add 64.6g of secondary amine composition B to the four-necked flask and continue the reaction for 1h. Raise the temperature to 50℃ and react for another 1h before discharging to obtain secondary amine crosslinking agent #1. The secondary amine crosslinking agent #1 was tested using a Nicolet iS5 Fourier transform infrared spectrometer (Thermo Fisher brand, USA). The infrared spectrum is shown below. Figure 1 .

[0071] like Figure 1 As shown, 2230cm -1 The absence of an absorption peak at this position indicates that the isocyanate group (-NCO) has completely reacted; 1686 cm⁻¹ -1The presence of absorption peaks at the specified positions indicates that the product contains an isocyanurate heterocyclic structure; 2853-2963 cm⁻¹ -1 The presence of absorption peaks at these positions indicates that the product contains a methylene structure; 3340, 3649 cm⁻¹ -1 The presence of an absorption peak at the position indicates that the product contains a -NH-secondary amine structure.

[0072] Application Example 1

[0073] Preparation of prepolymer A1

[0074] According to the formulation of Application Example 1 in Table 1 below, polyether polyols C2010, C2020, F3135 and 1,4-butanediol were added to a flask and dehydrated under vacuum at 95°C for 2 hours. After cooling the system to 70°C, TDI-80 was added and reacted for 1 hour, then the temperature was raised to 90°C and reacted for 4 hours. After that, plasticizer 3G8 was added to the flask, and the mixture was cooled to 50°C and discharged to obtain prepolymer A1.

[0075] Preparation of slurry B1

[0076] According to the formulation of Application Example 1 in Table 2, the various materials of the slurry components are mixed and dispersed at high speed at 1500 rpm for 1 hour, and then slurry B1 is discharged.

[0077] Preparation of membrane (sample)

[0078] Weigh out 87g of prepolymer A1 and 113g of slurry B1, totaling 200g. Then weigh out 0.1g of organic zinc catalyst Zn1910 (manufacturer Umicore) and place it in a 300ml mixing cup. To facilitate observation and sample preparation, add an extra 10g of dimethyl carbonate for dilution during preparation. Place the mixing cup under a high-speed disperser at 1000rpm for 2 minutes. After standing for 1 minute, pour the mixed sample solution into a PTFE mold, controlling the film thickness to be about 1.5mm.

[0079] Comparative Example 1

[0080] Preparation of prepolymer A2

[0081] According to the formulation of Comparative Example 1 in Table 1 below, polyether polyols C2010, C2020, F3135 and 1,4-butanediol were added to a flask and dehydrated under vacuum at 95°C for 2 hours. After cooling the system to 70°C, TDI-80 was added and reacted for 1 hour, then the temperature was raised to 90°C and reacted for 4 hours. After that, plasticizers 3G8 and HT-100 were added to the flask, and the mixture was cooled to 50°C and discharged to obtain prepolymer A2.

[0082] Preparation of slurry B2

[0083] According to the formulation of Comparative Example 1 in Table 2, the various materials of the slurry components were mixed and dispersed at high speed at 1500 rpm for 1 hour, and then slurry B2 was discharged.

[0084] Preparation of membrane (sample)

[0085] Weigh out 92.6g of prepolymer A2 and 107.4g of slurry B2, totaling 200g. Then weigh out 0.1g of organic zinc catalyst Zn1910 (manufacturer Umicore) and place it in a 300ml mixing cup. To facilitate observation and sample preparation, add an extra 10g of dimethyl carbonate for dilution during preparation. Place the mixing cup in a high-speed disperser at 1000rpm for 2 minutes. After standing for 1 minute, pour the mixed sample solution into a PTFE mold, controlling the film thickness to be about 1.5mm.

[0086] Table 1. Prepolymer component formulations for Application Example 1 and Comparative Example 1

[0087]

[0088] Table 2. Slurry composition formulations for Application Example 1 and Comparative Example 1.

[0089]

[0090]

[0091] Performance testing

[0092] (1-1) Observation of the state of the prepolymer

[0093] The prepolymers prepared in Application Example 1 and Comparative Example 1 were placed in a constant temperature and humidity room for 24 hours, and samples were taken to observe their condition. The results are shown in Table 3.

[0094] Table 3 Prepolymer State

[0095] Application Example 1 Comparative Example 1 Appearance of the prepolymer Colorless and transparent It is a milky white, opaque liquid.

[0096] As shown in Table 1, the only difference between the prepolymer components of Application Example 1 and Comparative Example 1 is that the prepolymer component of Application Example 1 does not contain HT-100, while the prepolymer component of Comparative Example 1 does contain HT-100. As shown in Table 3, the addition of HT-100 makes the prepolymer of Comparative Example 1 appear milky white and opaque, affecting the appearance of the prepolymer product and making it unacceptable to downstream customers. It also affects the storage stability of the prepolymer.

[0097] (2-1) Slurry storage stability test

[0098] 200g of each of the slurries prepared in Application Example 1 and Comparative Example 1 were placed in an oven at 50℃ and allowed to stand for 24 hours. The storage stability of the slurries was then observed, and the results are shown in Table 4.

[0099] Table 4 Results of slurry storage stability test

[0100]

[0101] As shown in Table 2, the only difference between the slurry components of Application Example 1 and Comparative Example 1 is that Application Example 1 uses a No. 1 secondary amine crosslinking agent instead of the aspartic resin F420 and other diamine chain extenders used in Comparative Example 1. The results in Table 4 show that, compared to the diamine chain extender, the No. 1 secondary amine crosslinking agent significantly improves the storage stability of the slurry.

[0102] The slurries prepared in Application Example 1 and Comparative Example 1 were placed in an open, temperature- and humidity-controlled room for 7 days, and then dispersed evenly again for later use.

[0103] (3-1) Service life test

[0104] In the sample preparation process of Application Example 1 and Comparative Example 1, starting from the beginning of mixing the prepolymer and slurry, after pouring the mixed sample solution into the PTFE mold, a 10cm long scratch was made vertically and uniformly with a scraper. After 30 seconds, it was observed whether there were any obvious scratches. If there were no obvious scratches, it was considered that it was still within the applicable period. The results are shown in Table 5:

[0105] Table 5. Pot life test results of the membranes in Application Example 1 and Comparative Example 1.

[0106]

[0107] As shown in Table 5, the coating system of Application Example 1 can have its pot life significantly extended by adding No. 1 secondary amine crosslinking agent to replace the di-secondary amine chain extender and HT-100 in Comparative Example 1.

[0108] (4-1) Mechanical property testing

[0109] After the samples from Application Example 1 and Comparative Example 1 were placed in a constant temperature and humidity room for 7 days, their tensile properties were evaluated according to GB / T19250-2013 Polyurethane Waterproof Coatings. The results are shown in Table 6.

[0110] Table 6. Tensile property test results of the membranes in Application Example 1 and Comparative Example 1.

[0111] Application Example 1 Comparative Example 1 Tensile strength / MPa 5.6 4.2 Elongation at break / % 405 320

[0112] As shown in Table 6, the coating system of Application Example 1, by adding No. 1 secondary amine crosslinking agent to replace the di-secondary amine chain extender and HT100 of Comparative Example 1, can increase the tensile strength and elongation at break of the product by 33% and 26%, respectively.

[0113] (5-1) Performance testing after heat treatment

[0114] First, the samples from Application Example 1 and Comparative Example 1 were placed in a constant temperature and humidity room for 7 days. Then, according to the heat treatment requirements in GB / T19250-2013 Polyurethane Waterproof Coatings, the samples were placed in an 80℃ oven for 7 days. After being removed and placed in a constant temperature and humidity room for 4 hours, tensile properties were tested. The results are shown in Table 7.

[0115] Table 7. Tensile property test results of the films in Application Example 1 and Comparative Example 1 after heat treatment.

[0116] Application Example 1 Comparative Example 1 Tensile strength before heat treatment / MPa 5.6 4.2 Tensile strength after heat treatment / MPa 6.3 4.4 Tensile strength improvement rate / % 13 5 Elongation at break before heat treatment / % 405 320 Elongation at break after heat treatment / % 393 266 Elongation at break loss (%) 3 17

[0117] As shown in Table 7, after replacing the diamine chain extender and HT100 in Comparative Example 1 with No. 1 secondary amine crosslinking agent in the coating system of Application Example 1, the strength improvement rate of the product after heat treatment was significantly increased and the loss rate of elongation at break was significantly reduced.

[0118] Example 2

[0119] Preparation of 2# secondary amine crosslinking agent

[0120] 196.8g of secondary amine compound 6200 was added to a 500ml four-necked flask. 80g of HT-600 was then added to the flask using a constant-pressure dropping funnel. Nitrogen gas was purged into the flask to replace the air. The reaction temperature was set to 35℃, and the stirring speed to 260rpm. HT-600 was added dropwise over 0.5 hours. The reaction continued for 1 hour, then the temperature was raised to 55℃, and the reaction was continued for another hour before the product was discharged to obtain secondary amine crosslinking agent #2. The secondary amine crosslinking agent #2 was tested using a Nicolet iS5 Fourier transform infrared spectrometer (Thermo Fisher Scientific, USA). The infrared spectrum is shown below. Figure 2 .

[0121] like Figure 2 As shown, 2230cm -1 The absence of an absorption peak at this position indicates that the isocyanate group (-NCO) has completely reacted; 1683 cm⁻¹ -1 The presence of absorption peaks at the specified positions indicates that the product contains an isocyanurate heterocyclic structure; 2872-2960 cm⁻¹ -1 The presence of an absorption peak at position 3343 cm⁻¹ indicates that the product contains a methylene structure; -1 The presence of an absorption peak at the position indicates that the product contains a -NH-secondary amine structure.

[0122] Example 3

[0123] Preparation of 3# secondary amine crosslinking agent

[0124] 221.5g of the secondary amine compound N,N'-(methylenedi-4,1-cyclohexanediyl)diaspartic acid tetraethyl ester (F420) was added to a 500ml four-necked flask. 50g of HT-600 was added to the flask using a constant-pressure dropping funnel. Nitrogen gas was introduced to purge the air from the flask. The reaction temperature was set to 40℃, and the stirring speed was 300rpm. HT-600 was added dropwise over 0.5h. The reaction continued for 1h, then the temperature was raised to 45℃, and the reaction was continued for another 1h before discharging to obtain secondary amine crosslinking agent #3. The secondary amine crosslinking agent #3 was tested using a Nicolet iS5 Fourier transform infrared spectrometer (Thermo Fisher Scientific, USA). The infrared spectrum is shown below. Figure 3 .

[0125] like Figure 3 As shown, 2230cm -1 The absence of an absorption peak at this position indicates that the isocyanate group (-NCO) has completely reacted; 1708 cm⁻¹ -1 The presence of absorption peaks at the specified positions indicates that the product contains an isocyanurate heterocyclic structure; 2850-2979 cm⁻¹ -1 The presence of an absorption peak at position 3650 cm⁻¹ indicates that the product contains a methylene structure; -1 The presence of an absorption peak at the position indicates that the product contains a -NH-secondary amine structure.

[0126] Application Example 2

[0127] Preparation of prepolymer A3

[0128] According to the formulation of Application Example 2 in Table 8 below, polyether polyol C2010, PTMEG2000 and BPA were added to a flask, heated to 95°C and then dehydrated under vacuum for 2 hours; the system was cooled to 70°C and TDI-80 was added, reacted for 1 hour, and then heated to 90°C and reacted for 3 hours; the system was cooled to 50°C and dimethyl carbonate was added, stirred for 0.5 hours and then discharged to obtain prepolymer A3.

[0129] Preparation of slurry B3

[0130] According to the formulation of Application Example 2 in Table 9, the various materials of the slurry components are mixed and dispersed at high speed at 1500 rpm for 1 hour, and then slurry B3 is discharged.

[0131] Preparation of membrane (sample)

[0132] Weigh out 135.5g of prepolymer A3 and 64.5g of slurry B3, totaling 200g, and then weigh out 0.4g of organozinc bismuth catalyst Valikat14H2 (manufacturer Umicore) and place them in a 300ml mixing cup. Place the mixing cup in a high-speed disperser and disperse for 2 minutes at a speed of 1000rpm. After standing for 1 minute, pour the mixed sample solution into a PTFE mold and control the film thickness to be about 1.5mm.

[0133] Comparative Example 2

[0134] Preparation of prepolymer A4

[0135] According to the formulation of Comparative Example 2 in Table 8 below, polyether polyol C2010, PTMEG2000 and BPA were added to a flask, heated to 95°C and then dehydrated under vacuum for 2 hours; the system was cooled to 70°C and TDI-80 was added, reacted for 1 hour, and then heated to 90°C and reacted for 3 hours; the system was cooled to 70°C and HT-600 was added, reacted for 1 hour, and then the system was cooled to 50°C and dimethyl carbonate was added. After stirring for 0.5 hours, the product was discharged to obtain prepolymer A4.

[0136] Preparation of Slurry B4

[0137] According to the formulation of Comparative Example 2 in Table 9, the various materials of the slurry components were mixed and dispersed at high speed at 1500 rpm for 1 hour, and then slurry B4 was obtained by discharge.

[0138] Preparation of membrane (sample)

[0139] Weigh out 147.4g of prepolymer A4 and 52.6g of slurry B4, totaling 200g, and then weigh out 0.4g of organozinc bismuth catalyst Valikat14H2 (manufacturer Umicore) and place them in a 300ml stirring cup. Place the stirring cup in a high-speed disperser and disperse for 2 minutes at a speed of 1000rpm. After standing for 1 minute, pour the mixed sample solution into a PTFE mold and control the film thickness to be about 1.5mm.

[0140] Application Example 3

[0141] The prepolymer A3 obtained in Application Example 2 was used directly for the subsequent membrane preparation.

[0142] Preparation of Slurry B5

[0143] According to the formulation of Application Example 3 in Table 9, the various materials of each slurry component are mixed and dispersed at high speed at 1500 rpm for 1 hour, and then slurry B5 is discharged.

[0144] Preparation of membrane (sample)

[0145] Weigh out 120g of prepolymer A3 and 80g of slurry B5, totaling 200g, and then weigh out 0.4g of organozinc bismuth catalyst Valikat14H2 (manufacturer Umicore) and place them in a 300ml mixing cup. Place the mixing cup in a high-speed disperser and disperse for 2 minutes at a speed of 1000rpm. After standing for 1 minute, pour the mixed sample solution into a PTFE mold and control the film thickness to be about 1.5mm.

[0146] Comparative Example 3

[0147] The prepolymer A4 obtained in Comparative Example 2 was used directly for subsequent membrane preparation.

[0148] Preparation of Slurry B6

[0149] According to the formulation of Comparative Example 3 in Table 9, the various materials of each slurry component were mixed and dispersed at high speed at 1500 rpm for 1 hour, and then slurry B6 was obtained by discharge.

[0150] Preparation of membrane (sample)

[0151] Weigh out 128.6g of prepolymer A4 and 71.4g of slurry B6, totaling 200g, and then weigh out 0.4g of organozinc bismuth catalyst Valikat14H2 (manufacturer Umicore) and place them in a 300ml mixing cup. Place the mixing cup in a high-speed disperser and disperse for 2 minutes at a speed of 1000rpm. After standing for 1 minute, pour the mixed sample solution into a PTFE mold and control the film thickness to be about 1.5mm.

[0152] Table 8. Prepolymer component formulations for Application Example 2 and Comparative Example 2

[0153]

[0154] Table 9 Slurry component formulations for Application Examples 2 to 3 and Comparative Examples 2 to 3

[0155]

[0156]

[0157] Performance testing

[0158] (1-2) Observation of the state of the prepolymer

[0159] Prepolymer A3 from Application Examples 2 and 3 and prepolymer A4 from Comparative Examples 2 and 3 were placed in a constant temperature and humidity room for 24 hours, and samples were taken to observe their condition. The results are shown in Table 10.

[0160] Table 10 shows the prepolymer states of Application Examples 2 to 3 and Comparative Examples 2 to 3.

[0161] Application Example 2 / Application Example 3 Comparative Example 2 / Comparative Example 3 Appearance of the prepolymer Colorless and transparent It is a milky white, opaque liquid.

[0162] As shown in Table 10, the only difference between the prepolymers of Application Examples 2 and 3 and Comparative Examples 2 and 3 is that prepolymer A3 of Application Examples 2 and 3 does not contain HT-600, while prepolymer A4 of Comparative Examples 2 and 3 does contain HT-600. The results in Table 10 show that the addition of HT-600 causes prepolymer A4 of Comparative Examples 2 and 3 to be milky white and opaque, affecting the appearance of the prepolymer product and making it unacceptable to downstream customers. It also affects the storage stability of the prepolymer.

[0163] (2-2) Slurry storage stability test

[0164] 200g of each of the slurries prepared in Application Examples 2 and 3 and Comparative Examples 2 and 3 were placed in an oven at 50℃ and allowed to stand for 24 hours. The storage stability of the slurries was then observed, and the results are shown in Table 4.

[0165] Table 11 Results of slurry storage stability tests in Application Examples 2 to 3 and Comparative Examples 2 to 3

[0166]

[0167]

[0168] As shown in Table 9, the only difference between the slurry components of Application Example 2 and Comparative Example 2 is that Application Example 2 uses secondary amine crosslinking agent #2 instead of the 6200 diamine chain extender in Comparative Example 2; the only difference between the slurry components of Application Example 3 and Comparative Example 3 is that Application Example 3 uses secondary amine crosslinking agent #3 instead of the F420 diamine chain extender in Comparative Example 3. The results in Table 11 show that, compared to the 6200 diamine chain extender, secondary amine crosslinking agent #2 significantly improves the storage stability of the slurry; compared to the F420 diamine chain extender, secondary amine crosslinking agent #3 significantly improves the storage stability of the slurry.

[0169] (3-2) Service life test

[0170] In the sample preparation process of Application Examples 2 to 3 and Comparative Examples 2 to 3, starting from the beginning of mixing the prepolymer and slurry, after pouring the mixed sample solution into the PTFE mold, a 10cm long scratch was made vertically and uniformly with a scraper. After 30 seconds, it was observed whether there were any obvious scratches. If there were no obvious scratches, it was considered that it was still within the applicable period. The results are shown in Table 12:

[0171] Table 12 shows the pot life test results of the membranes in Application Examples 2 and 3 and Comparative Examples 2 and 3.

[0172] Application Example 2 Comparative Example 2 Application Example 3 Comparative Example 3 Applicability period evaluation 50-minute shelf life 26-minute shelf life 56-minute shelf life 21-minute applicable period

[0173] As shown in Table 12, the pot life of the coating system in Application Example 2 was significantly extended by replacing the diamine chain extenders 6200 and HT-600 in Comparative Example 2 with secondary amine crosslinking agent #2. Compared to Comparative Example 2, the pot life of the system in Application Example 2 was extended by 92.3%. Similarly, the pot life of the coating system in Application Example 3 was significantly extended by replacing the diamine chain extenders F$20 and HT-600 in Comparative Example 3 with secondary amine crosslinking agent #3. Compared to Comparative Example 3, the pot life of the system in Application Example 3 was extended by 166%.

[0174] (4-2) Mechanical property testing

[0175] After the samples from Application Example 2-3 and Comparative Example 2-3 were placed in a constant temperature and humidity room for 7 days, their tensile properties were evaluated according to GB / T19250-2013 Polyurethane Waterproof Coatings. The results are shown in Table 13.

[0176] Table 13 shows the tensile property test results of the films in Application Examples 2 to 3 and Comparative Examples 2 to 3.

[0177] Application Example 2 Comparative Example 2 Application Example 3 Comparative Example 3 Tensile strength / MPa 12.8 9.2 14.1 10.5 Elongation at break / % 601 450 540 397

[0178] As shown in Table 13, the coating system of Application Example 2, by adding secondary amine crosslinking agent #2 to replace the diamine chain extenders 6200 and HT600 in Comparative Example 2, can increase the tensile strength and elongation at break by 39% and 34%, respectively. Similarly, the coating system of Application Example 3, by adding secondary amine crosslinking agent #3 to replace the diamine chain extenders F420 and HT600 in Comparative Example 3, can increase the tensile strength and elongation at break by 34% and 36%, respectively.

[0179] (5-2) Performance testing after heat treatment

[0180] First, the samples from Application Examples 2 to 3 and Comparative Examples 2 to 3 were placed in a constant temperature and humidity room for 7 days. Then, according to the heat treatment requirements in GB / T 19250-2013 Polyurethane Waterproof Coatings, the samples were placed in an 80℃ oven for 7 days. After being removed and placed in a constant temperature and humidity room for 4 hours, tensile properties were tested. The results are shown in Table 14.

[0181] Table 14. Results of tensile property tests on the films of Application Examples 2 to 3 and Comparative Examples 2 to 3 after heat treatment.

[0182]

[0183]

[0184] As shown in Table 14, in Application Example 2, after replacing the diamine chain extenders 6200 and HT600 in Comparative Example 2 with secondary amine crosslinking agent #2, the strength improvement rate of the product after heat treatment was significantly increased, and the loss rate of elongation at break was significantly reduced. Similarly, in Application Example 3, after replacing the diamine chain extenders F420 and HT600 in Comparative Example 3 with secondary amine crosslinking agent #3, the strength improvement rate of the product after heat treatment was significantly increased, and the loss rate of elongation at break was significantly reduced.

[0185] Application Example 2-1

[0186] Preparation of prepolymer A5

[0187] According to the formulation of Application Example 2-1 in Table 15 below, polyether polyol C2010, PTMEG1000 and 1,4-butanediol were added to a flask, heated to 95°C and then dehydrated under vacuum for 2 hours; the system was cooled to 70°C and IPDI was added, reacted for 1 hour, and then heated to 100°C and reacted for 6 hours; the system was cooled to 50°C and discharged to obtain prepolymer A5.

[0188] Table 15 Prepolymer component formulations for Application Example 2-1

[0189] Components Manufacturer Dosage (parts by weight) Polyether polyol C2010 Wanhua Chemical 100 PTMEG1000 Dalian Chemical 100 1,4-Butanediol Aladdin 8 Polyisocyanate IPDI Wanhua Chemical 130 Total 338

[0190] Preparation of slurry B3-1

[0191] Weigh 300g of B3 and add it to a mixing cup, then add 9g of titanium dioxide (Evonik, grade R706), and mix at 1000rpm for 30min using a high-speed disperser to obtain slurry B3-1.

[0192] Preparation of membrane (sample)

[0193] Weigh out 108.3g of prepolymer A5 and 91.7g of slurry B3-1, totaling 200g, and weigh out 0.4g of organometallic catalyst BiCAT8018 (manufacturer is a leading American company) and place them in a 300ml mixing cup. Place the mixing cup in a high-speed disperser and disperse for 2 minutes at a speed of 1000rpm. After standing for 1 minute, pour the mixed sample solution into a PTFE mold and control the film thickness to be about 1.5mm.

[0194] Application Example 3-1

[0195] The prepolymer A5 obtained in Application Example 2-1 was used directly for subsequent membrane preparation.

[0196] Preparation of Slurry B5-1

[0197] Weigh 300g of B5 and add it to a mixing cup, then add 7.5g of titanium dioxide (Evonik, grade R706), and mix at 1000rpm for 30min using a high-speed disperser to obtain slurry B5-1.

[0198] Preparation of membrane (sample)

[0199] Weigh out 90.7g of prepolymer A5 and 109.3g of slurry B5-1, totaling 200g, and then weigh out 0.4g of organometallic catalyst BiCAT8018 (manufacturer is a leading American company) and place them in a 300ml mixing cup. Place the mixing cup under a high-speed disperser and disperse for 2 minutes at a speed of 1000rpm. After standing for 1 minute, pour the mixed sample solution into a PTFE mold and control the film thickness to be about 1.5mm.

[0200] (6) Yellowing resistance test

[0201] First, the samples from Application Example 2-1 and Application Example 3-1 were placed in a constant temperature and humidity room for 7 days. Then, the Lab values ​​of the samples were measured using a colorimeter (CR-10, Keshengxing Instrument Co., Ltd.). Next, the samples were placed in a UV aging chamber (GT-7035-UB, High-Speed ​​Rail Equipment Co., Ltd.) for aging at 30W for 72 hours. After aging, the samples were removed, and their Lab values ​​were measured again using the colorimeter.

[0202] Lab values ​​represent luminance (L), red-green hue (a), and yellow-blue hue (b), respectively. Δb+ is the difference between the b-value after irradiation and the b-value before irradiation, used to indicate the degree of yellowness. The Lab and Δb+ values ​​of the two sets of samples before and after irradiation are shown in Table 16.

[0203] Table 16 Yellowing resistance test data for samples from Application Examples 2-1 and 3-1

[0204] 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

[0205] As shown in Table 16, the No. 3 secondary amine crosslinking agent used in Application Example 3-1 has good yellowing resistance and can be used in topcoat coatings; the No. 2 secondary amine crosslinking agent used in Application Example 2-1 is not resistant to yellowing and is suitable for non-exposed coatings or coatings that do not require yellowing resistance.

[0206] Unless otherwise specified, the terms used in this invention have the meanings commonly understood by those skilled in the art.

[0207] The embodiments described in this invention are for illustrative purposes only and are not intended to limit the scope of protection of this invention. Those skilled in the art can make various other substitutions, changes and improvements within the scope of this invention. Therefore, this invention is not limited to the above embodiments, but is only defined by the claims.

Claims

1. A compound having the following structure: in, R 11 R 21 R 31 They may be the same or different, and are independently selected from sec-butyl or (CH3CH2OOCCH2)(CH3CH2OOC)CH-; R 12 R 22 R 32 They may be the same or different, and are selected independently from the following structures: 。 2. The use of the compound of claim 1 as a crosslinking agent in polyurethane urea coatings.

3. A method for preparing a secondary amine crosslinking agent, comprising reacting a hexamethylene diisocyanate trimer with a bis-secondary amine compound to obtain the secondary amine crosslinking agent; wherein, The bis-secondary amine compound is selected from one or more of 4,4'-bis-sec-butylaminodiphenylmethane, 4,4'-bis-sec-butylaminodicyclohexylmethane, and N,N'-(methylenedi-4,1-cyclohexanediyl)diaspartic acid tetraethyl ester.

4. The preparation method according to claim 3, wherein, In the aforementioned di-secondary amine compound, the molar ratio of N,N'-(methylenedi-4,1-cyclohexanediyl)diaspartic acid tetraethyl ester, 4,4'-bis-sec-butylaminodiphenylmethane, and 4,4'-bis-sec-butylaminodicyclohexylmethane is 1:(0-10):(0-1); or, The molar ratio of 4,4'-bis-sec-butylaminodiphenylmethane, N,N'-(methylenedi-4,1-cyclohexanediyl)diaspartic acid tetraethyl ester and 4,4'-bis-sec-butylaminodicyclohexylmethane is 1:(0-10):(0-1).

5. The preparation method according to claim 3, wherein, The reaction temperature is 20–80°C; and / or, The reaction time is 1–10 h; and / or, The molar ratio of the diamine compound to the hexamethylene diisocyanate trimer is 3 to 10:

1.

6. The preparation method according to claim 3, wherein, The reaction temperature is 30–50°C; and / or, The reaction time is 2 to 8 hours.

7. A polyurethane urea coating composition comprising a prepolymer component and a slurry component; wherein the prepolymer component comprises a polyether polyol and a polyisocyanate, and the slurry component comprises a crosslinking agent, wherein the crosslinking agent comprises the compound of claim 1 or a secondary amine crosslinking agent prepared by any one of claims 3 to 6.

8. The composition according to claim 7, wherein, The prepolymer component comprises 30-85 parts by weight of the polyether polyol and 10-50 parts by weight of the polyisocyanate, and the slurry component comprises 15-80 parts by weight of the crosslinking agent; and / or The composition includes a catalyst component, which includes one or more of zinc neodecanoate, bismuth neodecanoate, and di(dodecyl sulfide)dibutyltin.

9. The composition according to claim 7, wherein, The prepolymer component comprises 30-85 parts by weight of the polyether polyol, 10-50 parts by weight of the polyisocyanate, 1-10 parts by weight of the small molecule alcohol, and 0-20 parts by weight of the first plasticizer and / or solvent; or... The slurry composition includes 15-80 parts by weight of the crosslinking agent, 5-20 parts by weight of the second plasticizer, 0-10 parts by weight of the chain extender, 0-10 parts by weight of the additives and / or solvents, and 10-60 parts by weight of inorganic fillers. The first plasticizer and the second plasticizer are each independently selected from one or more of long-chain chlorinated paraffin, triethylene glycol diisooctanoate, acetyl tributyl citrate, dioctyl terephthalate, methyl palmitate, and epoxidized soybean oleate; the solvent is selected from one or more of dimethyl carbonate, ethyl acetate, butyl acetate, and propylene carbonate. The chain extender is selected from one or more of dimethylthiodiaminotoluene, 3,5-diethyltoluenediamine, 4,4'-bis-sec-butylaminodiphenylmethane, 1,4-bis-sec-butylaminobenzene, isophoronediamine, diaminodicyclohexylmethane, and aspartic acid resin; the additives include one or more of defoamers, dispersants, and anti-settling agents; the inorganic filler is selected from one or more of calcium carbonate, talc, kaolin, silica, and magnesium oxide.

10. The composition according to claim 8, wherein, The mass of the catalyst component is 0.05 to 0.6% of the mass of the composition; and / or, The polyether polyol has an average functionality of 2 to 3 and a weight-average molecular weight of 1000 to 6500.

11. The composition according to claim 9, wherein, The polyisocyanate includes one or more of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, and dicyclohexylmethane diisocyanate; and / or The small molecule alcohol is selected from one or more of trimethylolpropane, 1,4-butanediol, ethylene glycol, and propylene glycol.

12. A polyurethane urea coating, prepared from the polyurethane urea coating composition according to any one of claims 7 to 11, wherein, The polyurethane urea coating comprises a prepolymer and a slurry; the prepolymer is prepared from the prepolymer components, and the slurry is prepared from the slurry components.

13. A coating formed by the polyurethane urea coating of claim 12.

Images