CN106397820B - A kind of hydrophilic modification method of polyethylene, polypropylene material surface endurance - Google Patents

A kind of hydrophilic modification method of polyethylene, polypropylene material surface endurance Download PDF

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CN106397820B
CN106397820B CN201610900944.3A CN201610900944A CN106397820B CN 106397820 B CN106397820 B CN 106397820B CN 201610900944 A CN201610900944 A CN 201610900944A CN 106397820 B CN106397820 B CN 106397820B
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polyethylene
polypropylene material
polypropylene
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immersed
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CN106397820A (en
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黄健
卢强
江国栋
常孟
王晓林
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Nanjing Tech University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/02—Chemical treatment or coating of shaped articles made of macromolecular substances with solvents, e.g. swelling agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • C08J9/40—Impregnation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • C08J9/40—Impregnation
    • C08J9/42—Impregnation with macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene

Abstract

The invention discloses a kind of polyethylene, the hydrophilic modification method of polypropylene material surface endurance.Polyethylene or polypropylene material are first immersed in progress surface swelling in the solution of the organic solvent containing radical polymerization initiator, it is modified that polyethylene or polypropylene material are then immersed progress surface in the aqueous solution of the double bond containing amphiphile, amphiphilic molecule in hydrophobic side.The free radical that decomposition of initiator generates can cause swelled surface lightly crosslinked, to improve surface swellbility, improve surface hydrophilic modification effect；In addition, free radical can promote the amphiphile, amphiphilic molecule of modified surface embedding and covalently key connection occurs for polyethylene, polypropylene molecular chain, to improve the stability of modified surface hydrophilicity.

Description

A kind of hydrophilic modification method of polyethylene, polypropylene material surface endurance
Technical field
The present invention relates to a kind of polyethylene, the hydrophilic modification method on polypropylene material surface, more specifically to one kind The hydrophilic modification method of polyethylene, polypropylene material surface endurance.
Background technique
Polyethylene and polypropylene are most common general-purpose plastics, because its good economy, mechanical performance, machinability, Corrosion resistance and electrical insulating property etc. are widely used in industrial and agricultural production and daily life.Polyethylene and polypropylene can It is conveniently fabricated the multiple products form such as injection-molded item, profile, tubing, film, fiber, porous diffusion barrier.Polyethylene or poly- third Alkene strand is made of inert methylene, methyl, while having high-crystallinity, its surface is caused to lack active group, surface Can low, surfaces hydrophobic, surface be easy to pollute, surface wettability and cementability are poor, limit polyethylene or polypropylene in water ring The application in the fields such as border or composite material.Therefore surface is carried out to polyethylene or polypropylene material to be modified, improve its surface energy, table Face polarity or hydrophily have great importance and broad application prospect.
In order to improve polyethylene or polyacrylic surface polarity or hydrophily, existing surface modifying method mainly has chemistry Oxidation, corona treatment, Corona discharge Treatment, surface grafting processing etc..Chemical oxidation, corona treatment, corona discharge The methods of processing effectively can introduce the polar group of small molecule in polyethylene or polypropylene surface, but these polar groups are unstable Fixed, modified surface performance has timeliness, and under air oxidation or the warm-up movement of strand effect, surface polarity is easy to lose. Surface grafting method can be in polyethylene or the polar polymer of polypropylene surface introducing high molecular weight, and modified surface has good Persistence, but the complex process of surface grafting method is high to the volume of product, shape need, and economy does not have advantage yet.
For polyolefin carriers such as polyethylene, polypropylene, Huang is strong etc. proposes the surface packet based on amphiphile, amphiphilic molecule modifying agent Bury method of modifying, including " one-step method " and " two-step method " two kinds of modified techniques.(the CN in " one-step method " embedding modified technique 200610161542.2；CN 200610161541.8), the surface of polyolefin is modified in the swelling dissolved with amphiphile, amphiphilic molecule modifying agent It is once completed in agent；In " two-step method " embedding modified technique (CN 200910032055.X), polyolefin carrier is first placed in swelling Surface swelling is carried out in agent, is then placed in the aqueous solution dissolved with amphiphile, amphiphilic molecule modifying agent and is carried out surface embedding modification.With " a step Method " is compared, and " two-step method " embedding modified technique can realize amphipathic molecule in the orientation insertion embedding of swelled surface, hydrophobic side Tend to be implanted into swelled surface, water-wet side is then exposed on the outside of modified surface, therefore surface modification effect is more preferable.
However, there is also some problems for surface embedding method of modifying.On the one hand, since surface embedding method of modifying is with low The amphiphile, amphiphilic molecule of molecular weight is modifying agent, and under long-term Soaking environment, the amphipathic molecule of modified surface implantation is flooded out Tendency, cause the decaying of modified surface polarity, hydrophilicity.Huang Jian etc. is on the basis of its " one-step method " embeds modified technique (CN 200610161541.8) uses the double bond containing amphiphile, amphiphilic molecule in hydrophobic side for modifying agent, and be aided with ultraviolet spoke to modified surface According to, can improve embedding modified surface performance stability.On the other hand, molten for the polyethylene of hemicrystalline, polypropylene carrier Swollen dose of solvation occurs mainly in the amorphous region on its surface.However in the solvent of the good solvents such as decahydronaphthalene, dimethylbenzene Under change effect, its amorphous strand also has the tendency that dissolution, loss when polyethylene, polypropylene surface are swollen, and causes surface molten Expansibility is low, swell layer thickness reduces, and is unfavorable for the surface implantation of amphipathic molecule, influences surface modification effect.
It is simple with the treatment process of upper surface embedding method of modifying, be not required to complicated equipment, it can be achieved that polyethylene, poly- third The hydrophilic modifying on the surfaces such as alkene, impregnation technology is particularly suitable for the complicated or porous of the product forms such as porous diffusion barrier, fiber The processing on gap surface.But the study found that can also further increase surface modification effect by improving process of surface treatment and change The stability and persistence of property surface property.
Summary of the invention
The problem of present invention is for existing " two-step method " surface embedding modified technique, i.e., in the swelling process of surface The dissolution of polyethylene or polypropylene amorphous chain, leakage, and the amphipathic molecule of long-term Soaking environment lower surface embedding The tendency being flooded out proposes new solution.Based on modified " two-step method " technique of surface embedding, by swelling table Face introduces the initiator of free radical polymerization, while using the double bond containing amphiphile, amphiphilic molecule in hydrophobic side for modifying agent, further improves The stability and persistence of surface modification effect and modified surface performance.
The present invention is achieved by the following technical solutions: based on modified " two-step method " technique of surface embedding, will first gather Ethylene or polypropylene material are immersed in progress surface swelling in the solution of the organic solvent containing radical polymerization initiator, then will It is modified that polyethylene or polypropylene material immerse progress surface in the aqueous solution of the double bond containing amphiphile, amphiphilic molecule modifying agent in hydrophobic side.The skill Art scheme introduces initiator while surface is swollen in swelled surface, free radical that decomposition of initiator generates or its derived from Peroxy radical can cause swelled surface lightly crosslinked, so that the dissolution of amorphous chain in the swelling process of surface, loss be inhibited to incline To improve surface swellbility and amphiphile, amphiphilic molecule in the implant density of modified surface；Using the double bond containing amphiphilic in hydrophobic side point Son is modifying agent, under the action of the free radical or peroxy radical derived from it that decomposition of initiator generates, modified surface embedding Amphiphile, amphiphilic molecule can with polyethylene, polypropylene molecular chain occur covalently key connection, to improve modified surface polarity and hydrophily The stability of energy.Amphiphile, amphiphilic molecule described in its processing method is Polyethylene Glycol Oleate.
The hydrophilic modification method of polyethylene, polypropylene material surface endurance of the invention, further technical solution are Method includes the following steps:
1) solution for containing 3 wt% radical polymerization initiators is prepared with organic solvent；
2) polyethylene or polypropylene material are immersed in the solution of step 1), 1~7 is handled at a temperature of 60~75 DEG C Hour；
3) polyethylene or polypropylene material that are swollen through step 2 surface are immersed in the water containing 1~6 wt% amphiphile, amphiphilic molecule In solution, handled 5 minutes~1 hour at a temperature of 60~75 DEG C；
4) surface deswelling processing is carried out to polyethylene or polypropylene with vacuum drying method, then washs with water poly- second Alkene or polypropylene surface remove the amphiphile, amphiphilic molecule of surface physics absorption.
In the hydrophilic modification method of above-mentioned polyethylene, polypropylene material surface endurance, the Polyethylene Glycol Oleate The degree of polymerization of middle polyethylene glycol is 4~10；
In the hydrophilic modification method of above-mentioned polyethylene, polypropylene material surface endurance, the organic solvent is insoluble In the decahydronaphthalene of water, naphthane, carbon tetrachloride, mineral oil or dimethylbenzene；
In the hydrophilic modification method of above-mentioned polyethylene, polypropylene material surface endurance, the free radical polymerization causes Agent is dibenzoyl peroxide or azodiisobutyronitrile.
The invention has the following advantages:
1) surface based on " two-step method " embeds modified technique, using swelled surface to the affine work of amphiphile, amphiphilic molecule hydrophobic side With and water to the orientation effect of amphiphile, amphiphilic molecule water-wet side, it can be achieved that amphiphile, amphiphilic molecule is implanted into embedding in the orientation of swelled surface, i.e., two Affinity molecule hydrophobic side is embedded in inside modified surface, plays fixed function, while amphiphile, amphiphilic molecule water-wet side is exposed to modified surface Outside provides surface hydrophilicity.
2) initiator, the free radical or its derivative peroxy radical that decomposition of initiator generates are introduced in swelled surface Swelled surface can be caused lightly crosslinked, to inhibit the dissolution of polyethylene or polypropylene amorphous chain in the swelling process of surface, stream Tendency is lost, to improve surface swellbility and amphiphile, amphiphilic molecule in the implant density of modified surface, it is modified to further improve surface Effect.
3) use the double bond containing amphiphile, amphiphilic molecule in hydrophobic side for modifying agent, in the free radical or its derivative of decomposition of initiator generation Peroxy radical under the action of, modified surface embedding amphiphile, amphiphilic molecule can with polyethylene, polypropylene molecular chain occur covalent bond Connection, to improve the stability of modified surface polarity and hydrophilicity.
4) processing method and simple process of the invention, without complicated equipment, modified effect is obvious, stablizes, and is suitable for Plant-scale surface treatment has complexity particularly suitable for porous diffusion barrier, fiber etc. based on polyethylene, polypropylene material Or the commercial scale surface treatment of porous surface product.
Specific embodiment
The present invention is further illustrated by the following examples:
Embodiment 1
1) solution for containing 3 wt% dibenzoyl peroxides is prepared with naphthane；
2) polythene material is immersed in the solution of step 1), is handled 6 hours at a temperature of 75 DEG C；
3) polythene material being swollen through step 2 surface is immersed in containing 6 wt% Polyethylene Glycol Oleate (polyethylene glycol The degree of polymerization is to handle 1 hour at a temperature of 70 DEG C in aqueous solution 4)；
4) surface deswelling processing is carried out to polyethylene with vacuum drying method, then washs with water polyethylene surface, Remove the Polyethylene Glycol Oleate of surface physics absorption.With the water contact angle on sessile drop method test modified poly ethylene surface after drying Value, as a result see the table below 1；
5) modified polyethylene is immersed in the water, changes water daily, sample and drying are taken out after 5 weeks, is tested with sessile drop method The water contact angle value on modified poly ethylene surface, as a result see the table below 1.
Embodiment 2
1) solution for containing 3 wt% dibenzoyl peroxides is prepared with decahydronaphthalene；
2) polythene material is immersed in the solution of step 1), is handled 4 hours at a temperature of 65 DEG C；
3) polythene material being swollen through step 2 surface is immersed in containing 4 wt% Polyethylene Glycol Oleate (polyethylene glycol The degree of polymerization is to handle 30 minutes at a temperature of 60 DEG C in aqueous solution 6)；
4) surface deswelling processing is carried out to polyethylene with vacuum drying method, then washs with water polyethylene surface, Remove the Polyethylene Glycol Oleate of surface physics absorption.With the water contact angle on sessile drop method test modified poly ethylene surface after drying Value, as a result see the table below 1；
5) modified polyethylene is immersed in the water, changes water daily, sample and drying are taken out after 5 weeks, is tested with sessile drop method The water contact angle value on modified poly ethylene surface, as a result see the table below 1.
Embodiment 3
1) solution for containing 3 wt% azodiisobutyronitriles is prepared with mineral oil；
2) polythene material is immersed in the solution of step 1), is handled 1 hour at a temperature of 60 DEG C；
3) polythene material being swollen through step 2 surface is immersed in containing 2 wt% Polyethylene Glycol Oleate (polyethylene glycol The degree of polymerization is to handle 6 minutes at a temperature of 75 DEG C in aqueous solution 8)；
4) surface deswelling processing is carried out to polyethylene with vacuum drying method, then washs with water polyethylene surface, Remove the Polyethylene Glycol Oleate of surface physics absorption.With the water contact angle on sessile drop method test modified poly ethylene surface after drying Value, as a result see the table below 1；
5) modified polyethylene is immersed in the water, changes water daily, sample and drying are taken out after 5 weeks, is tested with sessile drop method The water contact angle value on modified poly ethylene surface, as a result see the table below 1.
Embodiment 4
1) solution for containing 3 wt% dibenzoyl peroxides is prepared with naphthane；
2) polypropylene material is immersed in the solution of step 1), is handled 6 hours at a temperature of 75 DEG C；
3) polypropylene material being swollen through step 2 surface is immersed in containing 6 wt% Polyethylene Glycol Oleate (polyethylene glycol The degree of polymerization is to handle 60 minutes at a temperature of 70 DEG C in aqueous solution 4)；
4) surface deswelling processing is carried out to polypropylene with vacuum drying method, then washs with water polypropylene surface, Remove the Polyethylene Glycol Oleate of surface physics absorption.With the water contact angle on sessile drop method test modified polypropene surface after drying Value, as a result see the table below 1；
5) modified polypropylene is immersed in the water, changes water daily, sample and drying are taken out after 5 weeks, is tested with sessile drop method The water contact angle value on modified polypropene surface, as a result see the table below 1.
Embodiment 5
1) solution for containing 3 wt% azodiisobutyronitriles is prepared with carbon tetrachloride；
2) polypropylene material is immersed in the solution of step 1), is handled 5 hours at a temperature of 60 DEG C；
3) polypropylene material being swollen through step 2 surface is immersed in containing 4 wt% Polyethylene Glycol Oleate (polyethylene glycol The degree of polymerization is to handle 30 minutes at a temperature of 60 DEG C in aqueous solution 8)；
4) surface deswelling processing is carried out to polypropylene with vacuum drying method, then washs with water polypropylene surface, Remove the Polyethylene Glycol Oleate of surface physics absorption.With the water contact angle on sessile drop method test modified polypropene surface after drying Value, as a result see the table below 1；
5) modified polypropylene is immersed in the water, changes water daily, sample and drying are taken out after 5 weeks, is tested with sessile drop method The water contact angle value on modified polypropene surface, as a result see the table below 1.
Embodiment 6
1) solution for containing 3 wt% azodiisobutyronitriles is prepared with dimethylbenzene；
2) polypropylene material is immersed in the solution of step 1), is handled 2 hours at a temperature of 70 DEG C；
3) polypropylene material being swollen through step 2 surface is immersed in containing 2 wt% Polyethylene Glycol Oleate (polyethylene glycol The degree of polymerization is to handle 10 minutes at a temperature of 75 DEG C in aqueous solution 10)；
4) surface deswelling processing is carried out to polypropylene with vacuum drying method, then washs with water polypropylene surface, Remove the Polyethylene Glycol Oleate of surface physics absorption.With the water contact angle on sessile drop method test modified polypropene surface after drying Value, as a result see the table below 1；
5) modified polypropylene is immersed in the water, changes water daily, sample and drying are taken out after 5 weeks, is tested with sessile drop method The water contact angle value on modified polypropene surface, as a result see the table below 1.
Comparative example 1
1) polythene material is immersed in naphthane solution, is handled 6 hours at a temperature of 75 DEG C；
2) polythene material being swollen through step 1) surface is immersed in containing 6 wt% Polyethylene Glycol Oleate (polyethylene glycol The degree of polymerization is to handle 1 hour at a temperature of 70 DEG C in aqueous solution 4)；
3) surface deswelling processing is carried out to polyethylene with vacuum drying method, then washs with water polyethylene surface, Remove the Polyethylene Glycol Oleate of surface physics absorption.With the water contact angle on sessile drop method test modified poly ethylene surface after drying Value, as a result see the table below 1；
4) modified polyethylene is immersed in the water, changes water daily, sample and drying are taken out after 5 weeks, is tested with sessile drop method The water contact angle value on modified poly ethylene surface, as a result see the table below 1.
Comparative example 2
1) polypropylene material is immersed in naphthane solution, is handled 6 hours at a temperature of 75 DEG C；
2) polypropylene material being swollen through step 2 surface is immersed in containing 6 wt% Polyethylene Glycol Oleate (polyethylene glycol The degree of polymerization is to handle 60 minutes at a temperature of 70 DEG C in aqueous solution 4)；
3) surface deswelling processing is carried out to polypropylene with vacuum drying method, then washs with water polypropylene surface, Remove the Polyethylene Glycol Oleate of surface physics absorption.With the water contact angle on sessile drop method test modified polypropene surface after drying Value, as a result see the table below 1；
4) modified polypropylene is immersed in the water, changes water daily, sample and drying are taken out after 5 weeks, is tested with sessile drop method The water contact angle value on modified polypropene surface, as a result see the table below 1.
Table 1
It can be seen that from the result in table 1 using method of modifying (Examples 1 to 6) of the invention, polyethylene and polypropylene Material obtains good surface hydrophilic modification effect, and the hydrophilicity of modified surface is able to maintain after immersion 5 weeks.And do not add The surface hydrophilic modification effect of comparative example 1 and 2 of initiator is slightly poor, while the 5 weeks rear surface hydrophilicities that soak are lost substantially.Explanation It is handled through method of modifying of the invention, the hydrophilic modifying effect of modified surface is obvious and is able to maintain the persistence of hydrophilicity.

Claims (5)

1. the hydrophilic modification method of a kind of polyethylene, polypropylene material surface endurance, it is characterised in that this method is with hydrophobic side Double bond containing amphiphile, amphiphilic molecule is modifying agent, and the polyethylene or polypropylene material to surface swelling carry out surface and be modified, and described changes Property method is that first polyethylene or polypropylene material are immersed in the solution of the organic solvent containing radical polymerization initiator to carry out Then polyethylene or polypropylene material are immersed progress surface in the aqueous solution of the modifying agent containing amphiphile, amphiphilic molecule and are modified by surface swelling, Wherein the amphiphile, amphiphilic molecule is Polyethylene Glycol Oleate.
2. the hydrophilic modification method of polyethylene according to claim 1, polypropylene material surface endurance, it is characterised in that packet Include following steps:
1) solution for containing 3 wt% radical polymerization initiators is prepared with organic solvent；
2) polyethylene or polypropylene material are immersed in the solution of step 1), are handled 1~7 hour at a temperature of 60~75 DEG C；
3) polyethylene or polypropylene material that are swollen through step 2 surface are immersed in the aqueous solution containing 1~6 wt% amphiphile, amphiphilic molecule In, it is handled 5 minutes~1 hour at a temperature of 60~75 DEG C；
4) surface deswelling processing is carried out to polyethylene or polypropylene with vacuum drying method, then wash with water polyethylene or Polypropylene surface removes the amphiphile, amphiphilic molecule of surface physics absorption.
3. the hydrophilic modification method of polyethylene according to claim 1, polypropylene material surface endurance, it is characterised in that institute The degree of polymerization of polyethylene glycol is 4~10 in the Polyethylene Glycol Oleate stated.
4. the hydrophilic modification method of polyethylene according to claim 1 or 2, polypropylene material surface endurance, feature exist In the organic solvent be decahydronaphthalene not soluble in water, naphthane, carbon tetrachloride, mineral oil or dimethylbenzene.
5. the hydrophilic modification method of polyethylene according to claim 1 or 2, polypropylene material surface endurance, feature exist In the radical polymerization initiator be dibenzoyl peroxide or azodiisobutyronitrile.
CN201610900944.3A 2016-10-17 2016-10-17 A kind of hydrophilic modification method of polyethylene, polypropylene material surface endurance Active CN106397820B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1785526A (en) * 2005-11-09 2006-06-14 宁夏大学 Non-porous single dispersed polymer weak cation exchange resin, its preparation method and use
CN101011644A (en) * 2006-12-27 2007-08-08 南京工业大学 Method for persistent hydrophilic modification of polypropylene porous membrane surface
CN101601974A (en) * 2009-07-08 2009-12-16 南京工业大学 The hydrophilic modification method of double crystalline polyolefin porous membrane surface of a kind of amphipathic molecule

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1785526A (en) * 2005-11-09 2006-06-14 宁夏大学 Non-porous single dispersed polymer weak cation exchange resin, its preparation method and use
CN101011644A (en) * 2006-12-27 2007-08-08 南京工业大学 Method for persistent hydrophilic modification of polypropylene porous membrane surface
CN101601974A (en) * 2009-07-08 2009-12-16 南京工业大学 The hydrophilic modification method of double crystalline polyolefin porous membrane surface of a kind of amphipathic molecule

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