CN108060575A - A kind of surface-functionalized method of modifying of natural plant fibre - Google Patents
A kind of surface-functionalized method of modifying of natural plant fibre Download PDFInfo
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- CN108060575A CN108060575A CN201810106903.6A CN201810106903A CN108060575A CN 108060575 A CN108060575 A CN 108060575A CN 201810106903 A CN201810106903 A CN 201810106903A CN 108060575 A CN108060575 A CN 108060575A
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/61—Polyamines polyimines
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/144—Alcohols; Metal alcoholates
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
- D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
- D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
- D06M13/5135—Unsaturated compounds containing silicon atoms
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
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- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
A kind of surface-functionalized method of modifying of natural plant fibre of the present invention, natural plant fibre surface is activated using the method for Dopamine hydrochloride salt biomimetic modification first, secondary function is carried out as functional layer using the poly-dopamine layer of plant fibre surface deposition again, grafted silane coupling agent, plant fibre surface uniform ground after grafting coats one layer of silane coupling agent grafting layer, so that its surface introduces the active group that can be largely reacted with polymeric matrix, the interfacial bond property of plant fiber and polymer composites is significantly enhanced.The poly-dopamine functional layer that this method obtains has performance stable and reactivity, and nontoxic controllable, and reaction condition is mild, easy to operate.
Description
Technical field
The invention belongs to sponge improved properties technical fields, and in particular to a kind of natural plant fibre surface work
Method of modifying can be changed.
Background technology
Plant fiber (such as wood powder, wheat straw, bagasse, rice husk, flaxen fiber, bamboo fibre) is used as a kind of environmental-friendly fiber
Material, it is recyclable, degradable, renewable etc. because with abundance, cheap, processing cost is low compared with synthetic fibers
Advantage.As excellent reinforcing material in polymer composites, plant fiber based composites due to its lightweight, it is high-strength,
The features such as corrosion-resistant, can substitute timber, steel, aluminium and concrete etc., play an important role in building industry.Although
Composite material of plant fiber advantage is numerous, but containing substantial amounts of polar hydroxyl groups isopolarity functional group in plant fiber, and nonpolar
The poor compatibility of polymer, therefore be difficult to form good bonding between plant fiber and polymer matrix body interface, meanwhile, it is natural to plant
Fibres intramolecular hydrogen bonds, when heating, can flock together, its be caused to disperse unevenness in the base, so as to influence composite material
Comprehensive performance.To improve the interface cohesion of plant fiber and polymer, plant fiber need to be improved.
The content of the invention
The present invention provides a kind of plant fiber to solve the problems, such as plant fiber and polymeric matrix interface compatibility
Surface biomimetic modification method.
A kind of surface-functionalized method of modifying of natural plant fibre, which is characterized in that comprise the following steps:
(1) surface preparation
Plant fiber is immersed in absolute ethyl alcohol, is cleaned by ultrasonic 40min, then is dried for standby in 103 DEG C of baking oven；
(2) surface biomimetic is modified
The Dopamine hydrochloride aqueous solution of 0.5-2.0gL-1 is prepared, it is molten to add in Tri(Hydroxymethyl) Amino Methane Hydrochloride adjusting
The plant fiber of pretreatment is put into solution to 7-10, is stirred to react 0.1-48h, is passed through 10-100SCCM therebetween by liquid pH value
Oxygen, make dopamine occur oxidation autohemagglutination, be then cleaned by ultrasonic, remove the Dopamine hydrochloride of remained on surface, obtain
Obtain individual layer poly-dopamine biomimetic modification layer；Aforesaid operations are repeated to obtain multilayer poly-dopamine decorative layer, finally by biomimetic modification
Plant fiber be placed in baking oven and carry out thermal oxidation, obtain multilayer and be firmly combined with and the poly-dopamine with high reaction activity
Layer；
(3) secondary function
Configuration concentration is the secondary function monomer solution of 0.5-1%, and pH value is adjusted to 4-5 with organic acid or salt first,
Step (2) treated material is soaked in above-mentioned solution in being placed in, 0.1-48h is reacted at room temperature, deionization is used after taking-up
Water and ethyl alcohol clean repeatedly, are subsequently placed in 103 DEG C of baking ovens and are dried, final poly-dopamine biomimetic modification obtained and silane
The twice-modified plant fiber of coupling agent.
By the way that individual layer poly-dopamine biomimetic modification step is repeated several times in dopamine solution, gather its Surface Creation multilayer
DOPA amine layer.
The temperature of thermal oxidation will be carried out in the plant fiber baking oven of biomimetic modification as 103 DEG C in abovementioned steps (2).
In abovementioned steps (3) secondary function monomer solution be KH550 silane coupling agents, KH560 silane coupling agents,
Any one in KH570 silane coupling agents, Si69 silane coupling agents.
The concentration of Dopamine hydrochloride aqueous solution can be 0.5gL in abovementioned steps (1)-1、1.0g·L-1、1.5g·L-1、
2.0g·L-1。
When oxidation autohemagglutination occurs for dopamine in abovementioned steps (2), the concentration for being passed through oxygen is 60SCCM.
When oxidation autohemagglutination occurs for dopamine in abovementioned steps (2), the concentration for being passed through oxygen is 80SCCM.
When oxidation autohemagglutination occurs for dopamine in abovementioned steps (2), the concentration for being passed through oxygen is 100SCCM.
The invention has the beneficial effects that：A kind of surface-functionalized method of modifying technique letter of natural plant fibre of the present invention
List, reaction condition is mild, easy to operate, environment-protecting and non-poisonous, controllability is good, different type plant fiber progress surface can be gathered more
Bar amine biomimetic modification is modified, and meets plant fiber enhancing polymer composites performance requirement；Plant fibre surface biomimetic modification
The polar functional group of fiber surface can not only be improved, and poly-dopamine layer can be modified to provide for secondary functionization and react flat
Platform makes its biomimetic modification effect coupling agent modified better than traditional, and can be effectively improved plant fiber and be glued with polymer interface
Tie performance；The poly-dopamine functional layer obtained using this method has the characteristics that performance is stablized and reactivity is high.
Specific embodiment
Embodiment 1:
(1) surface preparation
A certain amount of plant fiber is immersed in absolute ethyl alcohol, ultrasonic 40min, then is dried for standby in 103 DEG C of baking ovens.
(2) surface biomimetic is modified
Prepare 0.5gL-1Dopamine hydrochloride aqueous solution, add in Tri(Hydroxymethyl) Amino Methane Hydrochloride adjust solution ph
To 7, the plant fiber of pretreatment is put into solution, is passed through the oxygen of 100SCCM therebetween, 48h taking-ups is stirred to react, removes table
The remaining Dopamine hydrochloride in face obtains individual layer poly-dopamine biomimetic modification layer；Aforesaid operations are repeated to obtain multilayer poly-dopamine
The plant fiber of biomimetic modification is finally placed in thermal oxidation in 103 DEG C of baking ovens, for use by decorative layer.
(3) secondary function
Configuration concentration is 1% KH550 silane coupler solutions, pH value is adjusted to 5 with organic acid or salt first, by step
(2) treated material is soaked in above-mentioned solution in being placed in, and reacts 48h at room temperature, anti-with deionized water and ethyl alcohol after taking-up
Multiple cleaning, is subsequently placed in 103 DEG C of baking ovens and is dried.
Embodiment 2
(1) surface preparation
A certain amount of plant fiber is immersed in absolute ethyl alcohol, ultrasonic 40min, then is dried in 103 DEG C of baking ovens.
(2) surface biomimetic is modified
Prepare 1gL-1Dopamine hydrochloride aqueous solution, add in Tri(Hydroxymethyl) Amino Methane Hydrochloride adjust solution ph to
7.5, the plant fiber of pretreatment is put into solution, is passed through the oxygen of 80SCCM therebetween, is stirred to react 36h taking-ups, for use；Weight
The plant fiber of biomimetic modification is finally placed in 103 DEG C of baking ovens hot by multiple aforesaid operations with obtaining multilayer poly-dopamine decorative layer
Oxidation processes, for use.
(3) secondary function
Configuration concentration is 1% KH560 silane coupler solutions, pH value is adjusted to 5 with organic acid or salt first, by step
(2) treated material is soaked in above-mentioned solution in being placed in, and reacts 48h at room temperature, anti-with deionized water and ethyl alcohol after taking-up
Multiple cleaning, is subsequently placed in 103 DEG C of baking ovens and is dried.
Embodiment 3:
(1) surface preparation
A certain amount of plant fiber is immersed in absolute ethyl alcohol, ultrasonic 40min, then is dried in 103 DEG C of baking ovens.
(2) surface biomimetic is modified
Prepare 1.5gL-1Dopamine hydrochloride aqueous solution, add in Tri(Hydroxymethyl) Amino Methane Hydrochloride adjust solution ph
To 8, the plant fiber of pretreatment is put into solution, the oxygen of 60SCCM is passed through therebetween, is stirred to react and takes out for 24 hours, for use；Weight
The plant fiber of biomimetic modification is finally placed in 103 DEG C of baking ovens hot by multiple aforesaid operations with obtaining multilayer poly-dopamine decorative layer
Oxidation processes, for use.
(3) secondary function
Configuration concentration is 1% KH570 silane coupler solutions, pH value is adjusted to 5 with organic acid or salt first, by step
(2) treated material is soaked in above-mentioned solution in being placed in, and reacts 48h at room temperature, anti-with deionized water and ethyl alcohol after taking-up
Multiple cleaning, is subsequently placed in 103 DEG C of baking ovens and is dried.
Embodiment 4:
(1) surface preparation
A certain amount of plant fiber is immersed in absolute ethyl alcohol, ultrasonic 40min, then is dried in 103 DEG C of baking ovens.
(2) surface biomimetic is modified
Prepare 2gL-1Dopamine hydrochloride aqueous solution, add in Tri(Hydroxymethyl) Amino Methane Hydrochloride adjust solution ph to
8, the plant fiber of pretreatment is put into solution, is passed through the oxygen of 60SCCM therebetween, is stirred to react 12h taking-ups, for use；It repeats
The plant fiber of biomimetic modification is finally placed in hot oxygen in 103 DEG C of baking ovens by aforesaid operations to obtain multilayer poly-dopamine decorative layer
Change is handled, for use.
(3) secondary function
Configuration concentration is 1% Si69 silane coupler solutions, pH value is adjusted to 5 with organic acid or salt first, by step
(2) treated material is soaked in above-mentioned solution in being placed in, and reacts 48h at room temperature, anti-with deionized water and ethyl alcohol after taking-up
Multiple cleaning, is subsequently placed in 103 DEG C of baking ovens and is dried.
Claims (8)
1. a kind of surface-functionalized method of modifying of natural plant fibre, which is characterized in that comprise the following steps:
(1) surface preparation
Plant fiber is immersed in absolute ethyl alcohol, is cleaned by ultrasonic 40min, then is dried for standby in 103 DEG C of baking oven；
(2) surface biomimetic is modified
Prepare 0.5-2.0gL-1Dopamine hydrochloride aqueous solution, add in Tri(Hydroxymethyl) Amino Methane Hydrochloride adjust solution ph
To 7-10, the plant fiber of pretreatment is put into solution, is stirred to react 0.1-48h, is passed through the oxygen of 10-100SCCM therebetween,
Make dopamine that oxidation autohemagglutination occur, be then cleaned by ultrasonic, remove the Dopamine hydrochloride of remained on surface, obtain individual layer and gather
Dopamine biomimetic modification layer；Aforesaid operations are repeated to obtain multilayer poly-dopamine decorative layer, it is finally that the plant of biomimetic modification is fine
Dimension, which is placed in baking oven, carries out thermal oxidation, obtains the poly-dopamine layer that multilayer is firmly combined with and has high reaction activity；
(3) secondary function
Configuration concentration is the secondary function monomer solution of 0.5-1%, and pH value is adjusted to 4-5 with organic acid or salt first, will be more
The sponge of bar amine biomimetic modification processing is soaked in above-mentioned solution in being placed in, and 0.1-48h is reacted at room temperature, after taking-up
It is cleaned repeatedly with deionized water and ethyl alcohol, is subsequently placed in 103 DEG C of baking ovens and is dried, final obtained poly-dopamine is bionical repaiies
Decorations and the twice-modified plant fiber of silane coupling agent.
2. a kind of surface-functionalized method of modifying of natural plant fibre according to claim 1, which is characterized in that by
Individual layer poly-dopamine biomimetic modification step is repeated several times in dopamine solution, makes its Surface Creation multilayer poly-dopamine layer.
A kind of 3. surface-functionalized method of modifying of natural plant fibre according to claim 2, which is characterized in that step
(2) temperature of thermal oxidation will be carried out in the plant fiber baking oven of biomimetic modification as 103 DEG C described in.
A kind of 4. surface-functionalized method of modifying of natural plant fibre according to claim 3, which is characterized in that step
(3) secondary function monomer solution described in be KH550 silane coupling agents, KH560 silane coupling agents, KH570 silane coupling agents,
Any one in Si69 silane coupling agents.
A kind of 5. surface-functionalized method of modifying of natural plant fibre according to claim 4, which is characterized in that step
(1) concentration of Dopamine hydrochloride aqueous solution described in can be 0.5gL-1、1.0g·L-1、1.5g·L-1、2.0g·L-1。
A kind of 6. surface-functionalized method of modifying of natural plant fibre according to claim 5, which is characterized in that step
(2) when oxidation autohemagglutination occurs for dopamine described in, the concentration for being passed through oxygen is 60SCCM.
A kind of 7. surface-functionalized method of modifying of natural plant fibre according to claim 5, which is characterized in that step
(2) when oxidation autohemagglutination occurs for dopamine described in, the concentration for being passed through oxygen is 80SCCM.
A kind of 8. surface-functionalized method of modifying of natural plant fibre according to claim 5, which is characterized in that step
(2) when oxidation autohemagglutination occurs for dopamine described in, the concentration for being passed through oxygen is 100SCCM.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108823990A (en) * | 2018-06-11 | 2018-11-16 | 安徽省创安体育用品有限公司 | A kind for the treatment of process improving apocynum fibre mechanical property |
| CN109762215A (en) * | 2019-01-17 | 2019-05-17 | 北京化工大学 | High-performance polyimide long fiber reinforcement rubber composite material and preparation method thereof |
| CN110065109A (en) * | 2019-04-26 | 2019-07-30 | 北京林业大学 | A kind of wood single-plate and high-density polyethylene plastics film bonding reinforcing technology based on poly-dopamine enhancing |
| CN110886087A (en) * | 2019-12-10 | 2020-03-17 | 华东理工大学 | Polypropylene fiber reinforced oleophylic modification method |
| CN111663324A (en) * | 2020-05-07 | 2020-09-15 | 安徽绿之态新材料有限公司 | Modified plant fiber and wear-resistant tableware containing same |
| CN113668237A (en) * | 2021-08-06 | 2021-11-19 | 常州工学院 | Method for preparing silane coupling agent-silicon dioxide-plant fiber composite |
| CN114163849A (en) * | 2021-12-08 | 2022-03-11 | 上海净颖环保科技股份有限公司 | Environment-friendly composite coating for buildings and preparation method thereof |
| CN115960445A (en) * | 2022-11-25 | 2023-04-14 | 东华大学 | Surface-modified long bamboo fiber reinforced polylactic acid composite board and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108823990A (en) * | 2018-06-11 | 2018-11-16 | 安徽省创安体育用品有限公司 | A kind for the treatment of process improving apocynum fibre mechanical property |
| CN109762215A (en) * | 2019-01-17 | 2019-05-17 | 北京化工大学 | High-performance polyimide long fiber reinforcement rubber composite material and preparation method thereof |
| CN110065109A (en) * | 2019-04-26 | 2019-07-30 | 北京林业大学 | A kind of wood single-plate and high-density polyethylene plastics film bonding reinforcing technology based on poly-dopamine enhancing |
| CN110886087A (en) * | 2019-12-10 | 2020-03-17 | 华东理工大学 | Polypropylene fiber reinforced oleophylic modification method |
| CN110886087B (en) * | 2019-12-10 | 2022-03-15 | 华东理工大学 | Polypropylene fiber reinforced oleophylic modification method |
| CN111663324A (en) * | 2020-05-07 | 2020-09-15 | 安徽绿之态新材料有限公司 | Modified plant fiber and wear-resistant tableware containing same |
| CN113668237A (en) * | 2021-08-06 | 2021-11-19 | 常州工学院 | Method for preparing silane coupling agent-silicon dioxide-plant fiber composite |
| CN114163849A (en) * | 2021-12-08 | 2022-03-11 | 上海净颖环保科技股份有限公司 | Environment-friendly composite coating for buildings and preparation method thereof |
| CN115960445A (en) * | 2022-11-25 | 2023-04-14 | 东华大学 | Surface-modified long bamboo fiber reinforced polylactic acid composite board and preparation method thereof |
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Application publication date: 20180522 |