CN110093022A - A kind of dopamine modified glass-fiber/unsaturated polyester composite preparation method - Google Patents
A kind of dopamine modified glass-fiber/unsaturated polyester composite preparation method Download PDFInfo
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- CN110093022A CN110093022A CN201910374651.XA CN201910374651A CN110093022A CN 110093022 A CN110093022 A CN 110093022A CN 201910374651 A CN201910374651 A CN 201910374651A CN 110093022 A CN110093022 A CN 110093022A
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- fiber
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- unsaturated polyester
- glass fibre
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0666—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0672—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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Abstract
A kind of dopamine modified glass-fiber/unsaturated polyester composite preparation method of the present invention carries out slurry to glass fibre raw material using acetone and handles, the glass fibre of slurry will be gone to be put into dopamine hydrochloric acid solution again to impregnate, thereafter glass fibre taking-up is cleaned with deionized water, it is dried to obtain modified glass-fiber, then modified glass fibre and unsaturated-resin are mixed with dopamine modified glass-fiber reinforced resin composite material.The present invention passes through dopamine modified glass-fiber, the interfacial structure between glass fibre and resin is designed, adjusts and controlled on a microscopic scale, the wellability and interface bond strength for increasing glass fibre and resin, significantly improve the comprehensive performance of modified glass fibre peacekeeping unsaturated polyester composite.And dopamine polymerizing condition is simple, environment is milder, and dopamine is controllable in the thickness that fiberglass surfacing deposits.Therefore, it is more advantageous to the industrialized production of glass fiber compound material and is more widely used.
Description
Technical field
The present invention relates to a kind of dopamine modified glass-fiber/unsaturated polyester composite preparation methods, particularly belong to
Fiberglass surfacing technical field of modification.
Background technique
Glass fibre is a kind of inorganic non-metallic material haveing excellent performance, and has that good insulating, heat resistance be strong, corrosion resistance
A series of excellent properties such as good, mechanical strength height, therefore, composite material is widely used in building, chemical, traffic
Transport and electronics industry etc..Unsaturated polyester (UP) has excellent processing performance, can solidify at room temperature, form under normal pressure, work
Skill performance is flexible, is particularly suitable for large-scale and scene glass fibre/unsaturated polyester composite preparation, and insatiable hunger after solidification
With polyester good combination property.But glass fibre and unsaturated polyester (UP) wellability are poor, compound tense is easy to form gap on interface
And defect, boundary strength is low, makes glass fibre and unsaturated polyester (UP) be difficult to form effective bonding, cannot effectively play glass
The excellent properties of fiber and unsaturated polyester (UP).Therefore in order to improve the compatibility of glass fibre and unsaturated polyester (UP), glass is improved
The comprehensive performance of interface binding power and its composite material between fiber and unsaturated polyester (UP), can be handled glass fibre.
Such as soda acid decorations lithography, modification by coupling, upper slurry processes, chemical graft process and coating.These methods improve to a certain extent
The interface performance of composite material, but in addition to upper slurry processes and coating, these methods often exist treatment process it is cumbersome, at
This is higher, the disadvantages of be easy to causeing damage and interface binding power weaker fiber.Dopamine is as a kind of novel modification material
Material, is easily oxidized in weak alkaline aqueous solution, then causes self-polymeric reaction, formed in almost all of solid material surface
The poly-dopamine coating of close attachment.Entire modifying process is completed in aqueous solution, and reaction condition is mild, is avoided using organic
Solvent pollution on the environment, and settling at one go to the modification of material surface, operating procedure is simple, reaction condition and is modified
Journey is easily controllable.Poly-dopamine can not only improve the surface roughness of glass fibre, improve between glass fibre and resin group
Mechanical snap effect, and poly-dopamine contains a large amount of amine groups, can react with unsaturated polyester (UP), glass fibre can be improved
With the interface binding power of resin group, to improve the comprehensive performance of glass fiber compound material.Therefore of the invention from raising glass
Glass fiber/unsaturated polyester composite interface and mechanical performance are answered from glass fibre/unsaturated polyester composite is expanded
From the aspect of field, glass fibre is modified using dopamine.
Summary of the invention
The object of the present invention is to provide a kind of dopamine modified glass-fiber/unsaturated polyester composite preparation method,
It is intended to improve the interface performance between glass fibre and unsaturated polyester (UP), is easy to industrialize dopamine modified glass-fiber and its answers
The production of condensation material.
A kind of dopamine modified glass-fiber/unsaturated polyester composite preparation method of the present invention the following steps are included:
Step 1: using acetone soak glass fibre raw material 4h, cleaned, be placed on deionized water after removing surface size agent
It is dry in 60 DEG C of baking ovens, obtain the glass fibre of slurry；
Step 2: preparing dopamine hydrochloric acid solution, adjust its pH to 8.5 or so, obtain the dopamine hydrochloric acid solution of 2.0g/L；
Step 3: impregnating 2-24h for going the glass fibre of slurry to be put into dopamine hydrochloric acid solution, cleaned after taking-up with deionized water
The extra dopamine of fiberglass surfacing is placed on drying in 60 DEG C of baking ovens, obtains dopamine modified glass-fiber；
Step 4: unsaturated polyester resin, curing agent and promotor being stirred evenly according to 100: 2: 1 mass ratio, obtained not
Saturated polyester resin glue is coated in and is covered on the glass plate of release cloth, spreads one layer of dopamine modified glass-fiber thereafter, then apply
One layer of unsaturated polyester resin glue is covered, until after having spread ten layers of dopamine modified glass-fiber, then through room temperature curing 4h, obtain
Dopamine modified glass-fiber/unsaturated polyester composite.
04 platinum of model of the glass fibre.
The model 191# unsaturated polyester resin of the unsaturated polyester resin.
The curing agent is cyclohexanone peroxide.
The promotor is epoxyeicosatrienoic acid cobalt.
Beneficial effects of the present invention: the present invention is impregnated by the way that glass fibre to be put into dopamine hydrochloric acid solution, makes fiber
Surface forms dopamine coating, to increase the specific surface area and roughness of glass fibre, improves between glass fibre and resin group
Mechanical snap effect so that the contact area between glass fibre and resin matrix increases, and poly-dopamine contains a large amount of amine
Base group can be reacted with unsaturated polyester (UP), and the interface binding power of glass fibre Yu resin group can be improved, and make glass fibre/poly-
The comprehensive performance for closing object based composites significantly improves.And dopamine polymerizing condition is simple, mild, and it is heavy in fiberglass surfacing
Long-pending thickness is controllable, convenient for the industrialized production and extensive use of glass fiber compound material.When dopamine concentration of hydrochloric acid solution
When for 2.0g/L, modification time being 10h, the bending strength of modified glass fibre/polymer matrix composite is improved
24.56%。
Detailed description of the invention
Fig. 1 is that the FE-SEM of unmodified glass fibre schemes；
The FE-SEM that Fig. 2 is dopamine modified glass-fiber 10h schemes.
Specific embodiment
Below with reference to embodiment to the present invention it is further details of illustrate, but the contents of the present invention be not limited solely to it is following
Embodiment.
Embodiment 1
10 piece of 04 platinum glass fibre (every piece of 20cm*30cm) is taken, with acetone soak 4h, is then cleaned up again with deionized water
It is taken out after 60 DEG C of forced air dryings spare.By 191# unsaturated polyester resin, cyclohexanone peroxide and epoxyeicosatrienoic acid cobalt according to 100: 2
: it after 1 ratio weighs, stirs evenly, coated on the glass plate for being covered with release cloth, spreads layer of glass, then brush one
Layer resin solution, until having spread 10 blocks of glass fabrics.Room temperature curing 4h obtains unmodified glass fiber compound material plate.
Embodiment 2
10 piece of 04 platinum glass fibre (every piece of 20cm*30cm) is taken, with acetone soak 4h, is then cleaned up again with deionized water
It is taken out after 60 DEG C of forced air dryings spare.The dopamine hydrochloric acid solution for preparing 2.0g/L will go the glass fibre of slurry to be put into DOPA
It is taken out after impregnating 2h in amine salt acid solution, is cleaned 1 time with deionized water, be placed in 60 DEG C of baking ovens and be dried for standby.By 191# insatiable hunger
After being weighed with polyester resin, cyclohexanone peroxide and epoxyeicosatrienoic acid cobalt according to 100: 2: 1 ratio, stirs evenly, be coated in
It is covered on the glass plate of release cloth, spreads layer of glass, then brush one layer of resin solution, until having spread 10 blocks of glass fabrics.
Room temperature curing 4h obtains the glass fiber compound material plate that dopamine modification time is 2h.
Embodiment 3
10 piece of 04 platinum glass fibre (every piece of 20cm*30cm) is taken, with acetone soak 4h, is then cleaned up again with deionized water
It is taken out after 60 DEG C of forced air dryings spare.The dopamine hydrochloric acid solution for preparing 2.0g/L will go the glass fibre of slurry to be put into DOPA
It is taken out after impregnating 6h in amine salt acid solution, is cleaned 1 time with deionized water, be placed in 60 DEG C of baking ovens and be dried for standby.By 191# insatiable hunger
After being weighed with polyester resin, cyclohexanone peroxide and epoxyeicosatrienoic acid cobalt according to 100: 2: 1 ratio, stirs evenly, be coated in
It is covered on the glass plate of release cloth, spreads layer of glass, then brush one layer of resin solution, until having spread 10 blocks of glass fabrics.
Room temperature curing 4h obtains the glass fiber compound material plate that modification time is 6h.
Embodiment 4
10 piece of 04 platinum glass fibre (every piece of 20cm*30cm) is taken, with acetone soak 4h, is then cleaned up again with deionized water
It is taken out after 60 DEG C of forced air dryings spare.The dopamine hydrochloric acid solution for preparing 2.0g/L will go the glass fibre of slurry to be put into DOPA
It is taken out after impregnating 10h in amine salt acid solution, is cleaned 1 time with deionized water, be placed in 60 DEG C of baking ovens and be dried for standby.By 191# insatiable hunger
After being weighed with polyester resin, cyclohexanone peroxide and epoxyeicosatrienoic acid cobalt according to 100: 2: 1 ratio, stirs evenly, be coated in
It is covered on the glass plate of release cloth, spreads layer of glass, then brush one layer of resin solution, until having spread 10 blocks of glass fabrics.
Room temperature curing 4h obtains the glass fiber compound material plate that modification time is 10h.
Embodiment 5
10 piece of 04 platinum glass fibre (every piece of 20cm*30cm) is taken, with acetone soak 4h, is then cleaned up again with deionized water
It is taken out after 60 DEG C of forced air dryings spare.The dopamine hydrochloric acid solution for preparing 2.0g/L will go the glass fibre of slurry to be put into DOPA
It impregnates in amine salt acid solution and takes out afterwards for 24 hours, cleaned 1 time with deionized water, be placed in 60 DEG C of baking ovens and be dried for standby.By 191# insatiable hunger
After being weighed with polyester resin, cyclohexanone peroxide and epoxyeicosatrienoic acid cobalt according to 100: 2: 1 ratio, stirs evenly, be coated in
It is covered on the glass plate of release cloth, spreads layer of glass, then brush one layer of resin solution, until having spread 10 blocks of glass fabrics.
It is glass fiber compound material plate for 24 hours that room temperature curing 4h, which obtains modification time,.
The performance test of comparative example 1- embodiment 4
The bending property of glass fiber compound material before and after dopamine modified glass-fiber is shown in Table 1.
。
Claims (5)
1. a kind of dopamine modified glass-fiber/unsaturated polyester composite preparation method, it is characterised in that: the preparation
Method the following steps are included:
Step 1: using acetone soak glass fibre raw material 4h, cleaned, be placed on deionized water after removing surface size agent
It is dry in 60 DEG C of baking ovens, obtain the glass fibre of slurry；
Step 2: preparing dopamine hydrochloric acid solution, adjust its pH to 8.5 or so, obtain the dopamine hydrochloric acid solution of 2.0g/L；
Step 3: impregnating 2-24h for going the glass fibre of slurry to be put into dopamine hydrochloric acid solution, cleaned after taking-up with deionized water
The extra dopamine of fiberglass surfacing is placed on drying in 60 DEG C of baking ovens, obtains dopamine modified glass-fiber；
Step 4: unsaturated polyester resin, curing agent and promotor being stirred evenly according to 100: 2: 1 mass ratio, obtained not
Saturated polyester resin glue is coated in and is covered on the glass plate of release cloth, spreads one layer of dopamine modified glass-fiber thereafter, then apply
One layer of unsaturated polyester resin glue is covered, until after having spread ten layers of dopamine modified glass-fiber, then through room temperature curing 4h, obtain
Dopamine modified glass-fiber/unsaturated polyester composite.
2. a kind of dopamine modified glass-fiber/unsaturated polyester composite preparation method according to claim 1,
It is characterized in that: 04 platinum of model of the glass fibre.
3. a kind of dopamine modified glass-fiber/unsaturated polyester composite preparation method according to claim 1,
It is characterized in that: the model 191# unsaturated polyester resin of the unsaturated polyester resin.
4. a kind of dopamine modified glass-fiber/unsaturated polyester composite preparation method according to claim 1,
Be characterized in that: the curing agent is cyclohexanone peroxide.
5. a kind of dopamine modified glass-fiber/unsaturated polyester composite preparation method according to claim 1,
Be characterized in that: the promotor is epoxyeicosatrienoic acid cobalt.
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Cited By (6)
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| CN111764169A (en) * | 2020-04-09 | 2020-10-13 | 上海大学 | Surface modified PBO fiber and preparation method thereof |
| CN113024995A (en) * | 2021-02-04 | 2021-06-25 | 东华大学 | High-strength high-modulus electromagnetic shielding functional structure integrated light material and preparation method thereof |
| CN115536912A (en) * | 2022-10-13 | 2022-12-30 | 安徽杰蓝特新材料有限公司 | Glass fiber for pipe and preparation method thereof |
| CN115725135A (en) * | 2022-10-28 | 2023-03-03 | 重庆会通科技有限公司 | Anti-floating fiber polypropylene reinforced composite material and preparation method thereof |
| CN116006789A (en) * | 2023-01-09 | 2023-04-25 | 康命源（贵州）科技发展有限公司 | High-strength and high-toughness polyolefin pipe and preparation method thereof |
| CN116813948A (en) * | 2023-07-17 | 2023-09-29 | 杭州马科森复合材料有限公司 | Preparation process of unidirectional prepreg tape with continuous fiber reinforced thermoplastic resin |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111764169A (en) * | 2020-04-09 | 2020-10-13 | 上海大学 | Surface modified PBO fiber and preparation method thereof |
| CN113024995A (en) * | 2021-02-04 | 2021-06-25 | 东华大学 | High-strength high-modulus electromagnetic shielding functional structure integrated light material and preparation method thereof |
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| CN116813948A (en) * | 2023-07-17 | 2023-09-29 | 杭州马科森复合材料有限公司 | Preparation process of unidirectional prepreg tape with continuous fiber reinforced thermoplastic resin |
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