A kind of organic glass fiber composite material and preparation method thereof
Technical field
The present invention relates to a kind of composite materials more particularly to a kind of organic glass fiber composite material and preparation method thereof.
Background technology
With social progress and expanding economy, miscellaneous material emerges one after another, and gives the production and living band of people
Facility is carried out, but with the needs under the continuous expansion of application range and extreme condition, material in the prior art can not expire
The demand of sufficient people, such as metal material since it with larger intensity is widely used in bridge, building material, but it is this
Material gets rusty easily in the long-term use, so that its performance is unstable, service life is short, and there are security risks, and
And its quality weight, difficult.
It is reinforcing material that fiberglass, which is with high-strength glass fibre, basalt fibre etc., synthetic resin and adjuvant etc. is bases
Body material draws a kind of molding advanced composite material (ACM) through pultrusion.It is the composite material of representative due to its light weight using fiberglass,
Intensity can match in excellence or beauty with metal steel, receive the warm welcome of people in recent years.But traditional glass Steel material price is relatively expensive,
Long-term high temperature resistance is poor, and shear strength is low, antioxygenic property and loss of properties on aging.
Chinese invention patent CN107446302A discloses a kind of roving glass fiber composite material, and composition is counted in parts by weight
It calculates, including 30-50 parts of acryl-butadiene-styrene, 8.7-13.5 parts of thermoplastic polyurethane elastic plastic cement, 8 parts of DOPO derive
Object, 0.4-0.6 part antioxidant, 2.4-3.6 parts of compatilizers and 20-30 parts of glass fibres.Roving glass fiber prepared by the present invention is compound
Not only excellent in mechanical performance, flame retardant property are all V0 grades to material, but also it is compound to solve short glass fiber enhancing roving glass fiber
" floating fibre " phenomenon that material occurs.But this composite material weatherability, high temperature resistance still need to be further increased.And
Addition is that ingredient is more complex, more or less there is dispersibility or consistency problem, in the long-term use, it is existing to there is " extravasation "
As.
Therefore, it develops the advanced composite material (ACM) that a kind of high temperature resistance is good, shearing force intensity is big, has excellent weather resistance and meets city
Field demand, to promoting the development of composite industry that there is positive effect.
Invention content
In order to overcome the defects of the prior art, a kind of organic glass fiber composite material of present invention offer and preparation method thereof,
Preparation method is simple for this, and raw material is easy to get, cheap, of less demanding to equipment and reaction condition, is suitble to industrialized production;
Perishable oxidation, carrying existing for traditional steel are overcome by organic glass fiber composite material that the preparation method is prepared
Difficult, the shortcomings of metals resources are limited, also overcome that the long-term high temperature resistance of fiberglass class composite material is poor, and shear strength is low,
The defect of antioxygenic property and loss of properties on aging has more preferable high temperature resistance, shearing force intensity bigger, weatherability more excellent
It is different, the service life is longer, more safety and environmental protection the advantages of.
To achieve the above object of the invention, the technical solution adopted by the present invention is a kind of organic glass fiber composite material, by as follows
The component of parts by weight is made:It is 100 parts of glass fibre graft modification benzimidazole carbonates resin, 3-5 parts of plasticizer, anti-oxidant
3-5 parts of agent.
Preferably, the plasticizer is in trioctyl trimellitate (TOTM), tri trimellitate nonyl ester, triisodecyl trimellitate
It is one or two kinds of.
Preferably, the antioxidant be antioxidant 1010, composite antioxidant B225, in antioxidant 1076 any one or
It is several.
Preferably, the preparation method of the glass fibre graft modification benzimidazole carbonates resin, including walk as follows
Suddenly:
1) bis- (2- chloroethyls) esters of carbonic acid, para-aminophenol, basic catalyst are dissolved in organic solvent, at 40-60 DEG C
Under be stirred to react 4-6 hours, rear washing 3-5 time takes organic layer, then with anhydrous magnesium sulfate water suction, filtering, revolving removing solvent,
Obtain compound A;
2) the compound A, 5,6- dichloro benzimidazole -2- mercaptan, the catalyst A that are prepared by step 1) are added to and are connect
Have in the there-necked flask of water knockout drum, add high boiling solvent and toluene, reaction system is heated to 90-110 DEG C, under nitrogen protection
It is stirred to react 2-3 hour, the azeotropic mixture of the water and toluene that are generated in reaction process is removed by water knockout drum, water is eliminated and later will
Reaction temperature is slowly increased to 120-130 DEG C, continues to be stirred to react 6-8 hour, reaction system is cooled to room temperature, and in water
Precipitation washes the polymer of precipitation 5-7 times with ethyl alcohol, is placed in vacuum drying chamber at 80-90 DEG C and dries 15-20 hours,
Obtain benzimidazole carbonates resin;
3) glass fibre is scattered in dichloromethane, and vinyltriethoxysilane is added thereto, at room temperature
Be stirred to react 2-4 hours, after by centrifugation, be placed in vacuum drying chamber at 80-90 DEG C for 3-5 times and dried with ethyl alcohol centrifuge washing
10-15 hours, obtain surface modified glass fiber;
4) the benzimidazole carbonates resin being prepared by step 2) is dissolved in n,N-Dimethylformamide, then
Surface modified glass fiber, the catalyst B being prepared by step 3) are added thereto, is stirred to react at 100-110 DEG C
It is 6-8 hours, rear to filter, after being used in combination tetrahydrofuran to wash 3-5 times, it is placed at 70-80 DEG C of vacuum drying chamber and dries 8-12 hours.
Preferably, bis- (2- chloroethyls) esters of carbonic acid described in step 1), para-aminophenol, basic catalyst are dissolved in organic molten
The mass ratio of agent is 1:1.2:(0.3-0.5):(5-10).
Preferably, the one kind or several of the basic catalyst in potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate
Kind.
Preferably, the organic solvent is selected from one or more of acetonitrile, acetone, ethyl acetate, ether.
Preferably, compound A described in step 2), 5,6- dichloro benzimidazole -2- mercaptan, catalyst A, higher boiling are molten
Agent, toluene mass ratio be 1.38:1:(0.3-0.5):(5-10):(2-4).
Preferably, the catalyst A in cesium carbonate, sodium hydride, tertiary butyl potassium alcoholate, potassium carbonate, potassium hydroxide one
Kind is several.
Preferably, the high boiling solvent is in dimethyl sulfoxide, n,N-Dimethylformamide, N-Methyl pyrrolidone
It is one or more of.
Preferably, glass fibre described in step 3), dichloromethane, vinyltriethoxysilane mass ratio be (2-
4):(5-10):1。
Preferably, the resin of benzimidazole carbonates described in step 4), n,N-Dimethylformamide, surface modified glass
Fiber, catalyst B mass ratio be 1:(5-10):(0.3-0.5):(0.1-0.3).
Preferably, the catalyst B in n-propylamine, diethylamide, 3,5-dimethylphenyl phosphorus, tetrabutylammonium bromide one
Kind is several.
Preferably, the preparation method of organic glass fiber composite material, includes the following steps:Each component is added in proportion
In homogenizer be uniformly mixed, after add twin-screw extrude melt blending extruding pelletization, obtain organic glass composite wood
Material.
It is using advantageous effect caused by above-mentioned technical proposal:
1) preparation method of organic glass fiber composite material provided by the invention, simple and practicable, raw material is easy to get, cheap,
It is of less demanding to equipment and reaction condition, it is suitble to industrialized production.
2) organic glass fiber composite material provided by the invention overcomes perishable oxidation existing for traditional steel, carries and be stranded
It difficult, the shortcomings of metals resources are limited, also overcomes that the long-term high temperature resistance of fiberglass class composite material is poor, and shear strength is low, resists
The defect of oxidation susceptibility and loss of properties on aging has more preferable high temperature resistance, shearing force intensity bigger, weatherability better,
The service life is longer, more safety and environmental protection the advantages of.
3) organic glass fiber composite material provided by the invention introduces benzimidazole and carbonic ester on molecular backbone, combines
The advantageous feature of makrolon and polybenzimidazole material enhances weatherability, the mechanical mechanics property of material, and with excellent
Resistance to UV aging and chemical stability.
4) organic glass fiber composite material provided by the invention, glass fibre are modified by surface and are grafted with molecular backbone, and one
Aspect enhances glass fibre dispersibility in the material, keeps it more preferable with other components compatibility;On the one hand, compound
Play the role of crosslinking agent in material so that three-dimensional net structure is presented in material, improves material comprehensive performance;On the other hand, glass
Glass fiber plays humidification in the material, is conducive to the comprehensive mechanical property for improving composite material.
Specific implementation mode
In order to make those skilled in the art more fully understand technical scheme of the present invention, and make the present invention features described above,
Purpose and advantage are more clear understandable, and with reference to embodiment, the present invention is described further.Embodiment is only used for
It is bright the present invention rather than limit the scope of the invention.
Raw material used in the following embodiments of the present invention is purchased from shellfish (Shanghai) bio tech ltd that rubs.
Embodiment 1
A kind of organic glass fiber composite material, is made of the component of following parts by weight:Glass fibre graft modification benzimidazole
100 parts of carbonates resin, 3 parts of trioctyl trimellitate (TOTM), 3 parts of antioxidant 1010.
The preparation method of the glass fibre graft modification benzimidazole carbonates resin, includes the following steps:
1) bis- (2- chloroethyls) the ester 10g of carbonic acid, para-aminophenol 12g, potassium hydroxide 3g are dissolved in acetonitrile 50g, 40
It is stirred to react at DEG C 4 hours, rear washing 3 times, takes organic layer, then solvent is removed with anhydrous magnesium sulfate water suction, filtering, revolving, obtain
To compound A;
2) compound A13.8g, 5,6- dichloro benzimidazole -2- mercaptan 10g, carbonic acid that step 1) is prepared will be passed through
Caesium 3g is added in the there-necked flask for being connected to water knockout drum, adds dimethyl sulfoxide 50g and toluene 20g, and reaction system is heated to 90 DEG C,
Stirred under nitrogen atmosphere reacts 2 hours, and the azeotropic mixture of the water and toluene that are generated in reaction process is removed by water knockout drum, is eliminated
Reaction temperature is slowly increased to 120 DEG C after water, continues to be stirred to react 6 hours, reaction system is cooled to room temperature, and in water
Middle Precipitation washes the polymer of precipitation 5 times with ethyl alcohol, is placed in vacuum drying chamber at 80 DEG C and dries 15 hours, obtains benzene
And imidazoles carbonates resin;
3) glass fibre 20g is scattered in dichloromethane 50g, and vinyltriethoxysilane 10g is added thereto,
Reaction 2 hours is stirred at room temperature, after by centrifugation, be placed in vacuum drying chamber at 80 DEG C for 3 times and dried with ethyl alcohol centrifuge washing
10 hours, obtain surface modified glass fiber;
4) the benzimidazole carbonates resin 10g being prepared by step 2) is dissolved in N,N-dimethylformamide
In 50g, then surface modified glass fiber 3g, the n-propylamine 1g being prepared by step 3) are added thereto, are stirred at 100 DEG C
Reaction 6 hours is mixed, it is rear to filter, after being used in combination tetrahydrofuran to wash 3 times, it is placed at 70 DEG C of vacuum drying chamber and dries 8 hours.
The preparation method of organic glass fiber composite material, includes the following steps:High-speed stirring is added in each component in proportion
Mix in machine be uniformly mixed, after add twin-screw extrude melt blending extruding pelletization, obtain organic glass fiber composite material.
Embodiment 2
A kind of organic glass fiber composite material, is made of the component of following parts by weight:Glass fibre graft modification benzimidazole
100 parts of carbonates resin, 3 parts of tri trimellitate nonyl ester, B2254 parts of composite antioxidant.
The preparation method of the glass fibre graft modification benzimidazole carbonates resin, includes the following steps:
1) bis- (2- chloroethyls) the ester 10g of carbonic acid, para-aminophenol 12g, sodium hydroxide 3.5g are dissolved in acetone 60g,
It is stirred to react at 45 DEG C 4.5 hours, afterwards washing 4 times, takes organic layer, then molten with anhydrous magnesium sulfate water suction, filtering, revolving removing
Agent obtains compound A;
2) compound A13.8g, 5,6- dichloro benzimidazole -2- mercaptan 10g, the hydrogenation that step 1) is prepared will be passed through
Sodium 3.5g is added in the there-necked flask for being connected to water knockout drum, adds n,N-Dimethylformamide 65g and toluene 23g, by reaction system
95 DEG C are heated to, stirred under nitrogen atmosphere reacts 2.3 hours, and the water and toluene generated in reaction process is removed by water knockout drum
Azeotropic mixture eliminates water and reaction temperature is slowly increased to 122 DEG C later, continues to be stirred to react 6.5 hours, reaction system is cooled down
To room temperature, and Precipitation in water, the polymer of precipitation is washed 6 times with ethyl alcohol, is placed in vacuum drying chamber and is dried at 83 DEG C
17 hours, obtain benzimidazole carbonates resin;
3) glass fibre 25g is scattered in dichloromethane 65g, and vinyltriethoxysilane 10g is added thereto,
Reaction 2.5 hours is stirred at room temperature, after by centrifugation, be placed in vacuum drying chamber at 83 DEG C for 4 times with ethyl alcohol centrifuge washing
It dries 12 hours, obtains surface modified glass fiber;
4) the benzimidazole carbonates resin 10g being prepared by step 2) is dissolved in N,N-dimethylformamide
In 70g, then surface modified glass fiber 3.5g, the diethylamide 1.5g being prepared by step 3) are added thereto, 103
It is stirred to react at DEG C 6.5 hours, it is rear to filter, after being used in combination tetrahydrofuran to wash 4 times, it is placed at 73 DEG C of vacuum drying chamber and dries 9 hours.
The preparation method of organic glass fiber composite material, includes the following steps:High-speed stirring is added in each component in proportion
Mix in machine be uniformly mixed, after add twin-screw extrude melt blending extruding pelletization, obtain organic glass fiber composite material.
Embodiment 3
A kind of organic glass fiber composite material, is made of the component of following parts by weight:Glass fibre graft modification benzimidazole
100 parts of carbonates resin, 4 parts of triisodecyl trimellitate, 4 parts of antioxidant 1076.
The preparation method of the glass fibre graft modification benzimidazole carbonates resin, includes the following steps:
1) bis- (2- chloroethyls) the ester 10g of carbonic acid, para-aminophenol 12g, sodium carbonate 4g are dissolved in ethyl acetate 80g,
It is stirred to react at 50 DEG C 5 hours, rear washing 4 times, takes organic layer, then solvent is removed with anhydrous magnesium sulfate water suction, filtering, revolving,
Obtain compound A;
2) compound A13.8g, 5,6- dichloro benzimidazole -2- mercaptan 10g, the tertiary fourth that step 1) is prepared will be passed through
Base potassium alcoholate 4g is added in the there-necked flask for being connected to water knockout drum, adds N-Methyl pyrrolidone 80g and toluene 30g, by reaction system
100 DEG C are heated to, stirred under nitrogen atmosphere reacts 2.6 hours, and the water and toluene that are generated in reaction process are removed by water knockout drum
Azeotropic mixture, eliminate and reaction temperature be slowly increased to 126 DEG C after water, continue to be stirred to react 7 hours, reaction system is cooled to
The polymer of precipitation is washed 6 times with ethyl alcohol, is placed in vacuum drying chamber and dries 18 at 86 DEG C by room temperature, and Precipitation in water
Hour, obtain benzimidazole carbonates resin;
3) glass fibre 32g is scattered in dichloromethane 85g, and vinyltriethoxysilane 10g is added thereto,
Reaction 3 hours is stirred at room temperature, after by centrifugation, be placed in vacuum drying chamber at 86 DEG C for 5 times and dried with ethyl alcohol centrifuge washing
13 hours, obtain surface modified glass fiber;
4) the benzimidazole carbonates resin 10g being prepared by step 2) is dissolved in N,N-dimethylformamide
In 85g, then surface modified glass fiber 43g, the 3,5-dimethylphenyl phosphorus 2g being prepared by step 3) are added thereto,
It is stirred to react at 107 DEG C 7 hours, it is rear to filter, after being used in combination tetrahydrofuran to wash 5 times, it is small to be placed in baking 10 at 76 DEG C of vacuum drying chamber
When.
The preparation method of organic glass fiber composite material, includes the following steps:High-speed stirring is added in each component in proportion
Mix in machine be uniformly mixed, after add twin-screw extrude melt blending extruding pelletization, obtain organic glass fiber composite material.
Embodiment 4
A kind of organic glass fiber composite material, is made of the component of following parts by weight:Glass fibre graft modification benzimidazole
100 parts of carbonates resin, 5 parts of plasticizer, 4 parts of antioxidant;The plasticizer is trioctyl trimellitate (TOTM), tri trimellitate
Nonyl ester, triisodecyl trimellitate in mass ratio 1:2:3 mixtures mixed;The antioxidant is antioxidant 1010, answers
Close antioxidant B225, antioxidant 1076 in mass ratio 1:3:2 mixtures mixed.
The preparation method of the glass fibre graft modification benzimidazole carbonates resin, includes the following steps:
1) bis- (2- chloroethyls) the ester 10g of carbonic acid, para-aminophenol 12g, sodium hydroxide 4.5g are dissolved in ether 90g,
It is stirred to react at 55 DEG C 5.5 hours, afterwards washing 5 times, takes organic layer, then molten with anhydrous magnesium sulfate water suction, filtering, revolving removing
Agent obtains compound A;
2) compound A13.8g, 5,6- dichloro benzimidazole -2- mercaptan 10g, carbonic acid that step 1) is prepared will be passed through
Potassium 4.5g is added in the there-necked flask for being connected to water knockout drum, adds dimethyl sulfoxide 90g and toluene 35g, and reaction system is heated to 105
DEG C, stirred under nitrogen atmosphere reacts 2.8 hours, and the azeotropic mixture of the water and toluene that are generated in reaction process is removed by water knockout drum,
It eliminates water and reaction temperature is slowly increased to 128 DEG C later, continue to be stirred to react 7.5 hours, reaction system is cooled to room temperature, and
Precipitation in water washes the polymer of precipitation 7 times with ethyl alcohol, is placed in vacuum drying chamber at 88 DEG C and dries 18 hours, obtains
To benzimidazole carbonates resin;
3) glass fibre 38g is scattered in dichloromethane 95g, and vinyltriethoxysilane 10g is added thereto,
Reaction 3.5 hours is stirred at room temperature, after by centrifugation, be placed in vacuum drying chamber at 88 DEG C for 5 times with ethyl alcohol centrifuge washing
It dries 14.5 hours, obtains surface modified glass fiber;
4) the benzimidazole carbonates resin 10g being prepared by step 2) is dissolved in N,N-dimethylformamide
In 90g, then surface modified glass fiber 4.5g, the tetrabutylammonium bromide 3g being prepared by step 3) are added thereto,
It is stirred to react at 108 DEG C 7.5 hours, it is rear to filter, after being used in combination tetrahydrofuran to wash 5 times, it is placed at 78 DEG C of vacuum drying chamber and dries 11
Hour.
The preparation method of organic glass fiber composite material, includes the following steps:High-speed stirring is added in each component in proportion
Mix in machine be uniformly mixed, after add twin-screw extrude melt blending extruding pelletization, obtain organic glass fiber composite material.
Embodiment 5
A kind of organic glass fiber composite material, is made of the component of following parts by weight:Glass fibre graft modification benzimidazole
100 parts of carbonates resin, 5 parts of trioctyl trimellitate (TOTM), B2255 parts of composite antioxidant.
The preparation method of the glass fibre graft modification benzimidazole carbonates resin, includes the following steps:
1) bis- (2- chloroethyls) the ester 10g of carbonic acid, para-aminophenol 12g, potassium hydroxide 5g are dissolved in acetonitrile 100g, 60
It is stirred to react at DEG C 6 hours, rear washing 5 times, takes organic layer, then solvent is removed with anhydrous magnesium sulfate water suction, filtering, revolving, obtain
To compound A;
2) compound A13.8g, 5,6- dichloro benzimidazole -2- mercaptan 10g, hydrogen-oxygen that step 1) is prepared will be passed through
Change potassium 5g to be added in the there-necked flask for being connected to water knockout drum, n,N-Dimethylformamide 100g and toluene 40g is added, by reaction system
110 DEG C are heated to, stirred under nitrogen atmosphere reacts 3 hours, and the water and toluene generated in reaction process is removed by water knockout drum
Azeotropic mixture eliminates water and reaction temperature is slowly increased to 130 DEG C later, continues to be stirred to react 8 hours, reaction system is cooled to room
Temperature, and Precipitation in water wash the polymer of precipitation 7 times with ethyl alcohol, and it is small to be placed in vacuum drying chamber baking 20 at 90 DEG C
When, obtain benzimidazole carbonates resin;
3) glass fibre 40g is scattered in dichloromethane 100g, and vinyltriethoxysilane is added thereto
Reaction 4 hours is stirred at room temperature in 10g, after by centrifugation, be placed in vacuum drying chamber 90 DEG C 5 times with ethyl alcohol centrifuge washing
It is lower to dry 15 hours, obtain surface modified glass fiber;
4) the benzimidazole carbonates resin 10g being prepared by step 2) is dissolved in N,N-dimethylformamide
In 100g, then surface modified glass fiber 5g, the tetrabutylammonium bromide 3g being prepared by step 3) are added thereto,
It is stirred to react at 110 DEG C 8 hours, it is rear to filter, after being used in combination tetrahydrofuran to wash 5 times, it is small to be placed in baking 12 at 80 DEG C of vacuum drying chamber
When.
The preparation method of organic glass fiber composite material, includes the following steps:High-speed stirring is added in each component in proportion
Mix in machine be uniformly mixed, after add twin-screw extrude melt blending extruding pelletization, obtain organic glass fiber composite material.
Comparative example
This example provides a kind of glass fiber composite material, according to Chinese invention patent CN 107446302A embodiments 1 formula and
Preparation method is prepared.
Composite sample described in embodiment 1-5 and comparative example is tested for the property, test result and test method are shown in
Table 1.
Table 1
As seen from Table 1, organic glass fiber composite material disclosed by the embodiments of the present invention, with composite material phase in the prior art
Than having excellent mechanical property and heat resistance.
The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.