CN110437572A - A kind of glass fiber reinforced plastics composite material and preparation method thereof - Google Patents
A kind of glass fiber reinforced plastics composite material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
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- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
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- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
The invention discloses a kind of glass fiber reinforced plastics composite materials, it is characterized in that, it is made of each raw material of following parts by weight: 30-40 parts of vinylbenzenesulfonic acid based polyamide, 20-30 parts of vinyl triazolyl triazine based polyamide, bis- (3- trimethoxy silicon propyl) 8-12 parts of fumarate modified glass fibers, 1,2,2- 3-6 parts of trifluoro vinyl triphenyl silicon, 1-2 parts of end-vinyl dimethyl silicone polymer, 3-5 parts of polyimide fiber, 0.3-0.8 parts of initiator.The invention also discloses the preparation methods of the glass fiber reinforced plastics composite material.Glass fiber reinforced plastics composite material disclosed by the invention is heat-resist, and mechanical performance, ageing-resistant performance are excellent, and wearability, water resistance, inoxidizability and flame retardant property are good.
Description
Technical field
The present invention relates to technical field of composite materials more particularly to a kind of glass fiber reinforced plastics composite material and preparation method thereof.
Background technique
Glass-reinforced plastic material is to be embedded in by fiber glass reinforcement in cured thermosetting resin or be wrapped to form by it
The material of composite construction.This kind of material usually has that strong light weight, hardness, corrosion-resistant, good electrical property, inner surface be smooth, conveying
Low energy consumption, long service life, it is easy to transportation and installation, be not required to maintenance and many advantages such as comprehensive cost is low, in petroleum, electric power, change
The industries such as work, papermaking, urban water supply and sewerage, plant effuent processing, sea water desalination, coal gas conveying, which achieve, to be widely applied.With
The continuous improvement of industrial expansion and science and technology and the application range of glass-reinforced plastic material constantly expand, and people are to glass-reinforced plastic material
Performance requirement is also higher and higher, and therefore, developing more excellent performance of glass-reinforced plastic material is particularly important.
Glass-reinforced plastic material in the prior art is different according to used resin variety, can be divided into organic toughened glass, ring
Oxygen glass reinforced plastic, phenolic fiberglass reinforced plastics etc., they are light and hard, non-conductive, and performance is stablized, high mechanical strength, recycle few, corrosion resistant
Erosion, can replace steel manufacture machine part and automobile, ship housing etc., but the generally existing heat-resisting ability of this kind of material
Difference is easily deformed aging, and wearability, water resistance, inoxidizability, anti-flammability need to be further increased, and raw material ratio is complicated, adds
Work is at high cost, and brittleness is bad, does not meet actual production requirement.
Chinese patent CN105482364A discloses a kind of environmentally friendly glass fiber reinforced plastics composite material, by the raw material of following mass fraction
It is mixed: 20-35 parts of glass fibre, 8-12 parts of epoxy resin, 20-30 parts of kaolin, 3-5 parts of silicon carbide micro-powder, leading benzene two
6-8 parts of formic acid dibutyl ester, 4-6 parts of calcium stearate, 10-12 parts of talcum powder.The invention feature of environmental protection is good, heating process free from extraneous odour, right
The health of people will not cause damages, and bubble and dark bubble will not be generated after processing, being capable of cycling and reutilization.But the glass reinforced plastic is compound
Material haves the shortcomings that temperature tolerance is poor, easy to aging, service life is short.
Therefore, develop a kind of heat-resist, mechanical performance, ageing-resistant performance are excellent, wearability, water resistance, inoxidizability
Good glass fiber reinforced plastics composite material accords with the demands of the market with flame retardant property, has extensive market value and application prospect, to promotion
The development of composite material has very important significance.
Summary of the invention
In order to overcome the defects of the prior art, the present invention provides a kind of glass fiber reinforced plastics composite material and preparation method thereof, should
Preparation method is simple to operation, small to device dependence, and reaction condition is mild, and safe preparation process is environmentally friendly, is suitble to scale
Change production requirement, application value with higher；The glass fiber reinforced plastics composite material being prepared is heat-resist, mechanical performance,
Ageing-resistant performance is excellent, and wearability, water resistance, inoxidizability and flame retardant property are good.
To achieve the above object of the invention, the technical solution adopted by the present invention is that, a kind of glass fiber reinforced plastics composite material, by weighing as follows
Amount part each raw material be made: 30-40 parts of vinylbenzenesulfonic acid based polyamide, 20-30 parts of vinyl triazolyl triazine based polyamide,
Bis- (3- trimethoxy silicon propyl) 8-12 parts of fumarate modified glass fibers, 3-6 parts of 1,2,2- trifluoro vinyl triphenyl silicon,
1-2 parts of end-vinyl dimethyl silicone polymer, 3-5 parts of polyimide fiber, 0.3-0.8 parts of initiator.
Further, the initiator is selected from azodiisobutyronitrile, azobisisoheptonitrile, tert-butyl hydroperoxide, peroxide
Change at least one of cyclohexanone.
Further, the preparation method of the vinylbenzenesulfonic acid based polyamide includes the following steps: 4,4'-, bis- (2-
Amino-benzene sulfonic acid) bisphenol-A ester, 4,4'- stilbenedicarboxylicacid acid, catalyst, polymerization inhibitor be dissolved in high boiling solvent formed it is molten
Liquid, then solution is added in reaction kettle, with air in nitrogen or inert gas replacement kettle, 105-115 DEG C of reaction 3-5 is small under normal pressure
When, after be warming up to 255-275 DEG C, carried out polycondensation reaction 18-22 hours at 50-250Pa, after be cooled to room temperature, be adjusted to normal pressure,
It settles out in water, with ethanol washing 3-5 times, then rotates removing ethyl alcohol, obtain vinylbenzenesulfonic acid based polyamide.
Preferably, 4,4'- bis- (2- amino-benzene sulfonic acid) the bisphenol-A ester, 4,4'- stilbenedicarboxylicacid acid, catalyst,
Polymerization inhibitor, high boiling solvent mass ratio be 2:1:(0.5-0.8): (0.1-0.3): (10-15).
Preferably, the catalyst is selected from least one of Thiophosphonate, phosphorous acid, thio-phosphamide.
Preferably, the polymerization inhibitor is selected from tetrachloroquinone, l, at least one of 4- naphthoquinones, p-hydroxyanisole.
Preferably, the high boiling solvent is in dimethyl sulfoxide, n,N-Dimethylformamide, N-Methyl pyrrolidone
It is at least one.
Preferably, the inert gas is selected from one of helium, neon, argon gas.
Further, the preparation method of the vinyl triazolyl triazine based polyamide, includes the following steps: 1,2,3-
Triazole -4,5- dicarboxylic acids, two allylamino -1,3,5- triazine of 2,4- diamino -6-, Thiophosphonate, p-hydroxyanisole are molten
It forms solution in N-Methyl pyrrolidone, then solution is added in reaction kettle, with air in nitrogen displacement kettle, 105- under normal pressure
115 DEG C reaction 3-5 hours, after be warming up to 250-270 DEG C, carried out polycondensation reaction 15-20 hours at 100-300Pa, it is rear cooling
To room temperature, it is adjusted to normal pressure, is settled out in water, with ethanol washing 3-5 times, then rotated removing ethyl alcohol, obtain vinyl triazolyl three
Piperazine based polyamide.
Preferably, 1,2,3-triazoles -4,5- dicarboxylic acids, 2,4- diamino -6-, two allylaminos -1,3,5-triazines,
Thiophosphonate, p-hydroxyanisole, N-Methyl pyrrolidone mass ratio be 1:1.31:(0.3-0.6): 0.2:(7-12).
Further, the preparation method of bis- (3- trimethoxy silicon propyl) fumarate modified glass fibers, including
Following steps: dispersing glass fibre in ethyl alcohol, and bis- (3- trimethoxy silicon propyl) fumarates, In are then added thereto
It is stirred to react at 30-40 DEG C 4-6 hours, then filters, with ethanol washing 3-5 times, ethyl alcohol is evaporated off in back spin, obtains bis- (3- tri-
Methoxyl group silicon propyl) fumarate modified glass fibers.
Preferably, the glass fibre, ethyl alcohol, bis- (3- trimethoxy silicon propyl) fumarates mass ratio be 1:(3-
5):0.1。
Further, the preparation method of the glass fiber reinforced plastics composite material includes the following steps: for each raw material to be added to high speed
It is uniformly mixed in batch mixer and obtains mixed material, then mixed material is put into double screw extruder, is blended, squeezed out
To glass fiber reinforced plastics composite material.
Preferably, the screw speed of the double screw extruder is 190-220rpm, extrusion pressure 32-38MPa, and double
Screw extruder is divided into 5 sections, since the feed opening temperature of each section be followed successively by 220-230 DEG C, 235-240 DEG C, 245-250 DEG C,
250-260 DEG C, 265-270 DEG C, head temperature are 260-270 DEG C.
The beneficial effects of adopting the technical scheme are that
(1) glass fiber reinforced plastics composite material provided by the invention, simple to operation, small to device dependence, reaction condition is mild,
Safe preparation process is environmentally friendly, is suitble to large-scale production demand, application value with higher.
(2) glass fiber reinforced plastics composite material provided by the invention overcomes the generally existing resistance to height of traditional glass steel composite material
Warm ability is poor, is easily deformed aging, and wearability, water resistance, inoxidizability, anti-flammability need to be further increased, raw material ratio
The technical issues of complexity, processing cost are high, and brittleness is bad, do not meet actual production requirement, have it is heat-resist, mechanical performance,
Ageing-resistant performance is excellent, wearability, water resistance, inoxidizability and the good advantage of flame retardant property.
(3) glass fiber reinforced plastics composite material provided by the invention, there are two types of resin contains, one is by (the 2- amino-benzene of 4,4'- bis-
Sulfonic acid) bisphenol-A ester, 4,4'- stilbenedicarboxylicacid acid polycondensation reaction be made, benzene sulfonic acid base structure is contained on this material main chain,
It more assigns material excellent mechanical mechanics property and anti-flammability, and by polycondensation, alkene structures is introduced on molecular backbone, after being
Continuous material formative stage crosslinking provides reaction site；Another kind is by 1,2,3- triazole -4,5- dicarboxylic acids, 2,4- diamino -6-
Two allylaminos -1,3,5-triazines is made by polycondensation reaction, and triazine, triazole structure are introduced on molecular backbone, improves material
Weatherability, anti-ultraviolet ageing and anti-flammability；Equally, vinyl structure is introduced on strand, forms rank for subsequent material
Section crosslinking provides reaction site；Fiberglass surfacing is modified by bis- (3- trimethoxy silicon propyl) fumarates, improves glass
The dispersibility of glass fiber and compatibility with other components；Vinyl is introduced, provides reaction for the crosslinking of subsequent material formative stage
Site.
(4) glass fiber reinforced plastics composite material provided by the invention, each component form three in material formative stage, by copolyreaction
Network structure is tieed up, material comprehensive performance is effectively improved；1,2,2- trifluoro vinyl triphenyl silicon of monomer is introduced, in formative stage,
Fluorine silicon structure is introduced in strand network structure, can further improve the weatherability, heat resistance and mechanical mechanics property of material；
Polyimide fiber is introduced, the advantages of acting synergistically together with glass fibre, combine inorfil and organic fiber, to material
Intensity has biggish promotion, and polyimide fiber is good with material of main part compatibility；Leading-in end vinyldimethicone
Structure can effectively improve the heat resistance and ageing-resistant performance of material；And there is preferable adhesive action, so that each ingredient is more preferable
Formation organic whole, to improve the comprehensive performances such as the wearability of material.
Specific embodiment
In order to make those skilled in the art more fully understand technical solution of the present invention, and make features described above of the invention,
Purpose and advantage are more clear understandable, and the present invention will be further explained with reference to the examples below.Embodiment is only used for
It is bright the present invention rather than limit the scope of the invention.
Present invention raw material as used in the following examples is commercially available.
Embodiment 1
A kind of glass fiber reinforced plastics composite material is made of each raw material of following parts by weight: 30 parts of vinylbenzenesulfonic acid based polyamide,
20 parts of vinyl triazolyl triazine based polyamide, bis- (3- trimethoxy silicon propyl) 8 parts of fumarate modified glass fibers, 1,2,
3 parts of 2- trifluoro vinyl triphenyl silicon, 1 part of end-vinyl dimethyl silicone polymer, 3 parts of polyimide fiber, two isobutyl of azo
0.3 part of nitrile.
The preparation method of the vinylbenzenesulfonic acid based polyamide includes the following steps: (the 2- amino-benzene sulphur of 4,4'- bis-
Acid) bisphenol-A ester 2kg, 4,4'- stilbenedicarboxylicacid acid 1kg, Thiophosphonate 0.5kg, tetrachloroquinone 0.1kg be dissolved in diformazan Asia
Solution is formed in sulfone 10kg, then solution is added in reaction kettle, and with air in nitrogen displacement kettle, the lower 105 DEG C of reactions 3 of normal pressure are small
When, after be warming up to 255 DEG C, carried out polycondensation reaction 18 hours at 50Pa, after be cooled to room temperature, be adjusted to normal pressure, settle out in water,
With ethanol washing 3 times, then removing ethyl alcohol is rotated, obtains vinylbenzenesulfonic acid based polyamide.
The preparation method of the vinyl triazolyl triazine based polyamide, includes the following steps: 1,2,3-triazoles -4,5-
Two allylamino -1,3,5- triazine 1.31kg of dicarboxylic acids 1kg, 2,4- diamino -6-, Thiophosphonate 0.3kg, para hydroxybenzene first
Ether 0.2kg, which is dissolved in N-Methyl pyrrolidone 7kg, forms solution, then solution is added in reaction kettle, with sky in nitrogen displacement kettle
Gas, normal pressure it is lower 105 DEG C react 3 hours, after be warming up to 250 DEG C, carried out polycondensation reaction 15 hours at 100Pa, after be cooled to room
Temperature is adjusted to normal pressure, settles out in water, with ethanol washing 3 times, then rotates removing ethyl alcohol, and it is poly- to obtain vinyl triazolyl triazine radical
Amide.
The preparation method of bis- (3- trimethoxy silicon propyl) fumarate modified glass fibers, includes the following steps:
It disperses glass fibre 1kg in ethyl alcohol 3kg, bis- (3- trimethoxy silicon propyl) fumarate 0.1kg is then added thereto,
It is stirred to react at 30 DEG C 4 hours, then filters, with ethanol washing 3 times, ethyl alcohol is evaporated off in back spin, obtains bis- (3- trimethoxies
Silicon propyl) fumarate modified glass fibers.
The preparation method of the glass fiber reinforced plastics composite material includes the following steps: for each raw material to be added in high speed mixer
It is uniformly mixed and obtains mixed material, then mixed material is put into double screw extruder, is blended, squeezes out to obtain glass reinforced plastic
Composite material；The screw speed of the double screw extruder is 190rpm, extrusion pressure 32MPa, and double screw extruder divides
It is 5 sections, temperature of each section is followed successively by 220 DEG C, 235 DEG C, 245 DEG C, 250 DEG C, 265 DEG C, head temperature 260 since the feed opening
℃。
Embodiment 2
A kind of glass fiber reinforced plastics composite material is made of each raw material of following parts by weight: 33 parts of vinylbenzenesulfonic acid based polyamide,
23 parts of vinyl triazolyl triazine based polyamide, bis- (3- trimethoxy silicon propyl) 9 parts of fumarate modified glass fibers, 1,2,
4 parts of 2- trifluoro vinyl triphenyl silicon, 1.2 parts of end-vinyl dimethyl silicone polymer, 3.5 parts of polyimide fiber, azo two
0.4 part of different heptonitrile.
The preparation method of the vinylbenzenesulfonic acid based polyamide includes the following steps: (the 2- amino-benzene sulphur of 4,4'- bis-
Acid) bisphenol-A ester 2kg, 4,4'- stilbenedicarboxylicacid acid 1kg, phosphorous acid 0.6kg, l, 4- naphthoquinones 0.15kg is dissolved in N, N- dimethyl
Solution is formed in formamide 11kg, then solution is added in reaction kettle, with air in helium replacement kettle, the lower 108 DEG C of reactions of normal pressure
3.5 hours, after be warming up to 260 DEG C, carried out polycondensation reaction 19 hours at 100Pa, after be cooled to room temperature, normal pressure is adjusted to, in water
In settle out, with ethanol washing 4 times, then rotate removing ethyl alcohol, obtain vinylbenzenesulfonic acid based polyamide.
The preparation method of the vinyl triazolyl triazine based polyamide, includes the following steps: 1,2,3-triazoles -4,5-
Two allylamino -1,3,5- triazine 1.31kg of dicarboxylic acids 1kg, 2,4- diamino -6-, Thiophosphonate 0.4kg, para hydroxybenzene first
Ether 0.2kg, which is dissolved in N-Methyl pyrrolidone 8.5kg, forms solution, then solution is added in reaction kettle, in nitrogen displacement kettle
Air, normal pressure it is lower 108 DEG C react 4 hours, after be warming up to 255 DEG C, carried out polycondensation reaction 17 hours at 150Pa, after be cooled to
Room temperature is adjusted to normal pressure, settles out in water, with ethanol washing 4 times, then rotates removing ethyl alcohol, obtains vinyl triazolyl triazine radical
Polyamide.
The preparation method of bis- (3- trimethoxy silicon propyl) fumarate modified glass fibers, includes the following steps:
It disperses glass fibre 1kg in ethyl alcohol 3.5kg, bis- (3- trimethoxy silicon propyl) fumarates is then added thereto
0.1kg is stirred to react 4.5 hours at 33 DEG C, then filters, and with ethanol washing 4 times, ethyl alcohol is evaporated off in back spin, obtains bis- (3-
Trimethoxy silicon propyl) fumarate modified glass fibers.
The preparation method of the glass fiber reinforced plastics composite material includes the following steps: for each raw material to be added in high speed mixer
It is uniformly mixed and obtains mixed material, then mixed material is put into double screw extruder, is blended, squeezes out to obtain glass reinforced plastic
Composite material；The screw speed of the double screw extruder is 200rpm, extrusion pressure 34MPa, and double screw extruder divides
It is 5 sections, temperature of each section is followed successively by 223 DEG C, 237 DEG C, 247 DEG C, 253 DEG C, 267 DEG C, head temperature 263 since the feed opening
℃。
Embodiment 3
A kind of glass fiber reinforced plastics composite material is made of each raw material of following parts by weight: 35 parts of vinylbenzenesulfonic acid based polyamide,
25 parts of vinyl triazolyl triazine based polyamide, bis- (3- trimethoxy silicon propyl) 10 parts of fumarate modified glass fibers, 1,
4.5 parts of 2,2- trifluoro vinyl triphenyl silicon, 1.5 parts of end-vinyl dimethyl silicone polymer, 4 parts of polyimide fiber, tertiary fourth
.6 parts of base hydrogen peroxidase 10.
The preparation method of the vinylbenzenesulfonic acid based polyamide includes the following steps: (the 2- amino-benzene sulphur of 4,4'- bis-
Acid) bisphenol-A ester 2kg, 4,4'- stilbenedicarboxylicacid acid 1kg, thio-phosphamide 0.65kg, p-hydroxyanisole 0.2kg be dissolved in N-
It forms solution in methyl pyrrolidone 13kg, then solution is added in reaction kettle, with air in neon displacement kettle, 109 under normal pressure
DEG C reaction 4 hours, after be warming up to 265 DEG C, carried out polycondensation reaction 20 hours at 150Pa, after be cooled to room temperature, be adjusted to normal pressure,
It settles out in water, with ethanol washing 4 times, then rotates removing ethyl alcohol, obtain vinylbenzenesulfonic acid based polyamide.
The preparation method of the vinyl triazolyl triazine based polyamide, includes the following steps: 1,2,3-triazoles -4,5-
Two allylamino -1,3,5- triazine 1.31kg of dicarboxylic acids 1kg, 2,4- diamino -6-, Thiophosphonate 0.5kg, para hydroxybenzene first
Ether 0.2kg, which is dissolved in N-Methyl pyrrolidone 9kg, forms solution, then solution is added in reaction kettle, with sky in nitrogen displacement kettle
Gas, normal pressure it is lower 110 DEG C react 4 hours, after be warming up to 260 DEG C, carried out polycondensation reaction 18 hours at 200Pa, after be cooled to room
Temperature is adjusted to normal pressure, settles out in water, with ethanol washing 4 times, then rotates removing ethyl alcohol, and it is poly- to obtain vinyl triazolyl triazine radical
Amide.
The preparation method of bis- (3- trimethoxy silicon propyl) fumarate modified glass fibers, includes the following steps:
It disperses glass fibre 1kg in ethyl alcohol 4kg, bis- (3- trimethoxy silicon propyl) fumarate 0.1kg is then added thereto,
It is stirred to react at 36 DEG C 5 hours, then filters, with ethanol washing 4 times, ethyl alcohol is evaporated off in back spin, obtains bis- (3- trimethoxies
Silicon propyl) fumarate modified glass fibers.
The preparation method of the glass fiber reinforced plastics composite material includes the following steps: for each raw material to be added in high speed mixer
It is uniformly mixed and obtains mixed material, then mixed material is put into double screw extruder, is blended, squeezes out to obtain glass reinforced plastic
Composite material；The screw speed of the double screw extruder is 205rpm, extrusion pressure 35MPa, and double screw extruder divides
It is 5 sections, temperature of each section is followed successively by 225 DEG C, 238 DEG C, 247 DEG C, 255 DEG C, 268 DEG C, head temperature 265 since the feed opening
℃。
Embodiment 4
A kind of glass fiber reinforced plastics composite material is made of each raw material of following parts by weight: 38 parts of vinylbenzenesulfonic acid based polyamide,
28 parts of vinyl triazolyl triazine based polyamide, bis- (3- trimethoxy silicon propyl) 11 parts of fumarate modified glass fibers, 1,
5.5 parts of 2,2- trifluoro vinyl triphenyl silicon, 4.5 parts of polyimide fiber, draws 1.8 parts of end-vinyl dimethyl silicone polymer
0.7 part of agent of hair；The initiator is azodiisobutyronitrile, azobisisoheptonitrile, tert-butyl hydroperoxide, cyclohexanone peroxide are pressed
Mass ratio 2:1:3:2 is mixed.
The preparation method of the vinylbenzenesulfonic acid based polyamide includes the following steps: (the 2- amino-benzene sulphur of 4,4'- bis-
Acid) bisphenol-A ester 2kg, 4,4'- stilbenedicarboxylicacid acid 1kg, catalyst 0.75kg, polymerization inhibitor 0.25kg be dissolved in high boiling solvent
Solution is formed in 14.5kg, then solution is added in reaction kettle, and with air in argon gas displacement kettle, the lower 113 DEG C of reactions 4.5 of normal pressure are small
When, after be warming up to 273 DEG C, carried out polycondensation reaction 21 hours at 240Pa, after be cooled to room temperature, be adjusted to normal pressure, sink in water
Out, with ethanol washing 5 times, then removing ethyl alcohol is rotated, obtains vinylbenzenesulfonic acid based polyamide；The catalyst is phosphonothiolic acid
Ester, phosphorous acid, thio-phosphamide 1:3:2 in mass ratio are mixed；The polymerization inhibitor is tetrachloroquinone, l, 4- naphthoquinones, to hydroxyl
Base methyl phenyl ethers anisole 1:3:4 in mass ratio is mixed；The high boiling solvent is dimethyl sulfoxide, N,N-dimethylformamide, N- first
Base pyrrolidones 1:2:4 in mass ratio is mixed.
The preparation method of the vinyl triazolyl triazine based polyamide, includes the following steps: 1,2,3-triazoles -4,5-
Two allylamino -1,3,5- triazine 1.31kg of dicarboxylic acids 1kg, 2,4- diamino -6-, Thiophosphonate 0.55kg, para hydroxybenzene
Methyl ether 0.2kg, which is dissolved in N-Methyl pyrrolidone 11kg, forms solution, then solution is added in reaction kettle, in nitrogen displacement kettle
Air, normal pressure it is lower 114 DEG C react 4.5 hours, after be warming up to 268 DEG C, is carried out polycondensation reaction 19 hours at 280Pa, afterwards cool down
To room temperature, it is adjusted to normal pressure, is settled out in water, with ethanol washing 5 times, then rotated removing ethyl alcohol, obtain vinyl triazolyl triazine
Based polyamide.
The preparation method of bis- (3- trimethoxy silicon propyl) fumarate modified glass fibers, includes the following steps:
It disperses glass fibre 1kg in ethyl alcohol 4.5kg, bis- (3- trimethoxy silicon propyl) fumarates is then added thereto
0.1kg is stirred to react 5.5 hours at 38 DEG C, then filters, and with ethanol washing 5 times, ethyl alcohol is evaporated off in back spin, obtains bis- (3-
Trimethoxy silicon propyl) fumarate modified glass fibers.
The preparation method of the glass fiber reinforced plastics composite material includes the following steps: for each raw material to be added in high speed mixer
It is uniformly mixed and obtains mixed material, then mixed material is put into double screw extruder, is blended, squeezes out to obtain glass reinforced plastic
Composite material；The screw speed of the double screw extruder is 215rpm, extrusion pressure 37MPa, and double screw extruder divides
It is 5 sections, temperature of each section is followed successively by 229 DEG C, 239 DEG C, 248 DEG C, 258 DEG C, 269 DEG C, head temperature 268 since the feed opening
℃。
Embodiment 5
A kind of glass fiber reinforced plastics composite material is made of each raw material of following parts by weight: 40 parts of vinylbenzenesulfonic acid based polyamide,
0 part of vinyl triazolyl triazine radical kymene, bis- (3- trimethoxy silicon propyl) 12 parts of fumarate modified glass fibers, 1,
6 parts of 2,2- trifluoro vinyl triphenyl silicon, 2 parts of end-vinyl dimethyl silicone polymer, 5 parts of polyimide fiber, peroxidating ring
0.8 part of hexanone.
The preparation method of the vinylbenzenesulfonic acid based polyamide includes the following steps: (the 2- amino-benzene sulphur of 4,4'- bis-
Acid) bisphenol-A ester 2kg, 4,4'- stilbenedicarboxylicacid acid 1kg, phosphorous acid 0.8kg, tetrachloroquinone 0.3kg be dissolved in dimethyl sulfoxide
Solution is formed in 15kg, then solution is added in reaction kettle, with air in nitrogen displacement kettle, lower 115 DEG C of normal pressure are reacted 5 hours,
After be warming up to 275 DEG C, carried out polycondensation reaction 22 hours at 250Pa, after be cooled to room temperature, be adjusted to normal pressure, settle out in water, use
Ethanol washing 5 times, then removing ethyl alcohol is rotated, obtain vinylbenzenesulfonic acid based polyamide.
The preparation method of the vinyl triazolyl triazine based polyamide, includes the following steps: 1,2,3-triazoles -4,5-
Two allylamino -1,3,5- triazine 1.31kg of dicarboxylic acids 1kg, 2,4- diamino -6-, Thiophosphonate 0.6kg, para hydroxybenzene first
Ether 0.2kg, which is dissolved in N-Methyl pyrrolidone 12kg, forms solution, then solution is added in reaction kettle, with sky in nitrogen displacement kettle
Gas, normal pressure it is lower 115 DEG C react 5 hours, after be warming up to 270 DEG C, carried out polycondensation reaction 20 hours at 300Pa, after be cooled to room
Temperature is adjusted to normal pressure, settles out in water, with ethanol washing 5 times, then rotates removing ethyl alcohol, and it is poly- to obtain vinyl triazolyl triazine radical
Amide.
The preparation method of bis- (3- trimethoxy silicon propyl) fumarate modified glass fibers, includes the following steps:
It disperses glass fibre 1kg in ethyl alcohol 5kg, bis- (3- trimethoxy silicon propyl) fumarate 0.1kg is then added thereto,
It is stirred to react at 40 DEG C 6 hours, then filters, with ethanol washing 5 times, ethyl alcohol is evaporated off in back spin, obtains bis- (3- trimethoxies
Silicon propyl) fumarate modified glass fibers.
The preparation method of the glass fiber reinforced plastics composite material includes the following steps: for each raw material to be added in high speed mixer
It is uniformly mixed and obtains mixed material, then mixed material is put into double screw extruder, is blended, squeezes out to obtain glass reinforced plastic
Composite material；The screw speed of the double screw extruder is 220rpm, extrusion pressure 38MPa, and double screw extruder divides
It is 5 sections, temperature of each section is followed successively by 230 DEG C, 240 DEG C, 250 DEG C, 260 DEG C, 270 DEG C, head temperature 270 since the feed opening
℃。
Comparative example 1
A kind of glass fiber reinforced plastics composite material, preparation method and formula are substantially the same manner as Example 1, the difference is that without addition second
Alkenyl benzene sulfonic acid based polyamide.
Comparative example 2
A kind of glass fiber reinforced plastics composite material, preparation method and formula are substantially the same manner as Example 1, the difference is that without addition second
Alkenyl triazolyl triazine based polyamide.
Comparative example 3
A kind of glass fiber reinforced plastics composite material, preparation method and formula are substantially the same manner as Example 1, the difference is that using glass fibre
Instead of bis- (3- trimethoxy silicon propyl) fumarate modified glass fibers.
Comparative example 4
A kind of glass fiber reinforced plastics composite material, preparation method and formula are substantially the same manner as Example 1, the difference is that without addition end
Vinyldimethicone.
Comparative example 5
A kind of glass fiber reinforced plastics composite material, preparation method and formula are substantially the same manner as Example 1, the difference is that without addition 1,
2,2- trifluoro vinyl triphenyl silicon.
Comparative example 6
A kind of glass fiber reinforced plastics composite material, preparation method and formula are substantially the same manner as Example 1, the difference is that poly- without addition
Imide fiber.
Comparative example 7
Available glass steel composite material.
The technical effect of glass fiber reinforced plastics composite material described in embodiment in order to further illustrate the present invention, to the glass in each example
Steel composite material carries out correlated performance test, and test method and test result are shown in Table 1.
Table 1
| Project | Anti- UV aging | Tensile strength | Bending strength | Limit oxygen index |
| Unit | KJ/m2 | MPa | MPa | % |
| Detection method | SAEJ1344 | GB/T1040.1-2006 | GB/T9341-2000 | GB/T2406-1993 |
| Embodiment 1 | 2750 | 75 | 86 | 27 |
| Embodiment 2 | 2760 | 78 | 89 | 29 |
| Embodiment 3 | 2780 | 82 | 93 | 30 |
| Embodiment 4 | 2805 | 85 | 97 | 32 |
| Embodiment 5 | 2820 | 89 | 99 | 33 |
| Comparative example 1 | 2300 | 60 | 60 | 22 |
| Comparative example 2 | 2270 | 58 | 62 | 20 |
| Comparative example 3 | 2280 | 61 | 61 | 23 |
| Comparative example 4 | 2250 | 60 | 60 | 22 |
| Comparative example 5 | 2240 | 59 | 57 | 20 |
| Comparative example 6 | 2400 | 53 | 54 | 21 |
| Comparative example 7 | 2150 | 50 | 51 | 18 |
From table 1 it follows that the glass fiber reinforced plastics composite material in embodiment 1-5, which has, is substantially better than commercial product (comparison
Example 7) performance, anti-UV ageing properties, tensile strength, bending strength are more excellent, and more preferably, this is the collaboration of each ingredient to anti-flammability
The result of effect.
The basic principles, main features and advantages of the present invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and what is described in the above embodiment and the description is only the present invention
Principle, various changes and improvements may be made to the invention without departing from the spirit and scope of the present invention, these variation and
Improvement is both fallen in the range of claimed invention.The present invention claims protection scope by appended claims and its
Equivalent defines.
Claims (10)
1. a kind of glass fiber reinforced plastics composite material, which is characterized in that be made of each raw material of following parts by weight: vinylbenzenesulfonic acid base is poly-
30-40 parts of amide, 20-30 parts of vinyl triazolyl triazine based polyamide, the modification of bis- (3- trimethoxy silicon propyl) fumarates
8-12 parts of glass fibre, 3-6 parts of 1,2,2- trifluoro vinyl triphenyl silicon, 1-2 parts of end-vinyl dimethyl silicone polymer, polyamides
3-5 parts of imine fiber, 0.3-0.8 parts of initiator.
2. a kind of glass fiber reinforced plastics composite material according to claim 1, which is characterized in that it is different that the initiator is selected from azo two
At least one of butyronitrile, azobisisoheptonitrile, tert-butyl hydroperoxide, cyclohexanone peroxide.
3. a kind of glass fiber reinforced plastics composite material according to claim 1, which is characterized in that the vinylbenzenesulfonic acid base polyamides
The preparation method of amine includes the following steps: 4,4'- bis- (2- amino-benzene sulfonic acid) bisphenol-A ester, 4,4'- talan dicarboxyl
Acid, catalyst, polymerization inhibitor, which are dissolved in high boiling solvent, forms solution, then solution is added in reaction kettle, with nitrogen or indifferent gas
Air in body displacement kettle, 105-115 DEG C reaction 3-5 hours under normal pressure, after be warming up to 255-275 DEG C, carried out at 50-250Pa
Polycondensation reaction 18-22 hours, after be cooled to room temperature, be adjusted to normal pressure, settle out in water, with ethanol washing 3-5 times, then rotate removing
Ethyl alcohol obtains vinylbenzenesulfonic acid based polyamide.
4. a kind of glass fiber reinforced plastics composite material according to claim 3, which is characterized in that 4,4'-, bis- (the 2- amino-benzene
Sulfonic acid) bisphenol-A ester, 4,4'- stilbenedicarboxylicacid acid, catalyst, polymerization inhibitor, high boiling solvent mass ratio be 2:1:(0.5-
0.8):(0.1-0.3):(10-15)。
5. a kind of glass fiber reinforced plastics composite material according to claim 3, which is characterized in that the catalyst is selected from phosphonothiolic acid
At least one of ester, phosphorous acid, thio-phosphamide；The polymerization inhibitor is selected from tetrachloroquinone, l, 4- naphthoquinones, p-hydroxyanisole
At least one of；The high boiling solvent in dimethyl sulfoxide, N,N-dimethylformamide, N-Methyl pyrrolidone extremely
Few one kind.
6. a kind of glass fiber reinforced plastics composite material according to claim 3, which is characterized in that the inert gas be selected from helium,
One of neon, argon gas.
7. a kind of glass fiber reinforced plastics composite material according to claim 1, which is characterized in that the vinyl triazolyl triazine radical
The preparation method of polyamide includes the following steps: 1,2,3-triazoles -4,5- dicarboxylic acids, 2,4- diamino -6-, two allylamine
Base -1,3,5-triazines, Thiophosphonate, p-hydroxyanisole, which are dissolved in N-Methyl pyrrolidone, forms solution, then solution is added
Enter in reaction kettle, with air in nitrogen displacement kettle, 105-115 DEG C reaction 3-5 hours under normal pressure, after be warming up to 250-270 DEG C, In
Carried out polycondensation reaction 15-20 hours under 100-300Pa, after be cooled to room temperature, be adjusted to normal pressure, settle out in water, use ethanol washing
3-5 times, then removing ethyl alcohol is rotated, obtain vinyl triazolyl triazine based polyamide.
8. a kind of glass fiber reinforced plastics composite material according to claim 1, which is characterized in that bis- (3- trimethoxy silicon third
Base) fumarate modified glass fibers preparation method, include the following steps: to disperse glass fibre in ethyl alcohol, then to
Bis- (3- trimethoxy silicon propyl) fumarates are wherein added, is stirred to react at 30-40 DEG C 4-6 hours, then filters, use second
Alcohol washs 3-5 times, and ethyl alcohol is evaporated off in back spin, obtains bis- (3- trimethoxy silicon propyl) fumarate modified glass fibers.
9. a kind of glass fiber reinforced plastics composite material according to claim 1-8, which is characterized in that the glass reinforced plastic is compound
The preparation method of material, include the following steps: for each raw material to be added in high speed mixer be uniformly mixed obtain mixed material, so
Mixed material is put into double screw extruder afterwards, is blended, squeezes out to obtain glass fiber reinforced plastics composite material.
10. a kind of glass fiber reinforced plastics composite material according to claim 9, which is characterized in that the spiral shell of the double screw extruder
Bar revolving speed is 190-220rpm, extrusion pressure 32-38MPa, and double screw extruder is divided into 5 sections, each section since the feed opening
Temperature is followed successively by 220-230 DEG C, 235-240 DEG C, 245-250 DEG C, 250-260 DEG C, 265-270 DEG C, head temperature 260-270
℃。
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111057351A (en) * | 2019-12-02 | 2020-04-24 | 苏州市新广益电子有限公司 | PBT (polybutylene terephthalate) environment-friendly packaging bag and production process thereof |
| CN111053312A (en) * | 2019-12-28 | 2020-04-24 | 顾正明 | Anti-radiation antibacterial fabric |
| CN111825983A (en) * | 2020-08-08 | 2020-10-27 | 湖南长重机器股份有限公司 | High-temperature-resistant composite material for rotary furnace and preparation method thereof |
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| CN111057351A (en) * | 2019-12-02 | 2020-04-24 | 苏州市新广益电子有限公司 | PBT (polybutylene terephthalate) environment-friendly packaging bag and production process thereof |
| CN111053312A (en) * | 2019-12-28 | 2020-04-24 | 顾正明 | Anti-radiation antibacterial fabric |
| CN111825983A (en) * | 2020-08-08 | 2020-10-27 | 湖南长重机器股份有限公司 | High-temperature-resistant composite material for rotary furnace and preparation method thereof |
| CN112852122A (en) * | 2021-01-05 | 2021-05-28 | 苏州市新广益电子有限公司 | Environment-friendly heat-insulating flame-retardant PBT waterproof and anti-seepage coiled material and production process thereof |
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Application publication date: 20191112 |