Flame-retardant polyurethane two-component corner adhesive and preparation method thereof

Abstract

The application relates to the technical field of building adhesives, and particularly discloses a fire-retardant polyurethane two-component corner adhesive and a preparation method thereof; the fire-retardant polyurethane two-component corner adhesive comprises an A component and a B component; the A component comprises, in mass parts, first polyether polyol: 40-55 parts; first filler: 20-35 parts; first thixotropic agent: 1-5 parts; compounded fire retardant: 20-25 parts; modifier: 1-2 parts; catalyst: 0.004-0.008 parts; the B component comprises, in mass parts, curing agent: 35-45 parts; second polyether polyol: 1-5 parts; plasticizer: 8-12 parts; second filler: 40-50 parts; and second thixotropic agent: 1-2 parts; the fire-retardant polyurethane two-component corner adhesive has good fire-retardant function, high hardness, high toughness and high bonding strength; and the fire-retardant polyurethane two-component corner adhesive also has excellent sealing function, structure reinforcing function, shock-absorbing function, sound insulation function and heat insulation function.

Description

Technical Field

[0001] This invention relates to the field of building adhesives, specifically to a flame-retardant two-component polyurethane corner adhesive and its preparation method. Background Technology

[0002] In recent years, with increasingly stringent requirements for energy conservation and emission reduction, building energy consumption, currently the largest contributor to national energy consumption, will inevitably become a major breakthrough point for energy conservation and emission reduction in the future. Windows and doors are the weakest points in a building's thermal insulation performance, accounting for 50% of the total energy consumption of the building envelope, bringing unprecedented opportunities and challenges to the development and reform of building windows and doors.

[0003] Europe developed high-performance system windows and doors as early as the 1980s, whose energy-saving performance, safety performance, and comfort far exceed those of ordinary windows and doors. In 2003, European window and door standards required a heat transfer coefficient (K-value) of no more than 1.3. Currently, high-performance system windows and doors are widely used in Europe, accounting for 70% of the total window and door market. In my country, the average K-value for windows and doors is approximately 3.5. Based on my country's current urban building area of ​​approximately 43 billion square meters... 2 Calculations show that if the current European standard K-value for doors and windows were implemented, 430 million tons of standard coal could be saved annually, which is about 20% of China's annual coal production, demonstrating significant energy-saving effects.

[0004] Currently, high-performance doors and windows are generally corner-clip type. Corner adhesive is a sealant product with polyurethane (PU) as the main component, specifically designed for corner-clip type doors and windows. It fills and bonds the corner clips to the cavity walls of the profile, playing a structural reinforcement role. It plays an important role in promoting the structural strength, service life, and sealing performance of doors and windows. The use of polyurethane corner adhesive, on the one hand, prevents the door and window frames from being misaligned and deformed due to temperature differences and external forces. On the other hand, it seals and bonds the gaps, ensuring the waterproof, airtight, heat insulation, and sound insulation performance of doors and windows. However, current corner adhesives have problems such as poor flame retardant performance, flammability at high temperatures, and easy smoke generation. Summary of the Invention

[0005] To address the aforementioned problems, the first objective of this invention is to provide a flame-retardant two-component polyurethane corner adhesive. This flame-retardant two-component polyurethane corner adhesive has excellent flame-retardant properties, as well as high hardness, high toughness, and high adhesive strength; it also has excellent sealing, structural reinforcement, shock absorption, sound insulation, and heat insulation properties.

[0006] The second objective of this invention is to provide a method for preparing a flame-retardant two-component polyurethane corner protectant.

[0007] The first technical solution adopted in this invention is: a flame-retardant polyurethane two-component corner adhesive, comprising component A and component B, wherein component A comprises the following components by mass:

[0008] First polyether polyol: 40 parts to 55 parts;

[0009] The first filler should be 20 to 35 parts;

[0010] 1 to 5 parts of the first thixotropic agent;

[0011] 20 to 25 parts of compound flame retardant;

[0012] 1 to 2 parts of modifier;

[0013] Catalyst: 0.004 parts to 0.008 parts;

[0014] Component B comprises the following components by mass:

[0015] 35 to 45 parts of curing agent;

[0016] 1 to 5 parts of the second polyether polyol;

[0017] Plasticizer: 8 to 12 parts;

[0018] 40 to 50 parts of the second filler;

[0019] 1 to 2 parts of the second thixotropic agent;

[0020] The compound flame retardant includes melamine orthophosphate, pentaerythritol, and 2-carboxyethylphenylphosphonic acid grafted polyether polyol.

[0021] Preferably, the molar ratio of melamine orthophosphate, pentaerythritol and 2-carboxyethylphenylphosphonic acid is (8-20):(10-24):(5-10).

[0022] Preferably, the first polyether polyol comprises polyether polyol A, polyether polyol B, and polyether polyol C; wherein polyether polyol A is a difunctional polyether polyol with a molecular weight range of 1000 to 3000, polyether polyol B is a trifunctional polyether polyol with a molecular weight range of 1000 to 3000, and polyether polyol C is a difunctional polyether polyol with a molecular weight range of 200 to 1000; the molar ratio of polyether polyol A, polyether polyol B, and polyether polyol C is (85 to 92):(8 to 15):1.

[0023] Preferably, the first filler is heavy calcium carbonate, which is subjected to stearic acid surface activation treatment;

[0024] The first thixotropic agent is one or more of fumed silica and sodium polyamide;

[0025] The modifier is one or more of γ-aminopropyltriethoxysilane and N-β-aminoethyl-γ-aminopropyltrimethoxysilane;

[0026] The catalyst is one or more of organobismuth or organotin.

[0027] Preferably, the second polyether polyol is a trifunctional polyether polyol D or / and a difunctional polyether polyol E, with a molecular weight range of 1000 to 3000.

[0028] Preferably, the curing agent is one or more of polymethylene polyphenyl isocyanate and liquefied diphenylmethane diisocyanate;

[0029] The plasticizer is one or more of petroleum ether, dibutyl phthalate, diisobutyl phthalate, and dinonyl phthalate;

[0030] The second filler is one or more of talc, calcium carbonate, kaolin, and bentonite;

[0031] The second thixotropic agent is fumed silica.

[0032] Preferably, the volume ratio of component A to component B is A:B = 1:1.

[0033] The second technical solution adopted in this invention is: a method for preparing a flame-retardant polyurethane two-component corner adhesive as described in the first technical solution, comprising the following steps:

[0034] Preparation of component A:

[0035] Weigh out the first polyether polyol, the first filler, the first thixotropic agent, the compound flame retardant, the modifier, and the catalyst; dry and dehydrate the first filler, and dehydrate the first polyether polyol under vacuum; mix the first thixotropic agent, the compound flame retardant, the modifier, the catalyst, and the dehydrated first filler and first polyether polyol to obtain component A; wherein the compound flame retardant includes melamine orthophosphate, pentaerythritol, and 2-carboxyethylphenylphosphonic acid grafted polyether polyol;

[0036] Preparation of component B:

[0037] Weigh out the curing agent, the second polyether polyol, the plasticizer, the second filler, and the second thixotropic agent; dry and dehydrate the second filler; pre-react the curing agent and the second polyether polyol to obtain an isocyanate-terminated polyether polyol prepolymer; mix the plasticizer, the second thixotropic agent, the dehydrated second filler, and the polyether polyol prepolymer to obtain component B;

[0038] The components A and B are respectively filled into the container to obtain the flame-retardant polyurethane two-component corner adhesive.

[0039] Preferably, the 2-carboxyethylphenylphosphonic acid grafted polyether polyol is prepared by the following method:

[0040] Using phosphoric acid as a catalyst, 2-carboxyethylphenylphosphonic acid was added dropwise to polyether polyol B to carry out an esterification grafting reaction, thereby preparing 2-carboxyethylphenylphosphonic acid-grafted polyether polyol; wherein the polyether polyol B is a trifunctional polyether polyol with a molecular weight range of 1000 to 3000.

[0041] Preferably, the molar ratio of 2-carboxyethylphenylphosphonic acid to polyether polyol B is 1:(1-2); the amount of phosphoric acid used is 1% of the total mass of 2-carboxyethylphenylphosphonic acid and polyether polyol B.

[0042] The beneficial effects of the above technical solution are as follows:

[0043] (1) The flame-retardant polyurethane two-component corner adhesive disclosed in this invention has the advantages of good stability, long storage time, fast curing speed and excellent filling ability of two-component corner adhesives on the market. It is more suitable for corner splicing and corner overall injection bonding and sealing of aluminum alloy doors and windows and curtain walls. At the same time, it has good flame-retardant properties. The self-made flame retardant 2-carboxyethylphenylphosphonic acid grafted polyether polyol molecule has active reactive groups, which are tightly combined with the cured polyurethane system through chemical bonds. It has good dispersion ability and forms a good compound flame-retardant effect with other intumescent flame retardants.

[0044] (2) This invention addresses the problems of leakage, deformation, and corner cracking in aluminum alloy (including insulated aluminum alloy) doors, windows, and curtain wall corners, especially large aluminum alloy doors, windows, and curtain wall corners. It is a specially designed and developed flame-retardant polyurethane two-component corner adhesive. This flame-retardant polyurethane two-component corner adhesive is an environmentally friendly, flame-retardant adhesive that is solvent-free, pollution-free, and free of harmful substances. It has high hardness, high toughness, and high bonding strength. It also has excellent sealing, structural reinforcement, shock absorption, sound insulation, heat insulation, and flame-retardant functions. It conforms to the national industrial policy of "high-polymer materials, low cost, and high-performance technology". It solves problems such as leakage, deformation, and corner cracking in doors and windows, improves the overall strength of aluminum alloy doors, windows, and curtain walls, further improves the energy conservation and emission reduction level of the domestic construction industry, and reduces fire losses. The price of domestically produced polyurethane two-component corner adhesive is much lower than that of similar imported products. It is also supplied in a timely manner and has a broad market prospect, with good economic and social benefits.

[0045] (3) Compared with traditional two-component corner adhesives, this invention adds a compound flame retardant; at the same time, compared with traditional flame retardants such as magnesium hydroxide and aluminum hydroxide, this invention uses low-functionality, high-activity polyether polyol, combined with polyurethane prepolymer and compound flame retardant, so that the flame-retardant polyurethane two-component corner adhesive prepared by this invention has a higher flame retardant rating and better dispersibility. Its quality is stable and its comprehensive performance is good. It can meet the flame retardant performance FV-0 level in GB / T 24267-09 "Flame-retardant sealants for building" and the fire resistance integrity 3h level in GB / T 23864-09 "Fireproof sealing materials", and has excellent flame retardant ability. Tests have shown that the flame-retardant polyurethane two-component corner adhesive with the compound flame retardant of this invention has comparable bonding strength, toughness and impact resistance compared with ordinary commercial products; and its flame retardant ability is greatly improved, with obvious effect.

[0046] (4) The flame-retardant polyurethane two-component corner adhesive disclosed in this invention has the advantages of fast curing speed, high hardness, high strength, high flame retardant efficiency, stable system and environmental protection. It has excellent performance and practicality in many environments such as corner splicing and corner overall injection bonding and sealing of aluminum alloy doors and windows and curtain walls. That is, it can be used for bonding, sealing and reinforcement of aluminum alloy doors and windows, curtain walls and large aluminum alloy doors and windows and curtain walls. Attached Figure Description

[0047] Figure 1 This is a schematic flowchart illustrating a method for preparing a flame-retardant two-component polyurethane corner adhesive according to an embodiment of the present invention. Detailed Implementation

[0048] The present invention will be further illustrated below with specific embodiments. It should be noted that those skilled in the art can make several modifications and improvements without departing from the principle of the present invention, and these should also be considered to fall within the protection scope of the present invention.

[0049] The terms “first,” “second,” etc. (if applicable) in the specification and claims are used to distinguish similar objects and are not necessarily used to describe a particular order or sequence. It should be understood that such data used in this way can be interchanged where appropriate so that the embodiments described herein can be implemented in orders other than those illustrated or described herein. Furthermore, the terms “comprising” and “having,” and any variations thereof, are intended to cover a non-exclusive inclusion, such as a process, method, system, product, or apparatus that comprises a series of steps or units, not necessarily limited to those explicitly listed, but may include other steps or units not explicitly listed or inherent to such processes, methods, products, or apparatus.

[0050] The contents not described in detail in this specification are common knowledge to those skilled in the art.

[0051] This invention discloses a flame-retardant polyurethane two-component corner adhesive, comprising component A and component B, wherein the volume ratio of component A to component B is A:B = 1:1;

[0052] Component A, by mass, includes the following components:

[0053] First polyether polyol: 40 parts to 55 parts;

[0054] The first filler should be 20 to 35 parts;

[0055] 1 to 5 parts of the first thixotropic agent;

[0056] 20 to 25 parts of compound flame retardant;

[0057] 1 to 2 parts of modifier;

[0058] Catalyst: 0.004 parts to 0.008 parts;

[0059] Component B comprises the following components by mass:

[0060] 35 to 45 parts of curing agent;

[0061] 1 to 5 parts of the second polyether polyol;

[0062] Plasticizer: 8 to 12 parts;

[0063] 40 to 50 parts of the second filler;

[0064] The second thixotropic agent is 1 to 2 parts.

[0065] The compound flame retardant comprises melamine orthophosphate, pentaerythritol, and 2-carboxyethylphenylphosphonic acid grafted polyether polyol, wherein the molar ratio of melamine orthophosphate, pentaerythritol, and 2-carboxyethylphenylphosphonic acid is (8-20):(10-24):(5-10); the 2-carboxyethylphenylphosphonic acid grafted polyether polyol is prepared by the following method:

[0066] Under conditions of 160°C and ≥0.09 MPa, using phosphoric acid as a catalyst, 2-carboxyethylphenylphosphonic acid is added dropwise to an excess of polyether polyol B (i.e., a trifunctional polyether polyol with a molecular weight range of 1000–3000) to carry out an esterification grafting reaction, thereby preparing 2-carboxyethylphenylphosphonic acid-grafted polyether polyol; the molar ratio of 2-carboxyethylphenylphosphonic acid to polyether polyol B is 1:(1–2); the amount of phosphoric acid used is 1% of the total mass of 2-carboxyethylphenylphosphonic acid and polyether polyol B.

[0067] The first polyether polyol includes polyether polyol A, polyether polyol B, and polyether polyol C; polyether polyol A is a difunctional polyether polyol with a molecular weight range of 1000 to 3000, polyether polyol B is a trifunctional polyether polyol with a molecular weight range of 1000 to 3000, and polyether polyol C is a difunctional polyether polyol with a molecular weight range of 200 to 1000; the molar ratio of polyether polyol A, polyether polyol B, and polyether polyol C is (85 to 92): (8 to 15): 1.

[0068] The first filler is heavy calcium carbonate, which is treated with stearic acid surface activation and has a fineness range of 8000-10000 mesh.

[0069] The first thixotropic agent is one or more of fumed silica and sodium polyamide.

[0070] The modifier is one or more of γ-aminopropyltriethoxysilane and N-β-aminoethyl-γ-aminopropyltrimethoxysilane.

[0071] The catalyst is one or more of organobismuth or organotin.

[0072] The curing agent is one or more of polymethylene polyphenyl isocyanate and liquefied diphenylmethane diisocyanate.

[0073] The second polyether polyol is a trifunctional polyether polyol D or / and a difunctional polyether polyol E, with a molecular weight range of 1000 to 3000.

[0074] The plasticizer is one or more of petroleum ether, dibutyl phthalate, diisobutyl phthalate, and dinonyl phthalate.

[0075] The second filler is one or more of talc, calcium carbonate, kaolin, and bentonite.

[0076] The second thixotropic agent is fumed silica, specifically hydrophobic fumed silica with a specific surface area ranging from 80 to 120 m². 2 / g.

[0077] like Figure 1 As shown, this invention also discloses a method for preparing a flame-retardant polyurethane two-component corner adhesive, comprising the following steps:

[0078] Preparation of component A:

[0079] Weigh out the first polyether polyol, the first filler, the first thixotropic agent, the compound flame retardant, the modifier, and the catalyst; dry and dehydrate the first filler at 100-105°C for 20-24 hours, and dehydrate the first polyether polyol under vacuum at 100-105°C for 1 hour; put the first thixotropic agent, the compound flame retardant, the modifier, the catalyst, and the dehydrated first filler and the first polyether polyol into a double planetary mixer, and mix under vacuum at 65-70°C for 3 hours to obtain component A.

[0080] Preparation of component B:

[0081] Weigh out the curing agent, the second polyether polyol, the plasticizer, the second filler, and the second thixotropic agent; dry and dehydrate the second filler at 100-105°C for 20-24 hours, and pre-react the curing agent and the second polyether polyol at 75-80°C for 2 hours to obtain an isocyanate-terminated polyether polyol prepolymer; add the plasticizer, the second thixotropic agent, the dehydrated second filler, and the polyether polyol prepolymer into a double planetary mixer and vacuum mix at 65-70°C for 3 hours to obtain component B.

[0082] The flame-retardant polyurethane two-component corner adhesive is obtained by filling the components A and B separately (for example, filling the components A and B separately into two-component tubes that are separated from each other).

[0083] Example 1

[0084] A flame-retardant two-component polyurethane corner adhesive includes component A and component B, wherein,

[0085] (1) The preparation of component A includes:

[0086] Weigh out 35 parts by weight of polyether polyol A, 5 parts by weight of polyether polyol B and 0.4 parts by weight of polyether polyol C, 35 parts by weight of heavy calcium carbonate, 5 parts by weight of the first thixotropic agent (the first thixotropic agent is silica and sodium polyamide compounded in a mass ratio of 1:1), 23 parts by weight of the compound flame retardant (the compound flame retardant is melamine orthophosphate, pentaerythritol and 2-carboxyethylphenylphosphonic acid compounded in a molar ratio of 10:20:5), 1 part by weight of γ-aminopropyltriethoxysilane and 0.005 parts by weight of organotin;

[0087] 35 parts by weight of heavy calcium carbonate were dried and dehydrated at 105°C for 24 hours. 35 parts by weight of polyether polyol A, 5 parts by weight of polyether polyol B and 0.4 parts by weight of polyether polyol C were mixed and dehydrated under vacuum at 100°C for 1 hour.

[0088] Five parts by mass of the first thixotropic agent, 23 parts by mass of the compound flame retardant, 1 part by mass of γ-aminopropyltriethoxysilane, 0.005 parts by mass of organotin, and dehydrated heavy calcium carbonate and the first polyether polyol (35 parts by mass of polyether polyol A, 5 parts by mass of polyether polyol B and 0.4 parts by mass of polyether polyol C) were added to a double planetary mixer and mixed under vacuum at 70°C for 3 hours.

[0089] (2) The preparation of component B includes:

[0090] Weigh out 42 parts by weight of curing agent (polymethylene polyphenyl isocyanate), 4 parts by weight of second polyether polyol (the second polyether polyol is a compound of trifunctional polyether polyol D and difunctional polyether polyol E in a mass ratio of 5:5), 11 parts by weight of plasticizer (the plasticizer is a compound of petroleum ether and dibutyl phthalate in a mass ratio of 5:5), 46 parts by weight of second filler (the second filler is a compound of talc, calcium carbonate, kaolin and bentonite in a mass ratio of 10:10:5:5), and 1 part by weight of fumed silica;

[0091] 46 parts by weight of the second filler were dried and dehydrated at 100°C for 20 hours, and 42 parts by weight of polymethylene polyphenyl isocyanate and 4 parts by weight of the second polyether polyol were pre-reacted at 75°C for 2 hours.

[0092] 11 parts by weight of plasticizer, 1 part by weight of fumed silica, dehydrated second filler, and isocyanate-terminated polyether polyol prepolymer obtained by pre-reaction of polymethylene polyphenyl isocyanate and second polyether polyol were put into a double planetary mixer and mixed under vacuum at 65°C for 3 hours.

[0093] (3) Filling

[0094] After the preparation of components A and B, components A and B are respectively filled into two-component tubes separated from each other in a volume ratio of 1:1 to obtain the flame-retardant polyurethane two-component corner adhesive.

[0095] Example 2

[0096] A flame-retardant two-component polyurethane corner adhesive includes component A and component B, wherein,

[0097] (1) The preparation of component A includes:

[0098] Weigh out 39 parts by weight of polyether polyol A, 5 parts by weight of polyether polyol B and 0.4 parts by weight of polyether polyol C, 24 parts by weight of heavy calcium carbonate, 1 part by weight of the first thixotropic agent (the first thixotropic agent is fumed silica and sodium polyamide compounded in a mass ratio of 10:8), 22 parts by weight of the compound flame retardant (the compound flame retardant is melamine orthophosphate, pentaerythritol and 2-carboxyethylphenylphosphonic acid compounded in a molar ratio of 8:16:10), 2 parts by weight of N-β-aminoethyl-γ-aminopropyltrimethoxysilane and 0.004 parts by weight of organic bismuth;

[0099] 24 parts by weight of heavy calcium carbonate were dried and dehydrated at 105°C for 22 hours. 39 parts by weight of polyether polyol A, 5 parts by weight of polyether polyol B and 0.4 parts by weight of polyether polyol C were mixed and dehydrated under vacuum at 105°C for 1 hour.

[0100] One part by mass of the first thixotropic agent, 22 parts by mass of the compound flame retardant, 2 parts by mass of N-β-aminoethyl-γ-aminopropyltrimethoxysilane, 0.004 parts by mass of organic bismuth, and dehydrated heavy calcium carbonate and the first polyether polyol (39 parts by mass of polyether polyol A, 5 parts by mass of polyether polyol B and 0.4 parts by mass of polyether polyol C) were added to a double planetary mixer and mixed under vacuum at 65°C for 3 hours.

[0101] (2) The preparation of component B includes:

[0102] Weigh out 45 parts by weight of curing agent (liquefied diphenylmethane diisocyanate), 2 parts by weight of second polyether polyol (the second polyether polyol is a compound of trifunctional polyether polyol D and difunctional polyether polyol E in a mass ratio of 6:4), 12 parts by weight of plasticizer (the plasticizer is a compound of petroleum ether and dibutyl phthalate in a mass ratio of 6:4), 42 parts by weight of second filler (the second filler is a compound of talc, calcium carbonate, kaolin and bentonite in a mass ratio of 12:12:3:3), and 1.5 parts by weight of fumed silica;

[0103] 42 parts by weight of the second filler were dried and dehydrated at 100°C for 21 hours, and 45 parts by weight of the curing agent and 2 parts by weight of the second polyether polyol were pre-reacted at 80°C for 2 hours.

[0104] 12 parts by weight of plasticizer, 1.5 parts by weight of fumed silica, dehydrated second filler, curing agent, and isocyanate-terminated polyether polyol prepolymer obtained by pre-reaction of the second polyether polyol were put into a double planetary mixer and vacuum mixed at 65°C for 3 hours.

[0105] (3) Filling

[0106] After the preparation of components A and B, components A and B are respectively filled into two-component tubes separated from each other in a volume ratio of 1:1 to obtain the flame-retardant polyurethane two-component corner adhesive.

[0107] Example 3

[0108] A flame-retardant two-component polyurethane corner adhesive includes component A and component B, wherein,

[0109] (1) The preparation of component A includes:

[0110] Weigh out 49 parts by weight of polyether polyol A, 5 parts by weight of polyether polyol B and 0.5 parts by weight of polyether polyol C, 20 parts by weight of heavy calcium carbonate, 4 parts by weight of the first thixotropic agent (the first thixotropic agent is fumed silica and sodium polyamide compounded in a mass ratio of 10:6), 21 parts by weight of the compound flame retardant (the compound flame retardant is melamine orthophosphate, pentaerythritol and 2-carboxyethylphenylphosphonic acid compounded in a molar ratio of 12:24:6), 1.5 parts by weight of N-β-aminoethyl-γ-aminopropyltrimethoxysilane and 0.007 parts by weight of organotin;

[0111] 20 parts by weight of heavy calcium carbonate were dried and dehydrated at 100°C for 23 hours. 49 parts by weight of polyether polyol A, 5 parts by weight of polyether polyol B and 0.5 parts by weight of polyether polyol C were mixed and dehydrated under vacuum at 103°C for 1 hour.

[0112] The first thixotropic agent (4 parts by weight), the compound flame retardant (21 parts by weight), the N-β-aminoethyl-γ-aminopropyltrimethoxysilane (1.5 parts by weight), the organotin (0.007 parts by weight), the dehydrated heavy calcium carbonate, and the first polyether polyol (49 parts by weight of polyether polyol A, 5 parts by weight of polyether polyol B, and 0.5 parts by weight of polyether polyol C) were added into a double planetary mixer and mixed under vacuum at 70°C for 3 hours.

[0113] (2) The preparation of component B includes:

[0114] Weigh out 40 parts by weight of curing agent (curing agent is polymethylene polyphenyl isocyanate and liquefied diphenylmethane diisocyanate compounded in a mass ratio of 1:1), 3 parts by weight of second polyether polyol (second polyether polyol is trifunctional polyether polyol D and difunctional polyether polyol E compounded in a mass ratio of 7:3), 9 parts by weight of plasticizer (plasticizer is petroleum ether and dibutyl phthalate compounded in a mass ratio of 7:3), 44 parts by weight of second filler (second filler is talc, calcium carbonate, kaolin and bentonite compounded in a mass ratio of 11:11:4:4), and 1.5 parts by weight of fumed silica;

[0115] 44 parts by weight of the second filler were dried and dehydrated at 105°C for 23 hours, and 40 parts by weight of the curing agent and 3 parts by weight of the second polyether polyol were pre-reacted at 77°C for 2 hours.

[0116] Nine parts by weight of plasticizer, 1.5 parts by weight of fumed silica, a second filler that has been dehydrated, a curing agent, and an isocyanate-terminated polyether polyol prepolymer obtained by pre-reaction of the second polyether polyol were added to a double planetary mixer and mixed under vacuum at 65°C for 3 hours.

[0117] (3) Filling

[0118] After the preparation of components A and B, components A and B are respectively filled into two-component tubes separated from each other in a volume ratio of 1:1 to obtain the flame-retardant polyurethane two-component corner adhesive.

[0119] Example 4

[0120] A flame-retardant two-component polyurethane corner adhesive includes component A and component B, wherein,

[0121] (1) The preparation of component A includes:

[0122] Weigh out 43 parts by weight of polyether polyol A, 5 parts by weight of polyether polyol B and 0.5 parts by weight of polyether polyol C, 28 parts by weight of heavy calcium carbonate, 2 parts by weight of the first thixotropic agent (the first thixotropic agent is fumed silica and sodium polyamide compounded in a mass ratio of 6:10), 25 parts by weight of the compound flame retardant (the compound flame retardant is melamine orthophosphate, pentaerythritol and 2-carboxyethylphenylphosphonic acid compounded in a molar ratio of 9:18:8), 1.5 parts by weight of γ-aminopropyltriethoxysilane and 0.008 parts by weight of organotin;

[0123] 28 parts by weight of heavy calcium carbonate were dried and dehydrated at 105°C for 21 hours. 43 parts by weight of polyether polyol A, 5 parts by weight of polyether polyol B and 0.5 parts by weight of polyether polyol C were mixed and dehydrated under vacuum at 102°C for 1 hour.

[0124] Two parts by mass of the first thixotropic agent, 28 parts by mass of the compound flame retardant, 1.5 parts by mass of γ-aminopropyltriethoxysilane, 0.008 parts by mass of organotin, and dehydrated heavy calcium carbonate and the first polyether polyol (43 parts by mass of polyether polyol A, 5 parts by mass of polyether polyol B and 0.5 parts by mass of polyether polyol C) were added to a double planetary mixer and mixed under vacuum at 65°C for 3 hours.

[0125] (2) The preparation of component B includes:

[0126] Weigh out 35 parts by weight of curing agent (polymethylene polyphenyl isocyanate), 1 part by weight of second polyether polyol (the second polyether polyol is a compound of trifunctional polyether polyol D and difunctional polyether polyol E in a mass ratio of 3:7), 10 parts by weight of plasticizer (the plasticizer is a compound of petroleum ether and dibutyl phthalate in a mass ratio of 3:7), 40 parts by weight of second filler (the second filler is a compound of talc, calcium carbonate, kaolin and bentonite in a mass ratio of 10:9:5:6) and 2 parts by weight of fumed silica;

[0127] 40 parts by weight of the second filler were dried and dehydrated at 105°C for 22 hours, and 35 parts by weight of the curing agent and 1 part by weight of the second polyether polyol were pre-reacted at 79°C for 2 hours.

[0128] Ten parts by weight of plasticizer, two parts by weight of fumed silica, a second filler that has been dehydrated, a curing agent, and an isocyanate-terminated polyether polyol prepolymer obtained by pre-reaction of the second polyether polyol were added to a double planetary mixer and mixed under vacuum at 65°C for 3 hours.

[0129] (3) Filling

[0130] After the preparation of components A and B, components A and B are respectively filled into two-component tubes separated from each other in a volume ratio of 1:1 to obtain the flame-retardant polyurethane two-component corner adhesive.

[0131] Example 5

[0132] A flame-retardant two-component polyurethane corner adhesive includes component A and component B, wherein,

[0133] (1) The preparation of component A includes:

[0134] Weigh out 46 parts by weight of polyether polyol A, 6 parts by weight of polyether polyol B and 0.4 parts by weight of polyether polyol C, 32 parts by weight of heavy calcium carbonate, 3 parts by weight of the first thixotropic agent (the first thixotropic agent is fumed silica and sodium polyamide compounded in a mass ratio of 8:10), 20 parts by weight of the compound flame retardant (the compound flame retardant is melamine orthophosphate, pentaerythritol and 2-carboxyethylphenylphosphonic acid compounded in a molar ratio of 10:20:10), 2 parts by weight of γ-aminopropyltriethoxysilane and 0.006 parts by weight of organic bismuth;

[0135] 32 parts by weight of heavy calcium carbonate were dried and dehydrated at 100°C for 20 hours. 46 parts by weight of polyether polyol A, 6 parts by weight of polyether polyol B and 0.4 parts by weight of polyether polyol C were mixed and dehydrated under vacuum at 101°C for 1 hour.

[0136] The first thixotropic agent (3 parts by weight), the compound flame retardant (20 parts by weight), the γ-aminopropyltriethoxysilane (2 parts by weight), the organic bismuth (0.006 parts by weight), the dehydrated heavy calcium carbonate, and the first polyether polyol (46 parts by weight of polyether polyol A, 6 parts by weight of polyether polyol B, and 0.4 parts by weight of polyether polyol C) were added into a double planetary mixer and mixed under vacuum at 65°C for 3 hours.

[0137] (2) The preparation of component B includes:

[0138] Weigh out 37 parts by weight of curing agent (liquefied diphenylmethane diisocyanate), 5 parts by weight of second polyether polyol (the second polyether polyol is a compound of trifunctional polyether polyol D and difunctional polyether polyol E in a mass ratio of 4:6), 8 parts by weight of plasticizer (the plasticizer is a compound of petroleum ether and dibutyl phthalate in a mass ratio of 4:6), 50 parts by weight of second filler (the second filler is a compound of talc, calcium carbonate, kaolin and bentonite in a mass ratio of 8:10:7:5) and 1 part by weight of fumed silica;

[0139] 50 parts by weight of the second filler were dried and dehydrated at 100°C for 24 hours, and 37 parts by weight of the curing agent and 5 parts by weight of the second polyether polyol were pre-reacted at 79°C for 2 hours.

[0140] Eight parts by weight of plasticizer, one part by weight of fumed silica, a second filler that has been dehydrated, a curing agent, and an isocyanate-terminated polyether polyol prepolymer obtained by pre-reaction of the second polyether polyol were added to a double planetary mixer and mixed under vacuum at 70°C for 3 hours.

[0141] (3) Filling

[0142] After the preparation of components A and B, components A and B are respectively filled into two-component tubes separated from each other in a volume ratio of 1:1 to obtain the flame-retardant polyurethane two-component corner adhesive.

[0143] Comparative Example 1

[0144] A flame-retardant polyurethane two-component corner adhesive includes component A and component B, the relevant components of which are the same as those in Example 4, except that the compounded flame retardant is replaced with commercially available aluminum hydroxide flame retardant.

[0145] Comparative Example 2

[0146] A flame-retardant polyurethane two-component corner adhesive includes component A and component B, the relevant components of which are the same as those in Example 4, except that 25 parts by weight of the compound flame retardant are replaced with 8 parts by weight of the compound flame retardant and 17 parts by weight of talc.

[0147] Comparative Example 3

[0148] A non-flame-retardant two-component polyurethane corner adhesive sold in a certain city.

[0149] According to GB / T 13477.3, JC / T 2560-2020, JC / T 2560-2020, GB / T 13477.5-2002, JC / T2560-2020, GB / T 531.1-2008, JC / T 2560-2020 7.3, GB / T 31541-2015 8.3, JC / T 2560-2020, and GB / T 23864-2009, the extrudability, overflow, surface drying time, hardness, bond strength, and fire resistance integrity of the flame-retardant polyurethane two-component corner adhesives prepared in Examples 1 to 5, Comparative Examples 1 to 2, and the non-flame-retardant polyurethane two-component corner adhesive in Comparative Example 3 were tested. The measured corner adhesive performance data are shown in Table 1.

[0150] Table 1. Performance data of the corner adhesive obtained from Examples 1-5 and the comparative examples.

[0151]

[0152] Based on the above experimental results, the flame-retardant polyurethane two-component corner adhesive disclosed in this invention, compared with Comparative Example 1 which used a traditional flame retardant, shows that, under the same addition amount, the self-made compound flame retardant used in this invention has better flame retardant ability. Compared with Comparative Example 2, Example 4 shows that the higher the content of the self-made flame retardant, the stronger the flame retardant performance. Compared with Comparative Example 3, Example 4 shows that the flame-retardant polyurethane two-component corner adhesive disclosed in this invention has excellent flame retardant ability while possessing considerable mechanical properties, and has stronger practicality.

[0153] The present invention has been described in detail above with reference to specific embodiments and exemplary examples. These descriptions are exemplary and not exhaustive, and are not limited to the disclosed embodiments; the above descriptions should not be construed as limiting the present invention. Those skilled in the art will understand that various equivalent substitutions, modifications, or improvements can be made to the technical solutions and implementation methods of the present invention without departing from the spirit and scope of the present invention, and all such modifications and improvements fall within the scope of the present invention; the scope of protection of the present invention is determined by the appended claims.

Claims

1. A flame-retardant two-component polyurethane corner adhesive, comprising component A and component B, characterized in that, Component A comprises the following components by mass: First polyether polyol: 40 parts to 55 parts; The first filler should be 20 to 35 parts; 1 to 5 parts of the first thixotropic agent; 20 to 25 parts of compound flame retardant; 1 to 2 parts modifier; Catalyst: 0.004 parts to 0.008 parts; Component B comprises the following components by mass: 35 to 45 parts of curing agent; 1 to 5 parts of the second polyether polyol; Plasticizer: 8 to 12 parts; The second filler should be 40 to 50 parts. 1 to 2 parts of the second thixotropic agent; The compound flame retardant comprises melamine orthophosphate, pentaerythritol, and 2-carboxyethylphenylphosphonic acid grafted polyether polyol; the molar ratio of melamine orthophosphate, pentaerythritol, and 2-carboxyethylphenylphosphonic acid is (8~20):(10~24):(5~10); the 2-carboxyethylphenylphosphonic acid grafted polyether polyol is prepared by the following method: Using phosphoric acid as a catalyst, 2-carboxyethylphenylphosphonic acid was added dropwise to polyether polyol B to carry out an esterification grafting reaction, thus preparing 2-carboxyethylphenylphosphonic acid grafted polyether polyol.

2. The flame-retardant polyurethane two-component corner adhesive according to claim 1, characterized in that, The first polyether polyol includes polyether polyol A, polyether polyol B, and polyether polyol C; polyether polyol A is a difunctional polyether polyol with a molecular weight range of 1000-3000, polyether polyol B is a trifunctional polyether polyol with a molecular weight range of 1000-3000, and polyether polyol C is a difunctional polyether polyol with a molecular weight range of 200-1000; the molar ratio of polyether polyol A, polyether polyol B, and polyether polyol C is (85-92):(8-15):

1.

3. The flame-retardant polyurethane two-component corner adhesive according to claim 1, characterized in that, The first filler is heavy calcium carbonate, which is subjected to stearic acid surface activation treatment; The first thixotropic agent is one or more of fumed silica and sodium polyamide; The modifier is one or more of γ-aminopropyltriethoxysilane and N-β-aminoethyl-γ-aminopropyltrimethoxysilane; The catalyst is one or more of organobismuth or organotin.

4. The flame-retardant polyurethane two-component corner adhesive according to claim 1, characterized in that, The second polyether polyol is a trifunctional polyether polyol D or / and a difunctional polyether polyol E, with a molecular weight range of 1000 to 3000.

5. The flame-retardant polyurethane two-component corner adhesive according to claim 1, characterized in that, The curing agent is one or more of polymethylene polyphenyl isocyanate and liquefied diphenylmethane diisocyanate; The plasticizer is one or more of petroleum ether, dibutyl phthalate, diisobutyl phthalate, and dinonyl phthalate; The second filler is one or more of talc, calcium carbonate, kaolin, and bentonite; The second thixotropic agent is fumed silica.

6. The flame-retardant polyurethane two-component corner adhesive according to claim 1, characterized in that, The volume ratio of component A to component B is A:B = 1:

1.

7. A method for preparing a flame-retardant polyurethane two-component corner protectant as described in any one of claims 1-6, characterized in that, Includes the following steps: Preparation of component A: Weigh out the first polyether polyol, the first filler, the first thixotropic agent, the compound flame retardant, the modifier, and the catalyst; dry and dehydrate the first filler, and dehydrate the first polyether polyol under vacuum; mix the first thixotropic agent, the compound flame retardant, the modifier, the catalyst, and the dehydrated first filler and first polyether polyol to obtain component A; wherein the compound flame retardant includes melamine orthophosphate, pentaerythritol, and 2-carboxyethylphenylphosphonic acid grafted polyether polyol; Preparation of component B: Weigh out the curing agent, the second polyether polyol, the plasticizer, the second filler, and the second thixotropic agent; dry and dehydrate the second filler; pre-react the curing agent and the second polyether polyol to obtain an isocyanate-terminated polyether polyol prepolymer; mix the plasticizer, the second thixotropic agent, the dehydrated second filler, and the polyether polyol prepolymer to obtain component B; The components A and B are respectively filled into the container to obtain the flame-retardant polyurethane two-component corner adhesive.

8. The preparation method according to claim 7, characterized in that, The 2-carboxyethylphenylphosphonic acid grafted polyether polyol is prepared by the following method: Using phosphoric acid as a catalyst, 2-carboxyethylphenylphosphonic acid was added dropwise to polyether polyol B to carry out an esterification grafting reaction, thereby preparing 2-carboxyethylphenylphosphonic acid-grafted polyether polyol; wherein the polyether polyol B is a trifunctional polyether polyol with a molecular weight range of 1000~3000.

9. The preparation method according to claim 8, characterized in that, The molar ratio of 2-carboxyethylphenylphosphonic acid to polyether polyol B is 1:(1~2); the amount of phosphoric acid used is 1% of the total mass of 2-carboxyethylphenylphosphonic acid and polyether polyol B.

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