CN105381724B - A kind of preparation method of high tensile PVDF hollow-fibre membranes - Google Patents
A kind of preparation method of high tensile PVDF hollow-fibre membranes Download PDFInfo
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Abstract
The present invention provides a kind of preparation methods of high tensile PVDF hollow-fibre membranes, are prepared and two steps of spinning including casting solution.Preparation method provided by the invention is simple for process, of low cost, and the PVDF doughnuts film dynamic performance of preparation is good, water flux is high.
Description
Technical field
The present invention relates to a kind of preparation method of hollow-fibre membrane, more particularly to a kind of hollow fibres of high tensile PVDF
Tie up the preparation method of film.
Background technology
PVDF is a kind of membrane material haveing excellent performance, using it as the doughnut micropore of main material development and production
Film has been applied successfully to the fields such as chemical industry, electronics, weaving, food, biochemistry.
In existing industrialized production, NIPS (phase separation) method is to prepare the main side of PVDF hollow-fibre membranes
Method.But its doughnut film strength prepared is not high, and homogeneous membrane (non-reinforcing rib and woven tube) is general all in below 2MPa.Separately
A kind of method for preparing PVDF hollow-fibre membranes be TIPS (Thermal inactive) method, prepare PVDF hollow-fibre membranes film wire
Universal elongation at break it is poor, easily occur brittle failure in application, while film prepared by TIPS methods is mostly microfiltration membranes, it is impossible to full
Foot largely uses the requirement of ultrafiltration membrane occasion.
For obtain higher-strength PVDF hollow-fibre membranes, Chinese patent CN200510013255.2 and
CN200510024195.4 improves NIPS methods, micro- come reinforced type polyvinylidene fluoride hollow fiber using polyester fiber etc.
Hole filter membrane can improve the tensile strength of film wire to 10~15MPa.This preparation process is complicated, not only needs to carry out fiber pre-
Processing, and compound tense technology difficulty is big, of high cost.
Therefore, it is necessary to develop a kind of preparation method of high tensile PVDF hollow-fibre membranes.
The content of the invention
It is an object of the invention to provide a kind of preparation methods of high tensile PVDF hollow-fibre membranes, have and prepare work
The advantages of skill is simple, of low cost, and PVDF doughnuts film dynamic performance prepared by the method is good, water flux is high.
It is to reach goal of the invention the technical solution adopted by the present invention：
A kind of preparation method of high tensile PVDF hollow-fibre membranes, comprises the following steps：
(1) PVDF resins, solvent and additive are stirred according to 5~20%, 65~83%, 1~15% mass percent
It mixes and is configured to homogeneous casting solution；
Inherent viscosity >=3.6dL/g of the PVDF resins, weight average molecular weight >=1,800,000；
The solvent be selected from DMAC N,N' dimethyl acetamide, N- methyl arsenic pyrrolidone, dimethylformamide, triethyl phosphate and
One kind, two or three of combination of the above in dimethyl alum；
The additive is selected from polyethylene glycol, polyvinylpyrrolidone, ethylene glycol, glycerine, water, ethyl alcohol, acetone and chlorination
One kind, two or three of combination of the above in lithium；
(2) by casting solution made from step (1) in temperature be 90~160 DEG C, pressure is 0.1~3MPa, core flow velocity is
1.0~15.0mL/min, winding-roller hauling speed carry out spinning for 5~30m/min, add in coagulating bath and fully form a film with after
PVDF hollow-fibre membranes are obtained after processing.
As preferred mode, 3.87~4.02dL/g of inherent viscosity of the above-mentioned PVDF resins used, weight average molecular weight
200~2,200,000；Above-mentioned solvent of stating preferably is selected from DMAC N,N' dimethyl acetamide, N- methyl arsenic pyrrolidones and dimethylformamide
It is a kind of, two or three；Above-mentioned additive preferably is selected from polyethylene glycol, polyvinylpyrrolidone, water, ethyl alcohol, acetone and lithium chloride
In one kind, two or three of combination of the above.
As preferred mode, above-mentioned PVDF resins, solvent and additive are according to 12~18%, 73~83%, 5~15%
Mass percent stirring be configured to homogeneous casting solution.
As preferred mode, in above-mentioned steps (2) casting solution in 130~160 DEG C of temperature, pressure be 1.5~3MPa, core
Flow velocity is 7.0~12.0mL/min, winding-roller hauling speed is that 10~20m/min carries out spinning；The coagulating bath is preferably
By water and selected from DMAC N,N' dimethyl acetamide, N- methyl arsenic pyrrolidone, dimethylformamide, triethyl phosphate and dimethyl alum
One kind, two or three of combination of the above according to 50~99%, 1~50% mass percentage composition；The core liquid is preferably
The aqueous solution of ethyl alcohol or the aqueous solution of n,N-dimethylacetamide, mass concentration are 1~50%；Rear place in the step (2)
Reason is preferably a step the PVDF hollow-fibre membranes that will fully form a film in coagulating bath and is immersed in 10 in the mixed solution of G ＆ W
~50 it is small when, the mass percent of glycerine is 10~60% in the mixed solution of the G ＆ W.
The tensile strength of PVDF hollow-fibre membranes prepared by the present invention is 1~6MPa, elongation at break is 80~300%,
Water flux is 100~400L/m2·h.As preferred mode, the tensile strengths of the PVDF hollow-fibre membranes is 4~6MPa,
Elongation at break is 150~300%, water flux is 180~250L/m2·h。
PVDF hollow-fibre membranes prepared by the present invention are suitable for preparing membrane bioreactor, the membrane bioreactor of preparation
It is suitable for the fields such as sewage disposal.
Specific embodiment
The following examples are for illustrating several specific embodiments of the present invention, but not limiting the invention to this
A little specific embodiments.One skilled in the art would recognize that present invention encompasses may be wrapped in Claims scope
All alternatives, improvement project and the equivalent scheme included.
The pure water flux of the pvdf membrane prepared in following embodiment is tested in accordance with the following methods：
Pvdf membrane component is fitted into water flux tester, at 25 DEG C, first using 0.15MPa to its precompressed 30min, so
The pure water quality penetrated afterwards in 0.10MPa lower-weighings 20min obtains its pure water flux finally by water flux calculation formula,
Water flux calculation formula is as follows：
J=permeate volume/(film effective area × time)
Embodiment 1
The preparation of casting solution：Weighing the PVDF resins that weight percent is 12%, (inherent viscosity 3.87dL/g, divides equally again
Son amount about 200 ten thousand), 81% n,N-dimethylacetamide, 5% polyvinylpyrrolidone, 1% ethyl alcohol and 1% acetone mix
It closes, be stirred and heated to 90 DEG C, it is made fully to dissolve, be configured to homogeneous casting solution.
Film preparation：Casting solution is transferred in the feed liquid filling of spinning-drawing machine, is stood to exclusion bubble.By feed liquid filling and metering pump
Temperature is set as 90 DEG C, heats simultaneously constant temperature.Nitrogen pressurization is poured to feed liquid filling simultaneously, reaches pressure 1.5MPa.Core liquid is 10%
N,N-dimethylacetamide aqueous solution, core liquid temperature degree are 40 DEG C.It is 8mL/min to adjust core flow velocity, and winding-roller hauling speed is
10m/min.Feed liquid valve is opened after operating steadily, die head wire vent enters in coagulating bath, then film wire traction is wound on winding-roller,
Cause uniform spinning.Coagulating bath is water, and coagulation bath temperature is 40 DEG C.Primary membrane on winding-roller is removed, is sufficiently displaced from pure water
Solvent, finally in the aqueous solution of immersion glycerine accounting 50%, when the time is 24 small.
Pvdf membrane obtained, film wire surfacing.Through Mechanics Performance Testing, tensile strength 2.01MPa, extension at break
Rate 173.1%, water flux 254.7L/m2·h。
Embodiment 2
The preparation of casting solution：Taking the PVDF that weight percent is 13%, (inherent viscosity 3.87dL/g, weight average molecular weight is about
For 200 ten thousand) resin, 80% n,N-dimethylacetamide, 5% polyvinylpyrrolidones, 1% ethyl alcohol and 1% acetone.Stirring is simultaneously
90 DEG C are heated to, is fully dissolved.
Film preparation：Casting solution is transferred in the feed liquid filling of spinning-drawing machine, is stood to exclusion bubble.By feed liquid filling and metering pump
Temperature is set as 90 DEG C, heats simultaneously constant temperature.Nitrogen pressurization is poured to feed liquid filling simultaneously, reaches pressure 1.8MPa.Core liquid is 10%
N,N-dimethylacetamide aqueous solution, core liquid temperature degree are 40 DEG C.It is 9mL/min to adjust core flow velocity, and winding-roller hauling speed is
12m/min.Feed liquid valve is opened after operating steadily, die head wire vent enters in coagulating bath, then film wire traction is wound on winding-roller,
Cause uniform spinning.Coagulating bath is water, and coagulation bath temperature is 40 DEG C.Primary membrane on winding-roller is removed, is sufficiently displaced from pure water
Solvent, finally in the aqueous solution of immersion glycerine accounting 50%, when the time is 24 small.
Pvdf membrane obtained, film wire surfacing.Through Mechanics Performance Testing, tensile strength 2.62MPa, elongation at break
147.2%, water flux 218.9L/m2·h。
Embodiment 3
The preparation of casting solution：Taking the PVDF that weight percent is 16%, (inherent viscosity 3.87dL/g, weight average molecular weight is about
For 200 ten thousand) resin, 70% N- methyl arsenic pyrrolidone, 8%N, N- dimethyl acetamides, 5% polyvinylpyrrolidone, 1% second
Glycol.90 DEG C are stirred and heated to, is fully dissolved.
Film preparation：Casting solution is transferred in the feed liquid filling of spinning-drawing machine, is stood to exclusion bubble.By feed liquid filling and metering pump
Temperature is set as 90 DEG C, heats simultaneously constant temperature.Nitrogen pressurization is poured to feed liquid filling simultaneously, reaches pressure 2.3MPa.Core liquid is 10%
N,N-dimethylacetamide aqueous solution, core liquid temperature degree are 40 DEG C.It is 10mL/min to adjust core flow velocity, and winding-roller hauling speed is
14m/min.Feed liquid valve is opened after operating steadily, die head wire vent enters in coagulating bath, then film wire traction is wound on winding-roller,
Cause uniform spinning.Coagulating bath is water, and coagulation bath temperature is 40 DEG C.Primary membrane on winding-roller is removed, is sufficiently displaced from pure water
Solvent, finally in the aqueous solution of immersion glycerine accounting 50%, when the time is 24 small.
Pvdf membrane obtained, film wire surfacing are slightly poor.Through Mechanics Performance Testing, tensile strength 5.41MPa, fracture is stretched
Long rate 223.7%, water flux very little are 136.4L/m2·h。
Embodiment 4
The preparation of casting solution：Taking the PVDF that weight percent is 16%, (inherent viscosity 3.87dL/g, weight average molecular weight is about
For 200 ten thousand) resin, 70% N- methyl arsenic pyrrolidone, 8%N, N- dimethyl acetamides, 5% polyvinylpyrrolidone, 1% second
Glycol.130 DEG C are stirred and heated to, is fully dissolved.
Film preparation：Casting solution is transferred in the feed liquid filling of spinning-drawing machine, is stood to exclusion bubble.By feed liquid filling and metering pump
Temperature is set as 130 DEG C, heats simultaneously constant temperature.Nitrogen pressurization is poured to feed liquid filling simultaneously, reaches pressure 2.3MPa.Core liquid is 25%
Glycol water, core liquid temperature degree are 70 DEG C.It is 12mL/min to adjust core flow velocity, and winding-roller hauling speed is 15m/min.Fortune
Feed liquid valve is opened after row is steady, die head wire vent enters in coagulating bath, then film wire traction is wound on winding-roller, causes uniformly to spin
Silk.Coagulating bath is water, and coagulation bath temperature is 40 DEG C.Primary membrane on winding-roller is removed, solvent is sufficiently displaced from pure water, finally
In the aqueous solution for impregnating glycerine accounting 50%, when the time is 24 small.
Pvdf membrane obtained, film wire surfacing.Through Mechanics Performance Testing, tensile strength 5.86MPa, elongation at break
195.7%, water flux 201.3L/m2·h。
Embodiment 5
The preparation of casting solution：Taking the PVDF that weight percent is 16%, (inherent viscosity 3.95dL/g, weight average molecular weight is about
For 206 ten thousand) resin, 78% N- methyl arsenic pyrrolidone, 5% polyethylene glycol -600,1%LiCl.140 DEG C are stirred and heated to,
Fully dissolving.
Film preparation：Casting solution is transferred in the feed liquid filling of spinning-drawing machine, is stood to exclusion bubble.By feed liquid filling and metering pump
Temperature is set as 140 DEG C, heats simultaneously constant temperature.Nitrogen pressurization is poured to feed liquid filling simultaneously, reaches pressure 2.3MPa.Core liquid is 50%
Glycol water, core liquid temperature degree are 70 DEG C.It is 14mL/min to adjust core flow velocity, and winding-roller hauling speed is 15m/min.Fortune
Feed liquid valve is opened after row is steady, die head wire vent enters in coagulating bath, then film wire traction is wound on winding-roller, causes uniformly to spin
Silk.Coagulating bath is water, and coagulation bath temperature is 60 DEG C.Primary membrane on winding-roller is removed, solvent is sufficiently displaced from pure water, finally
In the aqueous solution for impregnating glycerine accounting 50%, when the time is 24 small.
Pvdf membrane obtained, film wire surfacing.Through Mechanics Performance Testing, tensile strength 5.90MPa, elongation at break
212.1%, water flux 163.5L/m2·h。
Embodiment 6
The preparation of casting solution：Taking the PVDF that weight percent is 16%, (inherent viscosity 4.02dL/g, weight average molecular weight is about
For 202 ten thousand) resin, 78% N- methyl arsenic pyrrolidone, 5% polyethylene glycol -600,1%LiCl.160 DEG C are stirred and heated to,
Fully dissolving.
Film preparation：Casting solution is transferred in the feed liquid filling of spinning-drawing machine, is stood to exclusion bubble.By feed liquid filling and metering pump
Temperature is set as 160 DEG C, heats simultaneously constant temperature.Nitrogen pressurization is poured to feed liquid filling simultaneously, reaches pressure 2.5MPa.Core liquid is 50%
Glycol water, core liquid temperature degree are 70 DEG C.It is 14mL/min to adjust core flow velocity, and winding-roller hauling speed is 15m/min.Fortune
Feed liquid valve is opened after row is steady, die head wire vent enters in coagulating bath, then film wire traction is wound on winding-roller, causes uniformly to spin
Silk.Coagulating bath is water, and coagulation bath temperature is 60 DEG C.Primary membrane on winding-roller is removed, solvent is sufficiently displaced from pure water, finally
In the aqueous solution for impregnating glycerine accounting 50%, when the time is 24 small.
Pvdf membrane obtained, film wire surfacing.Through Mechanics Performance Testing, tensile strength 5.68MPa, elongation at break
208.5%, water flux, 184.0L/m2·h。
Comparative example 1：
The preparation of casting solution：Taking the PVDF that weight percent is 16%, (inherent viscosity 1.65dL/g, weight average molecular weight is about
For 64.6 ten thousand) resin, 70% N- methyl arsenic pyrrolidone, 8%N, N- dimethyl acetamides, 5% polyvinylpyrrolidone, 1%
Ethylene glycol.90 DEG C are stirred and heated to, is fully dissolved.
Film preparation：Casting solution is transferred in the feed liquid filling of spinning-drawing machine, is stood to exclusion bubble.By feed liquid filling and metering pump
Temperature is set as 90 DEG C, heats simultaneously constant temperature.Nitrogen pressurization is poured to feed liquid filling simultaneously, reaches pressure 2.0MPa.Core liquid is 10%
N,N-dimethylacetamide aqueous solution, core liquid temperature degree are 40 DEG C.It is 9mL/min to adjust core flow velocity, and winding-roller hauling speed is
12m/min.Feed liquid valve is opened after operating steadily, die head wire vent enters in coagulating bath, then film wire traction is wound on winding-roller,
Cause uniform spinning.Coagulating bath is water, and coagulation bath temperature is 40 DEG C.Primary membrane on winding-roller is removed, is sufficiently displaced from pure water
Solvent, finally in the aqueous solution of immersion glycerine accounting 50%, when the time is 24 small.
Film wire performance：Relatively steady smooth membrane, gained film wire tensile strength 1.55MPa, elongation at break 95.7%, water leads to
It measures as 223.7L/m2·h。
Comparative example 2：
The preparation of casting solution：Take PVDF (inherent viscosity 1.975dL/g, the weight average molecular weight that weight percent is 16%
About 79.8 ten thousand) resin, 70% N- methyl arsenic pyrrolidone, 8%N, N- dimethyl acetamides, 5% polyvinylpyrrolidone,
1% ethylene glycol.90 DEG C are stirred and heated to, is fully dissolved.
Film preparation：Casting solution is transferred in the feed liquid filling of spinning-drawing machine, is stood to exclusion bubble.By feed liquid filling and metering pump
Temperature is set as 130 DEG C, heats simultaneously constant temperature.Nitrogen pressurization is poured to feed liquid filling simultaneously, reaches pressure 2.0MPa.Core liquid is 10%
N,N-dimethylacetamide aqueous solution, core liquid temperature degree are 40 DEG C.It is 9mL/min to adjust core flow velocity, and winding-roller hauling speed is
12m/min.Feed liquid valve is opened after operating steadily, die head wire vent enters in coagulating bath, then film wire traction is wound on winding-roller,
Cause uniform spinning.Coagulating bath is water, and coagulation bath temperature is 40 DEG C.Primary membrane on winding-roller is removed, is sufficiently displaced from pure water
Solvent, finally in the aqueous solution of immersion glycerine accounting 50%, when the time is 24 small.
Film wire performance：Relatively steady smooth membrane, gained film wire is slightly poor for surfacing, tests mechanical property, tensile strength
1.78MPa, elongation at break 84.3%, water flux 209.0L/m2·h。
Claims (10)
1. a kind of preparation method of high tensile PVDF hollow-fibre membranes, it is characterised in that comprise the following steps：
(1) PVDF resins, solvent and additive are matched somebody with somebody according to 5~20%, 65~83%, 1~15% mass percent stirring
Homogeneous casting solution is made；
Inherent viscosity >=3.6dL/g of the PVDF resins, weight average molecular weight >=1,800,000；
The solvent is selected from DMAC N,N' dimethyl acetamide, N- methyl arsenic pyrrolidone, dimethylformamide, triethyl phosphate and diformazan
One kind, two or three of combination of the above in the alum of base Asia；
The additive is in polyethylene glycol, polyvinylpyrrolidone, ethylene glycol, glycerine, water, ethyl alcohol, acetone and lithium chloride
One kind, two or three of combination of the above；
(2) by casting solution made from step (1) in temperature is 90~160 DEG C, pressure is 0.1~3MPa, core flow velocity be 1.0~
15.0mL/min, winding-roller hauling speed carry out spinning for 5~30m/min, add in coagulating bath and fully form a film and post-process
After obtain PVDF hollow-fibre membranes.
2. the preparation method of high tensile PVDF hollow-fibre membranes described in accordance with the claim 1, it is characterised in that described
3.87~4.02dL/g of inherent viscosity of PVDF resins, weight average molecular weight 200~2,200,000, the solvent are selected from N, N- dimethyl
Acetamide, N- methyl arsenic pyrrolidones and one kind in dimethylformamide, two or three, the additive is selected from poly- second two
One kind, two or three of combination of the above in alcohol, polyvinylpyrrolidone, water, ethyl alcohol, acetone and lithium chloride.
3. the preparation method of high tensile PVDF hollow-fibre membranes described in accordance with the claim 1, it is characterised in that described
PVDF resins, solvent and additive are configured to homogeneous according to 12~18%, 73~83%, 5~15% mass percent stirring
Casting solution.
4. the preparation method of high tensile PVDF hollow-fibre membranes described in accordance with the claim 1, it is characterised in that the step
Suddenly in (2) casting solution in 130~160 DEG C of temperature, pressure be 1.5~3MPa, core flow velocity is 7.0~12.0mL/min, wrapping wire
Roller hauling speed carries out spinning for 10~20m/min.
5. the preparation method of high tensile PVDF hollow-fibre membranes described in accordance with the claim 1, it is characterised in that described solidifying
Gu bath is by water and selected from DMAC N,N' dimethyl acetamide, N- methyl arsenic pyrrolidone, dimethylformamide, triethyl phosphate and diformazan
One kind of base Asia alum, two or three of combination of the above according to 50~99%, 1~50% mass percentage composition.
6. the preparation method of high tensile PVDF hollow-fibre membranes described in accordance with the claim 1, it is characterised in that the core
Liquid is the aqueous solution of ethyl alcohol or the aqueous solution of n,N-dimethylacetamide, and mass concentration is 1~50%.
7. the preparation method of high tensile PVDF hollow-fibre membranes described in accordance with the claim 1, it is characterised in that the step
Suddenly the post-processing step in (2) is the mixing that the PVDF hollow-fibre membranes fully to form a film in coagulating bath are immersed in G ＆ W
In solution 10~50 it is small when, the mass percent of glycerine is 10~60% in the mixed solution of the G ＆ W.
8. the preparation method of high tensile PVDF hollow-fibre membranes described in accordance with the claim 1, it is characterised in that described
The tensile strength of PVDF hollow-fibre membranes is 1~6MPa, elongation at break is 80~300%, water flux is 100~400L/
m2·h。
9. according to the preparation method of the high tensile PVDF hollow-fibre membranes described in claim 8, it is characterised in that described
The tensile strength of PVDF hollow-fibre membranes is 4~6MPa, elongation at break is 150~300%, water flux is 180~250L/
m2·h。
10. according to the preparation method of the high tensile PVDF hollow-fibre membranes described in one of claim 1 to 9, feature exists
Membrane bioreactor is used to prepare in the PVDF hollow-fibre membranes.
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| CN108079795A (en) * | 2017-12-13 | 2018-05-29 | 浙江长兴求是膜技术有限公司 | A kind of classifying porous polyvinylidene fluoride hollow fiber composite membrane and its manufacturing method |
| CN108704493A (en) * | 2018-06-26 | 2018-10-26 | 黑龙江大学 | A kind of preparation method of flushing-free PVDF tube-type micropore films |
| CN108786468A (en) * | 2018-06-26 | 2018-11-13 | 黑龙江大学 | A kind of method that the thermotropic phase inversion of low temperature prepares flushing-free PVDF tube-type micropore films |
| CN108579441A (en) * | 2018-06-26 | 2018-09-28 | 黑龙江大学 | A kind of flushing-free tubular membrane component for water process |
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| CN101147848A (en) * | 2007-07-20 | 2008-03-26 | 天津工业大学 | Polyvinylidene fluoride film hydrophilically modified method |
| CN102266728A (en) * | 2011-07-05 | 2011-12-07 | 惠州七芯膜净化环保有限公司 | Polyvinylidene fluoride hollow fiber membrane and preparation method thereof |
| CN102527262A (en) * | 2011-12-09 | 2012-07-04 | 西安建筑科技大学 | Method for preparing chemically perforated polyvinylidene fluoride hollow fiber ultrafiltration membrane |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101147848A (en) * | 2007-07-20 | 2008-03-26 | 天津工业大学 | Polyvinylidene fluoride film hydrophilically modified method |
| CN102266728A (en) * | 2011-07-05 | 2011-12-07 | 惠州七芯膜净化环保有限公司 | Polyvinylidene fluoride hollow fiber membrane and preparation method thereof |
| CN102527262A (en) * | 2011-12-09 | 2012-07-04 | 西安建筑科技大学 | Method for preparing chemically perforated polyvinylidene fluoride hollow fiber ultrafiltration membrane |
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