CN104607058B - A kind of production method of polyvinyl chloride hollow fiber microfiltration membranes - Google Patents
A kind of production method of polyvinyl chloride hollow fiber microfiltration membranes Download PDFInfo
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- CN104607058B CN104607058B CN201410844355.9A CN201410844355A CN104607058B CN 104607058 B CN104607058 B CN 104607058B CN 201410844355 A CN201410844355 A CN 201410844355A CN 104607058 B CN104607058 B CN 104607058B
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Abstract
The present invention relates to a kind of production method of polyvinyl chloride hollow fiber microfiltration membranes, each substances in percentage by weight meter, polyvinyl chloride 16-25%, composite pore-forming 10-30%, balance of solvent are carried out according to the following steps：(1) by polyvinyl chloride, a certain amount of solvent input agitator, dissolving in 24 hours is stirred at 80 DEG C and forms uniform solution；(2) composite pore-forming and balance solvent are put into, continues to be stirred 24 hours at 80 DEG C；(3) deaeration in 48 hours is stood after filtering, and is cooled to 55 DEG C and obtain casting solution；(4) with conventional dry-wet spinning.The polyvinyl chloride hollow fiber microfiltration membranes for preparing in the process of the present invention, tensile strength is more than 2.5MPa, and bubble point pressure is 0.03-0.4MPa, and intensity is ensure that while uniform large aperture is obtained, and can be applied to the projects such as sewage disposal, concentrating and separating.
Description
Technical field
The present invention relates to a kind of production method of polyvinyl chloride hollow fiber microfiltration membranes, belong to technical field of membrane separation.
Background technology
Micro-filtration is one of membrane separation technique with pressure as motive force.For the purpose of macromolecular and separation of small molecuies, fenestra
Footpath is between 0.1-1 μm.UF membrane is not related to phase transition process, and energy consumption is relatively low, and relative to traditional water process, takes up an area less,
Treatment effect stabilization, micro-filter technology is largely used to the projects such as removal microorganism, clarification turbidity removal, stain disease treatment.It is common
Microfiltration membranes include organic film and the big classification of inoranic membrane two.Inoranic membrane has the advantages such as the high, heatproof of intensity, but unit space surface
Product is small and being manufactured into height is restricted its application.In organic film, often prepared as raw material with polyolefin resin, fluororesin
Microfiltration membranes.It is with polyolefin resin as former material such as CN201010580157.8 antibacterial polyolefin microfiltration membranes and preparation method thereof
The example of material, the spalttupfel of strip formed by stretching, filter effect is poor compared with the film of circular port.CN201310460500.9 mono-
Big flux anti-soil polyvinylidene fluoride hollow fiber microfiltration membranes and preparation method thereof are planted, is that raw material passes through inversion of phases legal system with fluororesin
Standby microporous barrier, its pore structure is more excellent, but fluororesin price is higher, and solid content is 8-16%, is made intensity after hollow-fibre membrane
Difference, it is difficult to practical application.
The content of the invention
The invention aims to the problem and defect that overcome prior art to exist, and provide a kind of PVC hollow
The production method of fiber microfiltration membranes, the method is used for solving the filtering effect that current hollow fiber microfiltration membrane is determined by the form in hole
The film cost three of film silk intensity, membrane material and filming technology decision that really, membrane process and high polymer solid content are determined is difficult to simultaneous
The problem of Gu.
The technical scheme is that：
A kind of production method of polyvinyl chloride hollow fiber microfiltration membranes, it is characterised in that each substances in percentage by weight meter,
Polyvinyl chloride 16-25%, composite pore-forming 10-30%, balance of solvent are carried out according to the following steps：(1) by polyvinyl fluoride,
A certain amount of solvent puts into agitator, dissolving in 24 hours is stirred at 80 DEG C and forms uniform solution；(2) composite pore-forming and surplus are put into
Solvent, continues to be stirred 24 hours at 80 DEG C；(3) deaeration in 48 hours is stood after filtering, and is cooled to 55 DEG C and obtain casting solution；
(4) with conventional dry-wet spinning.The polyvinyl chloride hollow fiber microfiltration membranes for preparing in the process of the present invention, tensile strength is more than
2.5MPa, bubble point pressure is 0.03-0.4MPa, can be applied to the projects such as sewage disposal, concentrating and separating.
It is described to be soluble in solvent but the less pore-foaming agent of solubility solubility in a solvent is that every 100 volume is big in water
In 100 volumes, the solubility in water is that every 100 volume is less than 30 volumes.
It is described to be soluble in solvent but the less pore-foaming agent of solubility is n-octyl alcohol, tetraethyl orthosilicate, propane diols in water
Butyl ether, titanate coupling agent, dimethicone, repefral, diethyl phthalate, the fourth of phthalic acid two
One or two or more kinds mixture in ester.
Described solvent is a kind of or two kinds of mixtures in dimethylacetylamide, N- methyl pyrrole network alkanones.
It is main membrane material with polyvinyl chloride in the technical program, reduces the cost of film.With dry-wet phase inversion system
Film, film surface is circular or approximate circle hole, it is ensured that the filter effect of film.In film formulation, high polymer content is improved, it is ensured that film
The intensity of silk.Topmost employing is soluble in solvent but indissoluble or is slightly soluble in the pore-foaming agent of water, different from known poly- second two
Alcohol, polyethylene pyrrole network alkanone etc. are to be soluble in solvent pore-foaming agent again soluble in water.When casting solution is contacted with coagulating bath, casting film
The pore-foaming agent of water is insoluble in liquid certain inhibition is mutually diffused with to solvent and water, simultaneously because polyvinyl chloride molecule
Measure relatively low (relative to the Kynoar of masking), the relaxation time is shorter, make stingy there is the more time to grow to be formed
Micropore is without falling in ultrafiltration category.
On November 14th, 2014, a kind of entitled " polyvinylidene fluoride of the Application No. 2014106536296 of Chen Quanxue applications
The production method of alkene microporous barrier ", a kind of production method of polyvinylidene fluoride microporous film, it is characterised in that each material by weight hundred
Divide than meter, Kynoar 10-25%, composite pore-forming 10-30%, balance of solvent are carried out according to the following steps：(1) will
Kynoar, solvent input agitator, stir dissolving in 24 hours and form uniform solution at 80 DEG C；(2) composite pore-forming is put into,
Continue to be stirred 24 hours at 80 DEG C；(3) deaeration in 48 hours is stood after filtering, and is cooled to 55 DEG C and obtain casting solution；(4) will casting
Film liquid scrapes diaphragm；Or conventional dry-wet spinning is used under coagulation bath condition, the coagulating bath is the water of not higher than 20% concentration
Solution.Described composite pore-forming is known pore-foaming agent not only soluble in water but also being soluble in solvent and is soluble in solvent but in water
The mixture of the middle less pore-foaming agent of solubility.It is described be soluble in solvent but in water the less pore-foaming agent of solubility weight
Percentage is 5-20%.It is described to be soluble in solvent but the less pore-foaming agent of solubility solubility in a solvent is every in water
100 volumes are more than 20 volumes, and the solubility in water is that every 100 volume is less than 5 volumes.
It is described to be soluble in solvent but the less pore-foaming agent of solubility is n-octyl alcohol, tetraethyl orthosilicate, propane diols in water
Butyl ether, titanate coupling agent, dimethicone, repefral, diethyl phthalate, the fourth of phthalic acid two
One or two or more kinds mixture in ester.
Patent application 2014106536296 is write according to the experimental data of research and development Kynoar film formulation, main sides
Focus on the membrane aperture done by this programme can than routine without property material composite pore-forming polyvinylidene fluoride film more
The characteristics of small, fenestra has finger-like pore and sponge hole concurrently, and coagulating bath does not need the solution of high concentration, and operation more facilitates and big
The big volatile quantity for reducing solvent.
With polyvinyl chloride hollow fiber microfiltration membranes prepared by this method, pore structure is uniform, and film silk intensity is high.
Present invention addition identical property material composite pore-forming, the membrane aperture for obtaining is preceding bigger than being not added with the contrary, makes
Obtain and microfiltration membranes have been obtained in the case of solid content high rather than milipore filter, with patent application 2014106536296《It is a kind of
The production method of polyvinylidene fluoride microporous film》The smaller experiment conclusion in middle aperture is completely opposite.And the microstructure of film relative to
Without property material, there is no any change, or double finger-like pore.
Specific embodiment
Invention is described further below in conjunction with example, but should not be limited the scope of the invention with this.It is each to implement
The consumption of example is by weight percentage.
Embodiment 1
By 25% polyvinyl chloride, 50% dimethylacetylamide input agitator, dissolving in 24 hours is stirred at 80 DEG C and forms equal
One solution；The tetraethyl orthosilicate and 7% dimethylacetylamide of 3% polyethylene pyrrole network alkanone K17 and 15% are put into again, are continued 80
Stirred 24 hours at DEG C；Deaeration in 48 hours is stood after filtering, and is cooled to 55 DEG C and obtain casting solution；Dry-wet spinning, film silk chi
Very little is 0.9mm/1.6mm.Film silk is tested after soaking 48H in clear water, and bubble point pressure is 0.4MPa, and film silk tensile strength is
3.9MPa。
Embodiment 2
By 16 % polyvinyl chloride, 50% dimethylacetylamide input agitator, dissolving in 24 hours is stirred at 80 DEG C and is formed
Uniform solution；The dimethicone and 24% dimethylacetylamide of 5% polyethylene glycol PEG400 and 5% are put into again, are continued
Stirred 24 hours at 80 DEG C；Deaeration in 48 hours is stood after filtering, and is cooled to 55 DEG C and obtain casting solution；Dry-wet spinning, film silk
Size is 0.9mm/1.6mm.Film silk is tested after soaking 48H in clear water, and bubble point pressure is 0.4MPa, and film silk tensile strength is
2.8MPa。
Embodiment 3
By 16% polyvinyl chloride, 50% dimethylacetylamide input agitator, dissolving in 24 hours is stirred at 80 DEG C and is formed
Uniform solution；The propandiol butyl ether and 4% dimethylacetylamide of 20% polyethylene glycol PEG6000 and 10% are put into again, are continued
Stirred 24 hours at 80 DEG C；Deaeration in 48 hours is stood after filtering, and is cooled to 55 DEG C and obtain casting solution；Dry-wet spinning, film
Silk size is 0.9mm/1.6mm.Film silk is tested after soaking 48H in clear water, and bubble point pressure is 0.03MPa, film silk tensile strength
It is 2.5MPa.
Embodiment 4
By 20 % polyvinyl chloride, 50% dimethylacetylamide input agitator, dissolving in 24 hours is stirred at 80 DEG C and is formed
Uniform solution；The laruyl alcohol and 7% dimethylacetylamide of 3% polyethylene pyrrole network alkanone K85 and 20% are put into again, are continued 80
Stirred 24 hours at DEG C；Deaeration in 48 hours is stood after filtering, and is cooled to 55 DEG C and obtain casting solution.Dry-wet spinning, film silk chi
Very little is 0.9mm/1.6mm.Film silk is tested after soaking 48H in clear water, and bubble point pressure is 0.1MPa, and film silk tensile strength is
3.2MPa。
Embodiment 5
17 % polyvinyl chloride, 30% dimethylacetylamide, 35% N- methyl pyrrole networks alkanone are put into agitator, 80 DEG C
Lower stirring dissolving in 24 hours forms uniform solution；1% lithium chloride, the neighbour of 6% polyethylene glycol PEG800 and 12% is put into again
Diethyl phthalate, continues to be stirred 24 hours at 80 DEG C；Deaeration in 48 hours is stood after filtering, and is cooled to 55 DEG C and cast
Film liquid；Dry-wet spinning, film silk size is 0.9mm/1.6mm.Film silk is tested after soaking 48H in clear water, and bubble point pressure is
0.2MPa, film silk tensile strength is 2.8MPa.
Claims (2)
1. a kind of production method of polyvinyl chloride hollow fiber microfiltration membranes, it is characterised in that each substances in percentage by weight meter, gathers
Vinyl chloride 16-25%, composite pore-forming 10-30%, balance of solvent are carried out according to the following steps：(1) by polyvinyl chloride, certain
Amount solvent input agitator, stirs dissolving in 24 hours and forms uniform solution at 80 DEG C；(2) input composite pore-forming and surplus are molten
Agent, continues to be stirred 24 hours at 80 DEG C；(3) deaeration in 48 hours is stood after filtering, and is cooled to 55 DEG C and obtain casting solution；(4)
With conventional dry-wet spinning；
Described composite pore-forming is known pore-foaming agent not only soluble in water but also being soluble in solvent and is soluble in solvent but in water
The mixture of the middle less pore-foaming agent of solubility；It is described be soluble in solvent but in water the less pore-foaming agent of solubility quality
Fraction is 5-20%；It is described to be soluble in solvent but the less pore-foaming agent of solubility is n-octyl alcohol, tetraethyl orthosilicate, third in water
Glycol butyl ether, titanate coupling agent, dimethicone, repefral, diethyl phthalate, phthalic acid
One or two or more kinds mixture in dibutyl ester;
It is described to be soluble in solvent but the less pore-foaming agent of solubility solubility in a solvent is that every 100 volume is more than in water
100 volumes, the solubility in water is that every 100 volume is less than 30 volumes.
2. the production method of a kind of polyvinyl chloride hollow fiber microfiltration membranes according to claim 1, it is characterised in that：It is described
Solvent be a kind of or two kinds of mixtures in dimethylacetylamide, N- methyl pyrrole network alkanones.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103143266A (en) * | 2013-03-05 | 2013-06-12 | 中国科学院生态环境研究中心 | Preparation method of hollow fiber membrane with spiral reinforcing ribs and spinning nozzle |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102397760B (en) * | 2010-09-08 | 2014-04-09 | 绵阳美能材料科技有限公司 | Polyether sulfone hollow fiber ultrafiltration membrane and preparation method thereof |
| CN103111189B (en) * | 2013-02-05 | 2015-03-25 | 江苏苏净集团有限公司 | High-flux polyvinylidene fluoride hollow fiber membrane |
| CN103316601A (en) * | 2013-07-10 | 2013-09-25 | 蒋雨菁 | Hydrophilic hollow fiber membrane and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103143266A (en) * | 2013-03-05 | 2013-06-12 | 中国科学院生态环境研究中心 | Preparation method of hollow fiber membrane with spiral reinforcing ribs and spinning nozzle |
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