A two-component flame-retardant reinforced resin putty and its preparation method

Abstract

The present invention belongs to the technical field of putties, and discloses a two-component flame-retardant reinforced resin putty and a preparation method thereof. The putty comprises component A and component B; component A comprises raw materials in the following mass parts: 60-80 parts of reinforced resin, 50-70 parts of filler, 5-10 parts of anti-settling agent, 15-25 parts of modified boron nitride, 1-2 parts of leveling agent, 7-10 parts of diluent, 5-8 parts of nano powder material, 2-4 parts of silane coupling agent, 2-4 parts of defoaming agent, and 1-2 parts of bactericide; component B is a curing agent; the mass ratio of component A to component B is (4-5):1. In the present invention, an allyl compound-modified bismaleimide resin and an acrylic acid-modified silicone resin are mixed as the matrix resin, and modified boron nitride and nano powder material are further added to enhance the flame-retardant performance, so that the putty has excellent flame-retardant performance while having good construction performance and storage stability.

Description

Technical Field

[0001] The present invention belongs to the technical field of putty, and particularly relates to a two-component flame-retardant reinforced resin putty and a preparation method thereof. Background Art

[0002] Putty is a decorative material for leveling the wall surface. With the gradual improvement of people's requirements for decorative materials, the functions of putty are constantly improved. Functional putties such as water resistance and moisture resistance have been gradually developed and applied. In order to further meet people's needs for safety, flame-retardant putty has also emerged. However, there are few flame-retardant putties on the market at present, and their flame-retardant performance is poor, making it difficult to achieve an effective fire prevention and flame-retardant effect.

[0003] Patent document CN106349796A discloses a building wall thermal insulation and flame-retardant putty, which only improves the flame-retardant performance of the putty by modifying polyester fibers. The improvement effect is general, so the flame-retardant effect is poor. Moreover, adding fly ash and graphene during the preparation process affects the color of the putty powder and makes the film-forming time of the putty powder longer during use, and it is difficult to polish, resulting in an extended construction period.

[0004] Therefore, there is an urgent need to develop a flame-retardant putty with excellent flame-retardant performance and construction performance. Summary of the Invention

[0005] The purpose of the present invention is to provide a two-component flame-retardant reinforced resin putty and a preparation method thereof. The allyl compound-modified bismaleimide resin and the acrylic acid-modified silicone resin are mixed as the matrix resin, and then modified boron nitride and nano powder materials are added to further enhance the flame-retardant performance, so that the putty has excellent flame-retardant performance while also having good construction performance and storage stability.

[0006] To solve the technical problems proposed by the present invention, the present invention provides a two-component flame-retardant reinforced resin putty, including component A and component B; component A includes the following raw materials in parts by mass: 60-80 parts of reinforced resin, 50-70 parts of filler, 5-10 parts of anti-settling agent, 15-25 parts of modified boron nitride, 1-2 parts of leveling agent, 7-10 parts of diluent, 5-8 parts of nano powder material, 2-4 parts of silane coupling agent, 2-4 parts of defoaming agent, and 1-2 parts of bactericide; component B is a curing agent; the mass ratio of component A to component B is (4-5):1.

[0007] In the above solution, the reinforced resin is a mixture of an allyl compound-modified bismaleimide resin and an acrylic acid-modified silicone resin.

[0008] Further, the mass ratio of the allyl compound-modified bismaleimide resin to the acrylic acid-modified silicone resin is (3-4):1.

[0009] In the above solution, the filler is one or more of heavy calcium carbonate, talcum powder, silica powder, and titanium dioxide.

[0010] In the above solution, the anti-settling agent is one or two of sodium methyl disulfonate and nano-silica.

[0011] In the above solution, the leveling agent is one or two of polyether siloxane copolymer and methyl aralkyl siloxane.

[0012] In the above solution, the diluent is one or two of C12-14 fatty glycidyl ether (AGE) and hydroxyethyl methacrylate.

[0013] In the above solution, the nano-powder material is one or two of nano-zirconia and nano-aluminum nitride.

[0014] In the above solution, the silane coupling agent is one or more of 3-aminopropyltrimethoxysilane, aminoalkoxysilane, and vinyltriethoxysilane.

[0015] In the above solution, the defoaming agent is an organosilicon defoaming agent.

[0016] In the above solution, the bactericide is an isothiazolinone bactericide.

[0017] Further, the bactericide is one or two of methylisothiazolinone and Kathon.

[0018] In the above solution, the curing agent is T31 or DMP-30.

[0019] In the above solution, the preparation method of the modified boron nitride is as follows:

[0020] 1) Mix polyaniline borate with vegetable oleic acid evenly, dissolve it in ethanol and diisopropylcarbodiimide, then add 4-N,N-dimethylpyridine and mix evenly. Place the obtained mixed solution in a high-pressure reaction kettle, heat and pressurize it under nitrogen protection, stir and react, and then distill under reduced pressure to obtain boron-containing vegetable oleic acid;

[0021] 2) Add boron nitride to the titanium-containing vegetable oleic acid, ultrasonically disperse it, then add chitosan and ammonium polyphosphate, ultrasonically disperse it again, and dry it under vacuum to obtain modified boron nitride.

[0022] Further, the vegetable oleic acid is one or more of cottonseed oleic acid, castor oil acid, and palmitoleic acid.

[0023] Further, the boron nitride is one or two of hexagonal boron nitride and cubic boron nitride.

[0024] Further, the chitosan is water-soluble chitosan with a viscosity of 50-200 mPa·s.

[0025] Further, the ammonium polyphosphate is water-soluble ammonium polyphosphate with a particle size of 300 - 500 mesh.

[0026] Further, the volume ratio of polyaniline boronic acid, vegetable oil fatty acid, ethanol, and diisopropylcarbodiimide is (3 - 4):(7 - 10):20:(4 - 6).

[0027] Further, the mass ratio of 4-N,N-dimethylpyridine to the volume of polyaniline boronic acid is (0.25 - 0.5) g:1 mL.

[0028] Further, in step 1), the temperature is raised to 55 - 70 °C, the pressure is increased to 15 - 20 MPa, and the mixture is stirred at a rate of 1000 - 1200 r / min for 10 - 12 h.

[0029] Further, the vacuum degree of the vacuum distillation is 0.05 - 0.1 MPa, the temperature is 30 - 40 °C, and the vacuum distillation time is 8 - 10 min.

[0030] Further, in step 2), the dosages of the raw materials are as follows by mass parts: 10 - 15 parts of boron nitride, 35 - 50 parts of boron-containing vegetable oil fatty acid, 2 - 4 parts of chitosan, and 3 - 5 parts of ammonium polyphosphate.

[0031] The present invention also provides a preparation method of a two-component flame-retardant reinforced resin putty, comprising the following steps:

[0032] 1) Add the reinforced resin to a stirring device, add the flame retardant under stirring conditions, stir evenly, then add the leveling agent, diluent, and silane coupling agent and stir; then increase the stirring rate, add the modified boron nitride and stir; increase the stirring rate again, add the filler, defoaming agent, anti-settling agent, and bactericide and stir to obtain component A;

[0033] 2) Before use, mix component A and component B and stir to obtain the flame-retardant reinforced resin putty, which can then be applied to the wall for construction.

[0034] In the above solution, the initial stirring rate in step 1) is 800 - 1000 r / min, it is 1000 - 1200 r / min after the first increase, and it is 1200 - 1500 r / min after the second increase.

[0035] In the above solution, in step 1), add the leveling agent, diluent, and silane coupling agent and stir for 8 - 10 min; add the modified boron nitride and stir for 25 - 20 min; add the filler, defoaming agent, anti-settling agent, and bactericide and stir for 15 - 20 min until the fineness is <70 μm.

[0036] In the above solution, the stirring rate in step 2) is 200 - 300 r / min, and the stirring time is 7 - 10 min.

[0037] In the above solution, after the combination A and the combination B are mixed, they need to be used up within 30 minutes.

[0038] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0039] 1) The matrix resin of the present invention adopts a mixture of an allyl compound-modified bismaleimide resin and an acrylic acid-modified silicone resin. Among them, the allyl compound-modified bismaleimide resin has good storage stability and can be cured at room temperature, and the acrylic acid-modified silicone resin has excellent heat resistance but generally needs to be cured and formed at high temperature; through reasonable matching, when the silicone resin in the matrix resin accounts for 20-25%, it is cured and dried by a heat-resistant unsaturated polyester resin at low temperature, and there is also an adhesion promotion of the acrylic acid-modified silicone resin at high temperature. The step-by-step curing method not only ensures that the putty can be dried at room temperature, but also ensures that the putty can be used for a long time at a high temperature below 380°C.

[0040] 2) The present invention mainly further enhances the flame retardant performance through modified boron nitride and nano powder materials. The preparation of the modified boron nitride uses boron nitride as the base material, and boron-containing vegetable oil acid, chitosan and ammonium polyphosphate are used as the shell materials for core-shell structure assembly. The assembly principle is to connect phytic acid and inorganic boron nitride through hydrogen bonds between boron-containing vegetable oil acid molecules. The negatively charged boron-containing phytic acid on the surface of boron nitride binds to chitosan and ammonium polyphosphate through electrostatic interaction, so as to cover a layer of boron-containing polyelectrolyte shell layer on the surface of boron nitride, making it have a higher critical temperature, low dielectric constant, fire resistance and mechanical enhancement performance; on this basis, further adding nano powder materials can not only effectively improve the heat preservation performance of the resin, but also the nano powder materials with smaller particle size will fully enter the hexagonal / cubic boron nitride and the resin, and improve the storage stability between the resin and the filler by improving the cross-linking property with the resin, so that the organic volatiles in the resin combustion process pass through a more complex path, thus delaying the release of pyrolysis volatiles during combustion ("labyrinth" effect). In summary, these synergistic effects significantly improve the fire safety and heat preservation performance of the putty. Detailed implementation manners

[0041] In order to better understand the present invention, the content of the present invention will be further clarified below in conjunction with embodiments, but the content of the present invention is not limited to the following embodiments only.

[0042] In the following examples, the allyl compound-modified bismaleimide resin used is the modified bismaleimide resin produced and sold by Dalian Jiangyu New Materials Technology Co., Ltd. It is a high-temperature resistant bismaleimide resin copolymerized and modified from a Cardo aromatic heterocyclic bismaleimide monomer and an allyl bisphenol A compound with a liquid crystal structure; the acrylic acid-modified silicone resin used is the acrylic acid-modified silicone resin produced and sold by Wuhan Huaxiang Kejie Co., Ltd. It is prepared from the silanols hydrolyzed from phenyl and methyl monomers and the acrylic resin through a specific process.

[0043] Example 1

[0044] A two-component flame-retardant reinforced resin putty, comprising component A and component B;

[0045] Component A comprises raw materials in the following parts by mass: 60 parts of reinforced resin (allyl compound-modified bismaleimide resin and acrylic acid-modified silicone resin with a mass ratio of 3:1), 50 parts of filler (heavy calcium carbonate and talcum powder with a mass ratio of 1:1), 5 parts of anti-settling agent (sodium methyl disulfonate), 15 parts of modified boron nitride, 1 part of leveling agent (polyether silicone copolymer), 7 parts of diluent (AGE), 5 parts of nano powder material (nano zirconia), 2 parts of silane coupling agent (3-aminopropyltrimethoxysilane), 2 parts of defoaming agent (organosilicon defoaming agent RXY-2040), 1 part of bactericide (methylisothiazolinone); Component B is curing agent T31; the mass ratio of component A to component B is 4:1.

[0046] Among them, the preparation method of the modified boron nitride is as follows:

[0047] 1) Mix 3 mL of polyaniline borate and 7 mL of palmitic acid evenly, dissolve them in 20 mL of ethanol and 4 mL of diisopropylcarbodiimide, then add 1 g of 4-N,N-dimethylpyridine and mix evenly. Place the obtained mixture in a high-pressure reactor. Under nitrogen protection, heat it to 60 °C, pressurize it to 20 MPa, and then stir and react at a rate of 1000 r / min for 12 h. Then, carry out vacuum distillation for 10 min under the conditions of a vacuum degree of 0.1 MPa and a temperature of 30 °C to obtain boron-containing vegetable oil acid;

[0048] 2) Add 15 g of hexagonal boron nitride to 50 g of boron-containing vegetable oil acid, ultrasonically disperse for 15 min, then add 4 g of water-soluble chitosan with a viscosity of 100 mPa·s and 5 g of water-soluble ammonium polyphosphate with a particle size of 300 mesh. After ultrasonic dispersion, carry out vacuum drying to obtain modified boron nitride.

[0049] The preparation method of the two-component flame-retardant reinforced resin putty in this example comprises the following steps:

[0050] 1) Add the reinforced resin to the stirring equipment, add the flame retardant at a stirring rate of 800 r / min, stir evenly and then add the leveling agent, diluent and silane coupling agent and stir for 10 min; then increase the stirring rate to 1000 r / min, add the modified boron nitride and stir for 20 min; increase the stirring rate to 1200 r / min again, add the filler, defoaming agent, anti-settling agent and fungicide and stir for 20 min until the fineness is <70 μm to obtain Component A;

[0051] 2) Before use, mix Component A and Component B, and stir at a rate of 200 r / min for 10 min to obtain the flame-retardant reinforced resin putty, which can be applied to the wall for construction.

[0052] Example 2

[0053] A two-component flame-retardant reinforced resin putty, comprising Component A and Component B;

[0054] Component A includes raw materials in the following mass parts: 70 parts of reinforced resin (allyl compound-modified bismaleimide resin and acrylic acid-modified silicone resin with a mass ratio of 4:1), 60 parts of filler (heavy calcium carbonate and titanium dioxide with a mass ratio of 2:1), 7 parts of anti-settling agent (nano-silica), 18 parts of modified boron nitride, 1 part of leveling agent (methyl aralkyl siloxane), 8 parts of diluent (hydroxyethyl methacrylate), 6 parts of nano-powder material (nano-aluminum nitride), 3 parts of silane coupling agent (aminoalkoxysilane), 3 parts of defoaming agent (organosilicon defoaming agent RXY-2040), 2 parts of fungicide (Kathon); Component B is the curing agent DMP-30; the mass ratio of Component A to Component B is 5:1.

[0055] Among them, the preparation method of the modified boron nitride is as follows:

[0056] 1) Mix 3 mL of polyaniline borate and 8 mL of cottonseed oleic acid evenly, dissolve them in 20 mL of ethanol and 5 mL of diisopropylcarbodiimide, then add 1.2 g of 4-N,N-dimethylpyridine and mix evenly. Place the obtained mixed solution in a high-pressure reaction kettle, under nitrogen protection, heat up to 65 °C, pressurize to 20 MPa, and stir and react at a rate of 1200 r / min for 10 h, and then carry out vacuum distillation for 8 min under the conditions of a vacuum degree of 0.1 MPa and a temperature of 35 °C to obtain boron-containing vegetable oil acid;

[0057] 2) Add 10 g of cubic boron nitride to 35 g of boron-containing vegetable oil acid, ultrasonically disperse for 15 min, then add 2 g of water-soluble chitosan with a viscosity of 200 mPa·s and 3 g of water-soluble ammonium polyphosphate with a particle size of 300 mesh, ultrasonically disperse and then vacuum dry to obtain the modified boron nitride.

[0058] The preparation method of the two-component flame-retardant reinforced resin putty in this example includes the following steps:

[0059] 1) Add the reinforced resin to the stirring equipment, add the flame retardant at a stirring rate of 900 r / min, stir evenly and then add the leveling agent, diluent and silane coupling agent and stir for 9 min; then increase the stirring rate to 1100 r / min, add the modified boron nitride and stir for 23 min; increase the stirring rate to 1300 r / min again, add the filler, defoaming agent, anti-settling agent and fungicide and stir for 18 min until the fineness is <70 μm to obtain Component A;

[0060] 2) Before use, mix Component A and Component B and stir at a rate of 300 r / min for 8 min to obtain the flame-retardant reinforced resin putty, which can be applied to the wall for construction.

[0061] Example 3

[0062] A two-component flame-retardant reinforced resin putty, comprising Component A and Component B;

[0063] Component A includes raw materials in the following mass parts: 80 parts of reinforced resin (allyl compound-modified bismaleimide resin and acrylic acid-modified silicone resin with a mass ratio of 3:1), 70 parts of filler (talc powder and silica powder with a mass ratio of 1:1), 10 parts of anti-settling agent (sodium methyl disulfonate), 20 parts of modified boron nitride, 2 parts of leveling agent (polyether silicone copolymer), 10 parts of diluent (2-hydroxyethyl methacrylate), 8 parts of nano powder material (nano zirconia and nano aluminum nitride with a mass ratio of 1:1), 4 parts of silane coupling agent (vinyltriethoxysilane), 4 parts of defoaming agent (organosilicon defoaming agent RXY-2040), 2 parts of fungicide (Kathon); Component B is the curing agent DMP-30; the mass ratio of Component A to Component B is 4:1.

[0064] Among them, the preparation method of the modified boron nitride is as follows:

[0065] 1) Mix 4 mL of polyaniline borate with 10 mL of ricinoleic acid evenly, dissolve it in 20 mL of ethanol and 6 mL of diisopropylcarbodiimide, then add 1.5 g of 4-N,N-dimethylpyridine and mix evenly. Place the obtained mixed solution in a high-pressure reaction kettle. Under nitrogen protection, heat it to 65 °C, pressurize it to 20 MPa, and stir and react at a rate of 1200 r / min for 11 h. Then carry out vacuum distillation for 10 min under the conditions of a vacuum degree of 0.1 MPa and a temperature of 35 °C to obtain boron-containing vegetable oil acid;

[0066] 2) Add 15 g of cubic boron nitride to 45 g of boron-containing vegetable oil acid, ultrasonically disperse for 15 min, then add 3 g of water-soluble chitosan with a viscosity of 200 mPa·s and 5 g of water-soluble ammonium polyphosphate with a particle size of 500 mesh, ultrasonically disperse and then vacuum dry to obtain the modified boron nitride.

[0067] The preparation method of the two-component flame-retardant reinforced resin putty in this embodiment includes the following steps:

[0068] 1) Add the reinforced resin to the stirring equipment, add the flame retardant at a stirring rate of 1000 r / min, stir evenly, then add the leveling agent, diluent and silane coupling agent and stir for 8 min; then increase the stirring rate to 1200 r / min, add the modified boron nitride and stir for 20 min; increase the stirring rate to 1500 r / min again, add the filler, defoaming agent, anti-settling agent and bactericide and stir for 15 min until the fineness is <70 μm to obtain Component A;

[0069] 2) Before use, mix Component A and Component B, and stir at a rate of 300 r / min for 8 min to obtain the flame-retardant reinforced resin putty, which can be applied to the wall for construction.

[0070] Comparative Example 1

[0071] The difference between Comparative Example 1 and Example 1 is only that 18 parts of the modified boron nitride in Component A are replaced by 18 parts of ordinary boron nitride.

[0072] Comparative Example 2

[0073] The difference between Comparative Example 2 and Example 1 is only that the reinforced resin in Component A is an acrylic-modified silicone resin.

[0074] Comparative Example 3

[0075] The difference between Comparative Example 3 and Example 1 is only that the reinforced resin in Component A is an allyl compound-modified bismaleimide resin.

[0076] Test the performances of Examples 1-3 and Comparative Examples 1-3. Among them, the method for testing the stability of Component A is: Take 18 kg of the prepared Component A and place it in a 20 L iron bucket, seal it and observe whether it layers; the method for testing the flame retardancy is: Apply the prepared putty on a cement board of 300×300×30 mm, with a coating thickness of 2 mm, then continuously burn it with an alcohol blowtorch for 30 s and then move it away, and check the self-extinguishing time of the putty layer; other performances are tested according to the JG / T 157-2009 standard; the results are shown in Table 1.

[0077] Table 1

[0078]

[0079]

[0080] As can be seen from Table 1, the putty prepared by the example has good construction performance, high bonding strength, excellent storage stability and excellent flame retardancy, while the comparative examples have the disadvantages of slower curing time, layering and poorer flame retardancy.

[0081] The above embodiments are merely examples for clear illustration and not limitations on the implementation manners. For those of ordinary skill in the art, based on the above description, other different forms of changes or alterations can be made. It is not necessary and impossible to enumerate all implementation manners here, and thus the obvious changes or alterations derived therefrom still fall within the protection scope of the present invention.

Claims

1. A two-component flame-retardant reinforced resin putty, characterized in that, It includes Component A and Component B; Component A includes raw materials in the following parts by mass: 60 - 80 parts of reinforcing resin, 50 - 70 parts of filler, 5 - 10 parts of anti-settling agent, 15 - 25 parts of modified boron nitride, 1 - 2 parts of leveling agent, 7 - 10 parts of diluent, 5 - 8 parts of nano powder material, 2 - 4 parts of silane coupling agent, 2 - 4 parts of defoaming agent, 1 - 2 parts of bactericide; Component B is a curing agent; the mass ratio of Component A to Component B is (4 - 5):1; The reinforcing resin is a mixture of allyl compound modified bismaleimide resin and acrylic modified silicone resin; the nano powder material is one or both of nano zirconia and nano aluminum nitride; The preparation method of the modified boron nitride is as follows: 1) Mix polyaniline borate with vegetable oleic acid evenly, dissolve it in ethanol and diisopropylcarbodiimide, then add 4-N,N-dimethylpyridine and mix evenly. Place the obtained mixture in a high-pressure reactor, heat up and pressurize under nitrogen protection, stir and react, and then carry out vacuum distillation to obtain boron-containing vegetable oleic acid; 2) Add boron nitride to the boron-containing vegetable oleic acid, ultrasonically disperse it, then add chitosan and ammonium polyphosphate, ultrasonically disperse it again, and dry it under vacuum to obtain modified boron nitride.

2. The two-component flame-retardant reinforced resin putty according to claim 1, wherein, The mass ratio of the allyl compound modified bismaleimide resin to the acrylic modified silicone resin is (3 - 4):

1.

3. The two-component flame-retardant reinforced resin putty according to claim 1, wherein The volume ratio of polyaniline borate, vegetable oleic acid, ethanol, and diisopropylcarbodiimide is (3 - 4):(7 - 10):20:(4 - 6); the mass ratio of 4-N,N-dimethylpyridine to the volume of polyaniline borate is (0.25 - 0.5) g:1 mL.

4. The two-component flame-retardant reinforced resin putty according to claim 1, characterized in that, In step 1), heat up to 55 - 70 °C, pressurize to 15 - 20 MPa, stir and react at a rate of 1000 - 1200 r / min for 10 - 12 h, and then carry out vacuum distillation for 8 - 10 min under the conditions of a vacuum degree of 0.05 - 0.1 MPa and a temperature of 30 - 40 °C.

5. The two-component flame-retardant reinforced resin putty according to claim 1, characterized in that, In step 2), the dosage of each raw material is in parts by mass: 10 - 15 parts of boron nitride, 35 - 50 parts of boron-containing vegetable oleic acid, 2 - 4 parts of chitosan, and 3 - 5 parts of ammonium polyphosphate.

6. The two-component flame-retardant reinforced resin putty according to claim 1, characterized in that, The vegetable oleic acid is one or more of cottonseed oleic acid, castor oil acid, and palmitoleic acid; the boron nitride is one or both of hexagonal boron nitride and cubic boron nitride; the chitosan is water-soluble chitosan with a viscosity of 50 - 200 mPa·s; the ammonium polyphosphate is water-soluble ammonium polyphosphate with a particle size of 300 - 500 mesh.

7. The two-component flame-retardant reinforced resin putty according to claim 1, wherein The anti-settling agent is one or both of sodium methyl disulfonate and nano silica; the silane coupling agent is one or more of 3-aminopropyltrimethoxysilane, aminoalkoxysilane, and vinyltriethoxysilane; the curing agent is T31 or DMP-30.

8. The preparation method of the two-component flame-retardant reinforced resin putty according to any one of claims 1-7, characterized in that, It includes the following steps: 1) Add the reinforcing resin to a stirring device, add a flame retardant under stirring conditions, stir evenly, then add a leveling agent, a diluent, and a silane coupling agent and stir; then increase the stirring rate, add the modified boron nitride and stir; increase the stirring rate again, add the filler, a defoaming agent, an anti-settling agent, and a bactericide and stir to obtain Component A; 2) Before use, mix the A combination and the B combination and stir to obtain a flame-retardant reinforced resin putty, which can then be applied to the wall for construction.

9. The preparation method of the two-component flame-retardant reinforced resin putty according to claim 8, characterized in that, The initial stirring rate in step 1) is 800 - 1000 r / min, 1000 - 1200 r / min after the first increase, 1200 - 1500 r / min after the second increase, and finally stir until the fineness of component A is < 70 μm; the stirring rate in step 2) is 200 - 300 r / min, and the stirring time is 7 - 10 min.

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