CN107641967A - A kind of compound PU fibers of graphene and preparation method - Google Patents
A kind of compound PU fibers of graphene and preparation method Download PDFInfo
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- CN107641967A CN107641967A CN201710781112.9A CN201710781112A CN107641967A CN 107641967 A CN107641967 A CN 107641967A CN 201710781112 A CN201710781112 A CN 201710781112A CN 107641967 A CN107641967 A CN 107641967A
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Abstract
The invention belongs to composite fibre preparation field, and in particular to a kind of compound PU fibers of graphene and preparation method, include each material of following parts by weight：30 50 parts of graphene, 10 20 parts of fluororesin, 5 15 parts of linear phenolic resin, 5 15 parts of surfactant, 30 50 parts of solvent.Its PU fiber being prepared not only has heat resistance, chlorine resistance, does not influence the PU fibers elasticity of itself also.
Description
Technical field
The invention belongs to composite fibre preparation field, and in particular to a kind of compound PU fibers of graphene and preparation method.
Background technology
Spandex fibre refers to the synthetic fibers made of polyurethane fiber and elastic yarn, than prior art nylon or wash
Synthetic fibre fiber, belong to high added value fiber.Spandex fibre is widely used in female because having the characteristics that easily stretching, in light weight, good toughness
The property gym suit such as underwear or swimming suit or silk stocking, the making of child's paper diaper.Therefore, spandex fibre is not only by international fiber system
The concern of company is made, moreover, domestic many synthetic fibers manufacturers also show keen interest to this.
With the continuous progress of society, people propose new requirement, such as anti-snag to the aesthetics and comfortableness of textile
Silk, spin crimping, frivolous, soft etc..The use of spandex makes fabric turn into composite, is the key factor of fabric quality lifting,
The new features of spandex will assign fabric new function.
However, the big shortcoming of spandex fibre is low heat resistance and chlorine resistance, and related technical problem is estimated will be into
To be elastic yarn and elastomer market if the problem can be solved therefore for the big obstacle for elastomer market development of being obstructed
Development make great contribution.
Be improved in the prior art for the heat resistance of fiber, as Chinese patent CN106592008A disclose it is a kind of heat-resisting
The preparation method of spandex fibre, the spinning solution of production meta-aramid fibers is added in the spinning solution of production spandex, including
The preparation of spandex fiber stoste, the preparation of meta-aramid spinning solution, spandex fibre spinning solution and meta-aramid spinning solution
Four mixing, dry spinning steps.A kind of and for example preparation methods of heat resistant spandex fiber of Chinese patent CN102220653A, belong to
High molecule spinning material and its preparing technical field, comprise the following steps：（1）PolyTHF and 4,4' methylene bis is (different
Phenyl-cyanate) mixed according to mol ratio 1/1.4~1/2.5, react to obtain prepolymer；（2）Added in the prepolymer prepared to step 1
Aprotic polar solvent so that prepolymer dissolves in aprotic polar solvent, obtains pre-polymer solution；（3）To step 2
Chain extender is added in the pre-polymer solution of acquisition, polymerisation obtains the spandex spinning fluid of molecular weight 20,000~300,000；Described chain extension
Agent is aromatic diamine, or the mixture of aromatic diamine and aliphatic diamine；（4）Spandex spinning fluid prepared by step 3,
Heat resistant spandex fiber is made using the method for solution-polymerized SBR.
Above-mentioned technical proposal or heat resistant spandex fiber is made using blending, or it is real using spandex molecular chain length is improved
The heat resistance of spandex is now improved, it is more strict to parameters control in course of reaction.
The content of the invention
The present invention provides a kind of composite master batch, PU（Polyurethane）Fiber and preparation method, its PU fiber being prepared（
It can be described as spandex）Not only there is heat resistance, chlorine resistance, do not influence the PU fibers elasticity of itself also.
To realize above-mentioned technical purpose, the concrete technical scheme that the present invention takes is a kind of composite master batch, including following weight
Measure each material of part：
Graphene 30-50 parts
Fluororesin 10-20 parts
Linear phenolic resin 5-15 parts
Surfactant 5-15 parts
Solvent 30-50 parts.
As the improved technical scheme of the present invention, fluororesin is ethylene-tetrafluoroethylene copolymer, ethylene-chlorinated
Copolymer or polyvinyl fluoride.
As the improved technical scheme of the present invention, surfactant is silane coupler, titanate coupling agent or single stearic
Acid glyceride.
As the improved technical scheme of the present invention, solvent is water, ethanol, methanol, propyl alcohol, acetone, ethylene glycol or acetic acid.
Another object of the present invention is to provide a kind of preparation method of composite master batch, comprise the following steps：Step 1: will
Graphene dispersion obtains graphene suspension in solvent；
Step 2: surfactant-dispersed is dissolved in graphene suspension, solution A is obtained；
Step 3: sequentially add linear phenolic resin and fluororesin into solution A, after stirring, stand, dry solidification into
Grain, produces composite master batch.
The present invention also provides a kind of graphene compound PU fibers, includes each material of following parts by weight,
Composite master batch 10-35 parts
PU 70-90 parts
Solvent 30-50 parts,
Wherein solvent is alcohol, preferably methanol, ethanol or propyl alcohol.
As the improved technical scheme of the present invention, in addition to zwitterionic surfactant, zwitterionic surfactant
Parts by weight be 5-10 parts.
Another object of the present invention is to provide a kind of preparation method of the compound PU fibers of graphene, comprise the following steps,
Step 1: disperseing zwitterionic surfactant using solvent, finely dispersed solution is obtained；
Step 2: adding composite master batch in the solution obtained to step 1, and it is uniformly dispersed, is mixed under conditions of stirring
Solution；
Step 3: heating melting PU, and the PU of melting is molded into silk using injection machine；
Step 4: in the case where the temperature range for ensureing PU is 90-130 DEG C, PU silks are at the uniform velocity obtained through step 2 mixed
Close in solution, obtain PU silks；
Step 5, the PU silks of melt modification are heated, and the compound PU fibers of graphene are prepared in the form of electrostatic spinning.
Beneficial effect
The present invention is melted through in composite master batch solution using obtained composite master batch such as fluororesin, linear phenolic resins, then by PU,
Because the toughness of the PU fibers of melting is optimal, also possess certain viscosity between fiber, PU silks is molten through composite master batch
When in liquid, the surface of PU silks can adhere to one layer of composite master batch, in PU remelting spinning, composite master batch it is each dispersed into branch
In PU fibers, and it is embedded between the compound PU filaments of graphene.So that the compound PU fibers of graphene prepared not only possess
PU good toughness in itself, is also equipped with good heat resistance and chlorine resistance.
Because phenolic resin selects linear structure, ensure that phenolic resin can be along the length direction of PU fibers to a certain extent
Lay, for avoiding the fusing of PU fibers and improving the resistance to chloride of PU fibers.
Fluororesin is preferably ethylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoro-ethylene copolymer or polyvinyl fluoride, molten
When melting, the soft segment of fluororesin energy part and PU fibers reacts, and improves the high-temperature stability and chlorine resistance of PU fibers.
To sum up, the PU fibers that prepared by the application have good toughness, heat-resisting quantity and chlorine resistance, and nontoxic, can be wide
It is general to be applied to all trades and professions.
Embodiment
To make the purpose of the embodiment of the present invention and technical scheme clearer, below in conjunction with the embodiment of the present invention, to this
The technical scheme of invention is clearly and completely described.Obviously, described embodiment is the part of the embodiment of the present invention,
Rather than whole embodiment.Based on described embodiments of the invention, those of ordinary skill in the art are without creative
The every other embodiment obtained on the premise of work, belongs to the scope of protection of the invention.
Those skilled in the art of the present technique are appreciated that unless otherwise defined, all terms used herein（Including technology art
Language and scientific terminology）With the general understanding identical meaning with the those of ordinary skill in art of the present invention.Should also
Understand, those terms defined in such as general dictionary, which should be understood that, to be had and the meaning in the context of prior art
The consistent meaning of justice, and unless defined as here, will not be with idealizing or the implication of overly formal be explained.
A kind of preparation method of the compound PU fibers of graphene, comprises the following steps,
Step 1: disperseing zwitterionic surfactant using solvent, finely dispersed solution is obtained；Here amphion table
Face activating agent elects amino acid type amphoteric surfactant, dodecyl dimethyl hydroxypropyl sulfobetaines or dodecyl second as
Epoxide sulfobetaines；
Step 2: adding composite master batch in the solution obtained to step 1, and it is uniformly dispersed, is mixed under conditions of stirring
Solution；
Step 3: heating melting PU, and the PU of melting is molded into silk using injection machine, heating-up temperature is preferably 150-200 DEG C,
Ensure that PU hard sections melt with soft segment；
Step 4: in the case where the temperature range for ensureing PU is 90-130 DEG C（Ensure that PU soft segments are in molten condition）, by PU
In the mixed solution that silk at the uniform velocity obtains through step 2, PU silks are obtained；
Step 5, the PU silks of melt modification are heated, and the compound PU fibers of graphene are prepared in the form of electrostatic spinning.
Embodiment 1
A kind of compound PU fibers of graphene, include each material of following parts by weight,
10 parts of composite master batch
90 parts of PU
30 parts of acetone
10 parts of zwitterionic surfactant.
Wherein, a kind of composite master batch, each material of following parts by weight is included：
30 parts of graphene
20 parts of ethylene-tetrafluoroethylene copolymer
5 parts of linear phenolic resin
15 parts of silane coupler
30 parts of water.
A kind of preparation method of composite master batch, comprises the following steps：
Step 1: dispersing graphene in solvent, graphene suspension is obtained；
Step 2: surfactant-dispersed is dissolved in graphene suspension, solution A is obtained；
Step 3: sequentially add linear phenolic resin and fluororesin into solution A, after stirring, stand, dry solidification into
Grain, produces composite master batch.
Embodiment 2
A kind of compound PU fibers of graphene, include each material of following parts by weight,
5 parts of composite master batch
70 parts of PU
50 parts of propyl alcohol,
5 parts of zwitterionic surfactant.
Wherein, a kind of composite master batch, each material of following parts by weight is included：
50 parts of graphene
10 parts of ethylene-chlorotrifluoro-ethylene copolymer
15 parts of linear phenolic resin
5 parts of titanate coupling agent
50 parts of ethanol.
Wherein ethanol can use methanol or propyl alcohol to replace.
A kind of preparation method of composite master batch, comprises the following steps：Step 1: dispersing graphene in solvent, obtain
Graphene suspension；
Step 2: surfactant-dispersed is dissolved in graphene suspension, solution A is obtained；
Step 3: sequentially add linear phenolic resin and fluororesin into solution A, after stirring, stand, dry solidification into
Grain, produces composite master batch.
Embodiment 3
A kind of compound PU fibers of graphene, include each material of following parts by weight,
10 parts of composite master batch
90 parts of PU
Propyl alcohol 30- parts,
10 parts of zwitterionic surfactant.
Wherein, a kind of composite master batch, each material of following parts by weight is included：
40 parts of graphene
10 parts of polyvinyl fluoride
10 parts of linear phenolic resin
10 parts of glycerin monostearate
40 parts of acetone.
A kind of preparation method of composite master batch, comprises the following steps：Step 1: dispersing graphene in solvent, obtain
Graphene suspension；
Step 2: surfactant-dispersed is dissolved in graphene suspension, solution A is obtained；
Step 3: sequentially add linear phenolic resin and fluororesin into solution A, after stirring, stand, dry solidification into
Grain, produces composite master batch.
Embodiment 4
A kind of compound PU fibers of graphene, include each material of following parts by weight,
25 parts of composite master batch
80 parts of PU
40 parts of ethanol,
7 parts of zwitterionic surfactant.
Wherein, a kind of composite master batch, each material of following parts by weight is included：
40 parts of graphene
15 parts of ethylene-chlorotrifluoro-ethylene copolymer
7 parts of linear phenolic resin
10 parts of glycerin monostearate
40 parts of ethylene glycol.
A kind of preparation method of composite master batch, comprises the following steps：Step 1: dispersing graphene in solvent, obtain
Graphene suspension；
Step 2: surfactant-dispersed is dissolved in graphene suspension, solution A is obtained；
Step 3: sequentially add linear phenolic resin and fluororesin into solution A, after stirring, stand, dry solidification into
Grain, produces composite master batch.
Embodiment 5
A kind of compound PU fibers of graphene, include each material of following parts by weight,
25 parts of composite master batch
76 parts of PU
45 parts of propyl alcohol,
8 parts of zwitterionic surfactant.
Wherein, a kind of composite master batch, each material of following parts by weight is included：
45 parts of graphene
15 parts of ethylene-chlorotrifluoro-ethylene copolymer
10 parts of linear phenolic resin
10 parts of silane coupler
45 parts of acetic acid.
A kind of preparation method of composite master batch, comprises the following steps：
Step 1: dispersing graphene in solvent, graphene suspension is obtained；
Step 2: surfactant-dispersed is dissolved in graphene suspension, solution A is obtained；
Step 3: sequentially add linear phenolic resin and fluororesin into solution A, after stirring, stand, dry solidification into
Grain, produces composite master batch.
Embodiment 6
A kind of compound PU fibers of graphene, include each material of following parts by weight,
10 parts of composite master batch
90 parts of PU
50 parts of methanol,
10 parts of zwitterionic surfactant.
Wherein, a kind of composite master batch, each material of following parts by weight is included：
40 parts of graphene
20 parts of ethylene-chlorotrifluoro-ethylene copolymer
10 parts of linear phenolic resin
10 parts of glycerin monostearate
34 parts of acetic acid.
A kind of preparation method of composite master batch, comprises the following steps：
Step 1: dispersing graphene in solvent, graphene suspension is obtained；
Step 2: surfactant-dispersed is dissolved in graphene suspension, solution A is obtained；
Step 3: sequentially add linear phenolic resin and fluororesin into solution A, after stirring, stand, dry solidification into
Grain, produces composite master batch.
Implementation result
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| Thermal weight loss temperature（℃） | 230 | 240 | 241 | 240 | 242 | 241 |
| 300% elongation stress（g） | 6.5±1.0 | 6.42±1.0 | 6.41±1.0 | 6.41±1.0 | 6.4±1.0 | 6.4±1.0 |
| Fracture strength（g）： | ≥30.0 | ≥35.6 | ≥35.5 | ≥35.7 | ≥35.0 | ≥36.0 |
| Extension at break（%）： | ≥535.0 | ≥545.0 | ≥546.0 | ≥545.0 | ≥546.0 | ≥546.0 |
| 300% elongation recovery percentage（%）： | ≥91.5 | ≥92.5 | ≥92.5 | ≥92.5 | ≥92.5 | ≥92.5 |
| Boiling water shrinkage： | ≤10.0 | ≤8.0 | ≤8.0 | ≤8.0 | ≤8.0 | ≤8.0 |
| Extension at break after chlorine-resistant experiment（%） | ≥535.0 | ≥540.0 | ≥540.0 | ≥541.0 | ≥541.0 | ≥541.0 |
| Antibacterial bacteriostatic (antibiotic rate) | 99.6% | 99.7% | 99.8% | 99.9% | 99.7% | 99.9% |
Chlorine-resistant experiment be, by the compound PU fiber impregnations of the graphene obtained in embodiment 1-6 effective chlorine density be 150ppm times
In sodium chlorate solution, taken out after 2 hours, rinse, then dried at 60 DEG C, got damp again 3 hours and detect.
Embodiments of the present invention are these are only, it describes more specific and in detail, but therefore can not be interpreted as pair
The limitation of the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, the present invention is not being departed from
On the premise of design, various modifications and improvements can be made, these belong to protection scope of the present invention.
Claims (7)
- A kind of 1. compound PU fibers of graphene, it is characterised in that each material including following parts by weight,Composite master batch 10-35 partsPU 70-90 partsSolvent 30-50 parts,Wherein solvent is alcohol, preferably methanol, ethanol or propyl alcohol,Described composite master batch includes each material of following parts by weight：Graphene 30-50 partsFluororesin 10-20 partsLinear phenolic resin 5-15 partsSurfactant 5-15 partsSolvent 30-50 parts.
- 2. the compound PU fibers of a kind of multiple graphene according to claim 1, it is characterised in that fluororesin is ethene-tetrafluoro Ethylene copolymer, ethylene-chlorotrifluoro-ethylene copolymer or polyvinyl fluoride.
- 3. the compound PU fibers of a kind of graphene according to claim 1, it is characterised in that surfactant is silane coupled Agent, titanate coupling agent or glycerin monostearate.
- A kind of 4. compound PU fibers of graphene according to claim 1, it is characterised in that solvent be water, ethanol, methanol, Propyl alcohol, acetone, ethylene glycol or acetic acid.
- 5. the compound PU fibers of a kind of graphene according to claim 1, it is characterised in that described composite master batch also includes Zwitterionic surfactant, the parts by weight of zwitterionic surfactant are 5-10 parts.
- 6. the preparation method of the compound PU fibers of a kind of graphene as claimed in claim 1, it is characterised in that including following step Suddenly,Step 1: disperseing zwitterionic surfactant using solvent, finely dispersed solution is obtained；Step 2: adding composite master batch in the solution obtained to step 1, and it is uniformly dispersed, is mixed under conditions of stirring Solution；Step 3: heating melting PU, and the PU of melting is molded into silk using injection machine；Step 4: in the case where the temperature range for ensureing PU is 90-130 DEG C, PU silks are at the uniform velocity obtained through step 2 mixed Close in solution, obtain PU silks；StepRapid five, the PU silks of melt modification are heated, and the compound PU fibers of graphene are prepared in the form of electrostatic spinning.
- 7. a kind of preparation method of composite master batch as claimed in claim 1, it is characterised in that comprise the following steps：Step 1: Disperse graphene in solvent, obtain graphene suspension；Step 2: surfactant-dispersed is dissolved in graphene suspension, solution A is obtained；Step 3: sequentially add linear phenolic resin and fluororesin into solution A, after stirring, stand, dry solidification into Grain, produces composite master batch.
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| CN104805680A (en) * | 2015-04-28 | 2015-07-29 | 武汉纺织大学 | Preparation method of functional fabric |
| CN105019052A (en) * | 2015-06-29 | 2015-11-04 | 浙江华峰氨纶股份有限公司 | Preparation method of high performance polyurethane elastic fiber |
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2017
- 2017-09-01 CN CN201710781112.9A patent/CN107641967A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104805680A (en) * | 2015-04-28 | 2015-07-29 | 武汉纺织大学 | Preparation method of functional fabric |
| CN105019052A (en) * | 2015-06-29 | 2015-11-04 | 浙江华峰氨纶股份有限公司 | Preparation method of high performance polyurethane elastic fiber |
| CN106589459A (en) * | 2016-12-12 | 2017-04-26 | 连云港杜钟新奥神氨纶有限公司 | Preparation method of polyurethane type graphene and application thereof in polyurethane fibers |
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