CN111205667B - Flame-retardant glass fiber reinforced plastic and preparation process thereof - Google Patents

Flame-retardant glass fiber reinforced plastic and preparation process thereof Download PDF

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CN111205667B
CN111205667B CN202010088392.7A CN202010088392A CN111205667B CN 111205667 B CN111205667 B CN 111205667B CN 202010088392 A CN202010088392 A CN 202010088392A CN 111205667 B CN111205667 B CN 111205667B
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parts
glass fiber
reinforced plastic
gel coat
fiber reinforced
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CN111205667A (en
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王立山
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Shandong Runsing Composite Co ltd
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Shandong Runsing Composite Co ltd
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    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • C08K5/5333—Esters of phosphonic acids
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    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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    • B32B2038/0052—Other operations not otherwise provided for
    • B32B2038/0076—Curing, vulcanising, cross-linking
    • 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
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    • B32B2262/101—Glass fibres
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    • B32—LAYERED PRODUCTS
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    • 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
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    • B32B2307/70—Other properties
    • B32B2307/712—Weather resistant
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    • B32B2307/726—Permeability to liquids, absorption
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Abstract

The invention discloses a flame-retardant glass fiber reinforced plastic and a preparation process thereof, belonging to the technical field of glass fiber reinforced plastic plate, profile, corrugated plate and checkered plate production, wherein the flame-retardant glass fiber reinforced plastic comprises a matrix layer, and the matrix layer comprises the following raw materials in parts by weight: 100 parts of unsaturated resin, 3-30 parts of expanded graphite, 15-70 parts of glass fiber, 5-50 parts of diluent and 2-3 parts of curing agent; the coating comprises a substrate layer and a gel coat layer arranged on the substrate layer, wherein the gel coat layer comprises the following raw materials in parts by weight: 100 parts of unsaturated resin, 3-30 parts of expanded graphite, 5-50 parts of diluent and 2-3 parts of curing agent. The invention adopts the expanded graphite or combines the expanded graphite and the nano inorganic flame retardant as the flame retardant of the glass fiber reinforced plastic, does not contain halogen compounds, is safe and environment-friendly, is nontoxic and nuisanceless, and improves the flame retardant property of the glass fiber reinforced plastic product.

Description

Flame-retardant glass fiber reinforced plastic and preparation process thereof
Technical Field
The invention relates to the technical field of glass fiber reinforced plastic plate, profile, corrugated plate and checkered plate production, in particular to flame-retardant glass fiber reinforced plastic and a preparation process thereof.
Background
The glass fiber reinforced plastic has the characteristics of corrosion resistance and light weight, is widely applied in various fields, mainly uses unsaturated resin as matrix resin, and emits a large amount of heat in the combustion process due to the fact that the unsaturated resin is a combustible material, generates dense smoke and releases toxic gas to become hidden danger of fire, and along with the increasing wide application fields of glass fiber reinforced plastic products, the performance requirements of people on the glass fiber reinforced plastic products are higher and higher, and the flame retardant performance of the glass fiber reinforced plastic products is more and more valued by people, so that the development of the flame retardant glass fiber reinforced plastic has great practical significance. The existing flame-retardant glass fiber reinforced plastic has low flame retardant property, most of halogen-containing compounds release toxic gas and smoke at high temperature, and the mechanical property, weather resistance and the like of the glass fiber reinforced plastic are poor due to the fact that the flame retardant is added into the glass fiber reinforced plastic raw material, so that the application of the glass fiber reinforced plastic in more fields is limited.
Disclosure of Invention
Aiming at the technical problems, the invention provides the flame-retardant glass fiber reinforced plastic and the preparation process thereof, wherein the expanded graphite or the combination of the expanded graphite and the inorganic flame retardant is adopted as the flame retardant of the glass fiber reinforced plastic, and the flame-retardant glass fiber reinforced plastic is free of halogen compounds, safe, environment-friendly, nontoxic and pollution-free, and the expanded graphite has better flame retardance, aging resistance, water resistance and corrosion resistance by adding the expanded graphite into the glass fiber reinforced plastic raw material, so that the glass fiber reinforced plastic product is endowed with good flame retardance, aging resistance, water resistance and corrosion resistance. Furthermore, the nano inorganic flame retardant and the expanded graphite are mixed in the glass fiber reinforced plastic raw material to achieve the synergistic flame retardant effect, improve the flame retardant property and improve the mechanical property of the glass fiber reinforced plastic.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the flame-retardant glass fiber reinforced plastic comprises a matrix layer, wherein the matrix layer comprises the following raw materials in parts by weight: 100 parts of unsaturated resin, 3-30 parts of expanded graphite, 15-70 parts of glass fiber, 5-50 parts of diluent and 2-3 parts of curing agent.
Preferably, the flame-retardant glass fiber reinforced plastic further comprises a gel coat layer arranged on the substrate layer, wherein the gel coat layer comprises the following raw materials in parts by weight: 100 parts of unsaturated resin, 3-30 parts of expanded graphite, 5-50 parts of diluent and 2-3 parts of curing agent.
Further preferably, the flame-retardant glass fiber reinforced plastic comprises a matrix layer and a gel coat layer arranged on the matrix layer, wherein the matrix layer comprises the following raw materials in parts by weight: 100 parts of unsaturated resin, 18 parts of expanded graphite, 40 parts of glass fiber, 25 parts of diluent and 2.5 parts of curing agent, wherein the gel coat layer comprises the following raw materials in parts by weight: 100 parts of unsaturated resin, 18 parts of expanded graphite, 25 parts of diluent and 2.5 parts of curing agent.
Further preferably, the gel coat layer further comprises raw material glass fibers, wherein the amount of the glass fibers is 15-70wt% of the unsaturated resin.
Further preferably, the matrix layer and the gel coat layer further comprise raw material inorganic flame retardants, and the dosage of the inorganic flame retardants is 10-200wt% of the unsaturated resin.
Further preferably, the inorganic flame retardant is a nano inorganic flame retardant.
Further preferably, the nano inorganic flame retardant is nano magnesium hydroxide and nano aluminum hydroxide, and the weight ratio of the nano magnesium hydroxide to the nano aluminum hydroxide is 1:1.
Preferably, the unsaturated resin is an m-phenylene unsaturated polyester resin.
Preferably, the diluent is dimethyl methylphosphonate.
The invention also provides a preparation process of the flame-retardant glass fiber reinforced plastic, which comprises the following steps:
(1) The raw materials of the matrix layer are respectively injected into a stirring tank according to a proportion, and are fully stirred and mixed in the stirring tank;
(2) Feeding the substrate, and feeding the stirred and mixed substrate layer raw materials to a bottom film through a feeding pump;
(3) Fiber mat laying section: laying a fiber mat on the substrate layer;
(4) A product thickness fixing press roller;
(5) Heating and curing through a curing oven;
(6) And (5) rolling and packaging.
The invention also provides another preparation process of the flame-retardant glass fiber reinforced plastic, which comprises the following steps:
(1) The raw materials of the matrix layer and the gel coat layer are respectively injected into different stirring tanks according to the proportion, and are fully stirred and mixed in the stirring tanks;
(2) The method comprises the steps of (1) performing gel coat feeding in a first working section of a continuous production line, and feeding the stirred and mixed gel coat layer raw materials to a gel coat bottom film;
(3) Under the action of the traction device, the gel coat layer is coated, and the thickness of the gel coat layer is controlled;
(4) Heating and curing through a curing oven;
(5) Feeding the matrix, namely feeding the stirred and mixed raw material of the matrix layer to the solidified gel coat layer through a feeding pump, and controlling the thickness of the matrix layer;
(6) Fiber mat laying section: laying a fiber mat on the substrate layer;
(7) A product thickness fixing press roller;
(8) Heating and curing through a curing oven;
(9) And (5) rolling and packaging.
The beneficial technical effects of the invention are as follows: the invention adopts the expanded graphite or combines the expanded graphite and the nano inorganic flame retardant as the flame retardant of the glass fiber reinforced plastic, does not contain halogen compounds, and is safe, environment-friendly, nontoxic and nuisanceless; by adding the expanded graphite into the glass fiber reinforced plastic raw material, the expanded graphite has better flame retardance, aging resistance, water resistance and corrosion resistance, and has wide sources and stable physical properties, thereby endowing the glass fiber reinforced plastic product with good flame retardance, aging resistance, water resistance and corrosion resistance; the nanometer inorganic flame retardant aluminum hydroxide and nanometer magnesium hydroxide are adopted to achieve synergistic flame retardant effect together with the expanded graphite, the nanometer inorganic flame retardant has better effect than other additive flame retardants, when the resin burns, decomposition and absorption heat are generated, meanwhile, moisture is released to achieve flame retardant effect, a charring layer is formed to block the burning of flame, the nanometer aluminum hydroxide and nanometer magnesium hydroxide are used together to achieve synergistic flame retardant effect, the flame retardant performance is improved, the mechanical property of the material is improved, the viscosity is reduced together with the glass fiber, and the product strength is ensured; the invention selects the m-benzene type unsaturated polyester resin, the m-benzene type unsaturated polyester resin has stronger ultraviolet resistance, and the weather resistance of the product is more effectively exerted; the diluent has the function of reducing the viscosity of the system, and the methyl dimethyl phosphate is used as the diluent, so that the diluent has the function of reducing the viscosity and also has a flame-retardant effect; the glass fiber reinforced plastic of the invention has improved weather resistance, yellowing resistance and the like while achieving the class of classA (testing according to ASTM E84 fireproof test standard), and can be applied to various building industries, interior decoration, refrigerated trucks, containers, refrigeration plates, cooling towers, environmental protection equipment, electrical components and the like.
Detailed Description
The invention will be further illustrated with reference to specific examples.
Example 1
The flame-retardant glass fiber reinforced plastic comprises a matrix layer and a gel coat layer arranged on the matrix layer, wherein the matrix layer comprises the following raw materials in parts by weight: 100 parts of unsaturated resin, 18 parts of expanded graphite, 40 parts of glass fiber, 25 parts of methyl dimethyl phosphate and 2.5 parts of curing agent, wherein the gel coat layer comprises the following raw materials in parts by weight: 100 parts of m-benzene type unsaturated polyester resin, 18 parts of expanded graphite, 25 parts of diluent and 2.5 parts of curing agent.
Example 2
The flame-retardant glass fiber reinforced plastic comprises a matrix layer and a gel coat layer arranged on the matrix layer, wherein the matrix layer comprises the following raw materials in parts by weight: 100 parts of unsaturated resin, 3 parts of expanded graphite, 15 parts of glass fiber, 5 parts of methyl dimethyl phosphate, 2 parts of curing agent, 5 parts of nano magnesium hydroxide and 5 parts of nano aluminum hydroxide, wherein the gel coating layer comprises the following raw materials in parts by weight: 100 parts of m-benzene type unsaturated polyester resin, 3 parts of expanded graphite, 5 parts of methyl dimethyl phosphate, 2 parts of curing agent, 5 parts of nano magnesium hydroxide and 5 parts of nano aluminum hydroxide.
Example 3
The flame-retardant glass fiber reinforced plastic comprises a matrix layer and a gel coat layer arranged on the matrix layer, wherein the matrix layer comprises the following raw materials in parts by weight: 100 parts of unsaturated resin, 30 parts of expanded graphite, 70 parts of glass fiber, 50 parts of methyl dimethyl phosphate, 3 parts of curing agent, 100 parts of nano magnesium hydroxide and 100 parts of nano aluminum hydroxide, wherein the gel coat layer comprises the following raw materials in parts by weight: 100 parts of m-benzene type unsaturated polyester resin, 30 parts of expanded graphite, 70 parts of glass fiber, 50 parts of methyl dimethyl phosphate, 3 parts of curing agent, 100 parts of nano magnesium hydroxide and 100 parts of nano aluminum hydroxide.
The preparation process of the flame-retardant glass fiber reinforced plastic described in the above embodiments 1-3 comprises the following steps:
(1) The raw materials of the matrix layer and the gel coat layer are respectively injected into different stirring tanks according to the proportion, and are fully stirred and mixed in the stirring tanks;
(2) The method comprises the steps of (1) performing gel coat feeding in a first working section of a continuous production line, and feeding the stirred and mixed gel coat layer raw materials to a gel coat bottom film;
(3) Under the action of the traction device, the gel coat layer is coated, and the thickness of the gel coat layer is controlled;
(4) Heating and curing through a curing oven;
(5) Feeding the matrix, namely feeding the stirred and mixed raw material of the matrix layer to the solidified gel coat layer through a feeding pump, and controlling the thickness of the matrix layer;
(6) Fiber mat laying section: laying a fiber mat on the substrate layer;
(7) A product thickness fixing press roller;
(8) Heating and curing through a curing oven;
(9) And (5) rolling and packaging.
Example 4
The flame-retardant glass fiber reinforced plastic comprises a matrix layer, wherein the matrix layer comprises the following raw materials in parts by weight: 100 parts of unsaturated resin, 3-30 parts of expanded graphite, 15-70 parts of glass fiber, 5-50 parts of diluent and 2-3 parts of curing agent.
The preparation process of the flame-retardant glass fiber reinforced plastic described in the embodiment 4 comprises the following steps:
(1) The raw materials of the matrix layer are respectively injected into a stirring tank according to a proportion, and are fully stirred and mixed in the stirring tank;
(2) Feeding the substrate, and feeding the stirred and mixed substrate layer raw materials to a bottom film through a feeding pump;
(3) Fiber mat laying section: laying a fiber mat on the substrate layer;
(4) A product thickness fixing press roller;
(5) Heating and curing through a curing oven;
(6) And (5) rolling and packaging.
Comparative example 1
The flame-retardant glass fiber reinforced plastic comprises a matrix layer and a gel coat layer arranged on the matrix layer, wherein the matrix layer comprises the following raw materials in parts by weight: 100 parts of unsaturated resin, 40 parts of glass fiber, 25 parts of methyl dimethyl phosphate and 2.5 parts of curing agent, wherein the gel coat layer comprises the following raw materials in parts by weight: 100 parts of m-benzene type unsaturated polyester resin, 25 parts of diluent and 2.5 parts of curing agent.
Compared with examples 1-3, the gel coat layer and the matrix layer of comparative example 1 are not added with expanded graphite, nano aluminum hydroxide and nano calcium hydroxide, and the other components are completely the same, and the preparation process is also completely the same.
And (3) performance detection:
1. flame retardant Properties
The glass fiber reinforced plastic products obtained in the above examples 1 to 3 and comparative example 1 were subjected to flame retardant property test (test according to ASTM E84 fire test standard), the test specimen specification was 7320X 630X 2.0mm, and the results are shown in Table 1:
TABLE 1
Figure BDA0002382860390000051
The rating of the ASTM E84 test results by the regulations is shown in Table 2:
TABLE 2
classA classB classC
Flame propagation index FSI 0-25 26-75 76-200
Smoke development index SDI 0-450 0-450 0-450
From the above detection, it can be seen that the glass fiber reinforced plastic products obtained in examples 1-3 of the present invention have flame propagation indexes FSI in the range of 0-25, and smoke development indexes SDI in the range of 0-450, meet the class requirement of classA, have good flame retardance, and can meet the use requirement, while the glass fiber reinforced plastic products obtained in comparative example 1 meet the class requirement of classC, and cannot meet the application in the field with the requirement of flame retardance.
2. Mechanical property detection
The glass fiber reinforced plastic products of the above examples 1-3 and comparative example 1 were subjected to mechanical property detection, and the detection results are shown in table 3:
TABLE 3 Table 3
Figure BDA0002382860390000052
Figure BDA0002382860390000061
The detection shows that the mechanical property of the glass fiber reinforced plastic product is reduced after the expanded graphite is doped, and the mechanical property is improved after the nano inorganic flame retardant is doped.
3. Aging resistance test
The glass fiber reinforced plastic product obtained in the above example 3 was subjected to aging resistance test (test according to GB/T14552-2008), which simulates damage caused by solar ultraviolet light, aging resistance test was performed on the material by exposing the material to be tested to light at a controlled high temperature, irradiation effect of sunlight was simulated by using ultraviolet lamp tubes, dew and rainwater were simulated by condensation and water spraying, and damage which would take several months or even years outdoors at present was simulated by ultraviolet irradiation equipment, including discoloration and color change. For example, the total radiation intensity is 1120W/m 2 At this time, the irradiance value measured at 340nm was 0.68, which we can infer that the set value was 0.68W/m 2 At 340nm, this corresponds to 6.55 times the outdoor irradiance. However, UV aging is closely related to temperature, and with reference to a mean annual temperature of 21.8 degrees in guangzhou, experience estimates that about 1.5-fold increase in aging effect when the temperature rises 1-fold, so at a set temperature of 60 degrees, there is 60/21.8 x 1.5 x 6.55 = 27 days, i.e.: the UV test was performed for 1 day, which corresponds to an outdoor aging effect of 27 days.
The detection conditions and results of this example are shown in tables 4 and 5 below:
TABLE 4 Table 4
Illumination time h Rain h Laser irradiation power W Blackboard temperature DEG C Number of cycles Detection result
8 4 1.2 60 25 See (Table 5)
TABLE 5
Figure BDA0002382860390000062
The color difference of the sample obtained by the detection and calculation is qualified, which shows that the glass fiber reinforced plastic product has good flame retardance and good weather resistance and ageing resistance.
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the present invention, so that various modifications and variations can be made by those skilled in the art without the need for inventive effort on the basis of the technical solutions of the present invention.

Claims (4)

1. The flame-retardant glass fiber reinforced plastic is characterized by comprising a matrix layer, wherein the matrix layer comprises the following raw materials in parts by weight: 100 parts of unsaturated resin, 3-30 parts of expanded graphite, 15-70 parts of glass fiber, 5-50 parts of diluent, 2-3 parts of curing agent and a gel coating layer arranged on the substrate layer, wherein the gel coating layer comprises the following raw materials in parts by weight: 100 parts of unsaturated resin, 3-30 parts of expanded graphite, 5-50 parts of diluent and 2-3 parts of curing agent, wherein the substrate layer and the gel coat layer also comprise raw material inorganic flame retardants, the dosage of the inorganic flame retardants is 10-200wt% of the unsaturated resin, the inorganic flame retardants are nano inorganic flame retardants, the nano inorganic flame retardants are nano magnesium hydroxide and nano aluminum hydroxide, the weight ratio of the nano magnesium hydroxide to the nano aluminum hydroxide is 1:1, the unsaturated resin is m-benzene type unsaturated polyester resin, and the diluent is dimethyl methylphosphonate.
2. The flame-retardant glass fiber reinforced plastic according to claim 1, comprising a matrix layer and a gel coat layer arranged on the matrix layer, wherein the matrix layer comprises the following raw materials in parts by weight: 100 parts of unsaturated resin, 18 parts of expanded graphite, 40 parts of glass fiber, 25 parts of diluent and 2.5 parts of curing agent, wherein the gel coat layer comprises the following raw materials in parts by weight: 100 parts of unsaturated resin, 18 parts of expanded graphite, 25 parts of diluent and 2.5 parts of curing agent.
3. A fire retardant glass fibre reinforced plastic according to claim 1, wherein the gel coat layer further comprises raw material glass fibre, and the glass fibre is 15-70wt% of unsaturated resin.
4. A process for preparing a flame retardant glass fiber reinforced plastic according to any one of claims 1 to 3, comprising the steps of:
(1) The raw materials of the matrix layer and the gel coat layer are respectively injected into different stirring tanks according to the proportion, and are fully stirred and mixed in the stirring tanks;
(2) The method comprises the steps of (1) performing gel coat feeding in a first working section of a continuous production line, and feeding the stirred and mixed gel coat layer raw materials to a gel coat bottom film;
(3) Under the action of the traction device, the gel coat layer is coated, and the thickness of the gel coat layer is controlled;
(4) Heating and curing through a curing oven;
(5) Feeding the matrix, namely feeding the stirred and mixed raw material of the matrix layer to the solidified gel coat layer through a feeding pump, and controlling the thickness of the matrix layer;
(6) Fiber mat laying section: laying a fiber mat on the substrate layer;
(7) A product thickness fixing press roller;
(8) Heating and curing through a curing oven;
(9) And (5) rolling and packaging.
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