CN109898322A - A kind of sulfonation non-woven cloth and preparation method - Google Patents
A kind of sulfonation non-woven cloth and preparation method Download PDFInfo
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- CN109898322A CN109898322A CN201910200952.0A CN201910200952A CN109898322A CN 109898322 A CN109898322 A CN 109898322A CN 201910200952 A CN201910200952 A CN 201910200952A CN 109898322 A CN109898322 A CN 109898322A
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Abstract
The invention discloses a kind of sulfonation non-woven cloths, it is characterised in that: the polymer-based material fiber that the non-woven cloth contains phenyl ring by main chain and/or side chain is made, fiber surface grafting sulfonic groups group (- SO3H), fiber surface sulfonation depth is 10 nanometers to 2000 nanometers.Ion exchange capacity is up to 0.2-1.8mmol/g, and surface ion exchange capacity is up to 5.1mmol/g.The sulfonation non-woven fabric material mechanical property keeps good, and high temperature resistant, solvent resistant can be used for or substitute various acid catalyzed reaction processes.The present invention also provides a kind of non-woven cloth method of sulfonating, and this method is easy to operate, rapid reaction, environmentally protective, with good economic efficiency.
Description
Technical field
The present invention relates to polymer matrix non-woven cloth catalysis material field, in particular to a kind of sulfonation non-woven cloth and
The method of its sulfonation modifying.
Background technique
Non-woven cloth because it is with pore structure abundant, excellent mechanical strength, be widely used in national defence, national economy and
Daily life etc..Non-woven cloth can further improve the service performance and application field of non-woven cloth by being modified.It is non-to knit
Making cloth sulfonation modifying is a kind of important modified method, is made on non-woven cloth fiber molecule chain by sulfonating reaction containing hydrophilic
Property sulfonic acid group can be used for various acid catalyzed reaction processes so that material be made to obtain hydrophily and ion-exchange capacity.
In the prior art, preparation sulfonation non-woven cloth is usually first that polymer raw materials are sulfonated, then utilizes sulphur
The material of acidification prepares sulfonation non-woven cloth.The fiber surface of the sulfonation non-woven cloth obtained in this way is identical with inner materials, all
Contain sulphonated polymers.But the sulphonated polymers of non-woven cloth fibrous inside can not be abundant because of fibre structure densification
It participates in acid catalyzed reaction or ion exchange and is wasted, simultaneously because sulfonic acid group is modified, sulfonated polymer usually easy quilt
Water or alcohols solvent swelling, thus reduce the mechanical property of non-woven cloth.
In addition, it is all aqueous chemical that the usually used sulfonated reagent of sulfonating reaction, which has the concentrated sulfuric acid, oleum, chlorosulfonic acid etc.,
Reagent.Liquid-liquid sulfonation is carried out using liquid sulfonated reagent and polymer solution, all suffers from liquid sulfonated reagent and reaction product
The problem of separation, it is subsequent industry in need to increase acid-base neutralization and washing and etc., necessarily lead to the processing problem of spent acid waste water；
And chlorosulfonic acid can generate a large amount of hydrogen chloride gas, seriously pollute environment when making sulfonated reagent in reaction process.Therefore, seek
A kind of efficient, economic and environment-friendly " green " sulfonation method is extremely urgent.
In view of the problems of the existing technology, the present invention provides a kind of sulfonation non-woven cloth, pass through the side of solid phase sulfonation
Method carries out sulfonating reaction to non-woven cloth fiber surface and is made.Resulting non-woven cloth can perform well in acid catalyzed reaction or from
Son exchange.
Summary of the invention
The present invention provides a kind of sulfonation non-woven cloth, have the mechanical property similar with the basis material of its unsulfonated,
Chemical stability and hot property can be used for high-temperature catalytic and the existing catalysis reaction of organic solvent, and very big due to having
Ion exchange capacity and can be used for ion exchange.
The technical solution adopted by the present invention is that:
A kind of sulfonation non-woven cloth, it is characterised in that: the non-woven cloth is contained the polymerization of phenyl ring by main chain and/or side chain
Object sill fiber is made, fiber surface grafting sulfonic groups group (- SO3H), fiber surface sulfonation depth is received for 10 nanometers to 2000
Rice.
The polymer-based material that the main chain and/or side chain contain phenyl ring preferably has the characteristics such as high temperature resistant, solvent resistant
Polymer material, preferably polyphenylene sulfide, poly- aramid fiber, polyarylether, polyimides and other aromatic polymers.
The sulfonation non-woven cloth fiber surface is porous structure, and fiber surface bore dia is 10 nanometers -5 microns.
The ion exchange capacity of the sulfonation non-woven cloth is big, and IEC value is 0.2-1.8mmol/g；Good hydrophilic property, moment
Contact angle can reach 0 degree.
Obtained sulfonation non-woven cloth still retains the basic structural feature of raw material non-woven cloth.
The invention further relates to a kind of methods of non-woven cloth sulfonation, comprising the following steps:
1) it is non-woven cloth in 1%-100% sulfonation agent solution that the non-woven cloth of certain mass, which, is added to mass concentration,
It is 0.5-4 with sulfonating agent mass ratio, reaction temperature is 10 DEG C -50 DEG C, the reaction time 1 minute to 2 hours.
2) a period of time, after reaction, is dried, non-woven cloth is then washed with water to neutrality, and is dried gained
Product obtains sulfonation non-woven cloth.
Reaction in step 1), which uses, continuously or intermittently to be carried out.
Resulting sulfonation non-woven cloth can be dried with any conventional drying methods well known by persons skilled in the art, example
Such as it is dried in vacuo at 0.08~0.09MPa, drying temperature is 55 DEG C -75 DEG C of temperature, such as 60 DEG C, drying time 18-
30h, such as 24 hours.
The polymer-based material fiber that non-woven cloth used in it contains phenyl ring by main chain and/or side chain is made, fine
The pore structure of accumulation is tieed up having a size of 500 nanometers to 20 microns, fibre diameter is 20 microns to 200 microns；Tensile strength is 2 to 8
Megapascal.The polymer-based material preferably has a polymer material of the characteristics such as high temperature resistant, solvent resistant, preferably polyphenylene sulfide,
Poly- aramid fiber, polyarylether, polyimides and other aromatic polymers.
Sulfonating agent used is the compound with sulfonic acid group, preferably the concentrated sulfuric acid, oleum, sulfur trioxide, chlorine sulphur
Acid.
Obtained sulfonation non-woven cloth fiber surface is grafted upper sulfonic acid group (- SO3H), fiber surface sulfonation depth is
10 nanometers to 2000 nanometers.The ion exchange capacity IEC value of gained sulfonation non-woven cloth is 0.2-1.8mmol/g, hydrophily
It increases substantially, instantaneous touch angle can reach 0 degree.
Sulfonation non-woven cloth according to the present invention or the sulfonation non-woven cloth obtained by the method for the invention still retain non-
The pore structure characteristic of woven cloth material, and there is good mechanical property, chemical stability and hot property, it can be used for high temperature
Catalysis and the existing catalysis reaction of organic solvent, can be used for or substitute various acid catalyzed reaction processes.In addition, sulfonation of the invention
Non-woven cloth can be used for ion exchange because it has very big ion exchange capacity.
Method of the invention passes through control sulfonating reaction condition, such as sulfonating agent concentration, sulfonation time, sulfonation temperature, from
And it is real
The control to non-woven cloth fiber surface sulfonation degree and sulfonation depth is showed, i.e., only to non-woven cloth fiber table
Face sulfonation largely remains the mechanics of original non-woven cloth without carrying out sulfonation to non-woven cloth fibrous inside in this way
Performance and chemical property；Simultaneously as infiltration and swelling action of the sulfonating agent to non-woven cloth fiber surface, in sulfonation process
Non-woven cloth fiber surface forms a large amount of holes, so that the sulfonic acid group for being conducive to fiber surface is sufficiently exposed to solution medium
In, and play maximum utility.
Acid catalyst used in the alternative existing acid catalyzed reaction system of sulfonation non-woven cloth of the invention, such as liquid acid and
Granular solids acid.Compared with liquid acid catalyst, sulfonation non-woven cloth of the invention is easy to separate with reaction system, reduces
Aftertreatment technology reduces discharging of waste liquid, is conducive to protect environment；Its Yi Huishou simultaneously, it is reusable, advantageously reduce work
Skill cost.And convenient for recycling compared with granular solids acid, simultaneously because pore structure abundant, advantageously reduces resistance to mass tranfer
With raising catalytic efficiency.
Attached drawing is described in detail
The XPS spectrum figure of S element in Fig. 1 raw material non-woven cloth of the present invention.
The XPS spectrum figure of S element in Fig. 2 sulfonation non-woven cloth of the present invention.
Specific embodiment
It is further discussed below the present invention with reference to embodiments, but does not limit the present invention in any way.
Material therefor and reagent in the embodiment of the present invention, can market be commercially available.
Embodiment 1:
Poly- aramid nonwoven cloth is cut into 1cm × 1cm size, 2g non-woven cloth is weighed and is added in 8g oleum and carry out
Sulfonating reaction, wherein oleum and non-woven cloth mass ratio are 4, and reaction temperature is 10 DEG C, reaction 1 hour, after reaction,
A period of time is dried, non-woven fabrics is then washed with water to neutrality, is finally dried in vacuo using vacuum oven.Vacuum drying
When vacuum degree be 0.08~0.09MPa, drying temperature be 60 DEG C, drying time be for 24 hours.Obtained sulfonation non-woven cloth ion
Exchange capacity is 1.8mmol/g, and measuring its porosity by mercury injection apparatus is 30%, and universal testing machine measures its tensile strength and is
2MPa, it is 0 degree that contact angle measurement, which measures its moment water contact angle,.
Embodiment 2:
Polyphenylene sulfide non-woven cloth is cut into 1cm × 1cm size, weigh 2g non-woven cloth be added to concentration be 9% three
Sulfonating reaction is carried out in sulfur oxide solution, wherein non-woven cloth and sulfur trioxide mass ratio are 0.5, and reaction temperature is 50 DEG C, instead
Answer 1 minute, after reaction, dry a period of time, non-woven fabrics is then washed with water to neutrality, finally using vacuum oven into
Row vacuum drying.Vacuum degree when vacuum drying is 0.08~0.09MPa, and drying temperature is 60 DEG C, and drying time is for 24 hours.?
The sulfonation non-woven cloth ion exchange capacity arrived is 0.5mmol/g, and measuring its porosity by mercury injection apparatus is 75%, universal test
It is 8MPa that machine, which measures its tensile strength, and it is 0 degree that contact angle measurement, which measures its moment water contact angle,.
Embodiment 3: the IEC value of measurement sulfonation non-woven cloth ion-exchange capacity
It weighs the dried sulfonation non-woven cloth of 1g to be placed in 100mL beaker, 20mL is then added in beaker and is saturated chlorine
Change sodium solution, sulfonation non-woven cloth is made to be impregnated with the H so that in sulfonic acid group completely+With Na+It is sufficiently exchanged, is exchanged 24 hours
After take out non-woven cloth, acid is carried out to the solution containing H+ with phenolphthalein indicator and with the standard solution of sodium hydroxide of known concentration
Alkalimetric titration.IEC value is calculated according to the concentration and its consumption volume of standard solution of sodium hydroxide, calculation formula is as follows:
Wherein, IEC- ion exchange capacity, mmol/g or meq/g；
The concentration of C- standard solution of sodium hydroxide, mol/L；
The volume of the standard solution of sodium hydroxide of V- consumption, mL；
The quality of m- sulfonation non-woven cloth, g.
Embodiment 4: fiber surface ion exchange capacity value is calculated by XPS analysis
Dried non-woven cloth is cut into 1cm × 0.5cm size, conductive metal plate is fixed in using conducting resinl
On, then test analysis is carried out with K-alpha type x-ray photoelectron spectroscopy.
XPS test data is fitted and is analyzed using Thermo Avantage software, with polyphenylene sulfide non-woven cloth
It calculates step to surface IEC value for XPS test result to be illustrated, the structural formula of Sulfonated Polyphenylene Sulfide are as follows:
Analysis is fitted to the XPS test result of sulphur (S) element in Sulfonated Polyphenylene Sulfide non-woven cloth, finds script sulphur
S element in ether and the S element fitting peak area in sulfonic acid group are approximately 1: 1, and peak area ratio is molar ratio, then can recognize
To have a sulfonic acid group on a polyphenylene sulfide repetitive unit within the scope of film XPS institute test depth (generally less than 10nm),
Thus the ion exchange capacity on polyphenylene sulfide fibre surface, which can be calculated, is(wherein 196 is poly- for sulfonation
The molecular mass of one repetitive unit of diphenyl sulfide), it is 5.1mmol/g that polyphenylene sulfide nonwoven fabric surface IEC value, which can be obtained,.
Claims (10)
1. a kind of sulfonation non-woven cloth, it is characterised in that: the non-woven cloth is contained the polymer of phenyl ring by main chain and/or side chain
Sill fiber is made, fiber surface grafting sulfonic groups group (- SO3H), fiber surface sulfonation depth is received for 10 nanometers to 2000
Rice.
2. sulfonation non-woven cloth according to claim 1, wherein the main chain and/or side chain contain the polymer matrix of phenyl ring
Material is polyphenylene sulfide, poly- aramid fiber, polyarylether, polyimides and other aromatic polymers.
3. sulfonation non-woven cloth according to claim 1, wherein the sulfonation non-woven cloth fiber surface is porous structure,
Fiber surface bore dia is 10 nanometers -5 microns.
4. sulfonation non-woven cloth according to claim 1, wherein the ion exchange capacity IEC value of the sulfonation non-woven cloth
For 0.2-1.8mmol/g.
5. sulfonation non-woven cloth according to claim 1, wherein the instantaneous touch angle of the sulfonation non-woven cloth is 0 degree.
6. a kind of method of non-woven cloth sulfonation, comprising the following steps:
1), by the non-woven cloth of certain mass be added to mass concentration be 1%-100% sulfonation agent solution in, non-woven cloth with
Sulfonating agent mass ratio is 0.5-4, and reaction temperature is 10 DEG C -50 DEG C, the reaction time 1 minute to 2 hours.
2) a period of time, after reaction, is dried, non-woven fabrics is then washed with water to neutrality, and be dried products therefrom, obtains
To sulfonation non-woven cloth.
7. according to the method described in claim 6, wherein the reaction use of step 1) continuously or intermittently carries out.
8. according to the method described in claim 6, non-woven cloth used in it is contained the polymerization of phenyl ring by main chain and/or side chain
Object sill fiber is made.
9. according to the method described in claim 6, wherein the sulfonating agent is the concentrated sulfuric acid, oleum, sulfur trioxide or chlorine sulphur
Acid.
10. according to preceding claims 1-5 is described in any item or the sulfonation of any one of preceding claims 6-9 preparation is non-woven
Cloth is used for various acid catalyzed reactions and the purposes for ion exchange.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112853741A (en) * | 2021-01-27 | 2021-05-28 | 东北大学 | Method for producing X-ray shielding material and X-ray shielding material |
| CN115702268A (en) * | 2020-05-11 | 2023-02-14 | Ddp特种电子材料美国有限责任公司 | Sulfonated polystyrene nonwovens |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115702268A (en) * | 2020-05-11 | 2023-02-14 | Ddp特种电子材料美国有限责任公司 | Sulfonated polystyrene nonwovens |
| CN112853741A (en) * | 2021-01-27 | 2021-05-28 | 东北大学 | Method for producing X-ray shielding material and X-ray shielding material |
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