A kind of dissolving method of p-aramid fiber and application thereof
Technical field
The invention belongs to aramid fiber dissolving technology field, the dissolving method of the p-aramid fiber that particularly a kind of preparation method is simple, gentle, effective, organic solvent range of choice is wide and application thereof.
Background technology
The chemical name of p-aramid fiber is poly terephthalic acid Ursol D (PPTA), and China is called aramid fiber-1414, and the product that commodity are called Kevlar is the development of du pont company's sixties in last century and in the high-performance p-aramid fiber of the seventies industrialization.PPTA due to its molecular chain height-oriented along its length, and there is extremely strong interchain force, thus give fiber unprecedented high strength, high-modulus and high-temperature stability, acid-fast alkali-proof, the premium properties such as lightweight.Feature outstanding in PPTA performance is high strength and high-modulus.The intensity of contraposition fiber is 3 times of hardness of steel, is 4 times of polyester industrial yarn.Its Young's modulus is 4 ~ 10 times of polyester industrial yarn, is more than 10 times of general tynex, is 4 ~ 5 times of trevira.And its thermostability is fine, at high temperature still can keep higher intensity, as experienced 100h at 200 DEG C, still can keep 75% of former intensity, still can keep 65% of former intensity at 260 DEG C, not decompose non-fusible under the high temperature of 560 DEG C.The performance of its excellence make its national defence, civilian in be widely used, prepare flak jackets and bulletproof armour etc. as being used as shellproof, protective material, rubber reinforcement material is used for the tire of light weight, and cord material is used for crane rope etc.
Therefore, the fundamental property grasp for p-aramid fiber has very important significance for production, application tool.Although Kevlar fiber has emerged fast half a century, due to the excellent properties of this material, every country and mainly manufacturer are still in confidential state for the information of p-aramid fiber, and we only have limited understanding to it.Therefore the discussion for its various aspects of performance seems necessary.
Effective dissolving of p-aramid fiber is the key effectively utilized it.What bring into use at first for p-aramid fiber is also that the processing mode the most often used is now dissolved in the vitriol oil to carry out processing treatment again, carries out fiber spinning from crystalline state prepare Kevlar fiber as it is dissolved in the vitriol oil.But the vitriol oil concentration requirement used in the method is high, and easy etching apparatus, and operational hazards, be unfavorable for suitability for industrialized production.The human hair such as Takayanagi understood a kind of method of dissolving p-aramid fiber newly afterwards, formed homogeneous polyanion solution with DMSO and highly basic as dissolution with solvents PPTA.Employ highly basic in this method and organic solvent is only limitted to DMSO, still have certain limitation for the application expanding PPTA.
Summary of the invention
In order to the shortcoming overcoming above-mentioned prior art is with not enough, primary and foremost purpose of the present invention be to provide a kind of preparation method simple, gentle, effectively, the dissolving method of p-aramid fiber that organic solvent range of choice is wide.
Another object of the present invention is to provide the dissolving method of above-mentioned p-aramid fiber dissolving the application in aramid fiber.
Object of the present invention is realized by following proposal:
A dissolving method for the p-aramid fiber that preparation method is simple, gentle, effective, organic solvent range of choice is wide, comprises the following steps:
Added by p-aramid fiber in the mixing solutions of protonic acid and organic solvent, heated and stirred is even, supersound process, and room temperature leaves standstill to solution transparent, filters, obtains p-aramid fiber solution.
Described protonic acid has H
+the structure of-M-R, wherein M is acid group, and R is carbon long-chain.
Preferably, described M is-SO
3,-COO
-, PO
4 3-in one; Described R is-C
10f
17, HOOCC
8f
17-,-C
8f
17,-C
6h
13,-C
8h
17,-C
17h
33,-C
17h
35,-C
17h
31,-C
11h
23,-ArC
12h
25in one.
Wherein, described-C
17h
33for oleic acid long-chain ,-C
17h
35for stearic acid long-chain ,-C
17h
31for linolic acid long-chain ,-C
11h
23for lauryl.
Described lauryl structural formula is as follows:
Described organic solvent is conventional organic solvent, is preferably the one in dimethyl sulfoxide (DMSO) (DMSO), dimethylbenzene, methyl chloride, meta-cresol, formic acid, toluene, perhydronaphthalene, chloroform and chlorobenzene.
More preferably, the R long-chain moiety in organic solvent used and protonic acid has good consistency.
The mass ratio of p-aramid fiber used and protonic acid is 1:1 ~ 1:3.
The mass ratio of protonic acid used and organic solvent is 1:10 ~ 1:20.
The temperature of described heating is 50 ~ 80 DEG C.
Described supersound process refers to process 36 ~ 72h under ultrasonic power is 120 ~ 200W.
Described p-aramid fiber is preferably pulp shape product.
The dissolving method of above-mentioned p-aramid fiber is dissolving the application in aramid fiber.
Mechanism of the present invention is:
P-aramid fiber is a kind of polymeric amide, and-the NH on amido linkage can by the protonated formation of acid-NH
2+, adopt the protonic acid H containing long-chain in the present invention
+-M-R and p-aramid fiber react,-NH on the protonated aramid fiber molecular chain of protonic acid, simultaneously-M-R as gegenion because electrostatic interaction is adsorbed on aramid fiber chain type, gegenion-M-R induces protonated p-aramid fiber molecular melting in organic solvent, and here protonic acid is equivalent to the effect of tensio-active agent.The organic solvent used in the present invention simultaneously can according to protonic acid H
+-R in-M-R regulates, and can disperse p-aramid fiber preferably with the good organic solvent of-R consistency.
The present invention, relative to prior art, has following advantage and beneficial effect:
(1) preparation method's mild condition of the present invention, the H in protonic acid
+n on p-aramid fiber molecular chain is combined, and gegenion-M-R induces protonated p-aramid fiber molecular melting in organic solvent, and here protonic acid is equivalent to the effect of tensio-active agent; Avoid the strong acid and strong base used in traditional p-aramid fiber dissolving method.The p-aramid fiber solution that concentration is 2 ~ 8wt% can be obtained.
(2) pass through for H in the present invention
+in-M-R-adjustment of R group makes aramid fiber can have good consistency with a lot of organic solvent, solves the problem that traditional method cannot be disperseed and apply in these organic solvents, expand p-aramid fiber dissolve after range of application.
(3) the present invention has the features such as preparation method is simple, easy to control, easy realization.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
Weigh 0.1g PPTA-pulp (purchase of Dupont company), getting 0.1g Witco 1298 Soft Acid is dissolved in the DMSO of 2g, putting into after aramid pulp stirs evenly, be heated to 50 DEG C, ultrasonic 48h, static to transparent at 20 DEG C, cross and filter a small amount of undissolved p-aramid fiber of lower floor, obtain the p-aramid fiber solution that massfraction is 5%.
Embodiment 2
Weigh 0.15g PPTA-pulp, the camphorsulfonic acid getting 0.3g is dissolved in the meta-cresol of 4g, putting into after aramid pulp stirs evenly, be heated to 60 DEG C, ultrasonic 36h, static to transparent at 25 DEG C, filtering lower floor does not dissolve p-aramid fiber on a small quantity excessively, obtains the p-aramid fiber solution that massfraction is 3.75%.
Embodiment 3
Weigh 0.2g PPTA-pulp, get the C of 0.25g
8h
17cOOH is dissolved in 2g toluene, putting into after aramid pulp stirs evenly, is heated to 60 DEG C, ultrasonic 64h, static to transparent at 35 DEG C, crosses to filter lower floor and do not dissolve p-aramid fiber on a small quantity, obtains the p-aramid fiber solution that massfraction is 8%.
Embodiment 4
Weigh 0.1g PPTA-pulp, get the C of 0.3g
8f
17sO
3 -+h is dissolved in 4g methyl chloride, putting into after aramid pulp stirs evenly, is heated to 80 DEG C, ultrasonic 72h, static to transparent at 25 DEG C, crosses to filter lower floor and do not dissolve p-aramid fiber on a small quantity, obtains the p-aramid fiber solution that massfraction is 2.5%.
Embodiment 5
Weigh 0.1g PPTA-pulp, get the C of 0.25g
8h
17sO
3 -+h is dissolved in 5g chloroform, putting into after aramid pulp stirs evenly, is heated to 70 DEG C, ultrasonic 56h, static to transparent at 30 DEG C, crosses to filter lower floor and do not dissolve p-aramid fiber on a small quantity, obtains the p-aramid fiber solution that massfraction is 2%.
Embodiment 6
Weigh 0.08g PPTA-pulp, get the C of 0.18g
8f
17cOOH is dissolved in 3g dimethylbenzene, putting into after aramid pulp stirs evenly, is heated to 60 DEG C, ultrasonic 60h, static to transparent at 28 DEG C, crosses to filter lower floor and do not dissolve p-aramid fiber on a small quantity, obtains the p-aramid fiber solution that massfraction is 2.6%.
Embodiment 7
Weigh 0.1g PPTA-pulp, get the C of 0.2g
6h
13sO
3 -+h is dissolved in the dimethylbenzene of 4g, putting into after aramid pulp stirs evenly, is heated to 80 DEG C, ultrasonic 50h, static to transparent at 25 DEG C, crosses to filter lower floor and do not dissolve p-aramid fiber on a small quantity, obtains the p-aramid fiber solution that massfraction is 2.5%.
Embodiment 8
Weigh 0.1g PPTA-pulp, get the C of 0.18g
8h
17cOOH is dissolved in 2.5g perhydronaphthalene, putting into after aramid pulp stirs evenly, is heated to 60 DEG C, ultrasonic 48h, static to transparent at 25 DEG C, crosses to filter lower floor and do not dissolve p-aramid fiber on a small quantity, obtains the p-aramid fiber solution that massfraction is 4%.
By compared with strong acid and strong base dissolution process PPTA, in embodiment 1 ~ 8, the dissolving of p-aramid fiber has the advantage of preparation condition gentleness, has more solvent washability simultaneously, has widened the application of p-aramid fiber.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.