Solvent-free polyurethane putty and preparation method thereof

Abstract

The invention belongs to the technical field of putty, provides solvent-free polyurethane putty and a preparation method thereof, and solves the problem of poor binding force between putty and a base material. The putty comprises the following raw materials in parts by mass: 45-95 parts of a hydroxyl resin composition, 5-15 parts of a plasticizer, 5-10 parts of a rheological agent, 1-5 parts of a dispersing agent, 4-6 parts of a defoaming agent, 40-60 parts of an isocyanate curing agent, 1-5 parts of a thixotropic agent, 40-60 parts of filler and 30-50 parts of an auxiliary agent. According to the invention, a hydroxyl resin composition is used as a matrix, an isocyanate curing agent is used for curing to obtain the polyurethane putty, a composition of methyl hydroxyl silicone oil, a titanate coupling agent and hydroxyl-terminated polybutadiene is selected as an auxiliary agent, and the titanate coupling agent can combine a polyurethane component with a filler, so that the compactness of the putty is improved, and cracking is prevented; the methyl hydroxyl silicone oil and the hydroxyl-terminated polybutadiene can react with the curing agent, so that the binding force of the putty and the base material is further improved.

Description

Technical Field

[0001] The present invention relates to the technical field of putties, in particular to a solvent-free polyurethane putty and a preparation method thereof. Background Art

[0002] Wind power generation is a rapidly developing green energy source. Wind power drives wind turbine blades to generate electricity through generators. To ensure power generation efficiency, wind power generation facilities are generally installed at wind vents. The wind is strong and needs to withstand severe weather changes, which places high demands on the surface performance of the substrate. If the substrate is not protected from any surface damage, the rate of pitting and surface defects will increase significantly, thereby affecting the working efficiency of the blades. Research in the prior art is to apply putty to the surface of the blades. However, practical testing has found that the existing putty has problems such as low adhesion, poor flexibility at low temperatures, and low strength, making it unsuitable for use in wind turbine blades. Summary of the Invention

[0003] The purpose of the present invention is to overcome the defects in the prior art and provide a solvent-free polyurethane putty and a preparation method thereof.

[0004] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0005] The present invention provides a solvent-free polyurethane putty, comprising the following raw materials in parts by mass: 45-95 parts of a hydroxyl resin composition, 5-15 parts of a plasticizer, 5-10 parts of a rheological agent, 1-5 parts of a dispersant, 4-6 parts of a defoaming agent, 40-60 parts of an isocyanate curing agent, 1-5 parts of a thixotropic agent, 40-60 parts of a filler, and 30-50 parts of an additive.

[0006] Preferably, the hydroxy resin composition comprises a resin having a structure of formula (1) and a resin having a structure of formula (2);

[0007] The resin of formula (1) is as follows:

[0008]

[0009] In formula (1), R is

[0010] The resin of formula (2) is as follows:

[0011]

[0012] In formula (2), n is an integer from 1 to 8;

[0013] In formula (2), R is

[0014] The mass ratio of the resin having the structure of formula (1) to the resin having the structure of formula (2) is 1:4-6.

[0015] Preferably, the plasticizer is one or more of dioctyl phthalate, dibutyl phthalate and chlorinated paraffin.

[0016] Preferably, the rheological agent is one or more of sodium polyacrylate, magnesium aluminum silicate and hydroxyethyl cellulose;

[0017] The dispersant is BYK-163 and / or BYK-161.

[0018] Preferably, the defoamer is BYK-141 or BYK-070;

[0019] The isocyanate curing agent comprises diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate and toluene diisocyanate;

[0020] The mass ratio of the diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate and toluene diisocyanate is 1 to 2:1 to 2:1.

[0021] Preferably, the thixotropic agent is one or more of fumed silica, bentonite and hydrogenated castor oil;

[0022] The fillers are talc powder and heavy calcium carbonate, and the mass ratio of the talc powder to the heavy calcium carbonate is 1:3-5.

[0023] Preferably, the auxiliary agent comprises methylhydroxy silicone oil, titanate coupling agent and hydroxyl-terminated polybutadiene;

[0024] The mass ratio of the methylhydroxy silicone oil, the titanate coupling agent and the terminal hydroxy polybutadiene is 1-2:6-8:1-2.

[0025] The present invention also provides a method for preparing the solvent-free polyurethane putty, comprising the following steps:

[0026] (1) mixing a hydroxy resin composition, a plasticizer, a rheological agent, and a dispersant to obtain a hydroxy resin system;

[0027] (2) mixing a hydroxy resin system, a defoamer, and a filler to obtain an intermediate system;

[0028] (3) The intermediate system, isocyanate curing agent, thixotropic agent and auxiliary agent are mixed to obtain the solvent-free polyurethane putty.

[0029] Preferably, the mixing speed in step (1) is 200-500 rpm, the temperature is 80-90° C., and the time is 1-2 h;

[0030] The mixing speed in step (2) is 200-500 rpm, the temperature is 40-50° C., and the time is 0.5-1.5 h.

[0031] Preferably, the mixing speed in step (3) is 500-1000 rpm, the temperature is 60-80° C., the vacuum degree is -0.05-0.1 MPa, and the time is 0.5-1 h.

[0032] The present invention provides a solvent-free polyurethane putty, comprising the following raw materials in parts by mass: 45-95 parts of a hydroxyl resin composition, 5-15 parts of a plasticizer, 5-10 parts of a rheological agent, 1-5 parts of a dispersant, 4-6 parts of a defoamer, 40-60 parts of an isocyanate curing agent, 1-5 parts of a thixotropic agent, 40-60 parts of a filler, and 30-50 parts of an auxiliary agent. The present invention uses a hydroxyl resin composition as a matrix and cures it with an isocyanate curing agent to obtain a polyurethane putty. By adding a rheological agent and a thixotropic agent, the processability of the putty can be effectively improved. The addition of a filler improves the mechanical properties of the putty, increases corrosion resistance, and improves flexibility. The auxiliary agent is a combination of methylhydroxy silicone oil, a titanate coupling agent, and hydroxy-terminated polybutadiene. The titanate coupling agent can combine the polyurethane component and the filler, increase the density of the putty, and prevent cracking. The use of methylhydroxy silicone oil and hydroxy-terminated polybutadiene can react with the curing agent to further improve the bonding strength between the putty and the substrate.

[0033] The present invention also provides a method for preparing the solvent-free polyurethane putty, comprising the following steps: (1) mixing a hydroxyl resin composition, a plasticizer, a rheological agent, and a dispersant to obtain a hydroxyl resin system; (2) mixing the hydroxyl resin system, a defoamer, and a filler to obtain an intermediate system; and (3) mixing the intermediate system, an isocyanate curing agent, a thixotropic agent, and an auxiliary agent to obtain the solvent-free polyurethane putty. The method provided by the present invention has low process requirements and can be obtained by simple mixing and stirring, and is suitable for large-scale preparation and promotion. DETAILED DESCRIPTION

[0034] The present invention provides a solvent-free polyurethane putty, comprising the following raw materials in parts by mass: 45-95 parts of a hydroxyl resin composition, 5-15 parts of a plasticizer, 5-10 parts of a rheological agent, 1-5 parts of a dispersant, 4-6 parts of a defoaming agent, 40-60 parts of an isocyanate curing agent, 1-5 parts of a thixotropic agent, 40-60 parts of a filler, and 30-50 parts of an additive.

[0035] In the present invention, the mass fraction of the hydroxy resin composition is preferably 50 to 90 parts, more preferably 60 to 80 parts, and even more preferably 65 to 75 parts.

[0036] In the present invention, the mass fraction of the plasticizer is preferably 6 to 14 parts, more preferably 7 to 13 parts, and even more preferably 8 to 12 parts.

[0037] In the present invention, the mass fraction of the rheological agent is preferably 5.5 to 9.5 parts, more preferably 6 to 9 parts, and even more preferably 7 to 8 parts.

[0038] In the present invention, the mass fraction of the dispersant is preferably 1.5 to 4.5 parts, more preferably 2 to 4 parts, and even more preferably 2.5 to 3.5 parts.

[0039] In the present invention, the mass fraction of the defoaming agent is preferably 4.5 to 5.5 parts, more preferably 4.6 to 5.4 parts, and even more preferably 4.8 to 5.2 parts.

[0040] In the present invention, the mass fraction of the isocyanate curing agent is preferably 45 to 55 parts, more preferably 46 to 54 parts, and even more preferably 48 to 52 parts.

[0041] In the present invention, the mass fraction of the thixotropic agent is preferably 1.5 to 4.5 parts, more preferably 2 to 4 parts, and even more preferably 2.5 to 3.5 parts.

[0042] In the present invention, the mass fraction of the filler is preferably 45 to 55 parts, more preferably 46 to 54 parts, and even more preferably 48 to 52 parts.

[0043] In the present invention, the mass fraction of the auxiliary agent is preferably 35 to 45 parts, more preferably 36 to 44 parts, and even more preferably 38 to 42 parts.

[0044] In the present invention, the hydroxy resin composition comprises a resin having a structure of formula (1) and a resin having a structure of formula (2);

[0045] The resin of formula (1) is as follows:

[0046]

[0047] In formula (1), R is

[0048] The resin of formula (2) is as follows:

[0049]

[0050] In formula (2), n is an integer from 1 to 8;

[0051] In formula (2), R is

[0052] The mass ratio of the resin having the structure of formula (1) to the resin having the structure of formula (2) is preferably 1:4 to 6, more preferably 1:4.5 to 5.5, and even more preferably 1:4.6 to 5.4.

[0053] In the present invention, the preparation methods of the resin of formula (1) and the resin of formula (2) are detailed in Chinese invention patent CN103059631A.

[0054] In the present invention, the plasticizer is one or more of dioctyl phthalate, dibutyl phthalate and chlorinated paraffin.

[0055] In the present invention, the rheological agent is one or more of sodium polyacrylate, magnesium aluminum silicate and hydroxyethyl cellulose.

[0056] In the present invention, the dispersant is BYK-163 and / or BYK-161.

[0057] In the present invention, the defoaming agent is BYK-141 or BYK-070.

[0058] In the present invention, the isocyanate curing agent comprises diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate and toluene diisocyanate.

[0059] In the present invention, the mass ratio of diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate and toluene diisocyanate is preferably 1-2:1-2:1, more preferably 1.2-1.8:1.2-1.8:1, and more preferably 1.4-1.6:1.4-1.6:1.

[0060] In the present invention, the thixotropic agent is one or more of fumed silica, bentonite and hydrogenated castor oil.

[0061] In the present invention, the fillers are talc and ground calcium carbonate, and the mass ratio of the talc to ground calcium carbonate is preferably 1:3-5, more preferably 1:3.5-4.5, and even more preferably 1:3.8-4.2.

[0062] In the present invention, the auxiliary agent comprises methylhydroxy silicone oil, titanate coupling agent and hydroxyl-terminated polybutadiene.

[0063] In the present invention, the mass ratio of the methylhydroxy silicone oil, titanate coupling agent and hydroxy-terminated polybutadiene is preferably 1-2:6-8:1-2, more preferably 1.2-1.8:6.5-7.5:1.2-1.8, and more preferably 1.4-1.6:6.8-7.2:1.4-1.6.

[0064] The present invention also provides a method for preparing the solvent-free polyurethane putty, comprising the following steps:

[0065] (1) mixing a hydroxy resin composition, a plasticizer, a rheological agent, and a dispersant to obtain a hydroxy resin system;

[0066] (2) mixing a hydroxy resin system, a defoamer, and a filler to obtain an intermediate system;

[0067] (3) The intermediate system, isocyanate curing agent, thixotropic agent and auxiliary agent are mixed to obtain the solvent-free polyurethane putty.

[0068] In the present invention, the mixing speed in step (1) is preferably 200-500 rpm, more preferably 250-450 rpm, more preferably 300-400 rpm; the temperature is preferably 80-90°C, more preferably 82-88°C, more preferably 84-86°C; and the mixing time is preferably 1-2 h, more preferably 1.2-1.8 h, more preferably 1.4-1.6 h.

[0069] In the present invention, the mixing speed in step (2) is preferably 200-500 rpm, more preferably 250-450 rpm, more preferably 300-400 rpm; the temperature is preferably 40-50°C, more preferably 42-48°C, more preferably 44-46°C; and the mixing time is preferably 0.5-1.5 h, more preferably 0.6-1.4 h, more preferably 0.8-1.2 h.

[0070] In the present invention, the mixing speed in step (3) is preferably 500-1000 rpm, more preferably 600-900 rpm, more preferably 700-800 rpm; the temperature is preferably 60-80°C, more preferably 65-75°C, more preferably 68-72°C; the vacuum degree is preferably -0.05-0.1 MPa, more preferably -0.06-0.09 MPa, more preferably -0.07-0.08 MPa; the time is preferably 0.5-1 h, more preferably 0.6-0.9 h, more preferably 0.7-0.8 h.

[0071] The technical solutions provided by the present invention are described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0072] Example 1

[0073] The following raw materials were prepared: 60 parts of hydroxy resin composition, 10 parts of plasticizer, 8 parts of rheological agent, 3 parts of dispersant, 5 parts of defoamer, 50 parts of isocyanate curing agent, 4 parts of thixotropic agent, 50 parts of filler, and 40 parts of additive.

[0074] Among them, the resin of formula (1) in the hydroxy resin composition is

[0075] R is

[0076] The resin of formula (2) is

[0077] R is n is 4.

[0078] The mass ratio of the resin having the structure of formula (1) to the resin having the structure of formula (2) is 1:5.

[0079] The plasticizer is dioctyl phthalate, the rheological agent is sodium polyacrylate, the dispersant is BYK-163, the defoamer is BYK-141, the mass ratio of diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate and toluene diisocyanate is 1:2:1; the thixotropic agent is bentonite, the mass ratio of talc and heavy calcium carbonate is 1:4; the mass ratio of methylhydroxy silicone oil, titanate coupling agent and terminal hydroxy polybutadiene is 1:7:1.

[0080] The hydroxyl resin composition, plasticizer, rheological agent and dispersant were mixed at 85°C and 400 rpm for 1.5 hours to obtain a hydroxyl resin system; the hydroxyl resin system, defoamer and filler were mixed at 40°C and 300 rpm for 1 hour to obtain an intermediate system; the intermediate system, isocyanate curing agent, thixotropic agent and additive were mixed, and stirred at 70°C and -0.06 MPa at 600 rpm for 1 hour to obtain a solvent-free polyurethane putty.

[0081] Example 2

[0082] The following raw materials were prepared: 50 parts of hydroxy resin composition, 8 parts of plasticizer, 7 parts of rheological agent, 4 parts of dispersant, 5.3 parts of defoaming agent, 58 parts of isocyanate curing agent, 2 parts of thixotropic agent, 47 parts of filler, and 46 parts of auxiliary agent.

[0083] Among them, the resin of formula (1) in the hydroxy resin composition is

[0084] R is

[0085] The resin of formula (2) is

[0086] R is n is 2.

[0087] The mass ratio of the resin having the structure of formula (1) to the resin having the structure of formula (2) is 1:4.

[0088] The plasticizer is dibutyl phthalate, the rheological agent is magnesium aluminum silicate, the dispersant is BYK-161, the defoamer is BYK-070, the mass ratio of diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate and toluene diisocyanate is 2:2:1; the thixotropic agent is fumed silica, the mass ratio of talc and heavy calcium carbonate is 1:5; the mass ratio of methyl hydroxy silicone oil, titanate coupling agent and terminal hydroxy polybutadiene is 2:6:1.

[0089] The hydroxyl resin composition, plasticizer, rheological agent and dispersant were mixed at 80°C and 300 rpm for 2 hours to obtain a hydroxyl resin system; the hydroxyl resin system, defoamer and filler were mixed at 50°C and 400 rpm for 1.5 hours to obtain an intermediate system; the intermediate system, isocyanate curing agent, thixotropic agent and additive were mixed, and stirred at 800 rpm for 0.7 hours at 60°C and -0.09 MPa to obtain a solvent-free polyurethane putty.

[0090] Example 3

[0091] The following raw materials were prepared: 80 parts of hydroxy resin composition, 11 parts of plasticizer, 7 parts of rheological agent, 4 parts of dispersant, 5.5 parts of defoaming agent, 60 parts of isocyanate curing agent, 1.6 parts of thixotropic agent, 55 parts of filler, and 50 parts of auxiliary agent.

[0092] Among them, the resin of formula (1) in the hydroxy resin composition is

[0093] R is

[0094] The resin of formula (2) is

[0095] R is n is 6.

[0096] The mass ratio of the resin having the structure of formula (1) to the resin having the structure of formula (2) is 1:6.

[0097] The plasticizer is chlorinated paraffin, the rheological agent is hydroxyethyl cellulose, the dispersant is BYK-163, the defoaming agent is BYK-070, the mass ratio of diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate and toluene diisocyanate is 2:1.5:1; the thixotropic agent is hydrogenated castor oil, the mass ratio of talc and heavy calcium carbonate is 1:5; the mass ratio of methylhydroxy silicone oil, titanate coupling agent and terminal hydroxy polybutadiene is 2:2:1.5.

[0098] The hydroxyl resin composition, plasticizer, rheological agent and dispersant were mixed at 90°C and 500 rpm for 2 hours to obtain a hydroxyl resin system; the hydroxyl resin system, defoamer and filler were mixed at 50°C and 400 rpm for 0.8 hours to obtain an intermediate system; the intermediate system, isocyanate curing agent, thixotropic agent and auxiliary agent were mixed, and stirred at 80°C and -0.08 MPa at 500 rpm for 1 hour to obtain a solvent-free polyurethane putty.

[0099] The solvent-free polyurethane putty prepared in Examples 1-3 was tested for adhesion. The sample substrate used for the adhesion test was epoxy fiberglass reinforced plastic (GFRP) with a thickness of ≥4 mm. The putty film was dried for at least 7 days under the environmental conditions specified in GB / T 9278-2008 before testing. The impact resistance of the putty film was tested after drying for 24 hours under the environmental conditions specified in GB / T 9278-2008. The results are recorded in Table 1.

[0100] Table 1 Test results

[0101] Test standards Example 1 Example 2 Example 3 Flexibility / mm GB / T1748-1979 50 50 50 Adhesion / MPa GB / T5210-2006 9.5 9.3 9.5 Impact resistance / (kg·cm) GB / T1732-1993 50 50 50

[0102] It can be seen from the above embodiments that the present invention provides a solvent-free polyurethane putty. In the case of a specific hydroxyl resin composition, the flexibility is significantly improved by adding a rheological agent, a thixotropic agent and a filler; the selection of a combination of auxiliary agents improves the bonding strength between the putty and the substrate, the adhesion reaches 9.5 MPa, and the impact resistance reaches 50 kg·cm. It is a solvent-free polyurethane putty with excellent performance that can be used on wind turbine blades.

[0103] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A solvent-free polyurethane putty, characterized in that, The invention comprises the following raw materials in parts by mass: 45 to 95 parts of hydroxyl resin composition, 5 to 15 parts of plasticizer, 5 to 10 parts of rheological agent, 1 to 5 parts of dispersant, 4 to 6 parts of defoaming agent, 40 to 60 parts of isocyanate curing agent, 1 to 5 parts of thixotropic agent, 40 to 60 parts of filler and 30 to 50 parts of auxiliary agent.

2. The solvent-free polyurethane putty according to claim 1, wherein The hydroxy resin composition comprises a resin having a structure of formula (1) and a resin having a structure of formula (2); The resin of formula (1) is as follows: In formula (1), R is The resin of formula (2) is as follows: In formula (2), n is an integer from 1 to 8; In formula (2), R is The mass ratio of the resin having the structure of formula (1) to the resin having the structure of formula (2) is 1:4-6.

3. The solvent-free polyurethane putty according to claim 1, wherein The plasticizer is one or more of dioctyl phthalate, dibutyl phthalate and chlorinated paraffin.

4. The solvent-free polyurethane putty according to claim 3, wherein: The rheological agent is one or more of sodium polyacrylate, magnesium aluminum silicate and hydroxyethyl cellulose; The dispersant is BYK-163 and / or BYK-161.

5. The solvent-free polyurethane putty according to claim 4, wherein: The defoamer is BYK-141 or BYK-070; The isocyanate curing agent comprises diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate and toluene diisocyanate; The mass ratio of the diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate and toluene diisocyanate is 1 to 2:1 to 2:

1.

6. The solvent-free polyurethane putty according to claim 5, wherein: The thixotropic agent is one or more of fumed silica, bentonite and hydrogenated castor oil; The fillers are talc powder and heavy calcium carbonate, and the mass ratio of the talc powder to the heavy calcium carbonate is 1:3-5.

7. The solvent-free polyurethane putty according to claim 6, wherein: The auxiliary agent comprises methylhydroxy silicone oil, titanate coupling agent and terminal hydroxy polybutadiene; The mass ratio of the methylhydroxy silicone oil, the titanate coupling agent and the terminal hydroxy polybutadiene is 1-2:6-8:1-2.

8. The method for preparing the solvent-free polyurethane putty according to any one of claims 1 to 7, characterized in that: It includes the following steps: (1) mixing a hydroxy resin composition, a plasticizer, a rheological agent, and a dispersant to obtain a hydroxy resin system; (2) mixing a hydroxy resin system, a defoamer, and a filler to obtain an intermediate system; (3) The intermediate system, isocyanate curing agent, thixotropic agent and auxiliary agent are mixed to obtain the solvent-free polyurethane putty.

9. The method for preparing solvent-free polyurethane putty according to claim 8, wherein: The mixing speed in step (1) is 200-500 rpm, the temperature is 80-90° C., and the time is 1-2 h; The mixing speed in step (2) is 200-500 rpm, the temperature is 40-50° C., and the time is 0.5-1.5 h.

10. The method for preparing the solvent-free polyurethane putty according to claim 9, wherein: The mixing speed in step (3) is 500-1000 rpm, the temperature is 60-80° C., the vacuum degree is -0.05-0.1 MPa, and the time is 0.5-1 h.

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