CN102731960A - High-toughness flame retardation phenolic prepreg composite material, its preparation method and its application - Google Patents
High-toughness flame retardation phenolic prepreg composite material, its preparation method and its application Download PDFInfo
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Abstract
The invention relates to a high-toughness flame retardation phenolic prepreg composite material, its preparation method and its application, which is characterized in that a reasonable molecular structure design and a synthesis technology are combined for substantially raising the reaction activity of a phenolic resin prepolymer under the low temperature, on the basis of phenolic resin, a thermoplastic polymer and a rubber flexibilizer are introduced, and the toughness of the composite material can be substantially enhanced, a bromine/antimony system fire retardant is introduced for making up the disadvantages of decreased flame resistance performance caused by the addition of a flexibilizer; a preparation technology for regulation and control as well as optimization of the prepreg is used for controlling the solidification degree and the volatile matter content of the prepreg, thereby the soft feeling and moderate viscosity of the phenolic prepreg can be realized, and the composite material possesses good spreading technical performance. The composite material can be use for inner decoration parts of airplane ceilings, luggage compartments and sidewall plates, ship wallboards and cabinets, and high speed train ceilings and sidewall plates and the like.
Description
Technical field
The present invention relates to a kind of H.T. flame-proof phenolic prepreg matrix material.
Background technology
The fine prepreg matrix material of phenolic aldehyde/glass and phenolic aldehyde/carbon has favorable manufacturability ability, excellent flame-retardant and outstanding cost performance; Be used widely at present, especially bringing into play vital role aspect the fire savety that improves products such as aircraft, boats and ships and electronic apparatus in fields such as aerospace, communications and transportation and electric insulations.For example; The Cycom 2265 of Cytec company and Cycom 2290 matrix materials such as prepreg such as phenolic aldehyde such as the trade mark such as grade have become the material of main part of interior trim structure units such as making Air Passenger and Boeing top ceiling, boot, wallboard, and 3240 epoxy phenolic glass cloth prepreg matrix materials are the main selections that prepare F class B insulation laminated wood in the world.
The distinctive high-crosslinking-degree structure of phenolic resin curing thing makes it have excellent intrinsic flame-retarding characteristic; Any fire retardant need not be added and V-0 level (UL-94 standard) can be reached; The resin carbonation retention rate is very high in the combustion processes, and the burst size of smog and poisonous gas is very little.Yet on the other hand; The chemical structure of high crosslink density also makes the shrinking percentage of phenolic resin curing thing and fragility very big; Prepreg matrix material impact resistance by its preparation is very low; Mechanical property is not good enough, can't satisfy the mechanical property requirements that the field proposed such as aerospace, communications and transportation and electric insulation.
In recent years; Toughening modifying research to resol is very many; Adopt thermoplastic polymer that Cycom 2265 is carried out toughening modifying with Cycom 2290 matrix materials such as prepreg such as phenolic aldehyde such as the trade mark such as grade like Cytec company, Lewcott company adopts the liquid nitrile rubber that phenolic aldehyde prepreg matrix material is carried out toughening modifying.Domestic toughening modifying research about resol concentrates on the prescription stage in later stage mostly; Do not carry out resol Molecular Structure Design and systematic Study such as synthetic technology, toughness reinforcing compounded technology, equipment of preimpregnated material manufacture technology and matrix material all round properties to the concrete application of flame-proof phenolic prepreg matrix material on aircraft and electronic isolation device as yet, cause existing phenolic aldehyde prepreg matrix material to have mostly that shop coating process property is poor, impact resistance is low, or because the introducing of toughner causes flame retardant properties obviously to descend the degradation shortcoming.
Summary of the invention
The object of the present invention is to provide a kind of H.T. flame-proof phenolic prepreg matrix material, this matrix material has H.T., high flame retardant and good shop coating process property, has important popularizing application prospect in fields such as aircraft, boats and ships and high ferros.
Another object of the present invention is to provide a kind of preparation method of H.T. flame-proof phenolic prepreg matrix material.
A further object of the present invention is to provide a kind of purposes of H.T. flame-proof phenolic prepreg matrix material.
Above-mentioned purpose of the present invention mainly is achieved through following technical scheme:
A kind of H.T. flame-proof phenolic prepreg matrix material comprises the component of following mass percentage content:
Phenolic resin as matrix resin 20～70%;
Fiber reinforced material 30～80%;
Wherein said phenolic resin as matrix resin comprises the component of following mass fraction:
Resol 100;
Toughner 5～20;
Tetrabromo-bisphenol 1～15;
Antimony Trioxide: 99.5Min 0.5～5;
Organic solvent 10～80.
In above-mentioned H.T. flame-proof phenolic prepreg matrix material, resol is selected from least a in hydrated barta catalysis phenolic aldehyde, Marinco H catalysis phenolic aldehyde or the aniline catalysis phenolic aldehyde.
In above-mentioned H.T. flame-proof phenolic prepreg matrix material, the aldehyde phenol mass ratio of resol is 1～3: 1, is preferably 1.5～2.5: 1.
In above-mentioned H.T. flame-proof phenolic prepreg matrix material, toughner is selected from least a in end carboxyl nitrile rubber, terminal hydroxy group nitrile rubber, carboxy terminated polybutadiene, hydroxy-terminated polybutadienes, polyvinylacetal or the polyvinyl butyral acetal.
In above-mentioned H.T. flame-proof phenolic prepreg matrix material, fiber reinforced material is spun glass one-way tape, glasscloth, carbon fiber one-way band or carbon cloth.
In above-mentioned H.T. flame-proof phenolic prepreg matrix material, organic solvent is ethanol, propyl alcohol, acetone or butanone.
The preparation method of H.T. flame-proof phenolic prepreg matrix material comprises the steps:
Step 1, preparation phenolic resin as matrix resin, specific as follows:
(1) adopts aldehyde cpd, phenolic compound and organic solvent novolak resin performed polymer, termination reaction when the gel time of performed polymer under 160 ℃ is 1～10min;
(2) in reaction kettle, add the resol performed polymer, add organic solvent, toughner, tetrabromo-bisphenol and Antimony Trioxide: 99.5Min under the high-speed stirring successively, fully stirred 60～120 minutes, promptly make phenolic resin as matrix resin;
Step 2, preparation phenolic aldehyde prepreg matrix material, specific as follows:
(3) adopt organic solvent that the proportion of phenolic resin as matrix resin is adjusted to 0.9g/m
2～1.2g/m
2Between, then phenolic resin as matrix resin and fiber reinforced material are prepared the phenolic aldehyde prepreg through the solution cement-dipping method through continuous impregnating, oven dry and winding process;
(4) carry out phenolic aldehyde prepreg laying according to thickness requirement, the folded piece of phenolic aldehyde prepreg is put into put into autoclave curing molding under the solidifying pressure of 80～200 ℃ solidification value, 0.1～3MPa after press or the vacuum coater afterwards.
In the preparation method of above-mentioned H.T. flame-proof phenolic prepreg matrix material, resol is selected from least a in hydrated barta catalysis phenolic aldehyde, Marinco H catalysis phenolic aldehyde or the aniline catalysis phenolic aldehyde.
In the preparation method of above-mentioned H.T. flame-proof phenolic prepreg matrix material, toughner is selected from least a in end carboxyl nitrile rubber, terminal hydroxy group nitrile rubber, carboxy terminated polybutadiene, hydroxy-terminated polybutadienes, polyvinylacetal or the polyvinyl butyral acetal
In the preparation method of above-mentioned H.T. flame-proof phenolic prepreg matrix material, fiber reinforced material is spun glass one-way tape, glasscloth, carbon fiber one-way band or carbon cloth.
In the preparation method of above-mentioned H.T. flame-proof phenolic prepreg matrix material, the solidification value of the folded piece curing molding of phenolic aldehyde prepreg is 100～160 ℃ in the step (4), and solidifying pressure is 0.1～1MPa.
H.T. flame-proof phenolic prepreg matrix material is used for aircraft top ceiling, luggage room and sidewall, boats and ships wallboard and cabinet and bullet train top ceiling and sidewall interior trim parts.
The present invention compared with prior art has following beneficial effect:
(1) the present invention selects the key process parameter of novolak resin---the proportioning of starting material aldehyde and phenol; Methylol group content through suitable raising resol performed polymer; Significantly improve resol performed polymer activity of curing reaction at a lower temperature on the one hand, realized phenolic aldehyde prepreg matrix material intermediate temperature setting; Contain a large amount of flexibility-CH in the phenolic composite behind the intermediate temperature setting on the other hand
2-O-CH
2-link obviously improves the toughness of matrix material;
(2) the present invention passes through to introduce thermoplastic polymer and rubber-like toughner on the basis of novolak resin; Improved the toughness of phenolic aldehyde prepreg matrix material greatly; Remedied because toughner adds the flame retardant properties decline shortcoming that causes through introducing bromine/Sb system fire retardant simultaneously, made phenolic aldehyde prepreg matrix material keep good flame retardancy;
(3) the present invention controls the state of cure and the volatile content of prepreg through regulation and control and the preparation technology that optimizes prepreg, has realized under the prepared phenolic aldehyde prepreg room temperature softly, and viscosity is moderate, has good shop coating process performance;
(4) phenolic composite of the present invention is that the concrete application requiring that is directed against fields such as aviation, boats and ships and high ferro designs; Can prepare in enormous quantities; Be specially adapted to aircraft top ceiling, luggage room and sidewall, boats and ships wallboard and cabinet and interior trim parts such as bullet train top ceiling and sidewall, have very wide range of application.
Embodiment
Explain through concrete embodiment below, but the present invention is not limited to following examples.
H.T. flame-proof phenolic prepreg composite material by adopting of the present invention is a matrix through Molecular Structure Design, toughness reinforcing and flame-retardant modified novel phenolic resins, with continuous glass-fiber or carbon fibre be strongthener, through after the solution method preimpregnation again through press hot pressing or autoclave technology is compound prepares.
Flame-proof phenolic prepreg matrix material of the present invention contains the component of following mass percentage content:
Phenolic resin as matrix resin 20～60%
Fiber reinforced material 30～80%
Wherein the component and the mass fraction of phenolic resin as matrix resin prescription are (mass fraction with resol is a benchmark):
Be selected from least a in hydrated barta catalysis phenolic aldehyde, Marinco H catalysis phenolic aldehyde, the aniline catalysis phenolic aldehyde through Molecular Structure Design and the resol of optimizing the back preparation; The aldehyde phenol mass ratio of resol is 1～3, is preferably 1.5～2.5; The gel time of resol under 160 ℃ is 1～30min, is preferably 1～10min.
Toughner is selected from least a in end carboxyl nitrile rubber, terminal hydroxy group nitrile rubber, carboxy terminated polybutadiene, hydroxy-terminated polybutadienes, polyvinylacetal, the polyvinyl butyral acetal.The toughner consumption can be 5～30 mass parts, is preferably 5～20 mass parts.If consumption greater than 30 mass parts, will cause resistance toheat, mechanical property and the flame retardant properties of prepreg matrix material obviously to descend.
The tetrabromo-bisphenol consumption can be 1～30 mass parts, is preferably 1～15 mass parts; The Antimony Trioxide: 99.5Min consumption can be 0.5～8 mass parts, is preferably 0.5～5 mass parts; The mass ratio of Antimony Trioxide: 99.5Min and tetrabromo-bisphenol is preferably 1: 2.3～and 1: 3.3.
Strongthener is selected from spun glass one-way tape, glasscloth, carbon fiber one-way band, carbon cloth and other all kinds of structural reinforcement materials.Glass fibre reinforcement is preferably the spun glass one-way tape and thickness is all types of plain weaves and the satin weave woven fiber glass of 0.1～0.5mm; Carbon fibre reinforcement is preferably the carbon fiber one-way band and thickness is all types of plain weaves and the satin weave carbon cloth of 0.1～0.5mm.
The preparation method of H.T. flame-proof phenolic prepreg matrix material is following:
Step 1, preparation phenolic resin as matrix resin, specific as follows:
(1) adopts aldehyde cpd, phenolic compound and organic solvent novolak resin performed polymer, termination reaction when the gel time of performed polymer under 160 ℃ is 1～10min;
(2) in reaction kettle, add the resol performed polymer, add organic solvent, toughner, tetrabromo-bisphenol and Antimony Trioxide: 99.5Min under the high-speed stirring successively, fully stirred 60 minutes～120 minutes, promptly make phenolic resin as matrix resin;
Step 2, preparation phenolic aldehyde prepreg matrix material, specific as follows:
(3) adopt organic solvent that the proportion of phenolic resin as matrix resin is adjusted to 0.9g/m
2～1.2g/m
2Between, then itself and fiber reinforced material are prepared the phenolic aldehyde prepreg through the solution cement-dipping method through continuous impregnating, oven dry and winding process; According to the thickness of fiber reinforced material and the regulation and control of equipment situation with optimize processing parameters such as tractive force, plastic squeeze roller spacing, walking speed, back baking temperature; The volatile content of realizing prepreg is 1～10%; (15～30 ℃) softness at room temperature, viscosity is moderate, is suitable for manual shop and covers.
(4) carry out phenolic aldehyde prepreg laying according to thickness requirement; Put into autoclave curing molding under certain temperature, pressure condition after afterwards the folded piece of phenolic aldehyde prepreg being put into press or vacuum coater; Wherein solidification value is selected from 80～200 ℃, is preferably 100～160 ℃; Solidifying pressure is selected from 0.1～3MPa, is preferably 0.1～1MPa.
The volatile content of prepreg is selected from 1～10%, is preferably 1～5%; Prepreg is (15～30 ℃) softness at room temperature, and viscosity is moderate, is suitable for manual shop and covers.
Flame-proof phenolic prepreg matrix material tensile strength>=250MPa; 60 seconds vertical combustion length≤100mm; Smoke density≤20; Have important popularizing application prospect in fields such as aircraft, boats and ships and high ferros, be particularly suitable for preparing aircraft top ceiling, luggage room and sidewall, boats and ships wallboard and cabinet and interior trim parts such as bullet train top ceiling and sidewall.
The physicals testing method of prepreg matrix material:
Fugitive constituent test: adopt suspension method that prepreg is toasted 10 ± 1min at 120 ℃ of constant temperature, the percent weight loss before and after the test baking.The resin content test: the prepreg that will pass through the fugitive constituent test burns down at 580 ± 20 ℃ and is burnt down percent weight loss before and after the test burning until resin fully.Gel time test: the folded piece of 24 layers of prepreg at 150 ℃ of 0.3MPa that pressurize down, is adopted iron wire point striking test gel time.
Prepreg performance of composites testing method:
Mechanical property and flame retardant test: adopt the impact property (laminated wood specification: four layer EW250F-120 prepreg process) of weighted-drop by BSS7326 normative testing composite-material laminates.Adopt INSTRON3365 universal testing machine (American I nstron company) to press the stretching and the compression performance of ASTM D 695 and ASTM D 638 standard testing materials.60 seconds vertical combustions and smoke density test adopt VC-2 type vertical combustion analyser and SD-1 type smoke density case to test by BSS 7230 and BSS 7238 standards.
Embodiment 1
As catalyzer, is solvent with ethanol with hydrated barta, is 1.5/1 novolak resin performed polymer by the molar ratio of formaldehyde and phenol, termination reaction when the gel time of performed polymer under 160 ℃ is 5～10min.The mass parts of above phenolic aldehyde performed polymer is that benchmark prepares phenolic aldehyde performed polymer compound prescription; In the 200L reaction kettle, add 100 mass parts synthetic resol performed polymers; Add 20 mass parts ethanol, 5 mass parts end carboxyl nitrile rubbers, 5 mass parts tetrabromo-bisphenols and 1.5 mass parts Antimony Trioxide: 99.5Mins under the high-speed stirring successively; Fully stirred 60 minutes, promptly make compound prescription phenolic aldehyde performed polymer.
With compound prescription phenolic aldehyde performed polymer is matrix, and (four pieces of satin weaves, thickness 0.11mm, faces weigh 110g/m with the EW110C type
2) woven fiber glass is strongthener, adopts the solution cement-dipping method to obtain H.T. phenolic aldehyde/glass prepreg through continuous impregnating, oven dry and winding process.Cover the folded piece of phenolic aldehyde/glass prepreg by the thickness requirement shop, adopt the press heat pressing process under 0.5MPa/140 ℃ of condition, to solidify and obtain H.T. phenolic aldehyde/glass fiber composite material.The typical performance of prepreg and matrix material is seen shown in the table 2.
Embodiment 2
As catalyzer, is solvent with ethanol with hydrated barta, is 1.5/1 novolak resin performed polymer by the molar ratio of formaldehyde and phenol, termination reaction when the gel time of performed polymer under 160 ℃ is 5～10min.The mass parts of above phenolic aldehyde performed polymer is that benchmark prepares phenolic aldehyde performed polymer compound prescription; In the 200L reaction kettle, add 100 mass parts synthetic resol performed polymers; Add 20 mass parts ethanol, 5 mass parts end carboxyl nitrile rubbers, 5 mass parts tetrabromo-bisphenols and 1.5 mass parts Antimony Trioxide: 99.5Mins under the high-speed stirring successively; Fully stirred 60 minutes, promptly make compound prescription phenolic aldehyde performed polymer.
With compound prescription phenolic aldehyde performed polymer is matrix, and (eight pieces of satin weaves, thickness 0.25mm, faces weigh 300g/m with the EW250F type
2) woven fiber glass is strongthener, adopts the solution cement-dipping method to obtain H.T. phenolic aldehyde/glass prepreg through continuous impregnating, oven dry and winding process.Cover the folded piece of phenolic aldehyde/glass prepreg by the thickness requirement shop, adopt the press heat pressing process under 0.5MPa/140 ℃ of condition, to solidify and obtain H.T. phenolic aldehyde/glass fiber composite material.The typical performance of prepreg and matrix material is seen shown in the table 2.
Embodiment 3
As catalyzer, is solvent with ethanol with hydrated barta, is 2/1 novolak resin performed polymer by the molar ratio of formaldehyde and phenol, termination reaction when the gel time of performed polymer under 160 ℃ is 5～10min.The mass parts of above phenolic aldehyde performed polymer is that benchmark prepares phenolic aldehyde performed polymer compound prescription; In the 200L reaction kettle, add 100 mass parts synthetic resol performed polymers; Add 20 mass parts ethanol, 5 mass parts end carboxyl nitrile rubbers, 5 mass parts tetrabromo-bisphenols and 1.5 mass parts Antimony Trioxide: 99.5Mins under the high-speed stirring successively; Fully stirred 60 minutes, promptly make compound prescription phenolic aldehyde performed polymer.
With compound prescription phenolic aldehyde performed polymer is matrix, and (four pieces of satin weaves, thickness 0.11mm, faces weigh 110g/m with the EW110C type
2) woven fiber glass is strongthener, adopts the solution cement-dipping method to obtain H.T. phenolic aldehyde/glass prepreg through continuous impregnating, oven dry and winding process.Cover the folded piece of phenolic aldehyde/glass prepreg by the thickness requirement shop, adopt the press heat pressing process under 0.5MPa/140 ℃ of condition, to solidify and obtain H.T. phenolic aldehyde/glass fiber composite material.The typical performance of prepreg and matrix material is seen shown in the table 2.
Embodiment 4
Hydrated barta is solvent as catalyzer with ethanol, is 2/1 novolak resin performed polymer by the molar ratio of formaldehyde and phenol, termination reaction when the gel time of performed polymer under 160 ℃ is 5～10min.The mass parts of above phenolic aldehyde performed polymer is that benchmark prepares phenolic aldehyde performed polymer compound prescription; In the 200L reaction kettle, add 100 mass parts synthetic resol performed polymers; Add 20 mass parts ethanol, 10 mass parts PVFs, 10 mass parts tetrabromo-bisphenols and 3 mass parts Antimony Trioxide: 99.5Mins under the high-speed stirring successively; Fully stirred 60 minutes, promptly make compound prescription phenolic aldehyde performed polymer.
With compound prescription phenolic aldehyde performed polymer is matrix, and (eight pieces of satin weaves, thickness 0.25mm, faces weigh 300g/m with the EW250F type
2) woven fiber glass is strongthener, adopts the solution cement-dipping method to obtain H.T. phenolic aldehyde/glass prepreg through continuous impregnating, oven dry and winding process.Cover the folded piece of phenolic aldehyde/glass prepreg by the thickness requirement shop, adopt the press heat pressing process under 0.5MPa/140 ℃ of condition, to solidify and obtain H.T. phenolic aldehyde/glass fiber composite material.The typical performance of prepreg and matrix material is seen shown in the table 2.
Embodiment 5
As catalyzer, is solvent with ethanol with hydrated barta, is 3/1 novolak resin performed polymer by the molar ratio of formaldehyde and phenol, termination reaction when the gel time of performed polymer under 160 ℃ is 5～10min.The mass parts of above phenolic aldehyde performed polymer is that benchmark prepares phenolic aldehyde performed polymer compound prescription; In the 200L reaction kettle, add 100 mass parts synthetic resol performed polymers; Add 20 mass parts ethanol, 5 mass parts end carboxyl nitrile rubbers, 5 mass parts tetrabromo-bisphenols and 1.5 mass parts Antimony Trioxide: 99.5Mins under the high-speed stirring successively; Fully stirred 60 minutes, promptly make compound prescription phenolic aldehyde performed polymer.
With compound prescription phenolic aldehyde performed polymer is matrix, and (four pieces of satin weaves, thickness 0.11mm, faces weigh 110g/m with the EW110C type
2) woven fiber glass is strongthener, adopts the solution cement-dipping method to obtain H.T. phenolic aldehyde/glass prepreg through continuous impregnating, oven dry and winding process.Cover the folded piece of phenolic aldehyde/glass prepreg by the thickness requirement shop, adopt the press heat pressing process under 0.3MPa/130 ℃ of condition, to solidify and obtain H.T. phenolic aldehyde/glass fiber composite material.The typical performance of prepreg and matrix material is seen shown in the table 2.
Embodiment 6
Marinco H is solvent as catalyzer with ethanol, is 3/1 novolak resin performed polymer by the molar ratio of formaldehyde and phenol, termination reaction when the gel time of performed polymer under 160 ℃ is 5～10min.The mass parts of above phenolic aldehyde performed polymer is that benchmark prepares phenolic aldehyde performed polymer compound prescription; In the 200L reaction kettle, add 100 mass parts synthetic resol performed polymers; Add 40 mass parts ethanol, 10 mass parts polyvinyl butyral acetals, 15 mass parts tetrabromo-bisphenols and 5 mass parts Antimony Trioxide: 99.5Mins under the high-speed stirring successively; Fully stirred 60 minutes, promptly make compound prescription phenolic aldehyde performed polymer.
With compound prescription phenolic aldehyde performed polymer is matrix, and (eight pieces of satin weaves, thickness 0.25mm, faces weigh 300g/m with the EW250F type
2) woven fiber glass is strongthener, adopts the solution cement-dipping method to obtain H.T. phenolic aldehyde/glass prepreg through continuous impregnating, oven dry and winding process.Cover the folded piece of phenolic aldehyde/glass prepreg by the thickness requirement shop, adopt the press heat pressing process under 0.5MPa/140 ℃ of condition, to solidify and obtain H.T. phenolic aldehyde/glass fiber composite material.The typical performance of prepreg and matrix material is seen shown in the table 2.
Embodiment 7
As catalyzer, is solvent with ethanol with hydrated barta, is 2/1 novolak resin performed polymer by the molar ratio of formaldehyde and phenol, termination reaction when the gel time of performed polymer under 160 ℃ is 5～10min.The mass parts of above phenolic aldehyde performed polymer is that benchmark prepares phenolic aldehyde performed polymer compound prescription; In the 200L reaction kettle, add 100 mass parts synthetic resol performed polymers; Add 40 mass parts ethanol, 10 mass parts end carboxyl nitrile rubbers, 5 mass parts tetrabromo-bisphenols and 1.5 mass parts Antimony Trioxide: 99.5Mins under the high-speed stirring successively; Fully stirred 60 minutes, promptly make compound prescription phenolic aldehyde performed polymer.
With compound prescription phenolic aldehyde performed polymer is matrix, and (four pieces of satin weaves, thickness 0.11mm, faces weigh 110g/m with the EW110C type
2) woven fiber glass is strongthener, adopts the solution cement-dipping method to obtain H.T. phenolic aldehyde/glass prepreg through continuous impregnating, oven dry and winding process.Cover the folded piece of phenolic aldehyde/glass prepreg by the thickness requirement shop, adopt the press heat pressing process under 0.3MPa/130 ℃ of condition, to solidify and obtain H.T. phenolic aldehyde/glass fiber composite material.The typical performance of prepreg and matrix material is seen shown in the table 2.
Embodiment 8
As catalyzer, is solvent with ethanol with aniline, is 2/1 novolak resin performed polymer by the molar ratio of formaldehyde and phenol, termination reaction when the gel time of performed polymer under 160 ℃ is 5～10min.The mass parts of above phenolic aldehyde performed polymer is that benchmark prepares phenolic aldehyde performed polymer compound prescription; In the 200L reaction kettle, add 100 mass parts synthetic resol performed polymers; Add 30 mass parts acetone, 10 mass parts terminal hydroxy group nitrile rubbers, 5 mass parts tetrabromo-bisphenols and 1.5 mass parts Antimony Trioxide: 99.5Mins under the high-speed stirring successively; Fully stirred 60 minutes, promptly make compound prescription phenolic aldehyde performed polymer.
With compound prescription phenolic aldehyde performed polymer is matrix, and (four pieces of satin weaves, thickness 0.11mm, faces weigh 110g/m with the EW110C type
2) woven fiber glass is strongthener, adopts the solution cement-dipping method to obtain H.T. phenolic aldehyde/glass prepreg through continuous impregnating, oven dry and winding process.Cover the folded piece of phenolic aldehyde/glass prepreg by the thickness requirement shop, adopt the press heat pressing process under 0.3MPa/130 ℃ of condition, to solidify and obtain H.T. phenolic aldehyde/glass fiber composite material.The typical performance of prepreg and matrix material is seen shown in the table 2.
The molar ratio of formaldehyde and phenol is 2/1, and the consumption of end carboxyl nitrile rubber is 10 mass parts, and other components of resin formula and consumption are with embodiment 1.(eight pieces of satin weaves, thickness 0.25mm, faces weigh 300g/m with the EW250F type
2) woven fiber glass is strongthener, prepreg and composite material and preparation method thereof are with embodiment 1.The typical performance of prepreg and matrix material is seen shown in the table 2.
Comparative example 1
The molar ratio of formaldehyde and phenol is 2/1, and the consumption of end carboxyl nitrile rubber is 0 mass parts, and other components of resin formula and consumption are with embodiment 1.(eight pieces of satin weaves, thickness 0.25mm, faces weigh 300g/m with the EW250F type
2) woven fiber glass is strongthener, prepreg and composite material and preparation method thereof are with embodiment 1.The typical performance of prepreg and matrix material is seen shown in the table 2.
Comparative example 2
The molar ratio of formaldehyde and phenol is 2/1, and the consumption of end carboxyl nitrile rubber is 5 mass parts, and other components of resin formula and consumption are with embodiment 1.(eight pieces of satin weaves, thickness 0.25mm, faces weigh 300g/m with the EW250F type
2) woven fiber glass is strongthener, prepreg and composite material and preparation method thereof are with embodiment 1.The typical performance of prepreg and matrix material is seen shown in the table 2.
Table 2 phenolic aldehyde prepreg and high-ductility composite material performance
Can find out that from the contrast of comparative example 1 and comparative example 2 after adding an amount of toughner in the phenolic resin as matrix resin, the impelling strength and the compressive strength of matrix material almost are doubled, and show that the toughness of matrix material increases substantially.The prepreg of H.T. flame-proof phenolic described in the embodiment 1～8 performance of composites test result shows; Selecting for use with appropriate aldehyde phenol is main matrix than the resol for preparing; Through introducing an amount of toughner and bromine Sb system fire retardant, under the processing condition that are fit to, can prepare a kind of phenolic composite that has good process property, H.T., high flame retardant, low smoke and non-toxic performance concurrently simultaneously.
The above; Be merely the best embodiment of the present invention, but protection scope of the present invention is not limited thereto, any technician who is familiar with the present technique field is in the technical scope that the present invention discloses; The variation that can expect easily or replacement all should be encompassed within protection scope of the present invention.
The content of not doing to describe in detail in the specification sheets of the present invention belongs to this area professional and technical personnel's known technology.
Claims (12)
1. H.T. flame-proof phenolic prepreg matrix material is characterized in that: the component that comprises following mass percentage content:
Phenolic resin as matrix resin 20～70%;
Fiber reinforced material 30～80%;
Wherein said phenolic resin as matrix resin comprises the component of following mass fraction:
Resol 100;
Toughner 5～20;
Tetrabromo-bisphenol 1～15;
Antimony Trioxide: 99.5Min 0.5～5;
Organic solvent 10～80.
2. a kind of H.T. flame-proof phenolic prepreg matrix material according to claim 1 is characterized in that: said resol is selected from least a in hydrated barta catalysis phenolic aldehyde, Marinco H catalysis phenolic aldehyde or the aniline catalysis phenolic aldehyde.
3. a kind of H.T. flame-proof phenolic prepreg matrix material according to claim 1 and 2, it is characterized in that: the aldehyde phenol mass ratio of said resol is 1～3: 1, is preferably 1.5～2.5: 1.
4. a kind of H.T. flame-proof phenolic prepreg matrix material according to claim 1 is characterized in that: said toughner is selected from least a in end carboxyl nitrile rubber, terminal hydroxy group nitrile rubber, carboxy terminated polybutadiene, hydroxy-terminated polybutadienes, polyvinylacetal or the polyvinyl butyral acetal.
5. a kind of H.T. flame-proof phenolic prepreg matrix material according to claim 1, it is characterized in that: said fiber reinforced material is spun glass one-way tape, glasscloth, carbon fiber one-way band or carbon cloth.
6. a kind of H.T. flame-proof phenolic prepreg matrix material according to claim 1, it is characterized in that: said organic solvent is ethanol, propyl alcohol, acetone or butanone.
7. the preparation method of the described a kind of H.T. flame-proof phenolic prepreg matrix material of claim 1 is characterized in that comprising the steps:
Step 1, preparation phenolic resin as matrix resin, specific as follows:
(1) adopts aldehyde cpd, phenolic compound and organic solvent novolak resin performed polymer, termination reaction when the gel time of performed polymer under 160 ℃ is 1～10min;
(2) in reaction kettle, add the resol performed polymer, add organic solvent, toughner, tetrabromo-bisphenol and Antimony Trioxide: 99.5Min under the high-speed stirring successively, fully stirred 60～120 minutes, promptly make phenolic resin as matrix resin;
Step 2, preparation phenolic aldehyde prepreg matrix material, specific as follows:
(3) adopt organic solvent that the proportion of phenolic resin as matrix resin is adjusted to 0.9g/m
2～1.2g/m
2Between, then phenolic resin as matrix resin and fiber reinforced material are prepared the phenolic aldehyde prepreg through the solution cement-dipping method through continuous impregnating, oven dry and winding process;
(4) carry out phenolic aldehyde prepreg laying according to thickness requirement, the folded piece of phenolic aldehyde prepreg is put into put into autoclave curing molding under the solidifying pressure of 80～200 ℃ solidification value, 0.1～3MPa after press or the vacuum coater afterwards.
8. the preparation method of a kind of H.T. flame-proof phenolic prepreg matrix material according to claim 7 is characterized in that: said resol is selected from least a in hydrated barta catalysis phenolic aldehyde, Marinco H catalysis phenolic aldehyde or the aniline catalysis phenolic aldehyde.
9. the preparation method of a kind of H.T. flame-proof phenolic prepreg matrix material according to claim 7 is characterized in that: said toughner is selected from least a in end carboxyl nitrile rubber, terminal hydroxy group nitrile rubber, carboxy terminated polybutadiene, hydroxy-terminated polybutadienes, polyvinylacetal or the polyvinyl butyral acetal.
10. the preparation method of a kind of H.T. flame-proof phenolic prepreg matrix material according to claim 7 is characterized in that: said fiber reinforced material is spun glass one-way tape, glasscloth, carbon fiber one-way band or carbon cloth.
11. the preparation method of a kind of H.T. flame-proof phenolic prepreg matrix material according to claim 7 is characterized in that: the solidification value of the folded piece curing molding of phenolic aldehyde prepreg is 100～160 ℃ in the said step (4), and solidifying pressure is 0.1～1MPa.
12. the described a kind of H.T. flame-proof phenolic prepreg matrix material of claim 1 is used for aircraft top ceiling, luggage room and sidewall, boats and ships wallboard and cabinet and bullet train top ceiling and sidewall interior trim parts.
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