CN105860430B - A kind of phenolic aldehyde glass fiber prepreg with light color and high-quality surface effect and preparation method thereof - Google Patents
A kind of phenolic aldehyde glass fiber prepreg with light color and high-quality surface effect and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- 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
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- 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
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2429/00—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 alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
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- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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Abstract
The present invention relates to a kind of phenolic aldehyde glass fiber prepregs with light color and high-quality surface effect and preparation method thereof, which mainly prepares in two steps：The slightly solubility inorganic particle mixed fillers handled in the epoxy in advance and being dispersed in the basic phenolic resin of light color synthesized through formulation optimization for other uniform fillings are prepared into modified phenolic resin lipoprotein solution by the first step；Second step prepares prepreg using Woven glass cloth by pre-impregnated resin solution.The prepeg process and good economy performance of the present invention, it can be cured under the conditions of high, medium and low temperature respectively, moulding process is flexible and required pressure is relatively low, it is suitble to be manufactured into all kinds of laminated and sandwich, there is excellent mechanics and FST performances, meet the requirement of CCAR25 and TB/T3237, particularly manufactured goods are in shallow milk yellow, shaded effect is notable, and surface quality is high, is easy to promote and apply in the inner-decoration component manufacture view of the trolley coach such as high ferro compartment and aircraft passenger compartment.
Description
Technical field
The present invention relates to a kind of phenolic aldehyde glass fiber prepreg and preparation method thereof, more particularly to a kind of function modified phenolic aldehyde glass
Fine prepreg and preparation method thereof belongs to functional composite material technical field.
Background technology
Material will not only have higher safety in the cabin of advanced large aircraft, also there is preferable comfort and warp
Ji property.Thermosetting phenolic resin is due to excellent intrinsic fire-retardant and low-smoke low-toxicity performance, being suitble to be prepared into fiberglass reinforced body
Prepreg is widely used in the manufacture of all kinds of laminate structures such as ceiling, sidewall paneling, partition board, door and sandwich inner-decoration component, with
Improve the fire savety of aircraft passenger compartment.Meanwhile in order to meet comfort requirement of the passenger in interior of aircraft space, above-mentioned interior trim
The surface of component must be that the ornament materials of color such as puts up Tedlar films or spray oil covered with the light color such as white or light gray
Enamelled coating.But due to after phenolic resin curing color compared with depth and light-proofness it is bad, resulting product is outer after prepreg molding
The sense of sight aberration is strong, surface quality is not high, and therefore, the phenolic composite element surface actually installed needs to cover compared with thick-layer
The surface sensory effects of Tedlar films or paint to cover its initial surface so as to reach relatively comfortable, this also directly results in material
Weight and cost are significantly increased, and economy is had a greatly reduced quality.
For airline carriers of passengers field, a little increased material cost is still dealt with, and still, civilian railway territory is come
It says, the slight change of material cost can all seem particularly critical, this is also China's early stage motor-car and the built-in decoration materials in compartment of high ferro
Material does not select phenolic material and is forced to select the major reason of polyester material.In recent years, with China's high ferro technology not
Ripe and development is broken into, high ferro manufactures the pillar for being not only the national economic development already, while is also just becoming ' walking out ' strategy
Bellwether.In order to adapt to the mainstream demand of international market and meet the railway standard of concerned countries, flame retarding efficiency is selected again
It is chopped used in existing weaponry and equipment in the lighter continuous glass-fiber enhancing phenolic resin-base composite surrogate of higher, Unit Weight
Fiberglass reinforcing polyester based molding compound plate material has become inevitable.Therefore, increasing substantially and unnecessary increasing for the cost of raw material is controlled
Length is a current vital task.One of those big breach is to reduce composite material component surface as far as possible to glue
The Tedlar films of patch or the dosage of institute's spray paint, under conditions of thinner layer ornament materials coating member surface is used
Reach the requirement of passenger's sensory comfort, this just need thoroughly to solve traditional phenolic resin and its composite product color compared with
Deeply, the problem of shaded effect is poor, surface quality is not high.
Invention content
It is a kind of with light color and high-quality surface effect the purpose of the invention is to overcome the deficiencies of the prior art and provide
Phenolic aldehyde glass fiber prepreg and preparation method thereof, the relatively shallower basic phenolic aldehyde of color can be synthesized by formulation optimization technology
Then resin is modified synthesized resin using light coloured inorganic powder mixed fillers, can prepare and meet use again
It is required that phenolic resin, and binding soln law technology prepares phenolic aldehyde glass fiber prepreg, the composite product being finally completed
Surface color is shallower in shallow milk yellow, and shaded effect is notable, and surface quality is high, in its surface mount thinner layer Tedlar film or spray
Covering is just can be completely achieved after applying thinner layer paint, meets the inner-decoration component color organoleptic requirements of motor-car and high-iron carriage, reaches
The performance indicator requirement of railway ministerial standard TB/T3237 can carry out entrucking application, and can be applied to it with further genralrlization
His trolley coach.In addition, the phenolic aldehyde glass fiber prepreg invented meets the requirement in CCAR25 portions of civil aviaton, aircraft visitor can be also used for
The manufacture of cabin inner-decoration component.
Above-mentioned purpose of the present invention is achieved through the following technical solutions.
A kind of phenolic aldehyde glass fiber prepreg with light color and high-quality surface effect of the present invention, using glass fabric
As reinforcing material, using phenol-formaldehyde resin modified as matrix, it is prepared by solution dipping method.
The glass fabric is four comprehensive satin weave alkali-free cloth or high-strength cloth, eight comprehensive satin weave alkali-free cloth or high-strength cloth, in
Any one, quality proportion is 35~50%.
The phenol-formaldehyde resin modified, quality proportion be 50~65%, including basic phenolic resin, organic polymer fillers,
Inorganic particle filler, epoxy resin and organic solvent, mass ratio 100：3~10:2~10:3~10:20~100.
The basis phenolic resin is catalyzed phenolic aldehyde for barium hydroxide, by the way that its aldehyde phenol ratio in resins synthesis formula is controlled to reach
The purpose of high tenacity, light color, specific preparation process are as follows：Phenol and 37% formalin are pressed 1:1.6~2 molar ratio is successively
It adds in reaction kettle with the stirring at low speed of 100~200r/min, is slowly added to Ba (OH)2·8H2O adjusts ph values to 8, Ran Houyou
Room temperature is to slowly warm up to more than 90~100 DEG C of temperature and isothermal reaction 2h, after reaction vacuum dehydration 1h, is added in a certain amount of weak
Property acid be neutralized to until its ph value reaches 7, precipitation is cooled to room temperature, and gained is basic phenolic resin.
The organic polymer fillers are selected from nbr carboxyl terminal, nanometer nitrile rubber, polyvinyl acetal, nanometer
At least one of organosilicon, melamine, red phosphorus microcapsule, polymer phosphoric acid ester are several.
The inorganic particle filler is selected from aluminium hydroxide, magnesium hydroxide, antimony oxide, polymer phosphate ammonium, titanium dioxide, receives
At least one of meter Meng Tuo soil, nano silicon dioxide are several.
The epoxy resin is bisphenol A type epoxy resin, between epoxide number is 0.20~0.45.
The organic solvent is industrial alcohol.
The phenol-formaldehyde resin modified is made by the steps：
A) the inorganic particle filler and epoxy resin of slightly solubility are added in the reaction kettle with heating function, are heated to
More than 30min is stirred after 70~100 DEG C, three-roll grinder is moved into later and carries out further grinding distribution, at least grind 2
Stop all over rear；
B) state stirred in basic phenolic resin and organic solvent mixed solution with the slow-speed of revolution of 200~500r/min
Under, it is firstly added organic polymer fillers, after 500~1000r/min high-speed stirreds, 30~60min, inorganic powder in adding in a)
Body-mixture of epoxy resins and other inorganic particle fillers, continue with the high rotating speed of 500~1000r/min stirring 60~
90min；
C) resin mixture liquor being stirred in b) through three-roll grinder is ground more than 2 times or is stirred through blender is sanded
More than 30min obtains phenol-formaldehyde resin modified.
The solution dipping method includes following process：
1) phenol-formaldehyde resin modified is diluted with an organic solvent to proportion in the range of 0.9~1.2, to pour into steeping vat,
And glass fabric is packed into the stock shelf of solution cement dipping machine；
2) it is switched on after setting Extruded roller spacing, the afterwards technological parameters such as baking temperature, walking speed, winding tension, fiber cloth is molten
Continuously impregnated on liquid cement dipping machine, cross Extruded roller, dry afterwards, cover isolation film and winding series of processes after, obtain phenolic aldehyde
Prepreg, wherein, prepreg volatile content should be less than 5%；
The main technologic parameters of the solution cement dipping machine include：Extruded roller spacing be 0.2~0.8mm, drying temperature 80
~120 DEG C, walking speed is 1~5m/min.
The present invention has the advantages that compared with prior art：
(1) present invention is increased by controlling the aldehyde phenol ratio in basic phenolic resin synthesizing formula on phenolic aldehyde backbone structure
The quantity of flexible unit, while barium catalysed phenolic resin original fire-retardant, heat-resisting feature is kept, toughness obtained 10~
20% raising, and resin is also provided with the feature of light color.
(2) present invention is modified phenolic resin using the inorganic particle filler of white, in further aufhellung resin
While color, characteristic possessed by partial filler component make resin matrix and its glass prepreg after hardening color it is uniform,
Shaded effect is notable, and since all inorganic particles used are without halogen element, make prepreg be provided with halogen-free flameproof,
4min burning smoke densitys are less than the characteristic of 150ppm less than poisonous gas release concentrations such as 10 and CO.
(3) present invention innovatively employs two-step method dispersion slightly solubility inorganic particle, i.e., powder is dispersed in heat first
In the epoxy resin of fusibleness, then said mixture is integrally dispersed in novolac solution again.The advantage of doing so is that：One side
Face, dispersing technology is simple, effect is good, mass production is suitble to prepare therefore easy to implement；On the other hand, bisphenol type epoxy tree
The introducing of fat has further functioned as the effect to phenolic resin as matrix resin toughening and color aufhellung.
(4) phenolic aldehyde glass fiber prepeg process of the invention and good economy performance, can be respectively can be at 110~160 DEG C
Temperature range in cured under the conditions of high, medium and low temperature, moulding process is flexible and required pressure is relatively low, is suitble to be manufactured into
Laminated and sandwich has higher mechanical property and excellent FST performances and is halogen-free, meets CCAR25 portions of civil aviaton
It is in shallower milk yellow with the requirement of railway TB/T3237 standards, particularly manufactured goods, shaded effect is notable, and surface quality is high,
Need not largely be repaired and the only Tedlar decorating films of paving 1mil, be suitable for the trolley coach such as high ferro compartment and
The manufacture of the built-in trim of aircraft passenger compartment.
Specific embodiment
Below by specific embodiment, the present invention is described in further detail, but the present invention is not limited to following implementation
Example.
Prepreg physical testing：Prepreg is toasted 8 ± 1min by volatile content using suspension method in 130 DEG C of constant temperature, is surveyed
The front and rear percent weight loss of examination baking；Resin content is continued using the prepreg that will pass through fugitive constituent test at 580 ± 20 DEG C
Burning is burnt down completely up to resin, percent weight loss before and after test burning.
The performance test methods of composite laminated plate：Bending property test is carried out according to GB/T1449；Fire-retardant and cigarette is malicious
Performance carries out dependence test according to the regulation of 25 annex F and TB/T 3237 of CCAR respectively.
The performance test methods of Nomex cellular composite material sandwich plates：Climbing drum peel strength is carried out according to ASTM D1781
Test；Long beam deflection performance is tested according to ASTM C393.
The appearance quality of composite material is analyzed using ocular estimate after phenolic aldehyde glass fiber prepreg and molding.
Embodiment 1
It 1) will be by 1 in the reaction kettle for being 200L in dischargeable capacity:1.8 molar ratio sequentially adds phenol and formalin,
It is stirred with the rotating speed of 100r/min, adds in Ba (OH)2·8H2O adjusts ph values to 8, is then to slowly warm up to 95 DEG C or so and constant temperature
More than 2h, later more than vacuum dehydration 1h are reacted, phosphoric acid is added in and be neutralized to until its ph value reaches 7, precipitation is cooled to room
Temperature, gained are basic phenolic resin, and it is spare in kettle to retain 100kg；
2) that 1kg titanium dioxides, 1kg polymer phosphates ammonium and 5kg E51 epoxy resin are added to the 10L with heating function is anti-
It answers in kettle, is stirred with the rotating speed of 300r/min, be then heated to 90 DEG C and keep the temperature more than 30min, move into three-roll grinder later
Stop after grinding 2 times, it is spare；
3) 50kg ethyl alcohol is added in into phenolic resin basic obtained by step 1), is stirred in mixed solution with the rotating speed of 300r/min
It mixes under state, is firstly added 5kg polyvinyl butyrals and 0.5kg polymer phosphoric acid esters, then stirred with the rotating speed of 750r/min
After 30~60min, add in mixture and 1kg nano silicon dioxides and 0.5kg aluminium hydroxides prepared by step 2) continue with
After the rotating speed of 750r/min stirs 60~90min, acquired solution is transferred to three-roll grinder and is ground 2 times, obtains modified phenolic
Resin is packed into plastic barrel and is sealed, spare；
4) the modification phenolic resin-based body that step 3) obtains is diluted with ethanol in proper amount, the proportion of obtained solution is
1.10；
5) the comprehensive satin weave alkali-free glass fiber cloth of solution and eight obtained step 4) is on solution cement dipping machine between Extruded roller
Away from for 0.63mm, drying temperature are 105 DEG C, walking speed is 3m/min technological parameter continuously impregnate, dry and winding process,
Fibre reinforced phenolic resin prepreg is finally obtained, wherein, the volatile content of fibre reinforced phenolic resin prepreg is less than
5.0%, resin content 39%~45%, the performance test results are as shown in table 1；
6) by prepreg made from step 5) respectively according to the requirement system of GB/T1449, CCAR25 annex F and TB/T3237
Standby bending property, flame retardant property and smoke toxicity can test laminate sample, laminated sheet metal forming uses vacuum bag autoclave
Technique：1~2 DEG C/min of heating rate, pressurization 0.3~0.4MPa pressure, reaches 130 DEG C when mold temperature reaches 78 DEG C~83 DEG C
When heat preservation solidification 60min~90min, pass hull closure treats mould temperature drop to 60 DEG C hereinafter, going out tank form removal.
7) by prepreg made from step 5) and the Nomex honeycomb cores of NH-1-1.83-48 specifications respectively according to ASTM
The requirement of D1781 and ASTM C393 is prepared into drum peel and the structural panel sandwich sample of long beam deflection test, wherein, it is preceding
For honeycomb core two sides, respectively one layer of prepreg of paving, the latter are honeycomb core two sides two layers of prepreg of each paving to person, and interlayer sheet metal forming is using true
Empty bag autoclave technique：1~2 DEG C/min of heating rate when mold temperature reaches 78 DEG C~83 DEG C, keeps the temperature 60min and in 30min
When pressurize 0.2~0.3MPa pressure, keep the temperature 60min~90min when reaching 130 DEG C, pass hull closure treat mould temperature drop to 60 DEG C hereinafter,
Go out tank form removal.
8) to step 6) and 7) obtained by sample test, as a result as shown in 2~table of table 3.
Embodiment 2
It 1) will be by 1 in the reaction kettle for being 200L in dischargeable capacity:1.8 molar ratio sequentially adds phenol and formalin,
It is stirred with the rotating speed of 100r/min, adds in Ba (OH)2·8H2O adjusts ph values to 8, is then to slowly warm up to 95 DEG C or so and constant temperature
More than 2h, later more than vacuum dehydration 1h are reacted, a certain amount of phosphoric acid is added in and be neutralized to until its ph value reaches 7, precipitation is cold
But to room temperature, gained is basic phenolic resin, and it is spare in kettle to retain 100kg；
2) that 1kg titanium dioxides, 1kg polymer phosphates ammonium and 5kg E51 epoxy resin are added to the 10L with heating function is anti-
It answers in kettle, is stirred with the rotating speed of 300r/min, be then heated to 90 DEG C and keep the temperature more than 30min, move into three-roll grinder later
Stop after grinding 2 times, it is spare；
3) 50kg ethyl alcohol is added in into phenolic resin basic obtained by step 1), is stirred in mixed solution with the rotating speed of 300r/min
In the state of mixing, 5kg polyvinyl butyrals and 0.5kg polymer phosphoric acid esters are firstly added, is then stirred with the rotating speed of 750r/min
After mixing 30~60min, add in mixture and 1kg nano silicon dioxides and 0.5kg aluminium hydroxides prepared by step 2) and continue
After stirring 60~90min with the rotating speed of 750r/min, acquired solution is transferred to three-roll grinder and is ground 2 times, obtains modified phenol
Urea formaldehyde is packed into plastic barrel and is sealed, spare；
4) the modification phenolic resin-based body that step 3) obtains is diluted with ethanol in proper amount, the proportion of obtained solution is
1.10；
5) the comprehensive satin weave high strength glass fiber sheet of solution and eight obtained step 4) is on solution cement dipping machine between Extruded roller
Away from for 0.63mm, drying temperature are 105 DEG C, walking speed is 3m/min technological parameter continuously impregnate, dry and winding process,
Fibre reinforced phenolic resin prepreg is finally obtained, wherein, the volatile content of fibre reinforced phenolic resin prepreg is less than
5.0%, resin content 39%~45%, the performance test results are as shown in table 1；
6) by prepreg made from step 5) respectively according to the requirement system of GB/T1449, CCAR25 annex F and TB/T3237
Standby bending property, flame retardant property and smoke toxicity can test laminate sample, laminated sheet metal forming uses vacuum bag autoclave
Technique：1~2 DEG C/min of heating rate, pressurization 0.3~0.4MPa pressure, reaches 130 DEG C when mold temperature reaches 78 DEG C~83 DEG C
When heat preservation solidification 60min~90min, pass hull closure treats mould temperature drop to 60 DEG C hereinafter, going out tank form removal.
7) by prepreg made from step 5) and the Nomex honeycomb cores of NH-1-1.83-48 specifications respectively according to ASTM
The requirement of D1781 and ASTM C393 is prepared into drum peel and the structural panel sandwich sample of long beam deflection test, wherein, it is preceding
For honeycomb core two sides, respectively one layer of prepreg of paving, the latter are honeycomb core two sides two layers of prepreg of each paving to person, and interlayer sheet metal forming is using true
Empty bag autoclave technique：1~2 DEG C/min of heating rate when mold temperature reaches 78 DEG C~83 DEG C, keeps the temperature 60min and in 30min
When pressurize 0.2~0.3MPa pressure, keep the temperature 60min~90min when reaching 130 DEG C, pass hull closure treat mould temperature drop to 60 DEG C hereinafter,
Go out tank form removal.
8) to step 6) and 7) obtained by sample test, as a result as shown in 2~table of table 3.
Embodiment 3
It 1) will be by 1 in the reaction kettle for being 200L in dischargeable capacity:1.8 molar ratio sequentially adds phenol and formalin,
It is stirred with the rotating speed of 100r/min, adds in Ba (OH)2·8H2O adjusts ph values to 8, is then to slowly warm up to 95 DEG C or so and constant temperature
More than 2h, later more than vacuum dehydration 1h are reacted, a certain amount of phosphoric acid is added in and be neutralized to until its ph value reaches 7, precipitation is cold
But to room temperature, gained is basic phenolic resin, and it is spare in kettle to retain 100kg；
2) that 1kg titanium dioxides, 1kg polymer phosphates ammonium and 5kg E51 epoxy resin are added to the 10L with heating function is anti-
It answers in kettle, is stirred with the rotating speed of 300r/min, be then heated to 90 DEG C and keep the temperature more than 30min, move into three-roll grinder later
Stop after grinding 2 times, it is spare；
3) 50kg ethyl alcohol is added in into phenolic resin basic obtained by step 1), is stirred in mixed solution with the rotating speed of 300r/min
In the state of mixing, 5kg polyvinyl butyrals and 0.5kg polymer phosphoric acid esters are firstly added, is then stirred with the rotating speed of 750r/min
After mixing 30~60min, add in mixture and 1kg nano silicon dioxides and 0.5kg aluminium hydroxides prepared by step 2) and continue
After 60~90min of rotating speed stirring stirring of 750r/min, acquired solution is transferred to three-roll grinder and is ground 2 times, obtains and changes
Property phenolic resin, be packed into plastic barrel be sealed, it is spare；
4) the modification phenolic resin-based body that step 3) obtains is diluted with ethanol in proper amount, the proportion of obtained solution is
1.10；
5) the comprehensive satin weave alkali-free glass fiber cloth of solution and four obtained step 4) is on solution cement dipping machine between Extruded roller
Away from for 0.34mm, drying temperature are 108 DEG C, walking speed is 3m/min technological parameter continuously impregnate, dry and winding process,
Fibre reinforced phenolic resin prepreg is finally obtained, wherein, the volatile content of fibre reinforced phenolic resin prepreg is less than
7.5%, resin content 42%~48%, the performance test results are as shown in table 1；
6) by prepreg made from step 5) respectively according to the requirement system of GB/T1449, CCAR25 annex F and TB/T3237
Standby bending property, flame retardant property and smoke toxicity can test laminate sample, laminated sheet metal forming uses vacuum bag autoclave
Technique：1~2 DEG C/min of heating rate, pressurization 0.3~0.4MPa pressure, reaches 130 DEG C when mold temperature reaches 78 DEG C~83 DEG C
When heat preservation solidification 60min~90min, pass hull closure treats mould temperature drop to 60 DEG C hereinafter, going out tank form removal.
7) by prepreg made from step 5) and the Nomex honeycomb cores of NH-1-1.83-48 specifications according to ASTM C393's
It is required that preparing the structural panel sandwich sample of growth beam deflection test, honeycomb core two sides respectively spreads one layer of prepreg, interlayer sheet metal forming
Using vacuum bag autoclave technique：1~2 DEG C/min of heating rate, when mold temperature reaches 78 DEG C~83 DEG C, heat preservation 60min is simultaneously
Pressurization 0.2~0.3MPa pressure in 30min keeps the temperature 60min~90min when reaching 130 DEG C, and pass hull closure treats mould temperature drop to 60
DEG C hereinafter, going out tank form removal.
8) to step 6) and 7) obtained by sample test, as a result as shown in 2~table of table 3.
Comparative example 1
Using embodiment 1 as comparison other, the phenol and the molar ratio of formalin that are added in step 1) are 1：1.2
Remaining is with embodiment 1, and the addition of titanium dioxide is 0 in step 2), other are with embodiment 1, other remaining steps are the same as embodiment 1
Unanimously, obtained prepreg physical property, laminate performance and Nomex honeycomb sandwich panels performance are as shown in table 1~3.
Comparative example 2
Using embodiment 1 as comparison other, the phenol and the molar ratio of formalin that are added in step 1) are 1：1.2
With embodiment 1, other remaining steps are consistent with embodiment 1 for remaining, obtained prepreg physical property, laminate performance with
And Nomex honeycomb sandwich panels performance is as shown in table 1~3.
Comparative example 3
Using embodiment 1 as comparison other, the addition of titanium dioxide is 0 in step 2), other with embodiment 1, it is remaining its
His step is consistent with embodiment 1, obtained prepreg physical property, laminate performance and Nomex honeycomb sandwich panel performances
As shown in table 1~3.
Comparative example 4
Using embodiment 1 as comparison other, the addition of polymer phosphate ammonium is 0 in step 2), other are the same as embodiment 1, step
It is rapid 3) in the addition of polymer phosphoric acid ester and aluminium hydroxide be 0, other are with embodiment 1, other remaining steps are the same as embodiment 1 one
It causes, obtained prepreg physical property, laminate performance and Nomex honeycomb sandwich panels performance are as shown in table 1~3.
Comparative example 5
Using embodiment 1 as comparison other, cancellation step 2), in step 3), adding in polyvinyl butyral and polymerization
After phosphate, add in 1kg titanium dioxides, 1kg polymer phosphates ammonium and nano silicon dioxide and aluminium hydroxide, other with embodiment 1,
Other remaining steps are consistent with embodiment 1, obtained prepreg physical property, laminate performance and Nomex honeycomb interlayers
Plate performance is as shown in table 1~3.
1 prepreg physical property of table and presentation quality
2 laminate performance of table and presentation quality
Table 3Nomex honeycomb sandwich panels performance and presentation quality
As it can be seen from table 1 the fugitive constituent of Examples 1 to 3 and the phenolic aldehyde glass fiber prepreg prepared by comparative example 1~5
It is consistent substantially with resin content.Novolak resin formula is can be seen that from embodiment 1 and Comparative Examples 1 and 2,3 comparison
Middle aldehyde phenol ratio and addition titanium dioxide filler have compared with Important Relations, therefore, to gained phenol the self color variation of phenolic resin
The color of composite product and surface quality also have important relationship after aldehyde glass prepreg and its curing molding.Increase formula
Middle aldehyde phenol than can effectively after aufhellung synthesis phenolic resin, prepreg and its composite product color, but can not simultaneously improve
The shaded effect of product.Titanium dioxide is added in resin can not only obtain the uniform phenolic composite system of lighter and color
Product, also substantially enhance the interception of material, and most direct effect is that can not see bee from the layer of the face of honeycomb sandwich panel
The marking at nest core wall end, and need to only use the Tedlar decorating films of 1mil that product surface can be completely covered, it plays extraordinary
Sensory comfort, accordingly, with respect to the ornament materials that nearly half can be saved for the phenolic aldehyde product without using titanium dioxide into
This expenditure.Aldehyde phenol than variation and titanium dioxide addition for phenolic aldehyde glass fiber prepreg composite mechanical property and anti-flammability
The influence of energy is relatively small, it can be seen that the test knot of the composite sample of several phenolic aldehyde glass fiber prepregs from table 2 and table 3
Fruit does not have significant change.The addition that can be seen that three kinds of fillers from the comparison of embodiment 1 and comparative example 4 is pre- for phenolic aldehyde glass fiber
Color and the shaded effect influence of leaching material and its product are smaller, however, it is possible to significantly improve the flame retardant property of composite material, reduce
Smoke toxicity of burning gas release.Titanium dioxide and polymer phosphate ammonium are can be seen that in epoxy from the comparison of embodiment 1 and comparative example 5
Pre-treating technology in resin is for the prepared color of phenolic aldehyde prepreg and its final composite product and surface matter
It measures most important.After pre-treating technology, two kinds of slightly solubility powder stuffings may be uniformly dispersed in the resin solution of dipping
In, it plays to resin function modified effect accordingly, and using pre-treating technology, two kinds of powders can not be dispersed in tree
In lipoprotein solution, it is very easy to reunite in the prepreg manufacturing process subsequently carried out, precipitates and may be presoaked in Woven glass cloth
It is precipitated after stain and adheres to its surface, directly influence the surface color of prepreg and its product and presentation quality and potential performance
Unstability.
From the properties test result of phenolic aldehyde glass fiber prepreg described in embodiment 1 and its composite product such as table 1~3
It is shown, show the inorganic particle epoxy that the basic phenolic resin of the light color synthesized by formulation optimization technology disperses with pre-treating technology
Modified phenolic resin lipoprotein solution and prepared using Woven glass cloth through solution pre-impregnating process prepared by the blending of resin mixed fillers
Uniformly light phenolic aldehyde glass fiber prepreg, the composite product surface color being finally completed are shallower in shallow yellow fraction for color
Color, shaded effect is notable, and surface quality is high, just can be completely achieved and covers in the Tedlar films of its surface mount thinner layer only 1mil thickness
Lid, meets the inner-decoration component color organoleptic requirements of motor-car and high-iron carriage, and reached railway ministerial standard TB/T3237 and the people
The performance indicator requirement in boat CCAR25 portions, this has absolutely proved the effect of the present invention.It can from the result of the test of embodiment 2,3
Go out, different using effects can be played as reinforcing material using different Woven glass cloths.It is prepared using high-strength fiber glass cloth
Prepreg is not changing prepreg physical property and color, is keeping composite product color, surface quality and flame retardant effect
Under the premise of, the mechanical property of material can be effectively improved, therefore increase its service life.And use more slim glass-fiber-fabric institute
By a relatively large margin less than thick glass-fiber-fabric prepreg in terms of the prepreg prepared only mechanical property, other aspect of performance are consistent
Property, therefore the thick glass-fiber-fabric prepreg that is more suitable for arranging in pairs or groups is used together.
The above, best specific embodiment only of the invention, but protection scope of the present invention is not limited thereto,
Any one skilled in the art in the technical scope disclosed by the present invention, the change or replacement that can be readily occurred in,
It should be covered by the protection scope of the present invention.
The content not being described in detail in description of the invention belongs to the known technology of professional and technical personnel in the field.
Claims (9)
1. a kind of phenolic aldehyde glass fiber prepreg with light color and high-quality surface effect, it is characterised in that the prepreg includes such as
The component of lower mass percentage content：
Modification phenolic resin-based body 35~50%；
Glass fabric 50~65%；
Wherein described modification phenolic resin-based body includes the component of following mass fraction, is calculated with basic 100 deal of phenolic resin：
Wherein, the basic phenolic resin is catalyzed phenolic aldehyde for barium hydroxide, it is by controlling its aldehyde phenol ratio in resins synthesis formula
Achieve the purpose that high tenacity, light color, complete to prepare by step in detail below：
A) phenol and formalin are pressed 1:1.6~2 molar ratio is sequentially added in reaction kettle with low turn of 100~200r/min
Speed stirring；
B) it is slowly added to Ba (OH) to a) mixed solution2·8H2O adjusts ph values to alkalescent value 8；
C) b) solution is to slowly warm up to more than 90~100 DEG C and isothermal reaction 2h by room temperature, carry out later vacuum dehydration 1h with
On；
D) solution adds in a certain amount of weak property acid and be neutralized to until its ph value reaches 7 in c), and precipitation is cooled to room temperature, gained
It is basic phenolic resin.
2. a kind of phenolic aldehyde glass fiber prepreg with light color and high-quality surface effect according to claim 1, feature
It is：The organic polymer fillers, which are selected from nbr carboxyl terminal, nanometer nitrile rubber, polyvinyl acetal, nanometer, to be had
At least one of machine silicon, melamine, red phosphorus microcapsule, polymer phosphoric acid ester are several.
3. a kind of phenolic aldehyde glass fiber prepreg with light color and high-quality surface effect according to claim 1, feature
It is：The inorganic particle filler is selected from aluminium hydroxide, magnesium hydroxide, antimony oxide, polymer phosphate ammonium, titanium dioxide, nanometer
It covers several in support soil, nano silicon dioxide.
4. a kind of phenolic aldehyde glass fiber prepreg with light color and high-quality surface effect according to claim 1, feature
It is：The organic solvent is ethyl alcohol, and mass fraction refers in particular to the content of solvent in resin solution used in prepreg preparation.
5. a kind of phenolic aldehyde glass fiber prepreg preparation side with light color and high-quality surface effect according to claim 1
Method, it is characterised in that the phenol-formaldehyde resin modified preparation includes the following steps：
A) the inorganic particle filler and epoxy resin of slightly solubility are added in the reaction kettle with heating function, it is heated to 70~
More than 30min is stirred after 100 DEG C, three-roll grinder is moved into later and carries out further grinding distribution, after at least grinding 2 times
Stop；
B) it is first in a state that basic phenolic resin and organic solvent mixed solution are stirred with the slow-speed of revolution of 200~500r/min
First add in organic polymer fillers, after 500~1000r/min high-speed stirreds, 30~60min, inorganic particle-epoxy in adding in a)
Resin mixture and other inorganic particle fillers continue to stir 60~90min with the high rotating speed of 500~1000r/min；
C) resin mixture liquor being stirred in b) through three-roll grinder is ground more than 2 times or is stirred through blender is sanded
More than 30min obtains phenol-formaldehyde resin modified.
6. a kind of phenolic aldehyde glass fiber prepreg with light color and high-quality surface effect according to claim 1, feature
It is：The glass fabric is woven using no alkali fiber or high-intensity fiber, and texture form is four comprehensive satin weaves or eight comprehensive satin weaves
Structure.
7. a kind of phenolic aldehyde glass fiber prepreg with light color and high-quality surface effect according to claim 1, feature
It is：The epoxy resin is bisphenol A type epoxy resin, between epoxide number is 0.20~0.45.
8. a kind of phenolic aldehyde glass fiber preimpregnation preparation method for material described in claim 1 with light color and high-quality surface effect,
It is characterized in that including the following steps：
A) in the range of the proportion of phenolic resin as matrix resin being diluted to 0.9~1.2 using organic solvent, then by the resin of gained
It pours into steeping vat；
B) glass fabric is packed into the stock shelf of cement dipping machine, technological parameter is set；
C) be switched on, fiber cloth through impregnating resin, cross Extruded roller, after dry, cover isolation film and winding series of processes after prepare
Into phenolic aldehyde prepreg, volatile content should be less than 5%.
9. a kind of preparation side with light and high-quality surface effect phenolic aldehyde glass fiber prepreg according to claim 8
Method, it is characterised in that：The technological parameter of the solution cement dipping machine includes：Extruded roller spacing is 0.2~0.8mm, and drying temperature is
80~120 DEG C, walking speed is 1~5m/min.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102731969A (en) * | 2012-06-18 | 2012-10-17 | 航天材料及工艺研究所 | Flame retardant epoxy prepreg composite material and its preparing method and its use |
| CN102731960A (en) * | 2012-06-18 | 2012-10-17 | 航天材料及工艺研究所 | High-toughness flame retardation phenolic prepreg composite material, its preparation method and its application |
| CN105255101A (en) * | 2015-10-16 | 2016-01-20 | 航天材料及工艺研究所 | Impact-resistant and fireproof glass fiber reinforced phenolic aldehyde board and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102731969A (en) * | 2012-06-18 | 2012-10-17 | 航天材料及工艺研究所 | Flame retardant epoxy prepreg composite material and its preparing method and its use |
| CN102731960A (en) * | 2012-06-18 | 2012-10-17 | 航天材料及工艺研究所 | High-toughness flame retardation phenolic prepreg composite material, its preparation method and its application |
| CN105255101A (en) * | 2015-10-16 | 2016-01-20 | 航天材料及工艺研究所 | Impact-resistant and fireproof glass fiber reinforced phenolic aldehyde board and preparation method thereof |
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