CN115534446A - Low-toxicity flame-retardant bulkhead composite material for ship and preparation method thereof - Google Patents

Low-toxicity flame-retardant bulkhead composite material for ship and preparation method thereof Download PDF

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Publication number
CN115534446A
CN115534446A CN202211166487.1A CN202211166487A CN115534446A CN 115534446 A CN115534446 A CN 115534446A CN 202211166487 A CN202211166487 A CN 202211166487A CN 115534446 A CN115534446 A CN 115534446A
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China
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bulkhead
vinyl resin
low
composite
retardant
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周俊
李凯
刘敬喜
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China Ship Development and Design Centre
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China Ship Development and Design Centre
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Priority to CN202211166487.1A priority Critical patent/CN115534446A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/30—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core
    • B29C70/36—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core and impregnating by casting, e.g. vacuum casting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/68—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts by incorporating or moulding on preformed parts, e.g. inserts or layers, e.g. foam blocks
    • B29C70/681—Component parts, details or accessories; Auxiliary operations
    • B29C70/682—Preformed parts characterised by their structure, e.g. form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/245—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it being a foam layer
    • C—CHEMISTRY; METALLURGY
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2266/00—Composition of foam
    • B32B2266/02—Organic
    • B32B2266/0214—Materials belonging to B32B27/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2266/00—Composition of foam
    • B32B2266/02—Organic
    • B32B2266/0214—Materials belonging to B32B27/00
    • B32B2266/0221—Vinyl resin
    • B32B2266/0235—Vinyl halide, e.g. PVC, PVDC, PVF, PVDF
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/12—Ships
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2363/10—Epoxy resins modified by unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2425/02—Homopolymers or copolymers of hydrocarbons
    • C08J2425/04—Homopolymers or copolymers of styrene
    • C08J2425/06—Polystyrene
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
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    • C08K7/00—Use of ingredients characterised by shape
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Abstract

The invention belongs to the technical field of ship materials, and discloses a low-toxicity flame-retardant bulkhead composite material for a ship and a preparation method thereof. The composite material comprises a lower panel, a foam core material and an upper panel which are sequentially arranged from bottom to top, wherein the foam core material is made of polyvinyl chloride or polyetherimide, and the upper panel and the lower panel are formed by curing modified vinyl resin impregnated fiber cloth layers. The composite material disclosed by the invention adopts a sandwich structure design of the panel-foam core material-panel, is made of the foam core material, is combined with a formula system design of panel resin, and is matched with the optimization of a production process, so that the composite material not only has the advantages of light weight, high strength, good rigidity, marine environment resistance and the like, but also meets the requirements of the internal bulkhead of the ship on low-toxicity flame retardance, and has a good application prospect.

Description

Low-toxicity flame-retardant bulkhead composite material for ship and preparation method thereof
Technical Field
The invention belongs to the technical field of ship materials, and particularly relates to a low-toxicity flame-retardant bulkhead composite material for a ship and a preparation method thereof.
Background
The ship can reduce fuel consumption and CO by light weight 2 Discharging, improving the rapidity of the ship and increasing the effective load capacity of the ship. The application of new materials is the most main and effective way for realizing the light weight of the ship structure and is an important method for improving the economy of ships. At present, the main materials of the bulkhead structure of the ship are hull steel, aluminum alloy and the like. However, the ship body steel member is heavy and is difficult to realize light weight. The aluminum alloy has lower weld strength and poorer fatigue performance. Therefore, there is a need to develop new marine composite components.
In recent years, sandwich structure composite materials are widely applied in the fields of carrier rockets, aviation, wind driven generator blades, sports equipment, medical equipment accessories, train locomotives and the like. The sandwich structure is a structural form consisting of a high-strength panel and a light core material, the thickness of the sandwich structure is increased by using a low-density sandwich material, the structural rigidity can be greatly improved on the premise of little weight increase, and the effects of weight reduction and reinforcement are achieved. Sandwich structure composite materials are generally composed of a core layer, a panel, an adhesive, etc., wherein the core layer material includes wood, foam materials, honeycomb materials, etc., and the panel material includes carbon fiber composite boards, glass fiber composite boards, etc.
However, in addition to the requirement for light weight, the cabin for personnel activities also imposes the requirement for low toxicity, flame retardancy, etc. on the material. The factors causing fire are more due to large passenger flow, dense equipment and closed environment on the ship. When a fire disaster happens, the non-metal material is easy to generate molten drops, and usually releases a large amount of toxic gas and smoke dust, so that people are not easy to evacuate; it is difficult to strive for valuable time for crowd evacuation and fire extinguishment. Therefore, a composite material for use in an interior cabin of a ship is required to have excellent flame retardancy and generate less smoke during combustion.
The current sandwich structure composite material is difficult to meet the use requirements of ships, such as: the wood is adopted as the core layer material, and the flame retardant and fireproof performance is difficult to solve; the aramid fiber honeycomb core composite material has good flame retardance, but is easy to absorb water, and can generate water seepage problem due to microcracks of a surface layer after being prepared into a sandwich structure, and when the moisture absorption or the water mechanical property is seriously reduced, the performance of the honeycomb composite material is reduced; the polyethylene foam core material has poor fireproof performance and potential safety hazard. In the current research data of marine composite materials, the marine composite materials are mainly used for external use, and the development of marine composite materials for internal bulkheads is very little. Therefore, the development of the low-toxicity flame-retardant marine bulkhead composite material is of great significance.
Disclosure of Invention
The invention aims to solve the technical problem of the prior art and provides a low-toxicity flame-retardant marine bulkhead composite material and a preparation method thereof.
In order to solve the technical problem provided by the invention, the invention provides a low-toxicity flame-retardant bulkhead composite material for a ship, which comprises a lower panel, a foam core material and an upper panel which are arranged from bottom to top in sequence; the upper panel and the lower panel are formed by solidifying a modified vinyl resin impregnated fiber cloth layer.
In the scheme, the thickness of the foam core material is 25-50 mm.
In the above scheme, the material of the foam core material is polyvinyl chloride or polyetherimide.
In the proposal, the density of the foam core material is 60 to 110kg/m 3 。
In the scheme, the upper panel and the lower panel are 1.8-5 mm thick.
In the above scheme, the fiber cloth is one of glass fiber plain cloth and glass fiber twill cloth.
In the scheme, the modified vinyl resin is prepared from the following raw materials in parts by mass: 85 to 110 portions of vinyl resin, 2 to 8 portions of flame retardant, 3 to 5 portions of curing agent, 0.05 to 0.8 portion of accelerant, 0.5 to 2 portions of coupling agent and 0.5 to 5 portions of diluent.
In the above aspect, the viscosity of the modified vinyl resin is 150 to 350mPa · s.
Further, the vinyl resin is a standard bisphenol A epoxy vinyl ester resin.
Further, the flame retardant is one or more of decabromodiphenylethane, polyphosphoric acid amine and brominated polystyrene.
Further, the curing agent is methyl ethyl ketone peroxide.
Furthermore, the accelerant is a cobalt salt accelerant, and the cobalt content is 0.8-1.5%.
Further, the coupling agent is a silane coupling agent.
Further, the diluent is styrene.
The invention also provides a preparation method of the low-toxicity flame-retardant bulkhead composite material for the ship, which comprises the following steps of:
1) Uniformly mixing raw materials of the modified vinyl resin according to the mass part to prepare the modified vinyl resin;
2) Laying a lower fiber cloth layer, a foam core material and an upper fiber cloth layer on a mold in sequence to form a preformed body;
3) Sequentially laying demoulding cloth and guide cloth on the preformed body, arranging a rubber outlet pipe and a rubber injection pipe, and finally finishing integral sealing by adopting a sealing adhesive tape and a vacuum bag film;
4) And injecting the modified vinyl resin by adopting a vacuum auxiliary forming process, curing and forming, and demoulding to obtain the low-toxicity flame-retardant bulkhead composite material for the ship.
In the scheme, the vacuum degree of the vacuum auxiliary forming process is-0.09 MPa to-0.1 MPa, and sufficient vacuum degree is an important guarantee for fiber lamination compaction and densification.
In the scheme, the curing temperature is 40-65 ℃, and the curing time is 12-24 h.
The design concept of the formula system of the modified vinyl resin is as follows:
the vinyl resin has good corrosion resistance, good solvent resistance, high mechanical strength, large elongation, good bonding property with materials such as metal, plastic and the like, good fatigue resistance, good electrical property, thermal aging resistance, low curing shrinkage rate, capability of being cured at normal temperature or heating and low price, so the glass fiber reinforced vinyl resin is an ideal structural composite material for ships. The proper type and amount of flame retardant are added into the unsaturated polyester resin, so that the heat resistance and the flame resistance of the unsaturated polyester resin are improved, the resin combustion and flame propagation can be prevented, and the requirements of reducing combustion smoke and toxicity are met. The silane coupling agent is added into the matrix, so that the silane coupling agent can react with groups on the surface of the reinforced material and also can react with matrix resin, the bonding strength is enhanced, the performance of the composite material is improved, other media are prevented from permeating to the interface, and the interface state is improved. Styrene is selected as a diluent, so that the viscosity of the vinyl resin can be properly reduced, and the curing and crosslinking of the resin can be promoted.
Compared with the prior art, the invention has the beneficial effects that:
1) The composite material adopts a sandwich structure design of panel-foam core material-panel; the foam core material adopts polyvinyl chloride or polyetherimide, has better flame retardant property, and improves the fireproof performance of the composite material to a certain extent; the panel adopts modified vinyl resin to impregnate fiber cloth, and proper low-emission flame retardant is selected through the design of a formula system of resin, and the panel is matched with the optimization of a production process, so that the panel has the performances of high oxygen index, low smoke and low toxicity; therefore, the composite material can meet the requirement of the internal bulkhead of the ship on low toxicity and flame retardance.
2) The panel and the foam core material used by the composite material are light materials, so that the lightweight design concept of the ship is met; the foam core material has good stress capacity, can bear the normal stress caused by bending, and enhances the bearing capacity of the structure; the resin impregnated fiber cloth is used as a panel material, has good structural strength, and is not easy to corrode and age; therefore, the composite material has the advantages of light weight, high strength, good rigidity, marine environment resistance and the like, and is suitable for popularization and application.
Drawings
FIG. 1 is a schematic view of the structure of a low-toxicity flame-retardant bulkhead composite material for a ship.
Reference numerals: 1. an upper panel; 2. a foam core material; 3. a lower panel.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
In the following examples, the curing agent used was Shuojin MEKP-925H, which comprises methyl ethyl ketone peroxide; the adopted accelerant is EC-100, and the cobalt content is 1.2%; the coupling agent used is KH560, i.e., gamma- (2, 3-glycidoxy) propyltrimethoxysilane.
Example 1
A low-toxicity flame-retardant bulkhead composite material for a ship comprises a lower panel, a foam core material and an upper panel which are arranged from bottom to top in sequence; wherein the foam core material has a density of 80kg/m 3 Polyvinyl chloride foam with the thickness of 40 mm; the upper panel and the lower panel are 3mm in thickness and are formed by impregnating a fiber cloth layer with modified vinyl resin with the viscosity of 260mPa & s and solidifying the fiber cloth layer, the fiber cloth is glass fiber plain cloth, and the modified vinyl resin is prepared from the following raw materials in parts by mass: 430 parts of vinyl resin, 6 parts of decabromodiphenylethane, 4 parts of curing agent MEKP-925H, 0.4 part of accelerator EC, 1 part of coupling agent KH560 and 3 parts of styrene.
A preparation method of a low-toxicity flame-retardant bulkhead composite material for a ship comprises the following steps:
1) Uniformly mixing raw materials of the modified vinyl resin according to the mass part to prepare the modified vinyl resin;
2) Laying a lower fiber cloth layer, a foam core material and an upper fiber cloth layer on a mold in sequence, and bonding the layers by using AB glue as a bonding agent to form a preformed body;
3) Sequentially laying demoulding cloth and guide cloth on the preformed body, arranging a rubber outlet pipe and a rubber injection pipe, and finally finishing integral sealing by adopting a sealing adhesive tape and a vacuum bag film;
4) And (3) adopting a vacuum auxiliary forming process, wherein the vacuum degree is-0.095 MPa, injecting the modified vinyl resin, curing and forming, the curing temperature is 65 ℃, the curing time is 18h, and demoulding to obtain the low-toxicity flame-retardant marine bulkhead composite material.
Example 2
A low-toxicity flame-retardant bulkhead composite material for a ship comprises a lower panel, a foam core material and an upper panel which are sequentially arranged from bottom to top; wherein the foam core material has a density of 110kg/m 3 Polyetherimide foam with a thickness of 32 mm; the upper panel and the lower panel are 4mm in thickness and are formed by impregnating a fiber cloth layer with modified vinyl resin with the viscosity of 200mPa & s and curing, the fiber cloth is glass fiber twill cloth, and the modified vinyl resin is prepared from the following raw materials in parts by mass: 100 parts of vinyl resin 880, 2 parts of polyphosphoric acid amine, 4 parts of curing agent MEKP-925H, 0.6 part of accelerant EC, 1.5 parts of coupling agent KH560 and 4 parts of styrene.
A preparation method of a low-toxicity flame-retardant bulkhead composite material for a ship comprises the following steps:
1) Uniformly mixing the raw materials of the modified vinyl resin according to the mass part to prepare the modified vinyl resin;
2) Sequentially laying a lower fiber cloth layer, a foam core material and an upper fiber cloth layer on a mold, and bonding the layers by using AB glue as a bonding agent to form a preformed body;
3) Sequentially laying demoulding cloth and guide cloth on the preformed body, arranging a rubber outlet pipe and a rubber injection pipe, and finally finishing integral sealing by adopting a sealing adhesive tape and a vacuum bag film;
4) And (3) adopting a vacuum auxiliary forming process, wherein the vacuum degree is-0.095 MPa, injecting the modified vinyl resin, curing and forming, the curing temperature is 40 ℃, the curing time is 24 hours, and demoulding to obtain the low-toxicity flame-retardant marine bulkhead composite material.
Example 3
A low-toxicity flame-retardant bulkhead composite material for a ship comprises a lower panel, a foam core material and an upper panel which are arranged from bottom to top in sequence; wherein the foam core material has a density of 60kg/m 3 Polyvinyl chloride foam with a thickness of 26 mm; the upper panel and the lower panel are 2mm in thickness and are formed by impregnating a fiber cloth layer with a modified vinyl resin with the viscosity of 340mPa & s and solidifying the fiber cloth layer, wherein the fiber cloth is glass fiber plain cloth, and the modified vinyl resin is prepared from the following raw materials in parts by mass: 430 parts of vinyl resin, 5 parts of brominated polystyrene, 3 parts of curing agent MEKP-925H, 0.1 part of accelerator EC, 0.6 part of coupling agent KH560 and 1 part of styrene.
A preparation method of a low-toxicity flame-retardant bulkhead composite material for a ship comprises the following steps:
1) Uniformly mixing the raw materials of the modified vinyl resin according to the mass part to prepare the modified vinyl resin;
2) Sequentially laying a lower fiber cloth layer, a foam core material and an upper fiber cloth layer on a mold, and bonding the layers by using AB glue as a bonding agent to form a preformed body;
3) Sequentially laying demolding cloth and flow guide cloth on the preformed body, arranging a rubber outlet pipe and a rubber injection pipe, and finally sealing the whole body by adopting a sealing adhesive tape and a vacuum bag film;
4) And (3) adopting a vacuum auxiliary forming process, wherein the vacuum degree is-0.1 MPa, injecting the modified vinyl resin, curing and forming, the curing temperature is 50 ℃, the curing time is 16h, and demoulding to obtain the low-toxicity flame-retardant marine bulkhead composite material.
Example 4
A low-toxicity flame-retardant bulkhead composite material for a ship comprises a lower panel, a foam core material and an upper panel which are sequentially arranged from bottom to top; wherein the foam core material has a density of 100kg/m 3 Polyvinyl chloride foam with a thickness of 44 mm; the upper and lower panels had a thickness of 4.5mm and were composed of a modified ethylene having a viscosity of 160 mPasThe base resin impregnated fiber cloth layer is formed by curing, the fiber cloth is glass fiber twill cloth, and the modified vinyl resin is prepared from the following raw materials in parts by mass: 110 parts of vinyl resin 880, 3 parts of decabromodiphenylethane, 4 parts of polyphosphoric acid amine, 5 parts of curing agent MEKP-925H, 0.7 part of accelerating agent EC, 1.8 parts of coupling agent KH560 and 4 parts of styrene.
A preparation method of a low-toxicity flame-retardant bulkhead composite material for a ship comprises the following steps:
1) Uniformly mixing the raw materials of the modified vinyl resin according to the mass part to prepare the modified vinyl resin;
2) Sequentially laying a lower fiber cloth layer, a foam core material and an upper fiber cloth layer on a mold, and bonding the layers by using AB glue as a bonding agent to form a preformed body;
3) Sequentially laying demolding cloth and flow guide cloth on the preformed body, arranging a rubber outlet pipe and a rubber injection pipe, and finally sealing the whole body by adopting a sealing adhesive tape and a vacuum bag film;
4) And (3) adopting a vacuum auxiliary forming process, wherein the vacuum degree is-0.09 MPa, injecting the modified vinyl resin, curing and forming, the curing temperature is 45 ℃, the curing time is 20 hours, and demoulding to obtain the low-toxicity flame-retardant marine bulkhead composite material.
Comparative example 1
Comparative example 1 was otherwise identical to example 1 except that: the flame retardant decabromodiphenylethane is not added in the raw material composition of the modified vinyl resin.
Comparative example 2
Comparative example 1 was identical to example 1 in all other conditions except that: the material of the foam core material is polymethacrylimide.
The composite materials in the examples 1-4 and the comparative examples 1-2 are subjected to performance tests, the tensile strength is tested according to GB/T1447-2005, the bending strength and the bending modulus are tested according to GB/T1449-2005, the smoke density is tested according to the fifth part of the International fire resistance test program application rules, the limit oxygen index is tested according to GB/T2406.2-2009, the rigidity retention rate after carrying out a salt spray test for 1000 hours according to GB/T1771-2007, and the rigidity retention rate after carrying out an alternating damp-heat test for 14 cycles according to GB/T2573-2008, and the results are shown in Table 1.
TABLE 1
Figure BDA0003861609970000061
Figure BDA0003861609970000071
From the test results, the composite materials in the examples and the comparative examples can meet the requirements of light weight, high strength and marine environment resistance, but in the aspect of low-toxicity flame retardance, the comparative examples can not meet the application requirements that the smoke density of the bulkhead, the lining plate or the ceiling surface does not exceed 200 and the oxygen index is more than or equal to 30 percent, and compared with the comparative examples, the smoke density is obviously reduced, the oxygen index is obviously increased, and the requirements of low-toxicity flame retardance are met.
The above embodiments are merely examples for clearly illustrating the present invention and do not limit the present invention. Other variants and modifications will be apparent to those skilled in the art in light of the foregoing description, which are not necessarily exhaustive of all embodiments and are therefore clearly encompassed within the scope of the invention.

Claims (10)

1. The low-toxicity flame-retardant marine bulkhead composite material is characterized by comprising a lower panel, a foam core material and an upper panel which are sequentially arranged from bottom to top; the foam core material is made of polyvinyl chloride or polyetherimide; the upper panel and the lower panel are formed by curing a modified vinyl resin impregnated fiber cloth layer; the modified vinyl resin is composed of vinyl resin, a flame retardant, a curing agent, an accelerator, a coupling agent and a diluent.
2. The low-toxicity flame-retardant marine bulkhead composite material as claimed in claim 1, wherein the modified vinyl resin is composed of the following raw materials in parts by mass: 85 to 110 portions of vinyl resin, 2 to 8 portions of flame retardant, 3 to 5 portions of curing agent, 0.05 to 0.8 portion of accelerator, 0.5 to 2 portions of coupling agent and 0.5 to 5 portions of diluent, and the viscosity of the modified vinyl resin is 150 to 350 mPas.
3. The bulkhead composite of claim 1, wherein the foam core material has a thickness of 25 to 50mm and a density of 60 to 110kg/m 3 。
4. The low toxicity flame retardant marine bulkhead composite of claim 1, wherein the upper and lower panels have a thickness of 1.8 to 5mm.
5. The low toxicity flame retardant marine bulkhead composite of claim 1, wherein the fiber cloth is one of a glass fiber plain cloth and a glass fiber twill cloth.
6. The low toxicity flame retardant marine bulkhead composite of claim 1, wherein the vinyl resin is a standard type bisphenol a epoxy vinyl ester resin; the flame retardant is one or more of decabromodiphenylethane, polyphosphoric acid amine and brominated polystyrene.
7. The low toxicity flame retardant marine bulkhead composite of claim 1, wherein the curing agent is methyl ethyl ketone peroxide; the promoter is a cobalt salt promoter, and the cobalt content is 0.8-1.5%; the coupling agent is a silane coupling agent; the diluent is styrene.
8. A method of making a low toxicity flame retardant marine bulkhead composite of claim 1, comprising the steps of:
1) Uniformly mixing raw materials of the modified vinyl resin according to the mass part to prepare the modified vinyl resin;
2) Sequentially laying a lower fiber cloth layer, a foam core material and an upper fiber cloth layer on the mold to form a preformed body;
3) Sequentially laying demoulding cloth and guide cloth on the preformed body, arranging a rubber outlet pipe and a rubber injection pipe, and finally finishing integral sealing by adopting a sealing adhesive tape and a vacuum bag film;
4) And injecting the modified vinyl resin by adopting a vacuum auxiliary forming process, curing and forming, and demoulding to obtain the low-toxicity flame-retardant bulkhead composite material for the ship.
9. The method for preparing a low-toxicity flame-retardant marine bulkhead composite material according to claim 8, wherein the vacuum degree of the vacuum auxiliary forming process is-0.09 MPa to-0.1 MPa.
10. The method for preparing a low-toxicity flame-retardant bulkhead composite for a ship according to claim 8, wherein the curing temperature is 40-65 ℃ and the curing time is 12-24 h.
CN202211166487.1A 2022-09-23 2022-09-23 Low-toxicity flame-retardant bulkhead composite material for ship and preparation method thereof Pending CN115534446A (en)

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