PMMA (polymethyl methacrylate) liquid resin with flame-retardant function and preparation method of ship based on PMMA liquid resin continuous fiber composite material

Abstract

The invention provides PMMA (polymethyl methacrylate) liquid resin with a flame-retardant function and a preparation method of a ship based on a PMMA liquid resin continuous fiber composite material, and belongs to the technical field of polymer composite material preparation. According to the invention, the continuous fiber material is uniformly laid in the mold, and a vacuum assisted resin transfer molding (VARTM) process is adopted to ensure that the material is fully infiltrated and bubbles are eliminated. The PMMA liquid resin and the continuous fibers are fully combined through normal-temperature curing or heating curing, and a firm hull structure is formed. According to the method, the lightweight, corrosion resistance, transparency and impact resistance of the ship can be effectively improved, and the problem that the thermosetting resin glass fiber reinforced plastic ship cannot be recycled is solved. The whole ship is completely prepared from acrylic resin, complete separation of PMMA and fibers can be achieved by adopting a recovery method with MMA as a solvent, no solid waste exists in the whole process, closed-loop recovery of resources is achieved, and the method has great significance in energy conservation and environmental protection.

Description

Technical Field

[0001] The present invention relates to the technical field of the preparation of polymer composite materials, and particularly relates to a PMMA liquid resin with a flame retardant function and a preparation method of a ship based on a continuous fiber composite material of the PMMA liquid resin. Background Art

[0002] Continuous fiber reinforced resin matrix composites, namely fiberglass, have been widely used in the field of shipbuilding. Especially glass fiber reinforced epoxy-based thermosetting composites have the advantages of light weight, high strength, corrosion resistance, etc., can reduce the overall weight of the ship by 20-30%, have obvious lightweight effects, and prevent water from corroding metals. Currently, there are more than 2 million fiberglass ships in the world. For military use, there are mine-hunting boats, mine-sweeping boats, landing boats, traffic boats, etc.; for civilian use, there are high-speed passenger boats, fishing boats, yachts, lifeboats, workboats, and racing boats, etc. Most fiberglass ships are formed by vacuum-assisted infusion of fiber laminates with thermosetting liquid resin and curing. The solid waste of the corner scraps, scrapped and retired products generated during the processing reaches tens of thousands of tons per year, and the resin and fiber in them cannot be recycled, becoming an environmental protection bottleneck problem in China and even the world.

[0003] Replacing thermosetting composites with thermoplastic composites is an inevitable trend in the development of the field of continuous fiber reinforced composites. PMMA (polymethyl methacrylate) is a polymer material with excellent transparency, and has excellent weather resistance, ultraviolet resistance and impact resistance. Combining PMMA with continuous fibers can significantly improve the comprehensive performance of the composite material, and PMMA as a thermoplastic resin can be used for recycling, especially suitable for the manufacture of ships.

[0004] How to obtain a ship preparation method that can be fully recycled without solid waste and improve the ship performance is a technical problem that needs to be solved currently. Summary of the Invention

[0005] The purpose of the present invention is to provide a PMMA liquid resin with a flame retardant function and a preparation method of a ship based on a continuous fiber composite material of the PMMA liquid resin, which is used to solve the technical problem of difficult recycling of solid waste materials for ship manufacturing in the prior art.

[0006] In order to achieve the above invention purpose, the present invention provides the following technical solutions:

[0007] The present invention provides a PMMA liquid resin with a flame retardant function, which is composed of components containing the following mass parts:

[0008]

[0009] Furthermore, the flash point of the high flash point methacrylic acid derivative is 30 to 200 °C. The high flash point methacrylic acid derivative includes one or more of isobutyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, glycidyl methacrylate, and 2-(dimethylamino)ethyl methacrylate; the flame retardant includes one or more of phosphorus-based flame retardants, hydroxide-based flame retardants, and acrylate monomers containing flame retardant groups.

[0010] The present invention also provides a method for preparing a ship based on a PMMA liquid resin continuous fiber composite material, comprising the following steps:

[0011] 1) Clean the stains on the surface of the hull mold, and apply gel coat on the surface of the hull mold;

[0012] 2) Cut a certain number of continuous fiber cloths according to the laying process requirements of the ship to be prepared, and lay the continuous fiber cloths into the cavity of the hull mold. Spray multi-functional strong glue between each layer of continuous fiber cloths, and lay sandwich panels at the load-bearing parts of the ship;

[0013] 3) After the laying of the continuous fiber cloths is completed, lay auxiliary materials for vacuum infusion, lay the release cloth, flow guide net and vacuum film in sequence, and seal with sealing tape;

[0014] 4) Unfold the vacuum film in the cavity of the hull mold that needs to be infused and fit it to the inner wall of the cavity, and then perform pre-tightening treatment so that the pressure in the first layer of vacuum film is -0.9 bar; Connect the vacuum film to the injection glue pipeline, the injection ports are spaced 10 to 60 cm apart, and test the infusion sealing performance after maintaining pressure for 1 to 3 hours;

[0015] 5) Mix the PMMA liquid resin and the initiator and then perform degassing treatment, and use vacuum infusion to inject into the hull mold, and then perform curing treatment;

[0016] 6) Demold after curing, trim, polish and fill the glue on the hull, and bond the hull mold with PMMA structural glue to obtain a complete ship.

[0017] Furthermore, the mass ratio of the PMMA liquid resin to the continuous fiber cloth is 30 to 45:55 to 70;

[0018] The hull mold includes a deck mold and a cabin mold.

[0019] Furthermore, the continuous fiber cloth includes one of glass fiber, carbon fiber, basalt fiber, and mixed woven fiber cloth; the number of laying layers of the continuous fiber cloth is ≥5;

[0020] The gel coat is a marine gel coat, which has water resistance and salt spray resistance, and the thickness of the gel coat is 0.4 to 0.8 mm.

[0021] Further, in the step 5), the initiator includes a redox initiator or a borane initiator;

[0022] The redox initiator includes a peroxide oxidant and a tertiary amine reducing agent.

[0023] Further, the peroxide oxidant includes one or more of tert-butyl peroxyneodecanoate, benzoyl peroxide, dibutyl peroxydicarbonate, tert-butyl peroxy(2-ethylhexanoate), tert-butyl peroxyacetate, tetramethylbutyl peroxyneodecanoate, lauroyl peroxide, bis(4-butylcyclohexyl) peroxydicarbonate, bis(2-ethylhexyl) peroxydicarbonate, butyl peroxyneodecanoate, dipropyl peroxydicarbonate, diisopropyl peroxydicarbonate, diethoxyethyl peroxydicarbonate, diethoxyhexyl peroxydicarbonate, hexyl peroxydicarbonate, methyl ethyl ketone peroxide, cyclohexanone peroxide, dimethoxybutyl peroxydicarbonate, bis(3-methoxy-3-methoxybutyl) peroxydicarbonate, dibutyl peroxydicarbonate, bis(hexadecyl) peroxydicarbonate, bis(tetradecyl) peroxydicarbonate, cumene hydroperoxide, tert-butyl peroxybenzoate, 1,1,3,3-tetramethylbutyl peroxy pivalate, hexyl peroxy pivalate, butyl peroxy pivalate, trimethylhexanoyl peroxide, dimethylhydroxybutyl peroxyneodecanoate, pentyl peroxyneodecanoate, butyl peroxyneodecanoate, tert-butyl peroxyneoheptanoate, pentyl peroxy pivalate, tert-butyl peroxy pivalate, tert-amyl peroxy(2-ethyl)hexanoate, lauroyl peroxide, dilauroyl peroxide, didecanoyl peroxide, peracetic acid, and potassium persulfate.

[0024] Further, the tertiary amine reducing agent includes one or more of N'-dimethylaniline, N,N'-dimethyl-p-toluidine, N,N'-bis(2-hydroxypropyl)-p-toluidine, N-methyl-N-2-hydroxyethyl-p-toluidine, N-methyl-N-(2-methacryloyloxyethyl)aniline, and N-methyl-N-(2-methacryloyloxyethyl)-p-toluidine;

[0025] The borane initiator includes one or several of diborane, borane, borane-tetrahydrofuran, and borane-dimethyl sulfide.

[0026] Further, the mass ratio of the PMMA liquid resin to the initiator is 100:0.5 to 2; the temperature of the curing treatment is 0 to 60 °C, and the time of the curing treatment is 2 to 48 h.

[0027] Further, the PMMA structural adhesive is a mixture of a PMMA liquid resin with a viscosity of 1000 to 2000 cP and an initiator, the supplementary adhesive used is the PMMA structural adhesive, and the process of the supplementary adhesive is a hand lay-up process.

[0028] Advantages of the present invention:

[0029] 1. The main components of the PMMA liquid resin of the present invention are polymethyl methacrylate and methyl methacrylate monomers added with flame retardants and high flash point acrylic compounds. The cost is lower than that of epoxy resin, which is beneficial to reducing the material cost of ships. And the resin can be polymerized and cured at room temperature, greatly saving electricity costs.

[0030] 2. For the whole ship prepared by the invention, the recovery method using MMA as the solvent can achieve the complete separation of PMMA and fibers. The PMMA + MMA recovery liquid can be recycled as liquid resin. There is no waste liquid and solid waste throughout the process, realizing closed-loop resource recovery, which has great significance for energy conservation and environmental protection. Description of the drawings

[0031] Figure 1 Photo of the ship deck after laying the laminate;

[0032] Figure 2 Photo of the ship cabin after laying the laminate;

[0033] Figure 3 Photo of the ship deck during vacuum infusion;

[0034] Figure 4 Photo of the ship cabin during vacuum infusion;

[0035] Figure 5 Photo of the cured deck;

[0036] Figure 6 Photo of the cured cabin;

[0037] Figure 7 Photo of the prepared ship. Detailed implementation manners

[0038] The present invention provides a PMMA liquid resin with flame retardant function, which is composed of components containing the following parts by mass:

[0039]

[0040] In the present invention, calculated by parts by mass, the content of the polymethyl methacrylate is preferably 10 - 40 parts, more preferably 15 - 35 parts.

[0041] In the present invention, calculated by parts by mass, the content of the methyl methacrylate is preferably 55 - 80 parts, more preferably 60 - 70 parts.

[0042] In the present invention, calculated by parts by mass, the content of the high flash point methacrylic acid derivative is preferably 20 - 30 parts, more preferably 25 parts.

[0043] In the present invention, by mass parts, the content of the flame retardant is 5 to 25 parts, more preferably 10 to 20 parts.

[0044] In the present invention, the flash point of the high flash point methacrylic acid derivative is 30 to 200 °C, preferably 50 to 200 °C, more preferably 100 to 200 °C; the high flash point methacrylic acid derivative includes one or more of isobutyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycidyl methacrylate, and dimethylaminoethyl methacrylate, preferably isobutyl methacrylate; the flame retardant includes one or more of a phosphorus-based flame retardant, a hydroxide-based flame retardant, and an acrylate monomer containing a flame retardant group, and the flame retardant is added directly or polymerized into the PMMA chain in the form of a flame retardant monomer.

[0045] The present invention also provides a method for preparing a ship based on a PMMA liquid resin continuous fiber composite material, comprising the following steps:

[0046] 1) Clean the stains on the surface of the hull mold, and apply gel coat on the surface of the hull mold;

[0047] 2) Cut a certain number of continuous fiber cloths according to the lay-up process requirements of the ship to be prepared, and lay the continuous fiber cloths in the cavity of the hull mold. Spray a multi-functional strong glue between each layer of continuous fiber cloths, and lay sandwich panels at the load-bearing parts of the ship;

[0048] 3) After the continuous fiber cloth lay-up is completed, lay auxiliary materials for vacuum infusion, lay the release cloth, the flow guide net, and the vacuum film in sequence, and seal with a sealing tape;

[0049] 4) Unfold the vacuum film in the cavity of the hull mold that needs to be infused and fit it to the inner wall of the cavity, and then perform a pre-tightening treatment so that the pressure in the first layer of vacuum film is -0.9 bar; Connect the vacuum film to the injection pipe, and the injection ports are spaced 10 to 60 cm apart. After maintaining the pressure for 1 to 3 hours, test the infusion tightness;

[0050] 5) Mix the PMMA liquid resin and the initiator and then perform a defoaming treatment, and use vacuum infusion into the hull mold, and then perform a curing treatment;

[0051] 6) Demold after curing, trim, polish, and repair the glue of the hull, and bond the hull mold with PMMA structural glue to obtain a complete ship.

[0052] In the present invention, the mass ratio of the PMMA liquid resin to the continuous fiber cloth is 30 to 45:55 to 70, preferably 35 to 40:60 to 65;

[0053] The hull mold includes a deck mold and a cabin mold.

[0054] In the present invention, the sandwich panel includes a lightweight core material or a flame retardant panel. The lightweight core material is a PMMA lightweight core material or a sandwich panel material, preferably a PMMA / glass bead sandwich panel, PET, PVC core material or sandwich panel infused with PMMA liquid resin.

[0055] In the present invention, the continuous fiber cloth includes one of glass fiber, carbon fiber, basalt fiber and hybrid woven fiber cloth; the number of laying layers of the continuous fiber cloth is ≥5. In the present invention, the continuous fiber material is evenly laid in the mold, and the vacuum assisted resin transfer molding (VARTM) process is adopted to ensure that the material is fully infiltrated and air bubbles are excluded. Through room temperature curing or heat curing, the PMMA liquid resin is fully combined with the continuous fiber to form a strong hull structure.

[0056] In the present invention, the gel coat is a marine gel coat with water resistance and salt spray resistance, and the thickness of the gel coat is 0.4 - 0.8 mm, preferably 0.5 - 0.6 mm.

[0057] In the present invention, in step 5), the initiator includes a redox initiator or a borane initiator, preferably a redox initiator;

[0058] The redox initiator includes a peroxide oxidant and a tertiary amine reducing agent.

[0059] In the present invention, the peroxide oxidant includes one or more of tert-butyl peroxyneodecanoate, benzoyl peroxide, bis(butyl) peroxydicarbonate, tert-butyl peroxy(2-ethylhexanoate), tert-butyl peroxyacetate, tetrabutylmethyl peroxyneodecanoate, lauroyl peroxide, bis(4-butylcyclohexyl) peroxydicarbonate, bis(2-ethylhexyl) peroxydicarbonate, butyl peroxyneodecanoate, dipropyl peroxydicarbonate, diisopropyl peroxydicarbonate, diethoxyethyl peroxydicarbonate, diethoxyhexyl peroxydicarbonate, hexyl peroxydicarbonate, methyl ethyl ketone peroxide, cyclohexanone peroxide, dimethoxybutyl peroxydicarbonate, bis(3-methoxy-3-methoxybutyl) peroxydicarbonate, dibutyl peroxydicarbonate, di(hexadecyl) peroxydicarbonate, ditetradecyl peroxydicarbonate, cumene hydroperoxide, tert-butyl peroxybenzoate, 1,1,3,3-tetramethylbutyl peroxyneopentanoate, hexyl peroxyneopentanoate, butyl peroxyneopentanoate, trimethylhexanoyl peroxide, dimethylhydroxybutyl peroxyneodecanoate, pentyl peroxyneodecanoate, butyl peroxyneodecanoate, tert-butyl peroxyneononanoate, pentyl peroxyneopentanoate, tert-butyl peroxyneopentanoate, tert-amyl peroxy(2-ethyl)hexanoate, lauroyl peroxide, dilauroyl peroxide, didecanoyl peroxide, peracetic acid and potassium persulfate.

[0060] In the present invention, the tertiary amine reducing agent includes one or more of N'-dimethylaniline, N,N'-dimethyl-p-toluidine, N,N'-bis(2-hydroxypropyl)-p-toluidine, N-methyl-N-2-hydroxyethyl-p-toluidine, N-methyl-N-(2-methacryloyloxyethyl)aniline, and N-methyl-N-(2-methacryloyloxyethyl)-p-toluidine;

[0061] The borane initiator includes one or several of diborane, borane, borane-tetrahydrofuran, and borane-dimethyl sulfide.

[0062] In the present invention, the mass ratio of the PMMA liquid resin to the initiator is 100:0.5 to 2, preferably 100:1; the temperature of the curing treatment is 0 to 60°C, preferably 20 to 40°C; the time of the curing treatment is 2 to 48 h, preferably 10 to 60 h, and more preferably 12 to 24 h.

[0063] In the present invention, the PMMA structural adhesive is a mixture of a PMMA liquid resin with a viscosity of 1000 to 2000 cP and an initiator, and the supplementary adhesive used is the PMMA structural adhesive, and the process of the supplementary adhesive is a hand lay-up process.

[0064] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0065] Example 1

[0066] A PMMA liquid resin with a flame retardant function is composed of the following components in parts by mass:

[0067]

[0068] Example 2

[0069] A PMMA liquid resin with a flame retardant function is composed of the following components in parts by mass:

[0070]

[0071] Example 3

[0072] A PMMA liquid resin with a flame retardant function is composed of the following components in parts by mass:

[0073]

[0074] Example 4

[0075] In this embodiment, the vacuum infusion technology is adopted to compound liquid PMMA resin with continuous glass fiber. The prepared inflatable boat is 4.6 meters long, 1.4 meters wide at the beam, 0.53 meters deep at the depth, with a draft of 0.25 meters and a full load displacement of 1.25 tons.

[0076] 1) The inflatable boat mold is divided into two parts: the deck mold (upper mold) and the cabin mold (lower mold). The glass fiber used is continuous glass fiber. Clean the dust and other stains on the surface of the inflatable boat mold, and evenly apply the gel coat on the surfaces of the upper and lower molds of the inflatable boat. The thickness of the gel coat is 0.8 mm. In this embodiment, the gel coat color of the deck mold is white, and the gel coat color of the cabin mold is red.

[0077] 2) Cut the glass fiber cloth into appropriate shapes according to the layup process requirements of the inflatable boat. First, cut five large-area fiber cloths that conform to the overall structure of the cabin. Lay the cut glass fiber cloths into the inflatable boat mold according to the layup requirements. Spray multi-functional strong glue between each layer of fiber cloths, and lay PMMA sandwich panels of a certain size at the load-bearing parts of the inflatable boat (such as the cabin seat board and the bow). Then lay small-area fiber cloths in the cabin area.

[0078] 3) After the continuous fiber layup is completed, lay the auxiliary materials for vacuum infusion. Lay the release cloth, flow net, and vacuum film in sequence and seal them with sealing tape. Unfold the vacuum film in the cavity of the hull mold that needs to be infused and fit it to the inner wall of the cavity. Then perform a pre-tightening treatment on the vacuum film so that the pressure in the vacuum film is -0.9 bar. Finally, connect the hull vacuum film to the injection pipeline. The injection ports are spaced at 30 cm intervals, and the pressure is maintained for 2 h and then the infusion seal is tested.

[0079] 4) After degassing the liquid resin, infuse it into the area to be infused in the hull mold. Mix the PMMA liquid resin in Example 1 with 1 wt% of redox initiator (mass ratio of benzoyl peroxide to N,N'-dimethylaniline is 1:1) and then perform degassing treatment, and then vacuum infuse it into the upper and lower molds. Cure the infused ship hull. Cure at 25 °C for 4 hours. After curing and demolding, trim and polish the ship hull, remove burrs and uneven parts, and repair the lack of glue parts by hand layup process; the mass ratio of PMMA liquid resin to glass fiber cloth is 35:65.

[0080] 5) Use PMMA liquid resin with a viscosity of 2000 cP, add 1 wt% of redox initiator (mass ratio of benzoyl peroxide to N,N'-dimethylaniline is 1:1), and then use it as a structural adhesive to bond the deck mold and the cabin mold.

[0081] Example 5

[0082] In this embodiment, the vacuum infusion technique is adopted to compound liquid PMMA resin with continuous carbon fiber. The prepared assault boat is 4.6 meters long, 1.4 meters wide at the beam, 0.53 meters deep in draft, with a draft depth of 0.25 meters and a full load displacement of 1.25 tons.

[0083] The assault boat mold is divided into two parts: a deck mold (upper mold) and a cabin mold (lower mold). The fiber used is continuous carbon fiber.

[0084] 1) Clean the dust and other stains on the surface of the assault boat mold, and evenly apply the gel coat on the surfaces of the upper and lower molds of the assault boat. The thickness of the gel coat is 0.7 mm. In this embodiment, the gel coat color of the deck mold is white, and the gel coat color of the cabin mold is red.

[0085] 2) Cut carbon fiber cloth of appropriate shapes according to the layup process requirements of the assault boat. First, cut five large-area fiber cloths that conform to the overall structure of the cabin. Lay the cut carbon fiber cloths into the assault boat mold according to the layup requirements. Spray multi-functional strong glue between each layer of fiber cloth, and lay fire-retardant plywood of a certain size that meets the national standard at the load-bearing parts of the assault boat (such as the cabin seat board and the bow). Then lay small-area fiber cloths in the cabin area.

[0086] 3) After the continuous fiber layup is completed, lay the auxiliary materials for vacuum infusion. Lay the release cloth, flow guide net, and vacuum film in sequence and seal them with sealing tape. Unfold the vacuum film in the cavity of the hull mold that needs to be infused and fit it to the inner wall of the cavity. Then perform a pre-tightening treatment on the vacuum film so that the pressure in the vacuum film is -0.9 bar. Finally, connect the hull vacuum film to the injection pipeline. The injection ports are spaced 30 cm apart, and the pressure is maintained for 2 h and then the infusion seal is tested.

[0087] 4) After degassing the liquid methyl methacrylate resin, pour it into the area to be infused in the hull mold. Mix the PMMA liquid resin of Example 2 with 1 wt% of redox initiator (the mass ratio of dibutyl peroxydicarbonate and N,N'-dimethyl-p-toluidine is 1:1), perform degassing treatment, and then vacuum infuse it into the upper and lower molds. Cure the infused ship hull. Cure it at 30 °C for 6 hours. After curing is completed and demolding, trim and polish the ship hull, remove burrs and uneven parts, and repair the glue-deficient parts using the hand layup process; the mass ratio of PMMA liquid resin to glass fiber cloth is 40:60.

[0088] 5) Use PMMA liquid resin with a viscosity of 1500 cP, add 1 wt% of redox initiator (the mass ratio of benzoyl peroxide and N'-dimethylaniline is 1:1), and use it as a structural adhesive to bond the deck mold and the cabin mold.

[0089] Example 6

[0090] In this embodiment, the vacuum infusion technology is adopted to compound liquid PMMA resin with continuous glass fibers. The prepared inflatable boat is 4.6 meters long, 1.4 meters wide at the waterline, 0.53 meters deep, with a draft of 0.25 meters and a full load displacement of 1.25 tons.

[0091] The inflatable boat mold is divided into two parts: a deck mold (upper mold) and a cabin mold (lower mold), and continuous glass fibers are used.

[0092] 1) Clean the dust and other stains on the surface of the inflatable boat mold, and evenly apply the gel coat on the surfaces of the upper and lower molds of the inflatable boat. The thickness of the gel coat is 0.5 mm. In this embodiment, the gel coat color of the deck mold is white, and the gel coat color of the cabin mold is red.

[0093] 2) Cut the fiberglass cloth into appropriate shapes according to the layup process requirements of the inflatable boat. First, cut five large-area fiberglass cloths that conform to the overall structure of the cabin. Lay the cut fiberglass cloths into the inflatable boat mold according to the layup requirements. Spray multi-functional strong glue between each layer of fiberglass cloth, and lay fire-retardant plywood of a certain size that meets national standards at the load-bearing parts of the inflatable boat (such as the cabin seat board and the bow). Then lay small-area fiberglass cloths in the cabin area.

[0094] 3) After the continuous fiber layup is completed, lay the auxiliary materials for vacuum infusion. Lay the release cloth, flow guide net, and vacuum film in sequence, and seal them with sealing tape. Unfold the vacuum film in the cavity of the hull mold that needs to be infused and fit it to the inner wall of the cavity. Then perform pre-tightening treatment on the vacuum film so that the pressure in the vacuum film is -0.9 bar. Finally, connect the hull vacuum film to the injection pipeline, with the injection ports spaced 30 cm apart, and test the infusion seal after maintaining pressure for 2 hours.

[0095] 4) After degassing the liquid methyl methacrylate resin, infuse it into the area to be infused in the hull mold. Mix the PMMA liquid resin of Example 3 with 1 wt% of borane-tetrahydrofuran and then perform degassing treatment, and vacuum infuse it into the upper and lower molds. Perform pre-curing treatment on the infused ship cabin. The curing temperature is 60 °C and the curing time is 2 hours. After the curing is completed and the mold is removed, trim and polish the ship cabin, remove burrs and uneven parts, and repair the glue-deficient parts by hand layup process; the mass ratio of the PMMA liquid resin to the fiberglass cloth is 45:55.

[0096] 5) Use PMMA liquid resin with a viscosity of 1000 cP, add 1 wt% of borane-tetrahydrofuran, and use it as a structural adhesive to bond the deck mold and the cabin mold.

[0097] As can be seen from the above embodiments, the present invention provides a PMMA liquid resin with flame retardant function and a preparation method of a ship based on a continuous fiber composite material of PMMA liquid resin. If high-temperature melting process is used for the infiltration and composite of PMMA and continuous fibers, the process is energy-consuming and not conducive to the preparation of large composite products such as ships. The PMMA liquid resin is a liquid resin with flame retardant function and certain viscosity, which is composed of polymethyl methacrylate, methyl methacrylate, and other acrylic high flash point substances (such as tert-butyl methacrylate, isobutyl methacrylate, isooctyl methacrylate), and a flame retardant. It is polymerized at high temperature (60-80 °C) by adding peroxide initiator, or by a redox initiator composed of peroxide and amine compounds, or polymerized at room temperature by borane initiator. In addition to heating injection molding extrusion recycling, new recycling methods for PMMA composites have also been developed, such as solvent dissolution method (Polymer Composites, 2025, 46, 3030-3041; A recycling method for PMMA thermoplastic resin / fiber reinforced composite material, application number 202410625070X). The whole ship of the present invention is entirely made of acrylic resin. By using the recycling method with MMA as the solvent, the complete separation of PMMA and fibers can be achieved, without solid waste throughout the process, realizing closed-loop resource recycling, which has great significance for energy conservation and environmental protection.

[0098] The ship preparation method of the present invention can effectively improve the lightweight, corrosion resistance, transparency and impact resistance of the ship, solve the problem that the thermosetting resin fiberglass ship is not recyclable, and at the same time reduce the manufacturing cost and maintenance difficulty.

[0099] The above are only the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and retouches can be made, and these improvements and retouches should also be regarded as the protection scope of the present invention.

Claims

1. A PMMA liquid resin with flame retardant function, characterized in that, It consists of components containing the following parts by mass: 5 - 50 parts of polymethyl methacrylate; 50 - 90 parts of methyl methacrylate; 10 - 40 parts of high - flash - point methacrylic acid derivatives; 0.5 - 30 parts of flame retardant.

2. The PMMA liquid resin with flame retardant function according to claim 1, characterized in that, The flash point of the high - flash - point methacrylic acid derivative is 30 - 200 °C, and the high - flash - point methacrylic acid derivative includes one or more of isobutyl methacrylate, 2 - hydroxyethyl methacrylate, 2 - hydroxypropyl methacrylate, glycidyl methacrylate, and dimethylaminoethyl methacrylate; the flame retardant includes one or more of phosphorus - based flame retardants, hydroxide - based flame retardants, and acrylate monomers containing flame - retardant groups.

3. A preparation method of a ship based on a PMMA liquid resin continuous fiber composite material, characterized in that, It includes the following steps: 1) Clean the stains on the surface of the hull mold and apply gel coat on the surface of the hull mold; 2) Cut a certain number of continuous fiber cloths according to the requirements of the prepared ship laying process, lay the continuous fiber cloths in the cavity of the hull mold, spray multi - functional strong glue between each layer of continuous fiber cloths, and lay sandwich panels at the load - bearing parts of the ship; 3) After the laying of the continuous fiber cloth is completed, lay the auxiliary materials for vacuum infusion, lay the release cloth, flow - guiding net, and vacuum film in sequence, and seal them with sealing tape; 4) Unfold the vacuum film in the cavity of the hull mold that needs to be infused and fit it to the inner wall of the cavity, then perform pre - tightening treatment to make the pressure in the first - layer vacuum film - 0.9 bar; connect the vacuum film to the injection pipeline, with the injection ports spaced 10 - 60 cm apart, and test the infusion tightness after maintaining pressure for 1 - 3 h; 5) Mix the PMMA liquid resin described in claim 1 or 2 with an initiator, perform degassing treatment, and then use vacuum infusion to inject it into the hull mold, and then perform curing treatment; 6) Demold after curing, trim, polish, and repair the hull with glue, and bond the hull mold with PMMA structural glue to obtain a complete ship.

4. The preparation method according to claim 3, characterized in that, The mass ratio of the PMMA liquid resin to the continuous fiber cloth is 30 - 45:55 - 70; The hull mold includes a deck mold and a cabin mold.

5. The preparation method according to claim 3 or 4, characterized in that, The continuous fiber cloth includes one of glass fiber, carbon fiber, basalt fiber, and hybrid woven fiber cloth; the number of laying layers of the continuous fiber cloth is ≥5; The gel coat is a marine gel coat with water resistance and salt - fog resistance, and the thickness of the gel coat is 0.4 - 0.8 mm.

6. The preparation method according to claim 5, characterized in that, In step 5), the initiator includes a redox initiator or a borane initiator; The redox initiator includes a peroxide oxidant and a tertiary amine reducing agent.

7. The preparation method according to claim 6, wherein, The peroxide oxidant includes one or more of tert-butyl peroxyneodecanoate, benzoyl peroxide, dibutyl peroxydicarbonate, tert-butyl peroxy(2-ethylhexanoate), tert-butyl peroxyacetate, tetramethylbutyl peroxyneodecanoate, lauroyl peroxide, bis(4-butylcyclohexyl) peroxydicarbonate, bis(2-ethylhexyl) peroxydicarbonate, butyl peroxyneodecanoate, dipropyl peroxydicarbonate, diisopropyl peroxydicarbonate, diethoxyethyl peroxydicarbonate, diethoxyhexyl peroxydicarbonate, hexyl peroxydicarbonate, methyl ethyl ketone peroxide, cyclohexanone peroxide, dimethoxybutyl peroxydicarbonate, bis(3-methoxy-3-methylbutyl) peroxydicarbonate, dibutyl peroxydicarbonate, di(hexadecyl) peroxydicarbonate, ditetradecyl peroxydicarbonate, cumene hydroperoxide, tert-butyl peroxybenzoate, 1,1,3,3-tetramethylbutyl peroxy pivalate, hexyl peroxy pivalate, butyl peroxy pivalate, trimethylhexanoyl peroxide, dimethylhydroxybutyl peroxyneodecanoate, pentyl peroxyneodecanoate, butyl peroxyneodecanoate, tert-butyl peroxyneoheptanoate, pentyl peroxy pivalate, tert-butyl peroxy pivalate, tert-amyl peroxy(2-ethyl)hexanoate, lauroyl peroxide, dilauroyl peroxide, didecanoyl peroxide, peracetic acid and potassium persulfate.

8. The preparation method according to claim 6 or 7, characterized in that, The tertiary amine reducing agent includes one or more of N'-dimethylaniline, N,N'-dimethyl-p-toluidine, N,N'-bis(2-hydroxypropyl)-p-toluidine, N-methyl-N-2-hydroxyethyl-p-toluidine, N-methyl-N-(2-methacryloyloxyethyl)aniline and N-methyl-N-(2-methacryloyloxyethyl)-p-toluidine; The borane initiator includes one or several of diborane, borane, borane-tetrahydrofuran and borane-dimethyl sulfide.

9. The preparation method according to claim 3, characterized in that, The mass ratio of the PMMA liquid resin to the initiator is 100:0.5 to 2; the temperature of the curing treatment is 0 to 60 °C, and the time of the curing treatment is 2 to 48 h.

10. The preparation method according to claim 3 or 9, characterized in that, The PMMA structural adhesive is a mixture of a PMMA liquid resin with a viscosity of 1000 to 2000 cP and an initiator. The glue filling uses the PMMA structural adhesive, and the process of the glue filling is a hand lay-up process.

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