CN108456401A - A kind of pipe composite and preparation method thereof - Google Patents
A kind of pipe composite and preparation method thereof Download PDFInfo
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- CN108456401A CN108456401A CN201810410229.0A CN201810410229A CN108456401A CN 108456401 A CN108456401 A CN 108456401A CN 201810410229 A CN201810410229 A CN 201810410229A CN 108456401 A CN108456401 A CN 108456401A
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- bamboo fibre
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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
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Chemical And Physical Treatments For Wood And The Like (AREA)
- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A kind of pipe composite, including modified bamboo fibre and epoxy resin；In terms of composite weight, wherein the content of modified bamboo fibre is 5 20wt%；The preparation method of the modified bamboo fibre includes the following steps：(1) bamboo fibre is pre-processed in subcritical water；(2) step (1) obtains pretreated bamboo fibre and lye, surfactant reaction；(3) and then with alkylene oxide it reacts, (4) and meta-aluminate aqueous solution are uniformly mixed, dipping, are adjusted pH value and to neutrality and are stirred aging, filtration drying.This method is simple for process, Environmental Safety, and the composite material pipe prepared using this method has high intensity and high tenacity, is widely used in a field such as chemical industry and agricultural production.
Description
Technical field
The invention belongs to pipeline production fields more particularly to a kind of pipe composite and preparation method thereof.
Background technology
Nonmetallic composite pipeline with corrosion-resistant, inner surface is smooth, the advantages such as conveying energy consumption is low be widely used in oil,
In the industries such as chemical industry, papermaking, urban water supply, with China's rapid economic development, market for composite material conduit approval and
Demand is growing.But there is also toughness deficiencies for nonmetallic composite pipeline, the shortcomings of high temperature resistance, therefore for non-
The research of metal compounded pipe material has very important realistic meaning.
The material of the object of two or more different tissues phases composition is become into composite material in materialogy.It typically will be high
Intensity, high-modulus fragile material be distributed in the toughness material of low-intensity, low modulus, such as it is glass fibre, carbon fiber is multiple
It closes in resin material, ceramics etc..Composite material can overcome the weakness of homogenous material, by collection the advantages of two or more materials
Altogether, operation principle is to transmit the shearing force between fiber by matrix using high strength fibre as stress base material.Together
When fiber be easy compressive buckling, matrix can play the role of preventing fiber buckling to a certain extent.Fibrous composite is
Through being widely used in industrial various aspects, in numerous composite materials, bamboo fiber composite material is that research is more
A kind of composite material, application are very wide.Bamboo fibre compound resin is using bamboo fibre as reinforcing material, using resin as matrix
The composite material of material.
Bamboo fibre is a kind of fiber from bamboo plant, and bamboo plant growth is rapid, resourceful, has very high
Value of exploiting and utilizing, and bamboo fibre has the advantages that intensity height, good toughness, rigidity are big, is easy to be longitudinally separated.Due to bamboo fibre table
Also contain the substances such as hemicellulose and lignin, pectin, esters, cellulose main composition fiber finer other than cellulose in face
The skeleton structure of cell wall, and hemicellulose, lignin and pectin are filled in lignin fibre gap, serve as adhesive.Bamboo is fine
In dimension, hemicellulose and lignin form complicated network structure with covalent bond, and cellulose is inlayed wherein.Cellulose itself has
The hydroxyl of higher crystallinity, a large amount of high reaction activities is closed in crystal region so that fibrin reaction activity is relatively low, causes
Group the basis materials such as fiber and resin surface polarity difference it is larger, therefore bamboo fibre used as composite material generally require into
Row surface modification treatment.
The common surface treatment method of bamboo fibre is the method using alkali cleaning, and it is apparent swollen that lye can be such that cellulose occurs
Swollen, specific surface area active increases, reactivity enhancing.Ultrasonication liquid also as common processing method, can reinforce alkali
The function and effect of liquid.Oxidation pre-treatment is also common method of modifying, oxidation processes can a large amount of lignin degradings, but to fibre
Dimension element and hemicellulose have little effect, and to significantly improve the content of cellulose, common oxidant mainly has oxygen, smelly
Oxygen and hydrogen peroxide etc..
Epoxy resin is a kind of organic material with good physical chemical stability and mechanical performance, is widely used in pipe
Road material, but epoxy resin since there are internal stress big, toughness and thermal stability difference defect, by the way that other components can be added
Composite material is constituted to use.
Pang Jin English et al. uses baby to refine at coupling agent A-174 processing, the processing of acetylation cladding and potassium permanganate grafting respectively
Reason prepares epoxy resin-base composite material to be modified banana fiber, then using modified banana fiber as filler.The study found that banana
Fiber can significantly improve the stretching, bending and compressive strength of epoxy resin, and compared with unmodified banana fiber, at 3 kinds of modifications
Reason can further increase the mechanical property of composite material.Liang Chunqun is modified bamboo fibre and asphalt mixtures modified by epoxy resin with silane resin acceptor kh-550
Fat E-44 is that raw material prepares epoxy resin-base composite material.The result shows that bamboo fibre can improve the impact and stretching of epoxy resin
Intensity, when bamboo fibre content is 20%, composite materials property is best.Zhou Zuowan of Southwest Jiaotong University et al. respectively with
2%NaOH solution and the coupling agent modified bamboo fibres of KH-560, then bamboo fibre and modified bamboo fibre are prepared into epoxy for filler respectively
Resin composite materials.The study found that when bamboo fibre content is 20%, composite material tensile strength, elongation at break and impact are strong
Degree is significantly improved relative to pure epoxy resin, and two kinds of modifications can further improve tensile strength and the fracture of composite material
Elongation.
In the prior art the main of bamboo fibre composite resin material is still concentrated on carrying out the surface of bamboo fibre
Modification so that the interface difference between bamboo fibre surface and resin minimizes, to improve the machine of bamboo fiber composite material
Tool performance.
Invention content
The present invention on the basis of existing technology, the interface difference being further improved between bamboo fibre and resin so that bamboo
More chemistry key connections are formed between fiber and resin material, to further increase the mechanical performance of composite material.Specifically
For, the present invention is by sub-critical treatment, the cellulose in partial hydrolysis bamboo fibre, and passes through the ratio for controlling bamboo fibre and water
And hydrolysis time, the degree of hydrolysis is controlled, under the premise of ensureing that bamboo fibre microstructure is not destroyed so that fiber
Space between plain molecule increases, and convenient for diffusing into for foreign molecules, improves the compatibility of bamboo fibre and polyester material, in turn
Improve the mechanical performance of obtained composite material.
The present invention provides a kind of pipe composite, including modified bamboo fibre and epoxy resin；In terms of composite weight,
The content of wherein modified bamboo fibre is 5-20wt%；The preparation method of the modified bamboo fibre includes the following steps：(1) bamboo fibre
It is pre-processed in subcritical water；(2) step (1) obtains pretreated bamboo fibre and lye, surfactant reaction；
(3) and then with alkylene oxide it reacts, (4) and meta-aluminate aqueous solution are uniformly mixed, dipping, are adjusted pH value to neutrality and are stirred old
Change, filtration drying.
Pretreated temperature described in step (1) is 300-370 DEG C, pressure 15-22MPa, preferably 350-370 DEG C,
Pressure is 20-22MPa；The pretreatment time is 10-100 seconds, preferably 20-50 seconds；Bamboo fibre and water described in step (1)
Mass ratio be 1:5-20, preferably 1:5-10.
Lye described in step (2) is the aqueous solution of sodium hydroxide, potassium hydroxide or ammonium hydroxide, and the pH value of the lye is
12-14, processing time 6-12h.Glass or plastic containers described in step (2), preferably polyoxy second
Alkene ether series.
Alkylene oxide described in step (3) is one kind in ethylene oxide, propylene oxide；The mass ratio of bamboo fibre and alkylene oxide
It is 1:10-20, reaction time 1-6h.
Step (4) neutralizes meta-aluminate aqueous solution and is uniformly mixed, and adjusts pH value 6-6.5 after impregnating 10-36h, stirs and old
Change 24-72h, filtering is dry at 110-120 DEG C.
In a preferred embodiment, in pre-treatment step described in step (1), a concentration of 0.1- can also be added
The ammonium hydroxide of 1wt%, pretreatment time are 10-20 seconds.
The preparation method of the composite material includes the following steps：By diluent, epoxy resin and modified bamboo fibre according to
0.1-0.5:1:0.01-0.15 is mixed, and is warming up to 80-150 DEG C, curing agent is then added, stir evenly to get the composite wood
Material.
The diluent is one kind in acetone or dimethyl carbonate；The curing agent is ethylenediamine；The curing agent
Addition is the 5-15wt% of epoxy resin quality.
The present invention is pre-processed by subcritical water, is removed lignin and the impurity such as colloid and esters in bamboo fibre, is increased
Gap between big cellulosic molecule, advantageously improves agent and gos deep into inside bamboo fibre；In the Process of Surface Modification of bamboo fibre,
The hydroxyl being added in alkylene oxide, with bamboo fibre reacts, and generates a large amount of carboxyl, is conducive to what cellulose was combined with modifying agent
It is even closer, to further increase the compatibility of bamboo fibre and resin；In the selection of modifying agent, conventional silicon is not used
It is modifying agent, uses the modifying agent of aluminium system, there is better compatibility with modified bamboo fibre.
The advantageous effects of the present invention：The gap structure and composition for further improving bamboo fibre, increase in cellulose
Porous structure, and it is as much as possible remove delignification and other impurity, improve the content of cellulose, further improve and change
Property resin composite materials be machined intensity.This method is simple for process, Environmental Safety, the composite material tube prepared using this method
Material has high intensity and high tenacity, is widely used in a field such as chemical industry and agricultural production.
Specific implementation mode
Embodiment 1
Pipe composite, including 5wt% are modified bamboo fibre；The preparation method of the modified bamboo fibre includes following step
Suddenly：(1) bamboo cellulose pre-processes 20 seconds, the wherein matter of bamboo fibre and water under 370 DEG C, the pressure of 21MPa in subcritical water
Amount is than being 1:10；(2) sodium hydroxide lye that the obtained pretreated bamboo fibre of step (1) and pH value are 13 handle 6h,
The OP-10 of 0.05wt% is added in lye；(3) in mass ratio 1:10 are added propylene oxide, react 1h, (4) are in meta-aluminic acid brine
It is impregnated in solution and adjusts pH value afterwards for 24 hours to 6-6.5, stirred simultaneously aging 48h, dry 10h after filtering at 110 DEG C.
Embodiment 2
Pipe composite, including 10wt% are modified bamboo fibre；The preparation method of the modified bamboo fibre includes following step
Suddenly：(1) bamboo cellulose pre-processes 20 seconds, the wherein matter of bamboo fibre and water under 370 DEG C, the pressure of 21MPa in subcritical water
Amount is than being 1:10；(2) sodium hydroxide lye that the obtained pretreated bamboo fibre of step (1) and pH value are 13 handle 6h,
The OP-10 of 0.05wt% is added in lye；(3) in mass ratio 1:10 are added propylene oxide, react 1h, (4) are in meta-aluminic acid brine
It is impregnated in solution and adjusts pH value afterwards for 24 hours to 6-6.5, stirred simultaneously aging 48h, dry 10h after filtering at 110 DEG C.
Embodiment 3
Pipe composite, including 15wt% are modified bamboo fibre；The preparation method of the modified bamboo fibre includes following step
Suddenly：(1) bamboo cellulose pre-processes 20 seconds, the wherein matter of bamboo fibre and water under 370 DEG C, the pressure of 21MPa in subcritical water
Amount is than being 1:10；(2) sodium hydroxide lye that the obtained pretreated bamboo fibre of step (1) and pH value are 13 handle 6h,
The OP-10 of 0.05wt% is added in lye；(3) in mass ratio 1:10 are added propylene oxide, react 1h, (4) are in meta-aluminic acid brine
It is impregnated in solution and adjusts pH value afterwards for 24 hours to 6-6.5, stirred simultaneously aging 48h, dry 10h after filtering at 110 DEG C.
Comparative example 1
Pipe composite, including the unmodified raw bamboo fibers of 15wt%.
Comparative example 2
Pipe composite, including 15wt% are modified bamboo fibre；Asia is not used in the preparation process of the modified bamboo fibre
Critical water process.Other steps are same as Example 3.
Comparative example 3
Pipe composite, including 15wt% are modified bamboo fibre；Water is used in the preparation process (4) of the modified bamboo fibre
Glass is modified.Other steps are same as Example 3.
Comparative example 4
Pipe composite, including 15wt% are modified bamboo fibre；The preparation method of the modified bamboo fibre uses existing skill
Base extraction oxygenation SiClx hydridization in art.The specific preparation process of the modified bamboo fibre includes the following steps：(1) raw bamboo is fine
Dimension is added 20wt% sodium hydroxide lyes and handles 3h, and ultrasonic wave is used in combination to carry out aid in treatment, dry at 105 DEG C after cleaning filtering
12h；(2) bamboo fibre of activation process is added the ethanol-water solution dipping of ethyl orthosilicate and adjusts pH value afterwards for 24 hours to faintly acid,
It is filtered after water-bath aging 36h, the dry 12h at 105 DEG C.
Comparative example 5
It is not added with the resin material of bamboo fibre.
Measuring mechanical property is carried out to the composite material that embodiment 1-3 and comparative example 1-4 are obtained, the results are shown in table below：
| Tensile strength (MPa) | Bending strength (MPa) | Impact strength (KJ/m2) | |
| Embodiment 1 | 51 | 116 | 4.3 |
| Embodiment 2 | 73 | 157 | 5.9 |
| Embodiment 3 | 86 | 195 | 7.0 |
| Comparative example 1 | 45 | 92 | 3.9 |
| Comparative example 2 | 55 | 108 | 4.1 |
| Comparative example 3 | 71 | 141 | 5.6 |
| Comparative example 4 | 65 | 123 | 4.8 |
| Comparative example 5 | 40 | 65 | 2.7 |
Heretofore described raw bamboo fiber refers to the not no bamboo fibre after stripping by any modification.
It can be seen that from the performance test results of the embodiment of the present invention and comparative example with bamboo fibre in composite material
The mechanical performance of the rising of the content of dimension, composite material dramatically increases, but bamboo fibre content is more than after 15%, mechanical performance
Improvement becomes unobvious, when the mechanical performance more than 20wt%, composite material declines instead.Asia using the present invention is faced
Boundary's method for treating water pre-processes bamboo fibre, can significantly improve the pore structure of bamboo fibre, and it is fine with bamboo to increase modifying agent
The bonding tightness of dimension, to improve the mechanical performance of composite material.
Claims (9)
1. a kind of pipe composite, including modified bamboo fibre and epoxy resin；In terms of composite weight, wherein modified bamboo is fine
The content of dimension is 5-20wt%；The preparation method of the modified bamboo fibre includes the following steps：(1) bamboo fibre is in subcritical water
It is pre-processed；(2) step (1) obtains pretreated bamboo fibre and lye, surfactant reaction；(3) and then and ring
Oxygen alkane reacts, and (4) and meta-aluminate aqueous solution are uniformly mixed, dipping, adjusts pH value and to neutrality and stirs aging, filtration drying.
2. composite material as described in claim 1, it is characterised in that pretreated temperature described in step (1) is 300-370
DEG C, pressure 15-22MPa, preferably 350-370 DEG C, pressure 20-22MPa；The pretreatment time is 10-100 seconds, excellent
It is selected as 20-50 seconds；The mass ratio of bamboo fibre and water described in step (1) is 1:5-20, preferably 1:5-10.
3. composite material as described in claim 1, it is characterised in that lye described in step (2) is sodium hydroxide, hydroxide
The pH value of the aqueous solution of potassium or ammonium hydroxide, the lye is 12-14, processing time 6-12h.
4. composite material as described in claim 1, it is characterised in that alkylene oxide described in step (3) is ethylene oxide, epoxy
One kind in propane；The mass ratio of bamboo fibre and alkylene oxide is 1:10-20, reaction time 1-6h.
5. composite material as described in claim 1, it is characterised in that step (4) neutralizes meta-aluminate aqueous solution and is uniformly mixed,
PH value 6-6.5 is adjusted after impregnating 10-36h, stirs and aging 24-72h, filtering is dry at 110-120 DEG C.
6. composite material as described in claim 1, it is characterised in that in pre-treatment step described in step (1), can also add
Enter the ammonium hydroxide of a concentration of 0.1-1wt%, pretreatment time is 10-20 seconds.
7. composite material as described in claim 1, it is characterised in that surfactant is non-ionic surface described in step (2)
Activating agent, preferably polyoxyethylene ether series.
8. the preparation method of composite material, includes the following steps as described in claim any one of 1-7：By diluent, asphalt mixtures modified by epoxy resin
Fat and modified bamboo fibre are according to 0.1-0.5:1:0.01-0.15 is mixed, and is warming up to 80-150 DEG C, curing agent is then added, and is stirred
Uniformly to get the composite material.
9. method as claimed in claim 8, it is characterised in that the diluent is one kind in acetone or dimethyl carbonate；Institute
It is ethylenediamine to state curing agent；The addition of the curing agent is the 5-15wt% of epoxy resin quality.
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| CN201810410229.0A CN108456401B (en) | 2018-05-02 | 2018-05-02 | Pipeline composite material and preparation method thereof |
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| CN201810410229.0A CN108456401B (en) | 2018-05-02 | 2018-05-02 | Pipeline composite material and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109265929A (en) * | 2018-09-27 | 2019-01-25 | 安徽原上草节能环保科技有限公司 | A kind of pipeline composite material and preparation method thereof |
| CN109836776A (en) * | 2019-01-24 | 2019-06-04 | 黄婷静 | A kind of high intensity chemical industry pipeline material and preparation method thereof |
| CN113372654A (en) * | 2021-05-19 | 2021-09-10 | 会通新材料股份有限公司 | Low-odor plant fiber reinforced polypropylene composite material and preparation method thereof |
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| CN108456401B (en) | 2021-04-23 |
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