CN106947244B - A kind of preparation method of nylon gel body - Google Patents
A kind of preparation method of nylon gel body Download PDFInfo
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- CN106947244B CN106947244B CN201710265997.7A CN201710265997A CN106947244B CN 106947244 B CN106947244 B CN 106947244B CN 201710265997 A CN201710265997 A CN 201710265997A CN 106947244 B CN106947244 B CN 106947244B
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
- C08K2003/162—Calcium, strontium or barium halides, e.g. calcium, strontium or barium chloride
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
- C08K2003/166—Magnesium halide, e.g. magnesium chloride
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
- C08K2003/168—Zinc halides
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Abstract
The invention discloses a kind of preparation methods of nylon gel body.The preparation method of intelligent gel body with electroresponse, comprising the following steps: by metal salt M+X‑It is stirred with ethylene chlorhydrin sealing, obtains nylon colloidal sol after nylon dissolution is added；Wherein, M+For Li+、K+、Ca2+、Zn2+、Mg2+、Ga3+In any one；X‑For Cl‑、Br‑、I‑、SCN‑In any one；By the nylon colloidal sol heated sealed, ultrasonic treatment, nylon gel body is can be obtained in sealing and standing at room temperature.The present invention has chosen a variety of nylon materials, is dissolved in M+X‑In the mixed solution of ethylene chlorhydrin, recyclable nylon gel body is obtained after heating stirring ultrasound, sensitive electrical response characteristics are shown under electric field action, have widened the application range of nylon gel body.
Description
Technical field
The invention belongs to intelligent gel body fields, and in particular to a kind of preparation of the intelligent gel body with sensitive electroresponse
Method.
Background technique
Contain amide group on nylon molecules main chain, be polar group, intermolecular there are strong hydrogen bond action, molecules
Chain arranged regular, so nylon crystallinity is high, mechanical performance and excellent shock resistance, metal salt can occur with amide group
Complex reaction destroys intermolecular hydrogen bond, can effectively control the crystallinity of nylon.Nylon is polar polymer, Zhi Nengrong
In the certain highly polar solvents of Xie Yu, but the mixed solution of the solvent of some low poles and inorganic salts can also dissolve nylon, lead to
Polymer intelligent gelinite can be prepared by crossing this solvent, can be used for weaving, the research of nylon aggregation state change and phase-change material.
In addition, currently the research of temperature sensitive intelligent gelinite and pH sensibility intelligent gel body is more concentrated, and to electricity
The research for responding intelligent gel body is less.It is not only cumbersome by changing temperature or pH value of solution for intelligent gel body, and
And the stimuli responsive speed of gelinite is slow.
There are mainly two types of the methods for preparing gel, one is forming crosslinking points by micro-crystallization and hydrogen bond to prepare gel, separately
One is form crosslinking points by coordinate bond to prepare gel.Crosslinking agent glutaraldehyde is added to prepare in gelatin by Liu Genqi et al. to coagulate
Glue.Liu Wei et al. is formed with 2- acrylamide-2-methyl propane sulfonic (AMPS) and diethylaminoethyl base ethyl ester (DEAEM)
Ion complex, novel ion is prepared for by free radicals copolymerization reaction and is crosslinked polyampholyte (ICPA), and is obtained
ICPA gel.The gelinite of both the above method preparation contains ionogen, destroys under electric field action three-dimensional netted
Structure shows as volume change i.e. electroresponse.And few people prepare gel by coordination mode using introducing ion salt, in this way
Obtained gelinite can show apparent phase transition under electric field action and quickly make electroresponse.
Under electric field action, directional migration occurs for the counter ion counterionsl gegenions in gelinite, and osmotic pressure and polyelectrolyte is caused to ionize
The variation of state leads to the change of reticular structure inside gelinite, can pass through the variation pair of the properties such as own vol, phase or mechanics
Electrical field stimulation makes sensitive response.By the exploration to such gel material, a kind of intelligence with sensitive electroresponse is prepared
Energy gelinite has huge researching value in the intelligent gels body field such as micromechanics and sensor.
Summary of the invention
It is an object of that present invention to provide a kind of preparation method of intelligent gel body with sensitive electroresponse, and technique mistake
Journey is simple, easily prepared.
It is as follows using technical solution in order to achieve the above objectives:
Intelligent gel body with electroresponse, it is evenly dispersed in nylon colloidal sol to have metal salt M+X-, stand after ultrasonic treatment
Obtain the intelligent gel body with electroresponse；Wherein, M+For Li+、K+、Ca2+、Zn2+、Mg2+、Ga3+In any one；X-For Cl-、
Br-、I-、SCN-In any one.
The preparation method of intelligent gel body with electroresponse, comprising the following steps:
1) by metal salt M+X-It is stirred with ethylene chlorhydrin sealing, obtains nylon colloidal sol after nylon dissolution is added；Wherein, M+For Li+、K+、Ca2+、Zn2+、Mg2+、Ga3+In any one；X-For Cl-、Br-、I-、SCN-In any one；
2) by the nylon colloidal sol heated sealed, ultrasonic treatment, nylon gel body is can be obtained in sealing and standing at room temperature.
It according to the above scheme, further include metal salt M+X-With the pretreatment of nylon；By metal salt M+X-It is ground into a powder and vacuum adds
Heated drying；By nylon vacuum heat drying.
According to the above scheme, the nylon is nylon 6, nylon66 fiber, nylon 7, nylon 9, nylon 11, nylon 12, nylon 13, Buddhist nun
One of dragon 610, nylon 612, nylon 1010.
According to the above scheme, each component is as follows by mass percentage in step 1:
Metal salt M+X-, 0.83~3.2wt%；Ethylene chlorhydrin, 64.8~90.1wt%, nylon, 8.9~32.7wt%.
According to the above scheme, it is 40~60 DEG C that step 2, which is heated to temperature,.
According to the above scheme, step 2 sonification power is 300~600W, and the time is 3~4h.
According to the above scheme, 8~12h of sealing and standing obtains gelinite to step 2 at room temperature.
It according to the above scheme, further include reheating gained nylon gel body, ultrasonic treatment realizes that gel turns to colloidal sol
Become；Sealing and standing realizes the transformation of colloidal sol to gel at room temperature again；The sonification power is 300~600W, time 3
~4h.
In nylon molecules chain between amide group hydrogen bond easy to form and make nylon crystallinity increase, due to metal ion
M+It is easy to form coordinate bond with amide group, destroys hydrogen bond structure, therefore metal salt M+X-Addition can effectively reduce nylon
Crystallinity.A kind of poor solvent of the ethylene chlorhydrin as nylon can play the role of swelling to it, effectively increase and gold
Belong to ion M+Contact area, metal ions M can be promoted in the case where heating ultrasonication+Movement so that metal ions M+Dispersion
Uniformly, to improve the probability of ligand complex, so that metal ions M+It is more easily formed with amide group ligand complex more
Ligand structure forms cross-linked structure in whole system, to form a kind of physical gel.
Under electric field action, it is fixed that the counter ion counterionsl gegenions of the charged group in gelinite occur nylon gel body prepared by the present invention
To migration, cause the variation of osmotic pressure and polyelectrolyte ionized state, leads to the change of reticular structure inside gelinite, can pass through
Sensitive response is made in the variation of the properties such as own vol, phase or mechanics to electrical field stimulation.The present invention passes through to this kind of gelinite
The intelligent gel body for the electroresponse that the exploration of material obtains, can be realized quick response under the application and regulation of electric field, in microcomputer
The intelligent gels body field such as tool and sensor has huge researching value.
Compared with prior art, the present invention having the advantage that
The present invention has obtained a kind of novel dissolvent (i.e. M for dissolving nylon+X-With the mixed solution of ethylene chlorhydrin), metal salt M+X-Addition effectively promote the dissolution of nylon, and can be realized the control to nylon crystallinity, nylon state of aggregation controls skill
Art is more perfect.
The present invention has chosen a variety of nylon materials, is dissolved in M+X-In the mixed solution of ethylene chlorhydrin, by heating stirring
Recyclable nylon gel body is obtained after ultrasound, the object that the technology of extending uses has nylon material relatively strong
Universality.
The nylon gel body that the present invention obtains shows sensitive electrical response characteristics under electric field action, and it is solidifying to have widened nylon
The application range of colloid.
Specific embodiment
Technical solution in order to enable those skilled in the art to better understand the present invention is below made the present invention further detailed
Description.But the contents of the present invention are not limited solely to the following examples.
Embodiment 1
A kind of novel nylon gelinite, is prepared via a method which to obtain:
(1) 0.3g metal salt CaCl is weighed first2, it is ground into a powder in mortar；3g nylon 6 is weighed, by treated
CaCl2With nylon 6, in a vacuum drying oven in 100 DEG C of dry 12h.
(2) 10mL ethylene chlorhydrin is measured, by CaCl dry in step (1)2Dissolution wherein, and is sealed and is stirred evenly
Obtain mixed solution.
(3) nylon 6 dry in step (1) is dissolved in the mixed solution in step (2), and heated sealed is to 40
DEG C, solution is transferred in homemade mold (4cm × 4cm × 1.5cm), room by the ultrasound 3h in the ultrasonic device that power is 600W
6 gelinite of nylon can be obtained in warm sealing and standing 8h.
(4) gel seal obtained in step (3) is heated to 40 DEG C, the ultrasound in the ultrasonic device that power is 600W
3h, it can be achieved that gel-sol transformation, by colloidal sol, gelinite is can be obtained in sealing and standing 8h at room temperature.
Embodiment 2
A kind of novel nylon gelinite, is prepared via a method which to obtain:
(1) 0.4g metal salt LiBr is weighed first, is ground into a powder in mortar；5g nylon66 fiber is weighed, by treated
LiBr and nylon66 fiber, in a vacuum drying oven in 100 DEG C of dry 12h.
(2) 20mL ethylene chlorhydrin is measured, wherein by LiBr dissolution dry in step (1), and seals and stirs evenly
To mixed solution.
(3) nylon66 fiber dry in step (1) is dissolved in the mixed solution in step (2), and heated sealed is to 50
DEG C, solution is transferred in homemade mold (4cm × 4cm × 1.5cm) by the ultrasound 3.5h in the ultrasonic device that power is 500W,
Room-temperature seal stands 10h, and nylon66 fiber gelinite can be obtained.
(4) gel seal obtained in step (3) is heated to 50 DEG C, the ultrasound in the ultrasonic device that power is 500W
3.5h, it can be achieved that gel-sol transformation, by colloidal sol, gelinite is can be obtained in sealing and standing 10h at room temperature.
Embodiment 3
A kind of novel nylon gelinite, is prepared via a method which to obtain:
(1) 0.5g metal salt MgCl is weighed first2, it is ground into a powder in mortar；6g nylon 9 is weighed, by treated
MgCl2With nylon 9, in a vacuum drying oven in 100 DEG C of dry 12h.
(2) 25mL ethylene chlorhydrin is measured, by MgCl dry in step (1)2Dissolution wherein, and is sealed and is stirred evenly
Obtain mixed solution.
(3) nylon 9 dry in step (1) is dissolved in the mixed solution in step (2), and heated sealed is to 60
DEG C, solution is transferred in homemade mold (4cm × 4cm × 1.5cm), room by the ultrasound 4h in the ultrasonic device that power is 300W
Warm sealing and standing 12h, can be obtained nylon gel body.
(4) gel seal obtained in step (3) is heated to 60 DEG C, the ultrasound in the ultrasonic device that power is 300W
4h, it can be achieved that gel-sol transformation, by colloidal sol, gelinite is can be obtained in sealing and standing 12h at room temperature.
Embodiment 4
A kind of novel nylon gelinite, is prepared via a method which to obtain:
(1) 0.3g metal salt GaCl is weighed first3, it is ground into a powder in mortar；6g nylon 612 is weighed, by treated
GaCl3With nylon 612, in a vacuum drying oven in 100 DEG C of dry 12h.
(2) 25mL ethylene chlorhydrin is measured, by GaCl dry in step (1)3Dissolution wherein, and is sealed and is stirred evenly
Obtain mixed solution.
(3) nylon 612 dry in step (1) is dissolved in the mixed solution in step (2), and heated sealed is to 40
DEG C, solution is transferred in homemade mold (4cm × 4cm × 1.5cm), room by the ultrasound 4h in the ultrasonic device that power is 400W
Warm sealing and standing 11h, can be obtained nylon gel body.
(4) gel seal obtained in step (3) is heated to 40 DEG C, the ultrasound in the ultrasonic device that power is 400W
4h, it can be achieved that gel-sol transformation, by colloidal sol, gelinite is can be obtained in sealing and standing 11h at room temperature.
Embodiment 5
A kind of novel nylon gelinite, is prepared via a method which to obtain:
(1) 0.5g metal salt ZnI is weighed first2, it is ground into a powder in mortar；Weigh 4g nylon, it will treated ZnCl2
With nylon 1010, in a vacuum drying oven in 100 DEG C of dry 12h.
(2) 15mL ethylene chlorhydrin is measured, by ZnI dry in step (1)2Dissolution wherein, and is sealed and is stirred evenly
To mixed solution.
(3) nylon dry in step (1) is dissolved in the mixed solution in step (2), and heated sealed is to 60 DEG C,
The ultrasound 4h in the ultrasonic device that power is 300W, solution is transferred in homemade mold (4cm × 4cm × 1.5cm), room temperature is close
Envelope stands 12h, and nylon gel body can be obtained.
(4) gel seal obtained in step (3) is heated to 60 DEG C, the ultrasound in the ultrasonic device that power is 300W
4h, it can be achieved that gel-sol transformation, by colloidal sol, gelinite is can be obtained in sealing and standing 8h at room temperature.
Embodiment 6
A kind of novel nylon gelinite, is prepared via a method which to obtain:
(1) 0.5g metal salt KSCN is weighed first, is ground into a powder in mortar；4g nylon 610 is weighed, by treated
KSCN and nylon 610, in a vacuum drying oven in 100 DEG C of dry 12h.
(2) 25mL ethylene chlorhydrin is measured, wherein by KSCN dissolution dry in step (1), and seals and stirs evenly
To mixed solution.
(3) nylon dry in step (1) is dissolved in the mixed solution in step (2), and heated sealed is to 50 DEG C,
The ultrasound 4h in the ultrasonic device that power is 400W, solution is transferred in homemade mold (4cm × 4cm × 1.5cm), room temperature is close
Envelope stands 10h, and nylon gel body can be obtained.
(4) gel seal obtained in step (3) is heated to 50 DEG C, the ultrasound in the ultrasonic device that power is 400W
4h, it can be achieved that gel-sol transformation, by colloidal sol, gelinite is can be obtained in sealing and standing 10h at room temperature.
Claims (8)
1. a kind of preparation method of the intelligent gel body with electroresponse, it is characterised in that the following steps are included:
1) by metal salt M+X-It is stirred with ethylene chlorhydrin sealing, obtains nylon colloidal sol after nylon dissolution is added；
2) by the nylon colloidal sol heated sealed, ultrasonic treatment, nylon gel body is can be obtained in sealing and standing at room temperature；
Wherein, M+For Li+、K+、Ca2+、Zn2+、Mg2+、Ga3+In any one；X-For Cl-、Br-、I-、SCN-In any one.
2. the preparation method of the intelligent gel body with electroresponse as described in claim 1, it is characterised in that further include metal
Salt M+X-With the pretreatment of nylon；By metal salt M+X-It is ground into a powder simultaneously vacuum and heating drying；By nylon vacuum heat drying.
3. the preparation method of the intelligent gel body with electroresponse as described in claim 1, it is characterised in that the nylon is
Nylon 6, nylon66 fiber, nylon 7, nylon 9, nylon 11, nylon 12, nylon 13, nylon 610, nylon 612, one in nylon 1010
Kind.
4. the preparation method of the intelligent gel body with electroresponse as described in claim 1, it is characterised in that each group in step 1
Divide as follows by mass percentage:
Metal salt M+X-, 0.83~3.2wt%；Ethylene chlorhydrin, 64.8~90.1wt%, nylon, 8.9~32.7wt%.
5. the preparation method of the intelligent gel body with electroresponse as described in claim 1, it is characterised in that step 2 is heated to
Temperature is 40~60 DEG C.
6. the preparation method of the intelligent gel body with electroresponse as described in claim 1, it is characterised in that at step 2 ultrasound
Reason power is 300~600W, and the time is 3~4h.
7. the preparation method of the intelligent gel body with electroresponse as described in claim 1, it is characterised in that step 2 is at room temperature
8~12h of sealing and standing obtains gelinite.
8. the preparation method of the intelligent gel body with electroresponse as described in claim 1, it is characterised in that further include by institute
It obtains nylon gel body to reheat, be ultrasonically treated, realize the transformation of gel to colloidal sol；Sealing and standing realizes colloidal sol at room temperature again
To the transformation of gel；The sonification power is 300~600W, and the time is 3~4h.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102807761A (en) * | 2011-06-02 | 2012-12-05 | 张晓� | Gel and manufacturing process thereof |
| CN105601955A (en) * | 2016-02-03 | 2016-05-25 | 合肥工业大学 | Electric-stimulation fluorescence-response aquagel |
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| FR3000080B1 (en) * | 2012-12-20 | 2015-01-30 | Oreal | WATER INSOLUBLE CYCLODEXTRIN POLYCONDENSATE; USES AS CAPTURE AGENT |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102807761A (en) * | 2011-06-02 | 2012-12-05 | 张晓� | Gel and manufacturing process thereof |
| CN105601955A (en) * | 2016-02-03 | 2016-05-25 | 合肥工业大学 | Electric-stimulation fluorescence-response aquagel |
Non-Patent Citations (1)
| Title |
|---|
| 智能聚合物凝胶的研究进展;马前;《广东化工》;20151231;第42卷(第302期);71-72 |
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