Bio-based polyurea sealant

Abstract

The invention provides a bio-based polyurea sealant, and relates to the technical field of sealant. The raw material components of the bio-based polyurea sealant comprise resin and a curing agent, the resin is composed of two aspartate resins with different curing activities, and the aspartate resin with low curing activity is subjected to ester exchange modification by a diol compound; the curing agent is a composition of a PDI prepolymer and a PDI tripolymer, wherein the PDI prepolymer is bio-based modified. The resin can also form a component A with hydrophobic gas silicon, color paste, an auxiliary agent and the like, and the curing agent can also form a component B with hydrophobic gas silicon, color paste, an auxiliary agent and the like. The bio-based polyurea sealant provided by the invention is stable in performance after being cured, the hardness is not reduced, and bubbles are not generated.

Description

Technical Field

[0001] This invention belongs to the field of tile grout technology and relates to a bio-based polyurea tile grout. Background Technology

[0002] Grout sealant is a filler used to seal the gaps between decorative materials such as tiles, mosaics, and stone, solving problems such as unsightly gaps and easy accumulation of dust and dirt. Aspartic polyurea grout sealant is a new type of grout sealant, using aspartic ester resin as a base material, combined with pigments, fillers, various additives, and curing agents. It features good weather resistance, high bonding strength, high mechanical strength, good toughness, and easy application. However, for some applications requiring better performance, such as outdoor use, bathrooms, and kitchens, further improvements in performance, such as weather resistance and waterproofing, are needed.

[0003] Furthermore, with increasing environmental awareness, the use of green and recyclable materials is growing, representing a major trend in the materials industry. However, the use of green and recyclable materials in aspartic polyurea grout is still relatively limited, requiring further technological breakthroughs. Summary of the Invention

[0004] To achieve better performance, such as a balance between working and curing times, aspartic polyurea grout is usually formulated with two or more aspartic ester resins, such as the F420 and F520 resins from Shenzhen Feiyang Junyan New Material Co., Ltd.

[0005] The structure of F420 resin is as follows:

[0006] The structure of F520 resin is as follows:

[0007] Compared to F420 resin, F520 resin has a methyl group on its cyclohexyl group, which creates a more significant steric hindrance to the secondary amino group, resulting in a significantly lower reactivity of F520 resin. The use of a blend of F420 and F520 resins (e.g., a 1:1 weight ratio) has been applied as a coating, with a thickness generally not exceeding 0.5 mm, and the coating exhibits relatively stable performance after curing. However, the inventors discovered that when using a blend of F420 and F520 resins as the base resin for tile grout, the hardness of the grout gradually decreases over time after curing, and bubbles are generated, affecting the performance of the grout.

[0008] To address the aforementioned technical problems, this invention provides a bio-based polyurea grout sealant.

[0009] The technical solution of the present invention is as follows:

[0010] A bio-based polyurea grout sealant, the raw material components of which include resin and curing agent;

[0011] The resin includes primary aspartic acid ester resin and secondary aspartic acid ester resin;

[0012] The structure of the first day-aspartic acid ester resin is shown in formula (Ⅰ).

[0013]

[0014] Among them, R 1 R 2 R 3 and R 4 The single element is selected from C1-C18 alkyl groups, and X is selected from...

[0015] One or more combinations of the following;

[0016] The second second aspartic acid ester resin is obtained by transesterification reaction of the compound shown in formula (II) with a diol compound;

[0017]

[0018] Among them, R 5 R 6 R 7 and R 8 Individually selected from C1-C18 alkyl groups;

[0019] The diol compound is selected from polyether diols with a number average molecular weight of 200-2000, polyester diols with a number average molecular weight of 300-5000, bihydroxyl-terminated polysiloxanes with a number average molecular weight of 250-5000, and compounds with the structure HOR. 9 One or more combinations of diols of OH, wherein R 9 Selected from C2-C12 alkyl groups.

[0020] Preferably, the weight ratio of the first terpartic acid ester resin to the second terpartic acid ester resin is 1:9-9:1.

[0021] More preferably, the weight ratio of the first aspartic acid ester resin to the second aspartic acid ester resin is 3:7-7:3.

[0022] Preferably, the molar ratio of the compound represented by formula (II) to the diol compound is 1:1 to 2:1.

[0023] More preferably, the molar ratio of the compound represented by formula (II) to the diol compound is 1.2:1-2:1.

[0024] Preferably, the volume activity equivalent of the resin and the curing agent is 1:0.9-1:1.2.

[0025] Preferably, the curing agent comprises 1,5-pentamethylene diisocyanate prepolymer and 1,5-pentamethylene diisocyanate trimer;

[0026] The 1,5-pentamethylene diisocyanate prepolymer is a reaction product of 1,5-pentamethylene diisocyanate and bio-based polyol, and the NCO group content in the 1,5-pentamethylene diisocyanate prepolymer is 3-10 wt%.

[0027] More preferably, the bio-based polyol is selected from one or a combination of two or more of bio-based polyether polyols and bio-based polyester polyols, wherein the number average molecular weight of the bio-based polyol is 500-2000 and the hydroxyl value is 50-300 mgKOH / g.

[0028] Preferably, the curing agent contains 8-15 wt% NCO groups.

[0029] Preferably, the raw material components further include one or a combination of two or more of pigments, fillers, and additives.

[0030] The beneficial effects of this invention are:

[0031] (1) The resin of the present invention contains secondary aspartic acid ester resin, which contains two or more secondary amino groups, greatly increasing the reactivity with the isocyanate groups in the curing agent. This avoids the situation of low reactivity and slow reaction that occurs with resins like F520, which causes the curing agent that does not participate in the curing reaction in time to gradually react with water, generate bubbles and form plasticizing effect, thereby reducing the hardness and other properties of the grout.

[0032] (2) In the preparation of the second aspartic ester resin of the present invention, a double-terminated hydroxyalkyl polysiloxane is used as one of the reaction raw materials. The polysiloxane structure can be introduced into the aspartic polyurea grout, which can improve the flexibility, weather resistance and waterproof properties of the aspartic polyurea grout.

[0033] (3) The curing agent of the present invention contains a high content of bio-based components, which increases the bio-based content of polyurea grout and has the characteristics of green recycling. Detailed Implementation

[0034] The technical solution of the present invention will be further explained and described below through specific embodiments.

[0035] In existing technologies, resins similar to F520 are used as one of the base resins for aspartic polyurea grout. However, the reaction between F520 resin and the curing agent is relatively slow, and the grout is generally applied in a thicker layer, usually more than 3mm, and sometimes even up to 1cm depending on the gap depth. After the grout has initially cured, there is still a lot of unreacted curing agent. This unreacted curing agent easily absorbs moisture from the air and reacts. First, the reaction produces bubbles, and second, the reaction products act as plasticizers for the grout, leading to a decrease in the performance and hardness of the grout. In some cases, the grout may even expand due to the formation of bubbles, resulting in a significant deterioration in appearance and a deviation from the original dimensions.

[0036] Therefore, the present invention provides a bio-based polyurea grout sealant. The raw material components of the bio-based polyurea grout sealant of the present invention include resin and a curing agent;

[0037] The resins include primary aspartic acid ester resin and secondary aspartic acid ester resin;

[0038] The structure of the first-day aspartic acid ester resin is shown in formula (Ⅰ).

[0039]

[0040] Among them, R 1 R 2 R 3 and R 4 The single element is selected from C1-C18 alkyl groups, and X is selected from...

[0041] One or more combinations of the following;

[0042] The second day, the aspartic acid ester resin was obtained by transesterification of the compound shown in formula (II) with a diol compound;

[0043]

[0044] Among them, R 5 R 6 R 7 and R 8 Individually selected from C1-C18 alkyl groups;

[0045] The diol compounds are selected from polyether diols with a number average molecular weight of 200-2000, polyester diols with a number average molecular weight of 300-5000, bihydroxyl-terminated polysiloxanes with a number average molecular weight of 250-5000, and compounds with the structure HOR. 9 One or more combinations of diols of OH, wherein R 9 Selected from C2-C12 alkyl groups.

[0046] In the bio-based polyurea grout sealant of this invention, the primary aspartic acid ester resin is used, which exhibits high reactivity with the curing agent. The secondary aspartic acid ester resin is obtained by transesterification of the compound shown in formula (II) with a diol compound, resulting in the secondary aspartic acid ester resin containing more than two secondary amino groups. This enhances the reactivity with the curing agent, accelerates the formation of cross-linked structures and consumes the curing agent during the curing process, and avoids the unreacted curing agent reacting with moisture, which could lead to problems such as bubbles, decreased hardness, and reduced performance in the grout sealant. In this invention, the catalyst used for transesterification can be a titanate ester or organotin, such as tetraethyl titanate, tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetraisobutyl titanate, diisobutyltin dilaurate, stannous octoate, etc.

[0047] For example, taking the compound shown in formula (II) as F520 resin and the diol compound as butanediol as an example, the structure of a transesterification product - teraspartic acid ester resin is shown in formula (III) below. One teraspartic acid ester resin molecule contains 4 secondary amino groups. The reaction opportunity between the secondary amino groups in the teraspartic acid ester resin and the curing agent is greatly increased, thereby avoiding the problem of foaming and softening caused by the slow reaction of some curing agents with secondary amino groups and their reaction with water vapor.

[0048]

[0049] In this invention, the structure of the double-terminated hydroxyalkyl polysiloxane is shown in formula (Ⅳ).

[0050] HO(CH2) m SiMe2O(SiOMe2) a (SiOMeR 10 ) b SiMe2(CH2) m OH(Ⅳ)

[0051] Where Me represents methyl, R 10 Selected from C1-C18 alkyl, C3-C18 fluoroalkyl, C3-C18 carbonyl-substituted alkyl, or C3-18 ester-substituted alkyl, m = 2-6, a = 5-100, b = 0-30. Polysiloxanes possess excellent high and low temperature resistance, flexibility, weather resistance, and hydrophobicity. Introduced into aspartic acid ester resins via transesterification, the incompatibility between the polysiloxane and aspartic acid ester structures allows the polysiloxane structure to migrate to the surface of the grout, imparting better hydrophobicity, weather resistance, and high and low temperature resistance. When R... 10 Long-chain alkyl groups (such as lauryl, stearyl, etc.) can impart good hydrophobic properties to the grout; when R... 10As a fluoroalkyl group, it can impart good hydrophobic and oleophobic properties to the grout. The preparation method of the bihydroxyalkyl polysiloxane can refer to existing technologies. For example, it can be obtained by hydrosilylation reaction of the corresponding bihydroxyalkyl polysiloxane with an alkenyl alcohol (such as allyl alcohol), or by ring-opening reaction of the end-capping agent dihydroxyalkyltetramethyldisiloxane with a siloxane cyclic compound under an alkaline catalyst.

[0052] In a preferred embodiment of the present invention, the weight ratio of the first-day aspartic acid ester resin to the second-day aspartic acid ester resin is 1:9-9:1. Adjusting the weight ratio of the first-day and second-day aspartic acid ester resins can adjust the working time, drying time, and performance of the bio-based polyurea grout. For example, the weight ratio of the first-day and second-day aspartic acid ester resins can be any value from 1:9, 2:9, 1:3, 4:9, 5:9, 2:3, 7:9, 8:9, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, etc., without particular limitation. In a more preferred embodiment, the weight ratio of the first-day and second-day aspartic acid ester resins is 3:7-7:3. For example, the weight ratio can be any value from 3:7, 4:7, 5:7, 6:7, 1:1, 7:6, 7:5, 7:4, 7:3, etc., without particular limitation.

[0053] In a preferred embodiment of the present invention, the molar ratio of the compound shown in formula (II) to the diol compound is 1:1 to 2:1. By adjusting the molar ratio of the compound shown in formula (II) to the diol compound, different structures of the obtained secondary aspartic acid ester resin can be adjusted. For example, when the molar ratio of the compound shown in formula (II) to the diol compound is 1:1, the secondary aspartic acid ester resin is a (AB)n type polymer; when the molar ratio of the compound shown in formula (II) to the diol compound is 2:1, the secondary aspartic acid ester structure is an ABA structure, such as as shown in formula (III) above, in which case the compound shown in formula (II) is an F520 resin. For example, the molar ratio of the compound shown in formula (II) to the diol compound can be 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, or 2:1. In a more preferred embodiment, the molar ratio of the compound shown in formula (II) to the diol compound can be 1.2:1 to 2:1.

[0054] In this invention, the diol compound is selected from bio-based polyether diols, bio-based polyester diols, or compounds with the structure HOR. 9 The bio-based diols of OH can increase the bio-based content of the bio-based polyurea grout of this invention.

[0055] In a preferred embodiment of the present invention, the volume activity equivalent of the resin and the curing agent is 1:0.9-1:1.2. For example, the volume activity equivalent of the resin and the curing agent can be 1:0.9, 1:0.95, 1:1, 1:1.05, 1:1.1, 1:1.15, or 1:1.2. Further, the volume activity equivalent of the resin and the curing agent is 1:1-1:1.2.

[0056] In a preferred embodiment of the present invention, the curing agent comprises 1,5-pentamethylene diisocyanate prepolymer and 1,5-pentamethylene diisocyanate trimer;

[0057] 1,5-Pentamethylene diisocyanate prepolymer is a reaction product of 1,5-pentamethylene diisocyanate and bio-based polyols, with an NCO group content of 3-10 wt%. 1,5-Pentamethylene diisocyanate (PDI) is a novel bio-based aliphatic diisocyanate, typically synthesized from bio-based 1,5-pentanediamine (PDA) via phosgenation.

[0058] This invention introduces a high content of bio-based components into the curing agent through the reaction of 1,5-pentamethylene diisocyanate with a bio-based polyol, thereby giving the polyurea grout a high bio-based content. In this invention, the 1,5-pentamethylene diisocyanate trimer can also be a bio-based 1,5-pentamethylene diisocyanate trimer, which can be obtained directly from the market or prepared according to the method of the prior art authorized by Chinese invention patent CN110183390B. For example, the NCO group content in the 1,5-pentamethylene diisocyanate prepolymer can be any value selected from 3wt%, 3.5wt%, 4wt%, 4.5wt%, 5wt%, 5.5wt%, 6wt%, 6.5wt%, 7wt%, 7.5wt%, 8wt%, 8.5wt%, 9wt%, 9.5wt%, and 10wt%.

[0059] In a more preferred embodiment of the present invention, the bio-based polyol is selected from one or a combination of two or more of bio-based polyether polyols and bio-based polyester polyols, wherein the number average molecular weight of the bio-based polyol is 500-2000 and the hydroxyl value is 50-300 mgKOH / g. In this invention, the bio-based polyols can be directly purchased from the market, such as bio-based polyols FHB-2502, FHB-275, FHB-195, FH-4320, FH-2010, and FH-2010 from Zhangjiagang Feihang Technology Co., Ltd., HZC-100 from Weifang Qiangyuan Chemical Co., Ltd., and H1000 and H2000 from Guangzhou Haoyi New Material Technology Co., Ltd., etc.

[0060] In a preferred embodiment of the present invention, the NCO group content in the curing agent is 8-15 wt%. By adjusting the NCO group content in the curing agent, the molar ratio of the 1,5-pentamethylene diisocyanate prepolymer to the 1,5-pentamethylene diisocyanate trimer in the curing agent can be adjusted. For example, the NCO group content in the curing agent can be any value selected from 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, etc.

[0061] In a preferred embodiment of the present invention, the raw material components further include one or more of pigments, fillers, and additives. For example, the pigments can be pigments of different colors, such as carbon black, phthalocyanine blue, phthalocyanine green, chrome yellow, etc., and the amount of pigment used can be 0.5-10% of the resin weight. The fillers can be inorganic or organic fillers, such as polyethylene micropowder, polytetrafluoroethylene micropowder, talc, kaolin, calcium carbonate, wollastonite, solid glass microspheres, hollow glass microspheres, titanium dioxide, silica, etc., and the average particle size of the filler can be 0.1-10 μm, and the amount of filler used can be 5-50% of the resin weight. The additives can be wetting agents, leveling agents, defoamers, thickeners, thixotropic agents, dispersants, etc., and the amount of additives used can be 0.5-5% of the resin weight. In this invention, the pigments, fillers, and additives can all be purchased directly from the market.

[0062] The preparation method of the bio-based polyurea grout sealant of the present invention can be as follows:

[0063] The first day's aspartic acid ester resin and the second day's aspartic acid ester resin were mixed evenly to obtain the resin.

[0064] PDI prepolymer and 1,5-pentamethylene diisocyanate trimer are mixed evenly in a certain weight ratio to obtain a curing agent;

[0065] The resin and curing agent are mixed evenly to obtain the sealant of the present invention;

[0066] Alternatively, pigments, fillers, and / or additives can be added to the resin, mixed evenly, and then a curing agent can be added and mixed evenly to obtain the sealant of the present invention.

[0067] The technical solutions of the present invention will be further described and explained below with reference to various embodiments.

[0068] Preparation Examples 1-5: Preparation of Second Aspartic Ester Resin

[0069] Preparation Example 1

[0070] 1 mol of F520 resin (Feiyang Junyan Company) and 1 mol of 1,6-hexanediol were added to the reaction vessel, along with 4 g of tetraisopropyl titanate. The temperature was raised to 120°C, and the pressure of the reaction system was maintained below -0.095 MPa. The reaction was carried out at a constant temperature for 8 hours to obtain the second-day aspartic acid ester resin.

[0071] Preparation Example 2

[0072] Bis-terminated hydroxybutyl polysiloxane HO(CH2)4SiMe2O(SiOMe2) 40.7 SiMe2(CH2)4OH

[0073] 1.2 mol of F520 resin (Feiyang Junyan Company) and 1 mol of the above-mentioned hydroxypropyl dimethyl polysiloxane were added to the reaction vessel, along with 8 g of tetraisopropyl titanate. The temperature was raised to 120°C, and the pressure of the reaction system was maintained below -0.095 MPa. The reaction was carried out at a constant temperature for 12 h to obtain the second-day aspartic acid ester resin.

[0074] Preparation Example 3

[0075] Bis-hydroxypropyl fluorinated polysiloxane HO(CH2)3SiMe2O(SiOMe2) 21.4 (SiOMeR f ) 12.6 SiMe2(CH2)3OH, R f It is -CH2CH2(CF2)6CF3.

[0076] 1.5 mol of F520 resin (Feiyang Junyan Company) and 1 mol of the above-mentioned hydroxypropyl-terminated fluorinated polysiloxane were added to the reaction vessel, along with 8 g of tetraisopropyl titanate. The temperature was raised to 120°C, and the pressure of the reaction system was maintained below -0.095 MPa. The reaction was carried out at a constant temperature for 12 h to obtain the second-day aspartic acid ester resin.

[0077] Preparation Example 4

[0078] Bis-hydroxypropyl polysiloxane HO(CH2)3SiMe2O(SiOMe2) 18.5 (SiOMeR 11 ) 7.7 SiMe2(CH2)3OH, R 11 -(CH2) 11 CH3.

[0079] 2 mol of F520 resin (Feiyang Junyan Company) and 1 mol of the above-mentioned hydroxypropyl dimethyl polysiloxane were added to the reaction vessel, along with 10 g of tetraisopropyl titanate. The temperature was raised to 120°C, and the pressure of the reaction system was maintained below -0.095 MPa. The reaction was carried out at a constant temperature for 12 h to obtain the second-day aspartic acid ester resin.

[0080] Preparation Example 5

[0081] 1.7 mol of F520 resin (Feiyang Junyan Company) and 1 mol of bio-based polyol FHB-275 (Zhangjiagang Feihang Technology Co., Ltd.) were added to the reaction vessel, along with 9 g of tetraisobutyl titanate. The temperature was raised to 120°C, and the pressure of the reaction system was maintained below -0.095 MPa. The reaction was carried out at a constant temperature for 12 h to obtain the second day's aspartic acid ester resin.

[0082] Preparation Examples 6-8: Preparation of 1,5-pentamethylene diisocyanate prepolymers

[0083] Preparation Example 6

[0084] Under nitrogen protection, 616 g of 1,5-pentamethylene diisocyanate (PDI) was added to the reaction vessel, followed by dropwise addition of 500 g of bio-based 1,3-propanediol polyether diol with a number-average molecular weight of 1000 and a hydroxyl value of 112 mgKOH / g. After the addition was complete, the temperature was raised to 80°C and the reaction was carried out for 2 hours. The crude product was purified by molecular distillation, and excess PDI was extracted to obtain the PDI prepolymer. The NCO content of the PDI prepolymer was tested to be 6.4 wt%, and the bio-based carbon content was 93.1 wt%.

[0085] Preparation Example 7

[0086] Under nitrogen protection, 1000g of PDI was added to the reaction vessel, followed by dropwise addition of 1000g of bio-based 1,3-propanediol polyether diol with a number-average molecular weight of 2000 and a hydroxyl value of 56mgKOH / g. After the addition was complete, the temperature was raised to 80℃ and the reaction was carried out for 2 hours. The crude product was purified by molecular distillation, and excess PDI was extracted to obtain the PDI prepolymer. The NCO content of the PDI prepolymer was tested to be 3.6wt%, and the bio-based carbon content was 96.1wt%.

[0087] Preparation Example 8

[0088] Under nitrogen protection, 616g of PDI was added to the reaction vessel, followed by dropwise addition of 500g of castor oil polyester diol with a number-average molecular weight of 1000 and a hydroxyl value of 112mgKOH / g. After the addition was complete, the temperature was raised to 80℃ and the reaction was carried out for 2 hours. The crude product was purified by molecular distillation, and excess PDI was extracted to obtain the PDI prepolymer. The NCO content of the PDI prepolymer was tested to be 6.5wt%, and the bio-based carbon content was 56.7wt%.

[0089] Example 1

[0090] Bio-based polyurea grout sealant is obtained by mixing resin and curing agent at a volume activity equivalent ratio of 1:1, followed by vacuum degassing. The resin weight is 500g.

[0091] The resin was composed of F420 resin from Feiyang Junyan Company and the second aspartic acid ester resin prepared in Preparation Example 1 in a weight ratio of 1:1.

[0092] The curing agent consists of the PDI prepolymer obtained in Preparation Example 6 and the 1,5-pentamethylene diisocyanate trimer, and the NCO content of the curing agent is 11 wt%.

[0093] Example 2

[0094] The difference between Example 2 and Example 1 is that in Example 1, the second-day aspartic acid ester resin obtained in Preparation Example 1 was replaced with an equal weight of the second-day aspartic acid ester resin in Preparation Example 2. The remaining steps remained unchanged.

[0095] Example 3

[0096] The difference between Example 3 and Example 1 is that in Example 1, the second aspartic acid ester resin obtained in Preparation Example 1 was replaced with an equal weight of the second aspartic acid ester resin in Preparation Example 3. The remaining steps remained unchanged.

[0097] Example 4

[0098] The difference between Example 4 and Example 1 is that in Example 1, the second aspartic acid ester resin obtained in Preparation Example 1 was replaced with an equal weight of the second aspartic acid ester resin in Preparation Example 4. The remaining steps remained unchanged.

[0099] Example 5

[0100] The difference between Example 5 and Example 1 is that in Example 1, the second aspartic acid ester resin obtained in Preparation Example 1 was replaced with an equal weight of the second aspartic acid ester resin in Preparation Example 5. The remaining steps remained unchanged.

[0101] Example 6

[0102] The difference between Example 6 and Example 3 is that in Example 3, the curing agent was replaced by the PDI prepolymer obtained in Preparation Example 6 with the PDI prepolymer obtained in Preparation Example 7, and the NCO content of the curing agent was 11 wt%. The remaining steps remained unchanged.

[0103] Example 7

[0104] The difference between Example 7 and Example 3 is that in Example 3, the curing agent was replaced by the PDI prepolymer obtained in Preparation Example 6, and the NCO content of the curing agent was 11 wt%. The remaining steps remained unchanged.

[0105] Comparative Example 1

[0106] The difference between Comparative Example 1 and Example 1 is that in Example 1, the aspartic acid ester resin was replaced with an equal weight of F520 resin (Feiyang Junyan Company) on the second day. That is, the resin in Comparative Example 1 consisted of F420 resin and F520 resin. The remaining steps remained unchanged.

[0107] Comparative Example 2

[0108] The difference between Comparative Example 2 and Example 1 is that in Example 1, the aspartic acid ester resin was replaced with an equal weight of F420 resin (Feiyang Junyan Company) on the second day, meaning that all the resin in Comparative Example 2 was F420 resin. The remaining steps remained unchanged.

[0109] Comparative Example 3

[0110] The difference between Comparative Example 3 and Example 1 is that in Example 1, the resin was replaced with an equal weight of F520 resin (Feiyang Junyan Company), meaning that all the resin in Comparative Example 3 was F520 resin. The remaining steps remained unchanged.

[0111] Comparative Example 4

[0112] The difference between Comparative Example 4 and Example 1 is that in Example 1, F420 resin replaced an equal weight of teraspartic acid ester resin, meaning that all the resin in Comparative Example 4 was teraspartic acid ester resin. The remaining steps remained unchanged.

[0113] Performance testing

[0114] Curing speed: The gelation time was tested at an ambient temperature of 25°C.

[0115] Hardness change: The Shore D hardness of the grout (5mm thick) was tested after being placed in an environment of 25℃ for 7 days, 2 months, 4 months and 6 months after curing, and the highest hardness value was taken.

[0116] Yellowing test: The yellowing coefficient was tested according to the method in T / CECS10158-2021 "Aspartic Polyurea Tile Grout". A fluorescent ultraviolet light device was used for the climate aging test, and the results were measured after 200 hours of continuous light exposure.

[0117] The results are shown in Table 1 below.

[0118] Table 1

[0119]

[0120] After the cured grout was left for 6 months, it was cut open to observe whether there were bubbles inside. The grout in Examples 1-7 and Comparative Example 2 had virtually no bubbles inside, and no significant change in volume was observed during the placement process; the grout in Comparative Examples 1, 3 and 4 had obvious bubbles inside, and expansion was observed during the placement process.

[0121] As can be seen from the above test data, the polyurea grout of the present invention has good performance stability after curing, and the operation time is appropriate.

[0122] Example 8

[0123] This bio-based polyurea grout sealant consists of component A and component B. Component A comprises resin, titanium dioxide with an average particle size of 1.2 μm, polyether-modified silicone oil leveling agent SF-732 (Guangdong Biaomei Silicon Fluorine New Materials Co., Ltd.), silicone defoamer SF-800 (Guangdong Biaomei Silicon Fluorine New Materials Co., Ltd.), polymeric dispersant 4010 (BASF, Germany), and hydrophobic silica AEROSIL R972 (Evonik Degussa). The weight of titanium dioxide is 5 wt% of the resin, the weight of polyether-modified silicone oil leveling agent is 0.8 wt% of the resin, the weight of silicone defoamer is 0.6 wt% of the resin, the weight of polymeric dispersant is 0.5 wt% of the resin, and the weight of hydrophobic silica is 10 wt% of the resin. Component B consists of a curing agent, defoamer SF-800, dispersant 4010, and hydrophobic silica AEROSIL R972. The curing agent accounts for 94% of the weight of component B, the defoamer accounts for 0.5% of the weight of component B, the dispersant accounts for 0.5% of the weight of component B, and the hydrophobic silica accounts for 5% of the weight of component B.

[0124] The volume activity equivalent of the resin and the curing agent is 1:1.1.

[0125] The resin was composed of F420 resin from Feiyang Junyan Company and the second aspartic acid ester resin prepared in Preparation Example 3 at a weight ratio of 7:3, and the resin weight was 500g.

[0126] The curing agent consists of the PDI prepolymer obtained in Preparation Example 6 and the 1,5-pentamethylene diisocyanate trimer, and the NCO content of the curing agent is 13 wt%.

[0127] Under nitrogen protection, titanium dioxide and polymeric dispersant 4010 were added to the resin and stirred at 1200 rpm for 15 min. Then SF-732 and SF-800 were added and stirred and dispersed at 1200 rpm for 10 min. Hydrophobic silica was added and stirred at 1500 rpm for 20 min to obtain component A.

[0128] Under nitrogen protection, defoamer, dispersant and hydrophobic silica were added to the curing agent and stirred and dispersed at 1500 rpm for 25 minutes to obtain component B.

[0129] When components A and B are mixed evenly, the bio-based polyurea grout is obtained.

[0130] Example 9

[0131] The difference between Example 9 and Example 8 is that in Example 8, the weight ratio of F420 resin and 2-day aspartic acid ester resin was adjusted from 7:3 to 1:1. The remaining steps remained unchanged.

[0132] Example 10

[0133] The difference between Example 10 and Example 8 is that in Example 8, the weight ratio of F420 resin and 2-day aspartic acid ester resin was adjusted from 7:3 to 3:7. The remaining steps remained unchanged.

[0134] Example 11

[0135] The difference between Example 11 and Example 8 is that in Example 8, the weight ratio of F420 resin and second-day aspartic acid ester resin was adjusted from 7:3 to 1:9. The remaining steps remained unchanged.

[0136] Comparative Example 5

[0137] The difference between Comparative Example 5 and Example 8 is that in Example 8, the aspartic acid ester resin was replaced with an equal weight of F520 resin (Feiyang Junyan Company) on the second day. The remaining steps remained unchanged.

[0138] Comparative Example 6

[0139] The difference between Comparative Example 6 and Example 10 is that in Example 8, the aspartic acid ester resin was replaced with an equal weight of F520 resin (Feiyang Junyan Company) on the second day. The remaining steps remained unchanged.

[0140] Hardness change: The Shore D hardness of the grout (5mm thick) was tested after being placed in an environment of 25℃ for 7 days, 2 months, 4 months and 6 months after curing.

[0141] Internal foam: After the grout has cured for 6 months, cut it open to observe whether there is foam inside.

[0142] The results are shown in Table 2 below.

[0143] Table 2

[0144]

[0145] As can be seen from the data in Table 2 above, in this invention, the resin is a combination of first-day aspartic acid ester resin and second-day aspartic acid ester resin, and the weight ratio is between 7:3 and 1:9, resulting in relatively stable performance of the sealant.

[0146] As described above, the basic principles, main features, and advantages of the present invention have been shown and described. Those skilled in the art should understand that the present invention is not limited to the above embodiments, which are merely preferred embodiments and should not be construed as limiting the scope of the invention. All equivalent changes and modifications made in accordance with the scope of the patent and the description should still fall within the scope of the present invention. The scope of protection of this invention is defined by the appended claims and their equivalents.

Claims

1. A bio-based polyurea caulk characterized in that, The raw material components include a resin and a curing agent; The resin includes a first aspartic ester resin and a second aspartic ester resin; The first aspartic ester resin has the following formula (I), wherein R 1 , R 2 , R 3 and R 4 are independently selected from C1-C18alkyl, and X is selected from one or a combination of two or more of the following: The second aspartic ester resin is obtained by an ester exchange reaction of a compound shown in formula (II) and a diol compound; wherein R 5 , R 6 , R 7 and R 8 are independently selected from C1-C18alkyl; said diol compound is selected from the group consisting of a polyether diol having a number average molecular weight of 200 to 2000, a double ended hydroxyalkyl polysiloxane having a number average molecular weight of 250 to 3000 and a diol having the structure HOR 9 OH in combination of one or more or more, wherein R 9 is selected from C2-C12 alkyl.

2. The bio-based polyurea caulk of claim 1, wherein, The weight ratio of the first aspartic ester resin to the second aspartic ester resin is 1:9-9:

1.

3. The bio-based polyurea caulk of claim 2, wherein, The weight ratio of the first aspartic ester resin to the second aspartic ester resin is 3:7-7:

3.

4. The bio-based polyurea caulk of claim 1, wherein, The molar ratio of the compound shown in formula (II) to the diol compound is 1:1-2:

1.

5. The bio-based polyurea caulk of claim 4, wherein, The molar ratio of the compound shown in formula (II) to the diol compound is 1.2:1-2:

1.

6. The bio-based polyurea caulk of claim 1, wherein, The volume activity equivalent of the resin to the curing agent is 1:0.9-1:1.

2.

7. The bio-based polyurea caulk of claim 1, wherein, The curing agent includes a 1,5-pentamethylene diisocyanate prepolymer and a 1,5-pentamethylene diisocyanate trimer; The 1,5-pentamethylene diisocyanate prepolymer is a reaction product of 1,5-pentamethylene diisocyanate and a bio-based polyol, and the NCO group content in the 1,5-pentamethylene diisocyanate prepolymer is 3-10wt%.

8. The bio-based polyurea caulk of claim 7, wherein, The bio-based polyol is selected from one or a combination of two or more of a bio-based polyether polyol and a bio-based polyester polyol, and the number average molecular weight of the bio-based polyol is 500-2000, and the hydroxyl value is 50-300mgKOH / g.

9. The bio-based polyurea caulk of claim 1, wherein, The NCO group content in the curing agent is 8-15wt%.

10. The bio-based polyurea caulk of claim 1, wherein, The raw material components further include one or a combination of two or more of a pigment, a filler, and an auxiliary.

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