Radix asparagi polyurea caulking glue composition

Abstract

The invention provides a radix asparagi polyurea caulking glue composition, and relates to the technical field of caulking glue. The invention discloses an aspartic polyurea joint sealant composition, which is prepared from the following raw material components in parts by weight: 100 parts of aspartic ester resin, 10 to 40 parts of inorganic filler, 30 to 80 parts of modified rubber powder, 2 to 5 parts of auxiliaries and a proper amount of curing agent, the surface of the modified rubber powder is grafted with an organic group, and the organic group is selected from C1-C12 alkyl, epoxy substituted C3-C12 alkyl or amino substituted C3-C18 alkyl. The modified rubber powder is added into the radix asparagi polyurea, so that the elasticity recovery rate of the radix asparagi polyurea can be obviously improved, the properties such as tensile strength and elongation at break are also facilitated, the radix asparagi polyurea can be applied to the field of joint mixtures, and the application field of the radix asparagi polyurea is widened.

Description

Technical Field

[0001] The invention belongs to the technical field of caulking adhesives and relates to an asparagine polyurea caulking adhesive composition. Background Art

[0002] The caulking of concrete, steel and other substrates needs to be treated with caulking agents. Commonly used caulking agents include polyurethane caulking agents, silicone caulking agents, etc. Polyurethane caulking agents have good elastic recovery rate and good adhesion. For example, the elastic recovery rate can reach 85%, the elongation at break can reach 780%, the bonding strength can reach 1.65MPa, and the tensile strength can reach 1.9MPa. However, it has poor aging resistance and is easy to damage. After 600 hours of UVB irradiation, the tensile strength retention rate is only about 60%, and the elongation at break retention rate is only about 70%. Silicone caulking agents have good weather resistance and high and low temperature resistance, but their elastic recovery rate and adhesion are poor.

[0003] Therefore, further research and improvement of the sealant are needed. Summary of the invention

[0004] Asparagine polyurea has good weather resistance, adhesion and other properties, but its elastic recovery rate is poor, with an elastic recovery rate of only about 60%, and is not suitable for direct use as a sealant. Based on the existing asparagine polyurea, the present invention finds that the elastic recovery rate of the asparagine polyurea sealant can be increased by adding rubber powder. Based on this, the present invention proposes an asparagine polyurea sealant composition.

[0005] The technical solution of the present invention is as follows:

[0006] An aspartic acid polyurea caulking adhesive composition, wherein the raw material components include, by weight: 100 parts of aspartic acid ester resin, 10-40 parts of inorganic filler, 30-80 parts of modified rubber powder, 2-5 parts of auxiliary agent and an appropriate amount of curing agent;

[0007] The surface of the modified rubber powder is grafted with an organic group, and the organic group is selected from a C1-C12 alkyl group, an epoxy-substituted C3-C12 alkyl group or an amino-substituted C3-C18 alkyl group.

[0008] Preferably, the weight ratio of the inorganic filler to the rubber powder is 1:1-5.

[0009] More preferably, the weight ratio of the inorganic filler to the rubber powder is 1:2-5.

[0010] Preferably, the particle size of the rubber powder is 100-500 mesh.

[0011] Preferably, the rubber powder is selected from tire rubber powder.

[0012] Preferably, the structure of the amino-substituted C3-C18 alkyl group is as shown in the following formula (1):

[0013] R 1 NHR 2 -(1)

[0014] Where R 1 is selected from H, C1-C6 alkyl, phenyl, C7-C12 substituted phenyl, cycloalkyl or substituted C6-C12 cycloalkyl, R 2 Selected from C2-C6 alkylene or substituted C3-C6 alkyl.

[0015] More preferably, the R 1 Selected from phenyl, C7-C12 substituted phenyl, cycloalkyl or substituted C6-C12 cycloalkyl.

[0016] Preferably, the auxiliary agent is selected from one or a combination of two or more of a defoaming agent, a wetting agent, an antioxidant, an anti-ultraviolet agent and a thixotropic agent.

[0017] Preferably, the curing agent is selected from isocyanate curing agent, and the molar equivalent ratio of the aspartic acid ester resin to the curing agent is 1:1-1.1.

[0018] Preferably, the raw material components further comprise 1-5 parts of a dewatering agent and 0.5-5 parts of a pigment, or a combination of the two.

[0019] The beneficial effects of the present invention are:

[0020] (1) The present invention adds a certain amount of modified rubber powder to the asparagine polyurea sealant composition, which can significantly improve the elastic recovery rate, tensile strength and elongation at break of the asparagine polyurea sealant, and has no adverse effects on properties such as weather resistance and bonding strength, making the asparagine polyurea more suitable for use as a sealant, thereby expanding the application of asparagine polyurea in the field of sealants.

[0021] (2) The modified rubber powder of the present invention is modified with an organic group on its surface, which has a more obvious effect on improving the performance of the aspartame polyurea, especially with an organic group containing a secondary amine group, which can not only improve the performance of the aspartame polyurea sealant, but also will not affect the application period. DETAILED DESCRIPTION

[0022] The technical solution of the present invention is further illustrated and described below through specific implementation methods.

[0023] In order to improve the elastic recovery rate of aspartic polyurea sealant, the present invention provides an aspartic polyurea sealant composition, wherein the raw material components include, by weight: 100 parts of aspartic acid ester resin, 10-40 parts of inorganic filler, 30-80 parts of modified rubber powder, 2-5 parts of auxiliary agent and an appropriate amount of curing agent;

[0024] The surface of the modified rubber powder is grafted with an organic group, and the organic group is selected from C1-C12 alkyl, epoxy-substituted C3-C12 alkyl or amino-substituted C3-C18 alkyl. The surface of the modified rubber powder can be grafted with an organic group by a silane coupling agent treatment method, such as methyltrimethoxysilane, KH-560, butyltrimethoxysilane, KH-792, KH-550, etc.

[0025] The present invention adds rubber powder to the asparagine polyurea caulking adhesive composition, and it is found that the elastic recovery rate of the asparagine polyurea can be significantly improved, and the tensile strength and elongation at break can also be improved, and there is no adverse effect on the performance of weather resistance, bonding strength, etc., so that the asparagine polyurea also has a great application prospect in the caulking adhesive, and the application field of the asparagine polyurea is broadened. In addition, the technical effect of the present invention cannot be achieved by directly using rubber powder that has not been surface-modified. The surface of the rubber powder needs to be grafted with an organic group. The possible reason is that this can improve the compatibility of the rubber powder with the asparagine polyurea, which is more conducive to the dispersion of the rubber powder in the asparagine polyurea and the exertion of the effect. The organic group grafted on the surface of the rubber powder is not particularly limited, and can be a saturated alkyl group, or an alkyl group substituted with an epoxy group or an amino group.

[0026] The asparagus polyurethane resin in the present invention is not particularly limited, and may be F420, F520, F220, F421, F330, etc. produced by Feiyang Junyan Company.

[0027] In a preferred embodiment of the present invention, the weight ratio of the inorganic filler to the rubber powder is 1:1-5. It is found in the present invention that the inorganic filler and the rubber powder can work together in a certain weight ratio range, and can better improve the performance of the asparagus polyurea sealant. In the present invention, the inorganic filler is not particularly limited, and can be wollastonite, alumina, silica, heavy calcium carbonate, light calcium carbonate, kaolin, glass beads, etc., and the average particle size of the inorganic filler can be 1-100 μm. In order to improve the dispersibility of the inorganic filler in asparagus polyurea, the surface of the inorganic filler can also be treated, such as with a silane coupling agent. For example, the weight ratio of the inorganic filler to the rubber powder can be any value of 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, etc., without special restrictions. More preferably, the weight ratio of the inorganic filler to the rubber powder is 1:2-5.

[0028] In a preferred embodiment of the present invention, the particle size of the rubber powder is 100-500 mesh. It is not suitable for the particle size of the rubber powder to be too coarse or too fine. If it is too coarse, it cannot improve the performance such as elastic recovery rate, and if it is too fine, it is difficult to disperse, which is not conducive to the improvement of performance. For example, the particle size of the rubber powder can be any value of 100 mesh, 120 mesh, 150 mesh, 180 mesh, 200 mesh, 220 mesh, 250 mesh, 300 mesh, 350 mesh, 400 mesh, 450 mesh, 500 mesh, etc., without special restrictions.

[0029] In a preferred embodiment of the present invention, the rubber powder is selected from tire rubber powder. Tire rubber powder is a common rubber powder with a wide range of sources and has good anti-aging and fatigue resistance.

[0030] In a preferred embodiment of the present invention, the structure of the amino-substituted C3-C18 alkyl group is shown in the following formula (1), R 1 NHR 2 -(1)

[0031] Where R 1 is selected from H, C1-C6 alkyl, phenyl, C7-C12 substituted phenyl, cycloalkyl or substituted C6-C12 cycloalkyl, R 2 Selected from C2-C6 alkylene or substituted C3-C6 alkyl.

[0032] The cross-linking and curing of aspartame polyurea is through the reaction between secondary amino groups and isocyanate groups. The organic groups grafted on the surface of the rubber powder contain amino groups, which can react with the curing agent and participate in the curing reaction of aspartame polyurea, which is more conducive to the stability of rubber powder dispersion and the improvement of the mechanical properties of aspartame polyurea sealant. For example, the amino group can be NH2CH2CH2NHCH2CH2CH2-, CH3NHCH2CH2CH2-, CH3CH2NHCH2CH2CH2-, PhNHCH2CH2CH2- (Ph represents phenyl), R 3 NHCH2CH2CH2-(R 3 represents cyclohexyl) etc.

[0033] In a more preferred embodiment of the present invention, the amino-substituted C3-C18 alkyl is a secondary amino group, R 1 is selected from phenyl, C7-C12 substituted phenyl, cycloalkyl or substituted C6-C12 cycloalkyl. 1 The organic group includes an aromatic group or a cycloalkyl group, which can provide a greater steric hindrance to the secondary amino group, thereby preventing the amino group from reacting with the isocyanate group too quickly and affecting the applicable period of the asparagine polyurea, which may shorten the applicable period.

[0034] In a preferred embodiment of the present invention, the auxiliary agent is selected from one or a combination of two or more of a defoamer, a wetting agent, an antioxidant, an anti-ultraviolet agent and a thixotropic agent. Each of the above auxiliary agents can be purchased directly from the market, for example, the defoamer can be a dimethyl silicone oil defoamer (such as TEGO Airex 900, TEGO Foamex N, etc.), the wetting agent can be a polyether modified silicone oil wetting agent (such as Tego 4100, BYK-333, etc.), the antioxidant can be antioxidant 1010, antioxidant 168, etc., the anti-ultraviolet agent can be UV-538, UV-326, etc., and the thixotropic agent can be fumed silica, organic bentonite, hydrogenated castor oil, etc.

[0035] In a preferred embodiment of the present invention, the curing agent is selected from an isocyanate curing agent, and the molar equivalent ratio of the aspartic acid resin and the curing agent is 1:1-1.1. In the present invention, the curing agent can be selected from commercially available isocyanate curing agents, such as HT-300 and HT-600 of Wanhua Chemical, GB5240B, GB5245B, GB805A-100, GB805B-100, GB906A-80, GB926-85, GB963C-100 of Feiyang Junyan Company, etc. The molar equivalent ratio of the aspartic acid resin and the curing agent refers to the ratio of the amino group and the isocyanate group therein. For example, the molar equivalent ratio can be any value of 1:1, 1:1.02, 1:1.05, 1:1.08, 1:1, etc., without special restrictions.

[0036] In a preferred embodiment of the present invention, the raw material components further comprise one or a combination of 1-5 parts of a dewatering agent and 0.5-5 parts of a pigment. The dewatering agent is not particularly limited and may be a molecular sieve, such as 3A molecular sieve, etc. The pigment is not particularly limited and may be selected as required, such as carbon black, titanium dioxide, phthalocyanine blue, phthalocyanine green, etc.

[0037] There is no particular limitation on the preparation method of the asparagine polyurea caulking adhesive composition of the present invention. The raw material components except the curing agent can be evenly mixed to prepare component A, and the curing agent is used as component B. Component A and component B can be evenly mixed before construction.

[0038] The technical solution of the present invention is further described and illustrated according to various embodiments below. Unless otherwise specified, the parts described in the following embodiments are parts by weight.

[0039] Example 1

[0040] The aspartic acid polyurea sealant composition comprises: 100 parts of aspartic acid ester resin F420, 30 parts of wollastonite with an average particle size of 10 μm, 30 parts of modified tire rubber powder, 0.6 parts of dimethyl silicone oil defoamer, 0.4 parts of polyether modified silicone oil wetting agent, 0.3 parts of antioxidant 1010 and curing agent GB905A-85.

[0041] The molar equivalent ratio of F420 to GB905A-85 is 1:1.05.

[0042] The preparation method of modified tire rubber powder is as follows: disperse 50 parts of unmodified tire rubber powder with an average particle size of 200 mesh into 200 parts of anhydrous ethanol, add 10 parts of water, stir and mix evenly, then add 5 parts of methyltrimethoxysilane, heat to 50°C and react for 4 hours, filter, wash the filtered solid with anhydrous ethanol for 3 times, and dry at 60°C for 5 hours to obtain modified tire rubber powder.

[0043] Example 2

[0044] The difference between this embodiment and embodiment 1 is that in embodiment 1, wollastonite is adjusted from 30 parts to 20 parts, and modified tire rubber powder is adjusted from 30 parts to 40 parts. The other steps remain unchanged.

[0045] Example 3

[0046] The difference between this embodiment and embodiment 1 is that in embodiment 1, wollastonite is adjusted from 30 parts to 15 parts, and modified tire rubber powder is adjusted from 30 parts to 45 parts. The other steps remain unchanged.

[0047] Example 4

[0048] The difference between this embodiment and embodiment 1 is that in embodiment 1, wollastonite is adjusted from 30 parts to 10 parts, and modified tire rubber powder is adjusted from 30 parts to 50 parts. The other steps remain unchanged.

[0049] Comparative Example 1

[0050] The difference between this comparative example and Example 1 is that in Example 1, wollastonite is adjusted from 30 parts to 60 parts, and modified tire rubber powder is adjusted from 30 parts to 0 parts. The other steps remain unchanged.

[0051] Comparative Example 2

[0052] The difference between this comparative example and Example 1 is that in Example 1, wollastonite is adjusted from 30 parts to 0 parts, and modified tire rubber powder is adjusted from 30 parts to 60 parts. The other steps remain unchanged.

[0053] Comparative Example 3

[0054] The difference between this comparative example and Example 1 is that in Example 1, the modified tire rubber powder is adjusted to an equal weight of unmodified tire rubber powder. The other steps remain unchanged.

[0055] Comparative Example 4

[0056] The difference between this comparative example and Example 1 is that in Example 1, wollastonite is adjusted from 30 parts to 40 parts, and modified tire rubber powder is adjusted from 30 parts to 20 parts. The other steps remain unchanged.

[0057] Example 5

[0058] The aspartic acid polyurea sealant composition comprises: 100 parts of aspartic acid ester resin F420, 10 parts of wollastonite with an average particle size of 15 μm, 40 parts of modified tire rubber powder, 0.6 parts of dimethyl silicone oil defoamer, 0.4 parts of polyether modified silicone oil wetting agent, 0.3 parts of antioxidant 1010, 4 parts of dewatering agent 3A molecular sieve and curing agent GB905A-85.

[0059] The molar equivalent ratio of F420 to GB905A-85 is 1:1.05.

[0060] The modified tire rubber powder is the modified tire rubber powder in Example 1.

[0061] Example 6

[0062] The difference between this embodiment and embodiment 5 is that the modified tire rubber powder in embodiment 5 is replaced by an equal weight of secondary amino modified tire rubber powder. The other steps remain unchanged.

[0063] The preparation method of secondary amino modified tire rubber powder is as follows: 50 parts of unmodified tire rubber powder with an average particle size of 300 mesh are dispersed in 200 parts of anhydrous ethanol, 10 parts of water are added, and the mixture is stirred and mixed evenly, and then 4 parts of N-methyl-3-aminopropyltrimethoxysilane are added, and the temperature is raised to 40°C to react for 3 hours, filtered, and the filtered solid is washed with anhydrous ethanol for 3 times, and dried at 60°C for 5 hours to obtain the modified tire rubber powder.

[0064] Example 7

[0065] The difference between this embodiment and embodiment 5 is that the modified tire rubber powder in embodiment 5 is replaced by an equal weight of secondary amino modified tire rubber powder. The other steps remain unchanged.

[0066] The preparation method of secondary amino modified tire rubber powder is as follows: 50 parts of unmodified tire rubber powder with an average particle size of 200 mesh are dispersed in 200 parts of anhydrous ethanol, 10 parts of water are added, and the mixture is stirred and mixed evenly, and then 4 parts of N-cyclohexyl-3-aminopropyltrimethoxysilane are added, and the temperature is raised to 40°C to react for 3 hours, filtered, and the filtered solid is washed with anhydrous ethanol for 3 times, and dried at 60°C for 5 hours to obtain the modified tire rubber powder.

[0067] The performance test of the asparagine polyurea sealants of Examples 1-7 and Comparative Examples 1-4 was performed after curing at room temperature for 24 hours. The results are shown in Table 1 below.

[0068] Tensile strength and elongation at break: tested according to the method of GB / T 528-2009.

[0069] Bond strength: tested according to the method of GB / T 39289-2020.

[0070] Elastic recovery rate: Tested according to method A in 8.2 of GB / T 13477.17-2017.

[0071] Aging resistance: The retention rate of tensile strength and elongation at break was tested after 600 hours of UVB irradiation.

[0072] Table 1

[0073]

[0074] It can be seen from the data results in Table 1 that in the present invention, adding inorganic fillers and modified rubber powder to asparagine polyurea can significantly improve the elastic recovery rate of asparagine polyurea, and also has a promoting effect on the tensile strength and elongation at break. In addition, the excellent weather resistance of asparagine polyurea itself broadens the application of asparagine polyurea in the field of caulking adhesives, especially the application of outdoor caulking adhesives.

[0075] As described above, the basic principles, main features and advantages of the present invention are shown and described. Those skilled in the art should understand that the present invention is not limited by the above embodiments, which are only preferred embodiments of the present invention and cannot be used to limit the scope of the present invention. That is, equivalent changes and modifications made according to the scope of the present invention and the content of the specification should still be within the scope of the present invention. The scope of protection required by the present invention is defined by the attached claims and their equivalents.

Claims

1. An asparagine polyurea sealant composition, characterized in that: The raw material components include, by weight: 100 parts of aspartic acid ester resin, 10-40 parts of inorganic filler, 30-80 parts of modified rubber powder, 2-5 parts of auxiliary agent and an appropriate amount of curing agent; The surface of the modified rubber powder is grafted with an organic group, and the organic group is selected from a C1-C12 alkyl group, an epoxy-substituted C3-C12 alkyl group or an amino-substituted C3-C18 alkyl group.

2. The asparagine polyurea sealant composition according to claim 1, characterized in that: The weight ratio of the inorganic filler to the rubber powder is 1:1-5.

3. The asparagine polyurea sealant composition according to claim 2, characterized in that: The weight ratio of the inorganic filler to the rubber powder is 1:2-5.

4. The asparagine polyurea sealant composition according to claim 1, characterized in that: The particle size of the rubber powder is 100-500 meshes.

5. The asparagine polyurea sealant composition according to claim 1, characterized in that: The rubber powder is selected from tire rubber powder.

6. The asparagine polyurea sealant composition according to claim 1, characterized in that: The structure of the amino-substituted C3-C18 alkyl group is shown in the following formula (1): R 1 NHR 2 -(1) Where R 1 is selected from H, C1-C6 alkyl, phenyl, C7-C12 substituted phenyl, cycloalkyl or substituted C6-C12 cycloalkyl, R 2 Selected from C2-C6 alkylene or substituted C3-C6 alkyl.

7. The asparagine polyurea sealant composition according to claim 6, characterized in that: The R 1 Selected from phenyl, C7-C12 substituted phenyl, cycloalkyl or substituted C6-C12 cycloalkyl.

8. The asparagine polyurea sealant composition according to claim 1, characterized in that: The auxiliary agent is selected from one or a combination of two or more of a defoaming agent, a wetting agent, an antioxidant, an anti-ultraviolet agent and a thixotropic agent.

9. The asparagine polyurea sealant composition according to claim 1, characterized in that: The curing agent is selected from isocyanate curing agents, and the molar equivalent ratio of the aspartic acid ester resin to the curing agent is 1:1-1.

1.

10. The asparagine polyurea sealant composition according to claim 1, characterized in that: The raw material components further comprise one or a combination of 1-5 parts of a dewatering agent and 0.5-5 parts of a pigment.

Images