Composition for modified polyurethane waterproof coating, modified polyurethane waterproof coating, preparation method and application thereof

Abstract

The present invention relates to the field of building waterproofing, and discloses a modified polyurethane waterproof coating composition, a modified polyurethane waterproof coating, and a preparation method and application thereof. The composition is composed of a main agent and an auxiliary agent, wherein the main agent is a polyether polyol, an acrylic polyol, and a polyisocyanate; based on the total weight of the composition, the content of the polyether polyol is 17-30wt%, the content of the acrylic polyol is 1-3wt%, and the content of the polyisocyanate is 3-8wt%; the polyether polyol is selected from at least one of polytetramethylene ether glycol, polypropylene glycol, and POP, and the POP is a vinyl polymer grafted polyether polyol; and the acrylic polyol is a polystyrene-allyl alcohol copolymer polyol. The modified polyurethane waterproof coating provided by the present invention has excellent wear resistance, hardness, and bonding properties.

Description

Technical Field

[0001] The present invention relates to the field of building waterproofing, and in particular to a modified polyurethane waterproof coating composition, a modified polyurethane waterproof coating, and a preparation method and application thereof. Background Art

[0002] The application of building waterproof materials is a key link in the development of the construction industry, and polyurethane waterproof coatings are an important component of all building waterproof materials. In recent years, with the comprehensive strengthening of my country's infrastructure construction, the waterproof industry has also ushered in broad development prospects.

[0003] Polyurethane waterproof coatings are one of the earliest and most widely used waterproofing materials. Traditionally, polyurethane waterproof coatings are made by mixing isocyanate-containing prepolymers, formed through the addition polymerization of isocyanates and polyethers, with additives such as fillers, solvents, and catalysts. They exhibit excellent elasticity, adhesion, chemical resistance, and weather resistance, making them widely used in a variety of fields, including construction, transportation, water conservancy, and industry. They provide reliable waterproofing and can effectively address the challenges of a variety of complex environments.

[0004] However, in some special scenarios such as underground garages and rooftops, due to the high friction frequency, load-bearing strength and hardness requirements, coupled with the erosion of groundwater, the application of ordinary polyurethane waterproof coatings will easily damage the waterproof layer, greatly reducing the waterproof life and making the waterproof effect unsatisfactory.

[0005] CN116875174A discloses a silane-modified polyurethane waterproof coating and its preparation method. The coating comprises the following raw materials by weight: 3-8 parts of isocyanate, 15-35 parts of polyether polyol, 10-20 parts of plasticizer, 40-60 parts of filler, 0.05-0.1 parts of catalyst, 0.15-0.25 parts of silane coupling agent, 0.5-1 parts of auxiliary agent, 5-10 parts of solvent, and 1-2 parts of curing agent. The silane coupling agent comprises a silane having two amino groups and an epoxysilane. This prior art improves the tensile strength, bonding strength, and waterproofing properties of the polyurethane waterproof coating to a certain extent. However, the material has low hardness and poor friction resistance, making it ineffective in high-stress applications such as parking lots and rooftops. The waterproof layer is easily damaged within a short period of time, and a long-lasting waterproofing effect is not achieved.

[0006] Therefore, it is of great significance to develop a new modified polyurethane waterproof coating with high hardness, excellent wear resistance and bonding properties and suitable for use in special scenarios such as underground garages and walkable roofs. Summary of the Invention

[0007] The purpose of the present invention is to solve the problem of poor hardness and wear resistance of polyurethane waterproof coatings in the prior art.

[0008] In order to achieve the above-mentioned object, the first aspect of the present invention provides a modified polyurethane waterproof coating composition, which is composed of a main agent and an auxiliary agent, wherein the main agent is polyether polyol, acrylic polyol and polyisocyanate;

[0009] Based on the total weight of the composition, the content of the polyether polyol is 17-30 wt %, the content of the acrylic polyol is 1-3 wt %, and the content of the polyisocyanate is 3-8 wt %;

[0010] The polyether polyol is selected from at least one of polytetramethylene glycol, polypropylene glycol and POP, and the POP is a vinyl polymer grafted polyether polyol;

[0011] The acrylic polyol is a polystyrene-allyl alcohol copolymer polyol.

[0012] The second aspect of the present invention provides a method for preparing a modified polyurethane waterproof coating, which is carried out using the components in the composition described in the first aspect. The method comprises: stirring and mixing the components in the main agent and the components in the auxiliary agent in the composition to obtain the modified polyurethane waterproof coating.

[0013] The third aspect of the present invention provides a modified polyurethane waterproof coating prepared by the method described in the second aspect.

[0014] The fourth aspect of the present invention provides the use of the modified polyurethane waterproof coating described in the third aspect in building waterproofing.

[0015] Through the above technical solution, the present invention has at least the following advantages:

[0016] (1) The modified polyurethane waterproof coating provided by the present invention has excellent strength, hardness, friction resistance and mechanical properties.

[0017] (2) The modified polyurethane waterproof coating provided by the present invention has good stain resistance and corrosion resistance. Its long-lasting and reliable waterproof effect can meet the application requirements in special scenarios such as underground garages and rooftops, and plays an important role in the quality assurance of building waterproofing projects. DETAILED DESCRIPTION

[0018] The endpoints of the ranges and any values ​​disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

[0019] As mentioned above, the first aspect of the present invention provides a modified polyurethane waterproof coating composition, the composition is composed of a main agent and an auxiliary agent, the main agent is polyether polyol, acrylic polyol and polyisocyanate;

[0020] Based on the total weight of the composition, the content of the polyether polyol is 17-30 wt %, the content of the acrylic polyol is 1-3 wt %, and the content of the polyisocyanate is 3-8 wt %;

[0021] The polyether polyol is selected from at least one of polytetramethylene glycol, polypropylene glycol and POP, and the POP is a vinyl polymer grafted polyether polyol;

[0022] The acrylic polyol is a polystyrene-allyl alcohol copolymer polyol.

[0023] In the present invention, the polypropylene glycol is abbreviated as PPG, the polytetramethylene ether glycol is abbreviated as PTMEG, the toluene diisocyanate is abbreviated as TDI, the diphenylmethane diisocyanate is abbreviated as MDI, the hexamethylene diisocyanate is abbreviated as HDI, and the dicyclohexylmethane diisocyanate is abbreviated as HMDI.

[0024] Preferably, the number average molecular weight of the polystyrene-allyl alcohol copolymer polyol is 1300-1800, and the hydroxyl value is 200-220 mgKOH / g.

[0025] Preferably, the polyether polyol is a combination of polytetramethylene glycol, polypropylene glycol, and POP in a weight ratio of 2-3:2-3:1. The inventors have found that in this preferred embodiment, the modified polyurethane waterproof coating provided by the present invention has better hardness and friction resistance.

[0026] More preferably, the number average molecular weight of the polytetramethylene ether glycol is 1800-2200, the number average molecular weight of the polypropylene glycol is 800-1200, and the solid content of the POP is 20-40 wt%.

[0027] More preferably, the density of the POP is 1.02-1.05 g / cm 3 and the hydroxyl value is 25-40 mgKOH / g. The inventors of the present invention have found that under this preferred embodiment, the modified polyurethane waterproof coating provided by the present invention has better tensile strength and bonding properties.

[0028] According to a preferred embodiment, the polyisocyanate is selected from one or a combination of aromatic diisocyanates, aliphatic diisocyanates and alicyclic diisocyanates.

[0029] Preferably, the polyisocyanate is selected from at least one of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and dicyclohexylmethane diisocyanate.

[0030] According to a preferred embodiment, the polyisocyanate is a combination of toluene diisocyanate and dicyclohexylmethane diisocyanate.

[0031] According to a more preferred embodiment, the polyisocyanate is a combination of toluene diisocyanate and dicyclohexylmethane diisocyanate in a weight ratio of 5-6:1. The inventors of the present invention have discovered that in this preferred embodiment, the modified polyurethane waterproof coating provided by the present invention has better bonding and mechanical properties.

[0032] Preferably, the auxiliary agents include plasticizers, defoamers, dispersants, color pastes, catalysts, latent curing agents, solvents and fillers.

[0033] Preferably, based on the total weight of the composition, the content of the plasticizer is 5-10wt%, the content of the defoamer is 0.1-0.3wt%, the content of the dispersant is 0.02-0.04wt%, the content of the color paste is 1-2wt%, the content of the catalyst is 0.03-0.05wt%, the content of the latent curing agent is 2-4wt%, the content of the solvent is 5-10wt%, and the content of the filler is 40-50wt%.

[0034] According to a preferred embodiment, the plasticizer is selected from at least one of phthalates, aliphatic dibasic acid esters, phosphates, and chlorinated paraffins.

[0035] According to a more preferred embodiment, the plasticizer is chlorinated paraffin-52.

[0036] The present invention has no special requirements on the type of the defoaming agent, the type of the catalyst and the specific type of the color paste. Those skilled in the art can use the defoaming agents, catalysts and color pastes known in the art in the scheme of the present invention. For example, the defoaming agent can be a silicone defoaming agent, the catalyst can be an organic metal catalyst, and the color paste can be selected according to specific needs. A color paste of suitable color can be selected.

[0037] According to a preferred embodiment, the filler is selected from at least one of calcined kaolin, talc, calcium carbonate, silica powder, mica powder, silica fume, titanium dioxide, and gypsum powder.

[0038] According to a more preferred embodiment, the filler is a combination of talc powder with an average particle diameter of 12-14 μm and ground calcium carbonate with an average particle diameter of 14-16 μm, at a weight ratio of 1:0.5-0.8. The inventors of the present invention have discovered that in this preferred embodiment, the modified polyurethane waterproof coating provided by the present invention has higher hardness and better wear resistance.

[0039] As mentioned above, the second aspect of the present invention provides a method for preparing a modified polyurethane waterproof coating, which is carried out using the components in the composition described in the first aspect. The method includes: stirring and mixing the components in the main agent and the components in the auxiliary agent in the composition to obtain the modified polyurethane waterproof coating.

[0040] Preferably, the stirring and mixing conditions are: rotation speed 200-1500 rpm, temperature 55-120° C., and time 5-200 min.

[0041] According to a preferred embodiment, the method for preparing a modified polyurethane waterproof coating comprises: stirring and mixing polyether polyol, acrylic polyol, plasticizer, defoamer, dispersant, color paste, filler, polyisocyanate, catalyst, latent curing agent, and solvent to obtain the modified polyurethane waterproof coating.

[0042] According to a particularly preferred embodiment, the method for preparing the modified polyurethane waterproof coating comprises the following steps:

[0043] (1) first mixing polyether polyol and acrylic polyol to obtain intermediate I;

[0044] (2) performing a second mixing of the intermediate I with a plasticizer, a defoamer, a dispersant, and a color paste to obtain an intermediate II;

[0045] (3) performing a third mixing of the intermediate II and the filler to obtain the intermediate III;

[0046] (4) mixing the intermediate III with polyisocyanate for the fourth time to obtain the intermediate IV;

[0047] (5) mixing the intermediate IV with a catalyst and a latent curing agent to obtain an intermediate V;

[0048] (6) The intermediate V is mixed with the solvent for the sixth time to obtain the modified polyurethane waterproof coating.

[0049] According to a more preferred embodiment, in step (3), the method further comprises dehydrating the intermediate III, wherein the dehydration conditions include: a temperature of 100-120°C, a pressure of -0.08 MPa to -0.1 MPa, and a time of 2-3 hours. That is, the present invention preferably includes the dehydrated intermediate III in the fourth mixing step.

[0050] According to a preferred embodiment, in step (1), the first mixing conditions include: a rotation speed of 200-500 rpm, a temperature of 100-120° C., and a time of 5-10 min.

[0051] According to a preferred embodiment, in step (2), the second mixing conditions include: a rotation speed of 200-500 rpm, a temperature of 100-120° C., and a time of 20-30 min.

[0052] According to a preferred embodiment, in step (3), the conditions for the third mixing include: a rotation speed of 1000-1500 rpm, a temperature of 100-120° C., and a time of 15-25 min.

[0053] According to a preferred embodiment, in step (4), the fourth mixing conditions include: a rotation speed of 1000-1500 rpm, a temperature of 80-90° C., and a time of 150-200 min.

[0054] According to a particularly preferred embodiment, the temperature of the fourth mixing is 85-88°C.

[0055] According to a particularly preferred embodiment, in step (5), the fifth mixing conditions include: temperature of 70-80° C., and time of 50-70 min.

[0056] According to a particularly preferred embodiment, in step (6), the conditions for the sixth mixing include: a temperature of 55-65° C. and a time of 20-30 min.

[0057] As mentioned above, the third aspect of the present invention provides a modified polyurethane waterproof coating prepared by the method described in the second aspect.

[0058] Preferably, the viscosity of the modified polyurethane waterproof coating is 7000-10000 MPa.s / (23±2)°C.

[0059] As mentioned above, the fourth aspect of the present invention provides the use of the modified polyurethane waterproof coating described in the third aspect in building waterproofing.

[0060] The present invention will be described in detail below by way of examples. In the following examples, unless otherwise specified, all instruments and raw materials used are commercially available.

[0061] Some of the raw materials and their sources used in the following examples are as follows:

[0062] Polytetramethylenetetramethylene ether glycol (PTMEG): number average molecular weight is 2000, brand name PolyTHF 2000, purchased from BASF;

[0063] Polypropylene glycol (PPG): number average molecular weight of 1000, brand DL-1000, purchased from Shandong Bluestar Dongda Chemical Company;

[0064] Vinyl polymer grafted polyether polyol-I (POP-I): solid content 24wt%, density 1.04g / cm 3 , hydroxyl value is 28mgKOH / g, brand POP-36, purchased from Shandong Bluestar Dongda Company;

[0065] Vinyl polymer grafted polyether polyol-II (POP-II): solid content 40wt%, density 1.06g / cm 3 , hydroxyl value 22mgKOH / g, brand MD22-40, purchased from Shell Chemical Company;

[0066] Toluene diisocyanate (TDI): brand WANNATE TDI-80, purchased from Wanhua Company;

[0067] Dicyclohexylmethane diisocyanate (HMDI): brand WANNATE-HMDI, purchased from Wanhua Company;

[0068] Diphenylmethane diisocyanate (MDI): brand WANNATE MDI-50, purchased from Wanhua Company;

[0069] Polymethylene polyphenyl isocyanate: brand PM-100, purchased from Yantai Wanhua Company;

[0070] Acrylic polyol-I: polystyrene-allyl alcohol copolymer polyol, number average molecular weight of 1500, hydroxyl value of 210 mgKOH / g, brand SAA-100, purchased from LyondellBasell;

[0071] Acrylic polyol-II: polystyrene-allyl alcohol copolymer polyol, number average molecular weight of 1200, hydroxyl value of 255 mgKOH / g, brand SAA-101, purchased from LyondellBasell;

[0072] Acrylic polyol-III: BASF hydroxy acrylic acid 804, trade name 804, purchased from BASF;

[0073] Plasticizer: Chlorinated paraffin-52, purchased from Guangzhou Yuting Chemical Company;

[0074] Defoaming agent: silicone defoaming agent, brand AP001, purchased from Guangzhou Lanxi Environmental Protection Technology Co., Ltd.

[0075] Dispersant: Phosphate ester dispersant, brand Diusper S18, purchased from Guangdong Core New Materials Company;

[0076] Catalyst: stannous octoate, brand T-19, purchased from Guihe Bei Weida Chemical;

[0077] Latent curing agent: aldimine latent curing agent, model YH-292, purchased from Shandong Yihang Company;

[0078] Solvent: toluene, analytical grade;

[0079] Color paste: green paste, purchased from Hangzhou Qianshan Paint Company;

[0080] Talc: average particle diameter is 14 μm;

[0081] Heavy calcium carbonate: The average particle diameter is 16μm.

[0082] Unless otherwise specified, the amounts of raw materials in the following examples are all parts by weight, and each part by weight represents 100 g.

[0083] Example 1

[0084] (1) Stirring polyether polyol and acrylic polyol for 10 min at a speed of 400 rpm and a temperature of 110° C. to obtain intermediate 1;

[0085] (2) stirring and mixing the intermediate I with the plasticizer, defoamer, dispersant, and color paste at a speed of 400 rpm and a temperature of 110° C. for 20 min to obtain the intermediate II;

[0086] (3) Stirring and mixing the intermediate II and the filler at a speed of 1200 rpm and a temperature of 110° C. for 20 min to obtain the intermediate III;

[0087] (4) Dehydrating the intermediate III, wherein the dehydration treatment conditions are: temperature 110° C., pressure -0.09 MPa, and time 3 h;

[0088] (5) At a rotation speed of 1200 rpm and a temperature of 86° C., the intermediate III and the polyisocyanate were stirred and mixed for 180 min to obtain the intermediate IV;

[0089] (6) Adjusting the temperature to 75° C., stirring and mixing the intermediate IV with the catalyst and the latent curing agent for 60 min to obtain the intermediate V;

[0090] (7) The temperature was adjusted to 60° C., and the intermediate V and the solvent were stirred and mixed for 20 minutes to obtain the modified polyurethane waterproof coating.

[0091] Unless otherwise specified, the following examples are carried out with reference to the method of Example 1, except that the types and amounts of raw materials used in the remaining examples are different. For details, see Table 1.

[0092] Table 1

[0093]

[0094]

[0095] Example 4

[0096] A method similar to Example 1 was used, except that acrylic polyol-I was replaced with acrylic polyol-II in equal parts by weight.

[0097] Example 5

[0098] The method was similar to that in Example 1, except that:

[0099] The polyether polyol in this embodiment is PTMEG, PPG and POP-I in a weight ratio of 1:1:1, and the total amount of the polyether polyol in this embodiment is the same as the total amount of the polyether polyol in Example 1.

[0100] Example 6

[0101] The method was similar to that in Example 1, except that:

[0102] The polyether polyol in this embodiment is PTMEG (polytetramethylene ether glycol), and the total amount of the polyether polyol in this embodiment is the same as the total amount of the polyether polyol in Example 1.

[0103] Example 7

[0104] The method was similar to that in Example 1, except that:

[0105] The polyether polyol in this embodiment is PTMEG, PPG and POP-II in a weight ratio of 3:2.5:1, and the total amount of the polyether polyol in this embodiment is the same as the total amount of the polyether polyol in Example 1.

[0106] Example 8

[0107] The method was similar to that in Example 1, except that:

[0108] The polyisocyanate in this embodiment is polymethylene polyphenyl isocyanate in equal parts by weight.

[0109] Comparative Example 1

[0110] The same method as in Example 1 was used, except that the amount of acrylic polyol was adjusted to 0.5 parts by weight, and the amount of solvent was adjusted to 8.75 parts by weight.

[0111] Comparative Example 2

[0112] The method was similar to that of Example 1, except that the amount of acrylic polyol was adjusted to 4 parts by weight and the amount of solvent was adjusted to 5.25 parts by weight.

[0113] Comparative Example 3

[0114] A method similar to Example 1 was used, except that acrylic polyol-I was replaced with acrylic polyol-III in equal parts by weight.

[0115] Test Case

[0116] The performance of the modified polyurethane waterproof coatings obtained in the above examples was tested in accordance with the performance requirements of GB / T 19250-2013, Polyurethane Waterproof Coatings. Hardness was measured using the Shore hardness test, and wear resistance was tested using an abrasion machine. Specific results are shown in Table 2.

[0117] Table 2

[0118]

[0119]

[0120] Table 2

[0121]

[0122] From the results in Table 2, it can be seen that the modified polyurethane waterproof coating provided by the present invention has significantly better strength, hardness, wear resistance and bonding performance, while also having excellent mechanical properties and corrosion resistance.

[0123] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, various simple variations of the technical solution of the present invention may be made, including combining the various technical features in any other appropriate manner. These simple variations and combinations should also be regarded as disclosed in the present invention and fall within the scope of protection of the present invention.

Claims

1. A modified polyurethane waterproof coating composition, characterized in that: The composition is composed of a main agent and auxiliary agents, wherein the main agent is polyether polyol, acrylic polyol and polyisocyanate; Based on the total weight of the composition, the content of the polyether polyol is 17-30wt%, the content of the acrylic polyol is 1-3wt%, and the content of the polyisocyanate is 3-8wt%; The polyether polyol is selected from at least one of polytetramethylene glycol, polypropylene glycol and POP, and the POP is a vinyl polymer grafted polyether polyol; The acrylic polyol is a polystyrene-allyl alcohol copolymer polyol.

2. The composition according to claim 1, wherein The number average molecular weight of the polystyrene-allyl alcohol copolymer polyol is 1300-1800, and the hydroxyl value is 200-220 mgKOH / g.

3. The composition according to claim 1 or 2, wherein The polyether polyol is a combination of polytetramethylene ether glycol, polypropylene glycol and POP in a weight ratio of 2-3:2-3:

1.

4. The composition according to claim 3, wherein The number average molecular weight of the polytetramethylene ether glycol is 1800-2200, the number average molecular weight of the polypropylene glycol is 800-1200, and the solid content of the POP is 20-40 wt %.

5. The composition according to claim 4, wherein The density of the POP is 1.02-1.05 g / cm 3 , the hydroxyl value is 25-40mgKOH / g.

6. The composition according to claim 1 or 2, wherein The polyisocyanate is selected from one or a combination of aromatic diisocyanates, aliphatic diisocyanates and alicyclic diisocyanates.

7. The composition according to claim 6, wherein The polyisocyanate is selected from at least one of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and dicyclohexylmethane diisocyanate.

8. The composition according to claim 7, wherein The polyisocyanate is a combination of toluene diisocyanate and dicyclohexylmethane diisocyanate.

9. The composition according to claim 8, wherein The polyisocyanate is a combination of toluene diisocyanate and dicyclohexylmethane diisocyanate in a weight ratio of 5-6:

1.

10. The composition according to claim 1 or 2, wherein The auxiliary agents include plasticizers, defoamers, dispersants, color pastes, catalysts, latent curing agents, solvents and fillers; Based on the total weight of the composition, the content of the plasticizer is 5-10wt%, the content of the defoamer is 0.1-0.3wt%, the content of the dispersant is 0.02-0.04wt%, the content of the color paste is 1-2wt%, the content of the catalyst is 0.03-0.05wt%, the content of the latent curing agent is 2-4wt%, the content of the solvent is 5-10wt%, and the content of the filler is 40-50wt%.

11. The composition according to claim 10, wherein In the auxiliary agent, the filler is selected from at least one of calcined kaolin, talc, calcium carbonate, silica powder, mica powder, silica fume, titanium dioxide, and gypsum powder.

12. A method for preparing a modified polyurethane waterproof coating, characterized in that: The method is carried out using the components in the composition according to any one of claims 1 to 11, and comprises: stirring and mixing the components in the main agent and the components in the auxiliary agent in the composition to obtain the modified polyurethane waterproof coating.

13. The method according to claim 12, wherein: The stirring and mixing conditions include: a rotation speed of 200-1500 rpm, a temperature of 55-120° C., and a time of 5-200 min.

14. A modified polyurethane waterproof coating prepared according to the method of claim 12 or 13.

15. Use of the modified polyurethane waterproof coating according to claim 14 in building waterproofing.

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