CN101570603B - Hydrophobic polymer material surface hydrophilicity improving method - Google Patents
Hydrophobic polymer material surface hydrophilicity improving method Download PDFInfo
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Abstract
The invention relates to a hydrophobic polymer material surface hydrophilicity improving method. In order to solve the problem that material surface hydrophilicity is unendurable in the current blended technology, amphipathic microgel containing thermosensitive core and non thermosensitive core is taken as hydrophile modification ingredient in the invention, and surface hydrophilization modification is carried out on hydrophobic polymer material by casting method and melt blending extrusion method respectively. (1) The casting method includes: dispersion liquid of the microgel and hydrophobic polymer solution are blended, the blended even dispersion liquid is casted into a film in a mold, and solvent is removed, thus obtaining a polymer film. (2) The melt blending extrusion method includes: dry microgel and hydrophilic polymer particles are blended and then put into a rotor internal mixer to be mixed for a short time at certain temperature; the material is crushed into particles after discharging, is extruded into sheet or wire by an extruder and forms film by a hot press. The invention has the advantages of easy technique and reliable treatment effect without a complex device and can effectively improve the surface hydrophilicity of the hydrophobic polymer.
Description
Technical field
The invention provides a kind of hydrophobic polymer material surface hydrophilicity method of improving.
Background technology
Be used widely at biomedical sector preferably by plasticity-, wearability, higher mechanical properties etc. with it for hydrophobic polymer.For example the intensity of high density polyethylene(HDPE), hardness, wear resisting property excellence have been used for surgical patching materials such as artificial hipbone, joint prosthesis; Polytetrafluoroethylene (PTFE) has excellent physical and mechanical properties and implants advantages such as back tissue reaction is little and be widely used in artificial organs and tissue renovation material.The material that directly links to each other as implant or with live body with the live body contact process in a series of problems such as allergy, rejection, blood coagulation and cell distortion might take place, and the surface of hydrophilization can stop hematoblastic absorption of sticking with plasma proteins, reduces the non-specific interaction between material and the live body.Therefore, hydrophilic modification being carried out on existing hydrophobic material surface is the effective way that overcomes the above problems.
Surface modifying method can be divided into two kinds of physically modified method and chemic modified methods.Blending method belongs to the physically modified method, and technology is simple, can realize the hydrophilic modification on hydrophobic polymer surface.CN01129834 is with polyvinyl chloride (PVC), polyethylene (PE), polypropylene hydrophobic polymer and hydrophilic high molecular material such as polyoxyethylene (PEO) blend such as (PP), plastics have been prepared with water-wetted surface, CN200410029758 pours into a mould film forming with polyvinylacetal superpolymer and PVC blend, also can improve the wetting ability of PVC film, but be to use the wetting ability linear polymer as properties-correcting agent, the hydrophilic polymer of material surface can very fast dissolving when the gained intermingling material contacts with water medium, and surface hydrophilicity and biocompatibility can not be lasting; CN200610161542 is immersed in polypropylene (PP) porous-film and carries out surface treatment in the swelling agent that contains the block structure amphiphile, amphiphilic molecule, amphiphile, amphiphilic molecule can carry out embedding and hydrophilic modification on the film surface, improved the stability of hydrophilic layer to a certain extent, the hydrophilic polymer of material surface can dissolve when but the gained intermingling material contacted with water medium, surface hydrophilicity still can not be lasting, and used the higher tetracol phenixin of toxicity, naphthane as swelling agent, may bring environmental issue; CN101301591 and CN03804097 carry out quaternary ammoniated crosslinking reaction on PTFE film surface and electron transfer reaction has formed stable surface hydrophilic layer, but the required apparatus expensive of electron transfer reaction that chemical reaction is especially implemented by heat energy or uv energy, reaction can damage the film surface, changes the film surface properties; US2008305348 provides a kind of method that forms the stable hydrophilic layer on the hydrophobic polymer surface, the solution and the high-pressure polyethylene (LDPE) of yeast invertase are heated to 120 ℃ in the reactor that has stirring and pressure, step-down fast then, add cold water simultaneously, the glycoprotein hydrophobic side is embedded in the LDPE micelle, water-wet side then stretches to water medium, but complex process, and condition is not gentle.Therefore, be necessary to redesign polymer-modified structure, give the hydrophobic polymer intermingling material with stable surface hydrophilicity to improve the effect of surface modification.
Summary of the invention
In order to solve the unendurable problem of material surface wetting ability in the existing blending technology, the present invention as the hydrophilic modifying component, adopts casting and melt blending extrusion molding that hydrophobic polymer material is carried out performing hydrophilic modification on surface with amphipathic microgel with temperature sensitive property nuclear and non-temperature sensitive property nuclear respectively.Micro-gel surface has the amphipathic side chain of " hair " shape, and is good with the consistency of hydrophobic polymer matrix, makes microgel to be scattered in the polymeric matrix.Be in the microgel of material surface, its surface " hair " shape amphiphilic side chain has water-soluble, forms hydrophilic microcell at material surface, improves the wetting ability of material surface, and the microcell yardstick can be controlled by the microgel particle diameter.The hydrophilic microcell that the anchor fluke effect of micro-gel surface amphiphilic side chain and the packing interaction between matrix and the microgel produce microgel can be by the water medium corrosion.
The present invention is achieved through the following technical solutions:
The present invention replaces present adopted linear hydrophilic polymer modified component by the amphipathic microgel that synthetic has temperature sensitive property nuclear and non-temperature sensitive property nuclear, adopts casting and melt blending extrusion molding that hydrophobic polymer material is carried out performing hydrophilic modification on surface respectively.In casting, the dispersion liquid mixing with hydrophobic polymer solution and microgel is cast into film with the dispersion liquid that mixes in mould, remove solvent, obtains polymeric film.In the melt blending extrusion molding, dry state microgel and hydrophobic polymer pellet are mixed in the input rotor Banbury mixer of back, and mixing at a certain temperature certain hour is broken into particle with material after the discharging, by forcing machine extrusion sheet or wire rod, utilize thermocompressor hot pressing film forming or sheet again.
The hydrophobic polymer material surface hydrophilicity method of improving of the present invention may further comprise the steps:
Synthesizing of microgel:
1) hydrophilic macromonomer with the two keys of deionized water, unsaturated vinyl monomer, linking agent and molecule chain end band adds reactor, stirs and logical nitrogen deoxygenation; Dosage of crosslinking agent is the 0.5mol%～5.0mol% of unsaturated vinyl monomer consumption; The hydrophilic macromonomer consumption of the two keys of molecule chain end band is the 0.5mol%～15mol% of unsaturated vinyl monomer consumption; The monomeric add-on of ethylenic unsaturation class for this moment add reactor the reactant total mass 0.2%～10%;
2) add initiator, under 60 ℃～80 ℃, stirring and logical condition of nitrogen gas, react 12h～48h; Initiator amount is the 0.2mol%～15mol% of unsaturated vinyl monomer consumption;
3) reaction finishes, and obtains aqueous solutions of polymers; Aqueous solutions of polymers is after the dialysis membrane dialysis, and lyophilize obtains the dry state microgel.
In the above-mentioned synthetic method, its described unsaturated vinyl monomer is N-isopropylacrylamide (NIPAM) or vinylbenzene (St); The hydrophilic macromonomer of the two keys of molecule chain end band comprises that number-average molecular weight is from 1000 to 10, polyvinylpyrrolidone (PVP) macromonomer of 000 polyoxyethylene (PEO) macromonomer and number-average molecular weight from 2000 to 8000, these macromonomers have polymerizable acrylate end group or vinyl benzene end group; Linking agent is N, N '-methylene-bisacrylamide (BIS) or Vinylstyrene (DVB); Initiator is Potassium Persulphate (KPS).
Described casting may further comprise the steps:
1) the dry state microgel is dispersed in to be configured to mass percent concentration in the organic solvent be 0.15%～5.0% dispersion liquid A;
2) hydrophobic polymer is dissolved in to be mixed with mass percent concentration in the organic solvent be 1%～20% polymers soln B;
3) dispersion liquid A is mixed with different weight ratios with solution B, be configured to mixed dispersion liquid; The quality of microgel is 0.01～0.25 of a hydrophobic polymer in this mixed dispersion liquid;
4) in mould, be cast into film under the room temperature, remove solvent, obtain polymeric film;
Organic solvent is the halogenated aryl hydrocarbon class;
Above-mentionedly hydrophobic polymer material is carried out in the content of performing hydrophilic modification on surface with casting, its described organic solvent is the halogenated aryl hydrocarbon class; Hydrophobic polymer is any one in polystyrene (PS), high-impact polystyrene (HIPS), polyvinyl chloride (PVC), polypropylene (PP), the polyethylene (PE).
The melt blending extrusion molding:
1) the hydrophobic polymer plastic grain is mixed with the dry state microgel, dry state microgel mass fraction is 0.5 to 25 part of per 100 parts of hydrophobic polymer.
2) with in the mixture input rotor Banbury mixer, mixing 10-30 minute discharging under 160-190 ℃ of temperature.
3) after the discharging polymkeric substance is broken into particle, by forcing machine extrusion sheet or wire rod.
4) place the press mold machine in 160-190 ℃ of hot pressing 10-30 minute sheet material or wire rod, obtain polymeric film or sheet material.
Above-mentionedly hydrophobic polymer material is carried out in the content of performing hydrophilic modification on surface with the melt blending extrusion molding, the feature of its described hydrophobic plastic polymkeric substance is identical with hydrophobic polymer in the casting.
The present invention has following effect:
1) adopt amphipathic microgel as modified component, construct hydrophilic microcell at material surface, the microcell yardstick can be controlled by the microgel particle diameter.The microcell yardstick has temperature-responsive when adopting temperature sensitive microgel.
2) the anchor fluke effect of micro-gel surface amphiphilic side chain and the packing interaction between matrix and the microgel are unlikely to by the water medium corrosion microgel.
3) technology of the present invention is simple, and treatment effect is reliable, need not complex apparatus, can effectively improve the surface hydrophilicity of hydrophobic polymer.
Embodiment:
Embodiment 1:
With the 100.0g deionized water, 5.00g vinylbenzene (St) monomer, 0.05g linking agent Vinylstyrene (DVB) and 1.00g massfraction are the polyethylene glycol methacrylate-styrene polymer (M of 50wt%
W=1000) the macromonomer aqueous solution joins in the reactor, stirs and logical nitrogen deoxygenation.Be warming up to 60 ℃, add the aqueous solution 2mL (containing 0.10g KPS) of initiator potassium persulfate (KPS), under the condition of stirring and logical nitrogen, react 12h.Reaction finishes, and product is after dialysis membrane (MWCO=14000) dialysis is refining, and lyophilize obtains the PS-PEO microgel that dry state has non-temperature sensitive nuclear.
With tetrahydrofuran (THF) (THF) is that solvent is prepared the PVC/THF solution of 10wt% and the PS/THF solution of 10wt% respectively; PS-PEO dry state microgel 0.04g is added among the 15mLTHF,, obtain the PS-PEO/THF dispersion liquid through ultra-sonic dispersion 30 minutes.4mL PS-PEO/THF dispersion liquid is mixed with 1mL PVC/THF solution, sonic oscillation 30 minutes, obtaining microgel/PVC mass percent is 10% mixed dispersion liquid; 7mL PS-PEO/THF dispersion liquid is mixed with 1mL PS/THF solution, sonic oscillation 30 minutes, obtaining microgel/PS mass percent is 19% mixed dispersion liquid.At room temperature two kinds of mixed dispersion liquid are injected mould respectively, remove THF, obtain PVC polymeric film and PS polymeric film.
40 parts of HIPS (trade mark 825E) particle is mixed with 10 parts of PS-PEO microgels with non-temperature sensitive nuclear, in the mixture input rotor Banbury mixer, discharging in mixing 30 minutes under 170 ℃ of temperature.After the discharging polymkeric substance is broken into particle, is extruded into wire rod by forcing machine.Wire rod places the press mold machine in 170 ℃ of hot pressing 20 minutes, obtains the polymer flake of blend HIPS.With gained blend HIPS polymer flake under the room temperature in deionized water with 120 times/minute frequencies 10h that in shaking table, vibrates, take out postlyophilization and obtain polymer flake through water treatment.
Measure the polymer flake of PVC polymeric film, PS polymeric film, blend HIPS and through the water contact angle of the polymer flake of water treatment; Measure the tensile strength of the polymer flake of blend HIPS.Water contact angle value and tensile strength values see Table 1.
Embodiment 2:
With the 100.0g deionized water, 2.50g St monomer, polyvinylpyrrolidone (PVP) the macromonomer aqueous solution (M of 0.03g DVB and 2.00g 50wt%
W=2000) add in the reactor, stir and logical nitrogen deoxygenation.Be warming up to 60 ℃, add KPS aqueous solution 1mL (containing 0.13g KPS), under the condition of stirring and logical nitrogen deoxygenation, react 36h.Reaction finishes, and product is after dialysis membrane (MWCO=14000) dialysis is refining, and lyophilize obtains having the PS-PVP microgel of non-temperature sensitive nuclear.
The preparation of PVC/THF solution and PS/THF solution is as implementing shown in the example 1.The PS-PVP dry state microgel 0.04g that will have non-temperature sensitive nuclear adds among the 15mLTHF, through ultra-sonic dispersion 30 minutes, obtains the PS-PVP/THF dispersion liquid.3.5mL PS-PVP/THF dispersion liquid is mixed with 0.5mL PVC/THF solution, sonic oscillation 30 minutes, obtaining microgel/PVC mass percent is 19% mixed dispersion liquid; 7mL PS-PVP/THF dispersion liquid is mixed with 1mL PS/THF solution, sonic oscillation 30 minutes, obtaining microgel/PS mass percent is 19% mixed dispersion liquid.At room temperature two kinds of mixed dispersion liquid are injected mould respectively, remove THF, obtain PVC polymeric film and PS polymeric film.
40 parts of HIPS particles are mixed with 10 parts of PS-PVP microgels with non-temperature sensitive nuclear.The method for preparing polymer blend thin slice and water treatment polymerization thin slice with mixture is as implementing shown in the example 1.
Measure the polymer flake of PVC polymeric film, PS polymeric film, blend HIPS and through the water contact angle of the polymer flake of water treatment; Measure the tensile strength of the polymer flake of blend HIPS.Water contact angle value and tensile strength values see Table 1.
Embodiment 3:
With the 250g deionized water, 2.00g N-isopropylacrylamide (NIPAM) monomer, 0.05g linking agent N, N '-methylene-bisacrylamide (BIS) and 8.70g massfraction are the polyethylene glycol methacrylate-styrene polymer (M of 50wt%
W=5000) the macromonomer aqueous solution adds in the reactor, stirs and logical nitrogen deoxygenation.Be warming up to 70 ℃, add KPS aqueous solution 10mL (containing 0.60g KPS), under stirring and logical condition of nitrogen gas, react 24h.Reaction finishes, and product is after dialysis membrane (MWCO=14000) dialysis is refining, and lyophilize obtains the PNIPAM-PEO microgel that dry state has temperature sensitive nuclear.
The preparation of PVC/THF solution and PS/THF solution is as implementing shown in the example 1.The PNIPAM-PEO dry state microgel 0.15g that will have temperature sensitive nuclear adds among the 60mLTHF, through ultra-sonic dispersion 30 minutes, obtains the PNIPAM-PEO/THF dispersion liquid.3.5mL PNIPAM-PEO/THF dispersion liquid is mixed with 0.5mLPVC/THF solution, sonic oscillation 30 minutes, obtaining microgel/PVC mass percent is 18% mixed dispersion liquid; 3mL PNIPAM-PEO/THF dispersion liquid is mixed with 1mL PS/THF solution, sonic oscillation 30 minutes, obtaining microgel/PS mass percent is 7.5% mixed dispersion liquid.At room temperature two kinds of mixed dispersion liquid are injected mould respectively, remove THF, obtain PVC polymeric film and PS polymeric film.
45 parts of HIPS particles are mixed with 5 parts of PNIPAM-PEO microgels with non-temperature sensitive nuclear.The method for preparing polymer blend thin slice and water treatment polymerization thin slice with mixture is as implementing shown in the example 1.
Measure the polymer flake of PVC polymeric film, PS polymeric film, blend HIPS and through the water contact angle of the polymer flake of water treatment; Measure the tensile strength of the polymer flake of blend HIPS.Water contact angle value and tensile strength values see Table 1.
Embodiment 4:
With the 250g deionized water, 1.00g NIPAM monomer, the PVP macromonomer (M of 0.05g BIS and 14.14g 50wt%
W=8000) aqueous solution adds in the reactor, stirs and logical nitrogen deoxygenation.Be warming up to 70 ℃, add KPS aqueous solution 6mL (containing 0.30g KPS), under stirring and logical condition of nitrogen gas, react 36.Stopped reaction, product is after dialysis membrane (MWCO=14000) dialysis is refining, and lyophilize obtains having the PNIPAM-PVP microgel of temperature sensitive nuclear.
The preparation of PVC/THF solution and PS/THF solution is as implementing shown in the example 1.The PNIPAM-PVP dry state microgel 0.10g that will have temperature sensitive nuclear adds among the 65mLTHF, through ultra-sonic dispersion 30 minutes, obtains the PNIPAM-PVP/THF dispersion liquid.5.5mL PNIPAM-PVP/THF dispersion liquid is mixed with 0.5mLPVC/THF solution, sonic oscillation 30 minutes, obtaining microgel/PVC mass percent is 17% mixed dispersion liquid; 5.5mL PNIPAM-PVP/THF dispersion liquid is mixed with 1mL PS/THF solution, sonic oscillation 30 minutes, obtaining microgel/PS mass percent is 8.5% mixed dispersion liquid.At room temperature two kinds of mixed dispersion liquid are injected mould respectively, remove THF, obtain PVC polymeric film and PS polymeric film.
45 parts of HIPS particles are mixed with 5 parts of PNIPAM-PVP microgels with non-temperature sensitive nuclear.The method for preparing polymer blend thin slice and water treatment polymerization thin slice with mixture is as implementing shown in the example 1.
Measure the polymer flake of PVC polymeric film, PS polymeric film, blend HIPS and through the water contact angle of the polymer flake of water treatment; Measure the tensile strength of the polymer flake of blend HIPS.Water contact angle value and tensile strength values see Table 1.
As can be seen from Table 1, compare with the HIPS control sample with pure PVC, PS, microgel is as the hydrophilic modifying component, make the contact angle on hydrophobic polymer material surface that in various degree decline all be arranged, with the sample of casting preparation, the decline degree of its contact angle is than big with the sample of melt blending extrusion molding preparation.The contact angle of contrast #HIPS sample and HIPS sample it can also be seen that through water medium and soaks vibration after 10 hours that the contact angle of blend HIPS slice surfaces changes very little, shows the wetting ability quite stable through the hydrophobic polymer material surface of microgel blending and modifying.Hydrophilic improvement helps the raising of material biocompatibility and blood compatibility, is expected to the application in technical field of biological material.The specific tensile strength variation is little mutually with control sample for the polymer membrane that the melt blending extrusion molding obtains, illustrate that microgel is improving the mechanical property that hydrophobic polymer material surface hydrophilicity can guarantee hydrophobic polymer simultaneously as hydrophilic component, this conclusion is significant concerning industrial application.
The tensile strength of the composition of each sample, water contact angle value and sample segment in table 1 embodiment
#HIPS: through the sample of water treatment
Claims (2)
1. one kind is improved the hydrophobic polymer material surface hydrophilicity method, it is characterized in that: at first synthetic microgel, adopt casting and melt blending extrusion molding that hydrophobic polymer material is carried out performing hydrophilic modification on surface then respectively;
Synthesizing of microgel:
1) hydrophilic macromonomer with the two keys of deionized water, unsaturated vinyl monomer, linking agent and molecule chain end band adds reactor, stirs and logical nitrogen deoxygenation; Dosage of crosslinking agent is the 0.5mol%～5.0mol% of unsaturated vinyl monomer consumption; The hydrophilic macromonomer consumption of the two keys of molecule chain end band is the 0.5mol%～15mol% of unsaturated vinyl monomer consumption; The monomeric add-on of ethylenic unsaturation class for this moment add reactor the reactant total mass 0.2%～10%;
2) add initiator, under 60 ℃～80 ℃, stirring and logical condition of nitrogen gas, react 12h～48h; Initiator amount is the 0.2mol%～15mol% of unsaturated vinyl monomer consumption;
3) reaction finishes, and obtains aqueous solutions of polymers; Aqueous solutions of polymers is after the dialysis membrane dialysis, and lyophilize obtains the dry state microgel;
Described unsaturated vinyl monomer is N-isopropylacrylamide or vinylbenzene; The hydrophilic macromonomer of the two keys of molecule chain end band is that number-average molecular weight is the polyvinylpyrrolidone macromonomer of from 1000 to 10,000 polyoxyethylene macromonomers or number-average molecular weight from 2000 to 8000; And the two keys of molecule chain end are acrylate end groups or vinyl benzene end group; Linking agent is N, N '-methylene-bisacrylamide or Vinylstyrene; Initiator is a Potassium Persulphate;
Described casting may further comprise the steps:
(1) the dry state microgel is dispersed in to be configured to mass percent concentration in the organic solvent be 0.15%～5.0% dispersion liquid A;
(2) hydrophobic polymer is dissolved in to be mixed with mass percent concentration in the organic solvent be 1%～20% polymers soln B;
(3) dispersion liquid A is mixed with different weight ratios with solution B, be configured to mixed dispersion liquid; The quality of microgel is 0.01～0.25 of a hydrophobic polymer in this mixed dispersion liquid;
(4) in mould, be cast into film under the room temperature, remove solvent, obtain polymeric film;
Organic solvent is the halogenated aryl hydrocarbon class;
Described melt blending extrusion molding may further comprise the steps:
A) hydrophobic polymer particle is mixed with the dry state microgel, dry state microgel mass fraction is that per 100 parts of hydrophobic polymers mix 0.5 to 25 part;
B) with in the mixture input rotor Banbury mixer, mixing 10-30 minute discharging under 160-190 ℃ of temperature;
C) polymkeric substance after the discharging is broken into particle, by forcing machine extrusion sheet or wire rod;
D) place the press mold machine in 160-190 ℃ of hot pressing 10-30 minute sheet material or wire rod, obtain polymeric film.
2. method according to claim 1 is characterized in that: hydrophobic polymer is any one in polystyrene, high-impact polystyrene, polyvinyl chloride, polypropylene, the polyethylene.
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| CN102070787A (en) * | 2010-11-17 | 2011-05-25 | 哈尔滨工业大学 | Method for preparing conductive polymer gel for reinforcing steel bar corrosion electrochemical control |
| CN103041454B (en) * | 2012-12-11 | 2014-11-05 | 浙江微度医疗器械有限公司 | Composite material for making degradable ureteral stent and degradable ureteral stent |
| US20170137592A1 (en) * | 2014-05-28 | 2017-05-18 | Sabic Global Technologies B.V. | Water expandable polymer beads |
| CN105733097A (en) * | 2016-05-06 | 2016-07-06 | 中山大学 | Carbon emission reduction type environment-friendly polypropylene composite material and preparation method thereof |
| CN105949651A (en) * | 2016-05-24 | 2016-09-21 | 重庆大学 | Polyvinyl chloride (PVC) size hydrophilic modification method |
| CN111012954B (en) * | 2018-10-10 | 2022-04-08 | 中国石油化工股份有限公司 | PVC composition for antibacterial hydrophilic catheter and preparation method thereof |
| US20220298309A1 (en) * | 2019-08-29 | 2022-09-22 | Dow Global Technologies Llc | Method of making a homogeneous mixture of polyvinyl chloride solids and additive |
| CN113980321B (en) * | 2021-11-30 | 2022-08-02 | 常州艾龙森汽车饰件有限公司 | High-temperature-resistant dispersing agent for surface of film substrate, preparation method, application and application method |
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