CN109679129A - A kind of method that polyolefine material surface is modified - Google Patents
A kind of method that polyolefine material surface is modified Download PDFInfo
- Publication number
- CN109679129A CN109679129A CN201811590800.8A CN201811590800A CN109679129A CN 109679129 A CN109679129 A CN 109679129A CN 201811590800 A CN201811590800 A CN 201811590800A CN 109679129 A CN109679129 A CN 109679129A
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- Prior art keywords
- polyolefine material
- material surface
- modified method
- surface according
- polyolefine
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- 239000000463 material Substances 0.000 title claims abstract description 82
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 18
- 150000003254 radicals Chemical class 0.000 claims abstract description 17
- 239000000460 chlorine Substances 0.000 claims abstract description 13
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 12
- 238000007348 radical reaction Methods 0.000 claims abstract description 10
- 230000001795 light effect Effects 0.000 claims abstract description 4
- -1 (methyl) hydroxy-ethyl Chemical group 0.000 claims description 41
- 239000000178 monomer Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 10
- 239000003638 chemical reducing agent Substances 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 8
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 claims description 7
- 230000005855 radiation Effects 0.000 claims description 7
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- HOPRXXXSABQWAV-UHFFFAOYSA-N anhydrous collidine Natural products CC1=CC=NC(C)=C1C HOPRXXXSABQWAV-UHFFFAOYSA-N 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 6
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 5
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 5
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 4
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 claims description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- WBYWAXJHAXSJNI-UHFFFAOYSA-N cinnamic acid Chemical compound OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 claims description 3
- 150000004696 coordination complex Chemical class 0.000 claims description 3
- 229910052762 osmium Inorganic materials 0.000 claims description 3
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- 150000003222 pyridines Chemical class 0.000 claims description 3
- 230000001052 transient effect Effects 0.000 claims description 3
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 2
- 238000005304 joining Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 238000006557 surface reaction Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 30
- 229920000573 polyethylene Polymers 0.000 description 17
- 239000004698 Polyethylene Substances 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 10
- 239000004743 Polypropylene Substances 0.000 description 9
- 229920001155 polypropylene Polymers 0.000 description 9
- 238000005286 illumination Methods 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 7
- 239000000835 fiber Substances 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 239000012327 Ruthenium complex Substances 0.000 description 4
- 238000007605 air drying Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000003851 corona treatment Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical class CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000012982 microporous membrane Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical group 0.000 description 3
- HCLXLZGAYCTHQJ-UHFFFAOYSA-N 1h-cyclohepta[b]pyridine Chemical compound C1=CC=CC=C2NC=CC=C21 HCLXLZGAYCTHQJ-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 238000010559 graft polymerization reaction Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 238000009740 moulding (composite fabrication) Methods 0.000 description 2
- HQLVTKPFFDAOGT-UHFFFAOYSA-N pyridine-2-carboxylic acid ruthenium Chemical compound [Ru].N1=C(C=CC=C1)C(=O)O HQLVTKPFFDAOGT-UHFFFAOYSA-N 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical group CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical class 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002397 thermoplastic olefin Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
Classifications
-
- 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
- C08J7/14—Chemical modification with acids, their salts or anhydrides
-
- 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
- C08J7/16—Chemical modification with polymerisable compounds
- C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
- D06M10/06—Inorganic compounds or elements
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
- D06M10/08—Organic compounds
- D06M10/10—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
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
-
- 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 present invention relates to a kind of modified methods in polyolefine material surface, it is the following steps are included: (a) makes polyolefine material obtain chlorinated polyolefin material containing progress surface chlorination in solutions of chlorine；(b) the chlorinated polyolefin material is immersed in graft reaction solution, photocatalysis-atom transferred free radical reaction is carried out under light effect of irradiation.Polyolefine material surface can be realized and be modified by carrying out surface chlorination and photocatalysis-atom transferred free radical reaction, do not cause depth to destroy polyolefin surfaces, and reaction temperature can be reduced to room temperature, greatly shorten grafting time；And the processing of polyolefine material surface functionalization is uniform, can obtain corresponding functional group on polyolefine material surface according to demand.
Description
Technical field
The invention belongs to field of material surface modification, are related to a kind of method that polyolefine material surface is modified, and in particular to
A kind of polyethylene, polypropylene and its copolymer matrix are in the surface treatment method of photocatalysis-ATPR crosslinking technology.
Background technique
Polyethylene, polypropylene and its copolymer be important universal thermoplastic, because its good mechanical performance, can
Processability, corrosion resistance and electrical insulating property etc. are widely used.Thermoplastic olefin material be convenient to using squeeze out,
The technological formings such as blow molding, injection molding, curtain coating, stretching, prepare the multiple products such as forming material, tubing, film, fiber, porous diffusion barrier
Form.Since polyolefin is made of inert methylene, methyl, while there is certain crystallinity, causes its surface to lack and live
Property group and surface can be low, keep its surface wettability and cementability poor, limit polyolefine material in water environment, external coating,
The application in the fields such as surface bonding and composite material, therefore there is weight by carrying out grafting modification to polyolefine material surface
The meaning and broad application prospect wanted.
Existing surface modifying method mainly have chemical oxidation, corona treatment, Corona discharge Treatment, at surface grafting
Reason etc..Though the methods of chemical oxidation, corona treatment, Corona discharge Treatment can effectively introduce on polyolefine material surface small
The polar group of molecule, but these polar groups are unstable, and modified surface performance has timeliness, in air oxidation or strand
Warm-up movement effect under, surface polarity be easy lose.Surface grafting method can introduce high molecular weight on polyolefine material surface
Polar polymer, modified surface has good persistence, but that there are grafting efficiencies is low for conventional polyolefins surface grafting method,
The disadvantages of reaction temperature is high, and the reaction time is long, limits its application, and ZL201610587498.5 proposes a kind of utilization ARTP skill
The method of the modified ultra-high polyethylene fiber of art, but the method polymerization temperature is high, and solvent is volatile, and grafting time is long, does not utilize continuous
Change and produce and use, it is therefore desirable to develop a kind of not only polymerized at normal temperature, but also the ARTP process for modifying surface that grafting time shortens.
Summary of the invention
It is provided the invention aims to overcome the deficiencies in the prior art a kind of based on photocatalysis-ATPR crosslinking technology
The modified method in polyolefine material surface.
In order to achieve the above objectives, the technical solution adopted by the present invention is that: a kind of modified method in polyolefine material surface, it
The following steps are included:
(a) polyolefine material is made to obtain chlorinated polyolefin material containing progress surface chlorination in solutions of chlorine；
(b) the chlorinated polyolefin material is immersed in graft reaction solution, photocatalysis-original is carried out under light effect of irradiation
Sub- transferred free radical reaction.
Optimally, in step (a), the component containing solutions of chlorine comprising following parts by weight:
90~95 parts of deionized water；
5~10 parts of sodium hypochlorite；
0.5~1 part of sodium bicarbonate.
Further, in step (a), the condition of the surface chlorination are as follows: the temperature containing solutions of chlorine is 30~40 DEG C
And UV light irradiates 5~20min.
Further, in step (a), the surface chlorination degree 30~50% of the chlorinated polyolefin material.
Optimally, in step (b), the graft reaction solution includes the component of following parts by weight:
100 parts of grafted monomers, the grafted monomers are propylene derived species monomer or/and styrene derived species monomer；
0.1~0.2 part of reducing agent, the reducing agent is organic amine；
0.001~0.003 part of photochemical catalyst, the photochemical catalyst is transient metal complex.
Further, in step (b), the condition of the light irradiation are as follows: the monochromatic light or wave band light source, spoke of 400~500nm
Penetrate 0.3~0.7W/m of intensity2And 2~10min of normal-temperature reaction.
Further, the grafted monomers are selected from (methyl) hydroxy-ethyl acrylate, (methyl) hydroxypropyl acrylate, (first
Base) acrylic acid, (methyl) glycidyl acrylate, acrylamide, to one of carboxyl styrene and 4-Vinyl phenol
Or the mixture of a variety of compositions.
Further, the reducing agent be selected from three n-propyl amine, triethylamine, triethanolamine, pentamethyldiethylenetriamine,
The mixture of one of diethyl acetamide and diethylenetriamine or a variety of compositions.
Further, the photochemical catalyst is transition metal ruthenium, iridium or/and osmium and ligand bipyridine, connection dimethyl pyrazole
Pyridine, union II carboxyl pyridine, union II itrile group pyridine, ter cycloheptapyridine, three itrile group pyridines of connection trimethylpyridine, three carboxyl pyridines of connection and connection
In one or more compositions complex.
Optimally, it in step (b), also cleaned, dried after carrying out photocatalysis-atom transferred free radical reaction.
Due to the above technical solutions, the present invention has the following advantages over the prior art: polyolefin material of the present invention
Expect the modified method in surface, polyene can be realized by carrying out surface chlorination and photocatalysis-atom transferred free radical reaction
Polyolefin surfaces are not caused depth to destroy by hydrocarbon material surface modifying, and reaction temperature can be reduced to room temperature, greatly shorten
Grafting time；And the processing of polyolefine material surface functionalization is uniform, and it can be according to demand in the acquisition pair of polyolefine material surface
The functional group answered.
Detailed description of the invention
Attached drawing 1 is photocatalysis in the present invention-atom transferred free radical reaction schematic diagram.
Specific embodiment
The modified method in polyolefine material surface of the present invention, it is the following steps are included: (a) makes polyolefine material molten containing chlorine
Surface chlorination is carried out in liquid obtains chlorinated polyolefin material；(b) the chlorinated polyolefin material is immersed into graft reaction solution
In, photocatalysis-atom transferred free radical reaction is carried out under light effect of irradiation.It is urged by carrying out surface chlorination and light
Change-atom transferred free radical reaction can be realized polyolefine material surface and be modified, and not cause depth to destroy polyolefin surfaces, and
And reaction temperature can be reduced to room temperature, greatly shorten grafting time；And the processing of polyolefine material surface functionalization is uniform, and it can
To obtain corresponding functional group on polyolefine material surface according to demand.Atom transfer radical polymerization (ATRP), which is divided into, draws
Hair increases and terminates three phases.Initiating stage: initiator R-Cl is in lower valency transition metal ions RuII/ L (ligand) is urged
Halogen Cl is lost under change as free radical R, corresponding RuII/ L, which can be oxidized, becomes high-valence state RuIII/L.Monomer M is being added
Afterwards, free radical R-C and monomer reaction generate free radical R-M, it can continue to obtain long-chain free radical R- with monomer reaction
MnIt completes to increase, deactivated suspend mode kind R-M can also be formed by capturing halogen atomn- X reacts to terminate.Due to low
Valence state transition-metal catalyst controls the concentration of living radical, so that R concentration is controlled in lower range, although preventing
Free radical coupling termination, but but also graft polymerization reaction speed substantially reduces.In the present invention, above-mentioned photocatalysis-ATRP is connect
The principle of branch reaction is shown in Fig. 1: under the excitation of light, passing through metal-ligand charge transfer effect, RuII/ L (ligand) is activated into
(RuII/L)*, while surface chlorinated polyethylene PE-Cl aoxidizes (RuII/L)*, form PE chain free radical R and Cl-, accordingly
(RuII/L)*Become high-valence state RuIII/L.After monomer M is added, PE chain free radical R and monomer carry out ATPR graft reaction.
In step (a), the component that following parts by weight are preferably comprised containing solutions of chlorine: 90~95 parts of deionized water, secondary
5~10 parts of sodium chlorate, 0.5~1 part of sodium bicarbonate.Specifically, the condition of above-mentioned surface chlorination are as follows: the temperature containing solutions of chlorine
For 30~40 DEG C and UV light irradiates 5~20min, so that the surface chlorination degree 30~50% of chlorinated polyolefin material.And polyolefin
Material is conventional polyethylene, polypropylene and polyethylene-propylene copolymer etc..
In step (b), the graft reaction solution includes the component of following parts by weight: 100 parts of grafted monomers, described to connect
Branch monomer is propylene derived species monomer or/and styrene derived species monomer；0.1~0.2 part of reducing agent, the reducing agent is
Organic amine；0.001~0.003 part of photochemical catalyst, the photochemical catalyst is transient metal complex, and the graft reaction solution is in light
There is catalytic effect in the low-down situation of catalyst content.Specifically, the condition of the light irradiation are as follows: 400~500nm's
Monochromatic light or wave band light source, 0.3~0.7W/m of radiation intensity2And (surface tension can reach 35 to 2~10min of normal-temperature reaction at this time
~40mN/m), reaction condition is simple, is convenient for industrialized production.Above-mentioned grafted monomers be selected from (methyl) hydroxy-ethyl acrylate,
(methyl) hydroxypropyl acrylate, (methyl) acrylic acid, (methyl) glycidyl acrylate, acrylamide, to carboxyl styrene
With the mixture of one of 4-Vinyl phenol or a variety of compositions.Above-mentioned reducing agent is selected from triethylamine, triethanolamine, five first
The mixture of one of base diethyl triamine, diethyl acetamide and diethylenetriamine or a variety of compositions.Above-mentioned photochemical catalyst
For transition metal ruthenium, iridium or/and osmium and ligand bipyridine, union II picoline, union II carboxyl pyridine, union II itrile group pyridine,
Ter cycloheptapyridine, connection trimethylpyridine, three carboxyl pyridines of connection and the complex for joining one or more compositions in three itrile group pyridines；When connecing
Branch monomer is hydroxy propyl methacrylate, reducing agent is pentamethyldiethylenetriamine, photochemical catalyst RuII/ union II carboxyl pyridine
When complex, modified to polyolefine material surface have that reaction speed is fast, grafting efficiency is high and surface tension improves big advantage,
Effect is best.
The invention will be further described for the embodiment to shown in below.
Embodiment 1
The present embodiment provides a kind of modified method in polyolefine material surface, it the following steps are included:
(a) commercial polyethylene sheet material is immersed in the aqueous sodium hypochlorite solution that mass content is 10%, a small amount of carbonic acid is added
PH of the hydrogen sodium (the 0.5~1% of solution quality content) to adjust aqueous solution carries out UV under conditions of 30~40 DEG C for 5.5~6
Illumination 20min (UV wavelength be 280~400nm), to carry out chlorinated handling to obtain chlorinated polyolefin material (chlorinated polyolefin material
Surface chlorination degree be 30~50%)；
(b) by chlorinated polyolefin material (i.e. surface it is chlorinated after polyethylene sheets) be immersed in graft reaction solution into
Row photocatalysis-ATPR is graft-polymerized, and contains in graft reaction solution: 100 parts of hydroxyethyl methacrylates, 0.2 part of pentamethyl
Diethyl triamine and 0.002 part of bipyridine ruthenium complex, the graft reaction temperature are 30 DEG C, are shone using the LED light of 410nm
It penetrates: radiation intensity 0.6W/m2, irradiation reaction time 5min, the polythene material after graft reaction is through deionized water cleaning, 80 DEG C
Heated-air drying, can be obtained the polyethylene sheets that hydroxyl is contained on surface, and polyethylene surface tension is improved extremely by 31mN/m or so
40±2mN/m。
Embodiment 2
The present embodiment provides a kind of modified method in polyolefine material surface, it the following steps are included:
(a) commercial polypropylene biaxially oriented film is immersed in 5% aqueous sodium hypochlorite solution, a small amount of sodium bicarbonate is added
For 5.5~6, it is (same to carry out UV under conditions of 30~40 DEG C by the pH of (the 0.5~1% of solution quality content) to adjust aqueous solution
In embodiment 1) illumination 10min, to carry out chlorinated handling to obtain chlorinated polyolefin material (the surface chlorine of chlorinated polyolefin material
Change degree is 30~50%)；
(b) by chlorinated polyolefin material (i.e. surface it is chlorinated after polypropylene double-way stretched film) be immersed in graft reaction
Photocatalysis-ATPR is carried out in solution to be graft-polymerized, and is contained in graft reaction aqueous solution: 100 parts of hydroxyethyl methacrylates,
0.1 part of pentamethyldiethylenetriamine and 0.001 part of union II carboxyl pyridine ruthenium complex, the graft reaction temperature are 30 DEG C, are used
Xenon lamp irradiation: radiation intensity 0.5W/m2@340nm, irradiation reaction time 3min, the polypropylene material after graft reaction gone from
The polypropylene film that sub- water cleaning, 80 DEG C of heated-air dryings, i.e. acquisition surface contain hydroxyl, polypropylene surface tension is by the left side 29mN/m
It is right to improve to 42 ± 2mN/m.
Embodiment 3
The present embodiment provides a kind of modified method in polyolefine material surface, it the following steps are included:
(a) commercial polyethylene-propylene copolymerization film is immersed in 8% aqueous sodium hypochlorite solution, a small amount of bicarbonate is added
PH of the sodium (the 0.5~1% of solution quality content) to adjust aqueous solution carries out UV under conditions of 30~40 DEG C for 5.5~6
(in embodiment 1) illumination 15min, to carry out chlorinated handling to obtain the chlorinated polyolefin material (table of chlorinated polyolefin material
Face chlorination degree is 30~50%)；
(b) chlorinated polyolefin material (polyethylene-propylene after i.e. surface is chlorinated is copolymerized film) is immersed in grafting instead
It answers and carries out photocatalysis-ATPR graft polymerization in solution, contain in graft reaction aqueous solution: 100 parts of acrylamides, 0.2 part
Triethanolamine and 0.0015 part of three itrile group pyridine complex of iridium of connection, the graft reaction temperature are room temperature, are irradiated using xenon lamp: spoke
Penetrate intensity 0.5W/m2@340nm, reaction time 3min is irradiated, the polyethylene-propylene copolymerization film after graft reaction is through deionization
The polypropylene material that water cleaning, 80 DEG C of heated-air dryings, i.e. acquisition surface contain amino, polyethylene-propylene surface tension is by 30mN/
M or so is improved to 40 ± 2mN/m.
Embodiment 4
The present embodiment provides a kind of modified method in polyolefine material surface, it the following steps are included:
(a) commercially available ultra high molecular weight polyethylene fiber is immersed in 5% aqueous sodium hypochlorite solution, a small amount of bicarbonate is added
PH of the sodium (the 0.5~1% of solution quality content) to adjust aqueous solution carries out UV under conditions of 30~40 DEG C for 5.5~6
(in embodiment 1) illumination 10min, to carry out chlorinated handling to obtain the chlorinated polyolefin material (table of chlorinated polyolefin material
Face chlorination degree is 30~50%)；
(b) by chlorinated polyolefin material (i.e. surface it is chlorinated after high molecular weight polyethylene fiber) be immersed in graft reaction
Photocatalysis-ATPR is carried out in solution to be graft-polymerized, and is contained in graft reaction aqueous solution: 100 parts of methyl propenoic acid glycidyls
Ester, 0.2 part of diethylenetriamine and 0.0015 part of union II carboxyl pyridine ruthenium complex, the graft reaction temperature are room temperature, are adopted
With the LED illumination of 410nm: radiation intensity 0.5W/m2, irradiation reaction time 3min, the superhigh molecular weight polyethylene after graft reaction
Alkene fiber is cleaned through deionized water, 55 DEG C of hot winds are urged dry, is obtained surface and is contained the ultra high molecular weight polyethylene fiber of ester group, table
Face tension is up to 38 ± 3mN/m.
Embodiment 5
The present embodiment provides a kind of modified method in polyolefine material surface, it the following steps are included:
(a) commercial polyethylene microporous barrier is immersed in 5% aqueous sodium hypochlorite solution, a small amount of sodium bicarbonate (solution is added
The 0.5~1% of mass content) to adjust the pH of aqueous solution as 5.5~6, UV (same embodiment is carried out under conditions of 30~40 DEG C
In 1) illumination 10min, with carry out it is chlorinated handle chlorinated polyolefin material (the surface chlorination degree of chlorinated polyolefin material is
30~50%)；
(b) by chlorinated polyolefin material (i.e. surface it is chlorinated after polyethene microporous membrane) be immersed in graft reaction solution
It carries out photocatalysis-ATPR to be graft-polymerized, contains in graft reaction aqueous solution: 100 parts of hydroxyethyl methacrylates, 0.15 part
Diethyl acetamide and 0.002 part of union II picoline osmium complex, which is room temperature, using 450nm's
LED illumination: radiation intensity 0.4W/m2, irradiation reaction time 10min, the polyethene microporous membrane after graft reaction is through deionized water
Cleaning, 80 DEG C of hot winds are urged dry, are obtained surface and are contained the polyethene microporous membrane of hydroxyl；Film pressure at both sides is 0.2atm, before unmodified
Water flux is 0, and modified water flux is 30kg/hm2, hydrophilic effect is obvious.
Comparative example 1
This example provides a kind of polyolefine material surface treatment method of comparison comprising the steps of:
(a) commercial polyethylene sheet material is immersed in the aqueous sodium hypochlorite solution that mass content is 10%, a small amount of carbonic acid is added
PH of the hydrogen sodium (the 0.5~1% of solution quality content) to adjust aqueous solution carries out UV under conditions of 30~40 DEG C for 5.5~6
Illumination 20min (UV wavelength be 280~400nm), to carry out chlorinated handling to obtain chlorinated polyolefin material (chlorinated polyolefin material
Surface chlorination degree be 30~50%)；
(b) by chlorinated polyolefin material (i.e. surface it is chlorinated after polyethylene sheets) be immersed in 100 parts of methacrylic acids
(pentamethyldiethylenetriamine and part bipyridine ruthenium complex are not added) in hydroxyl ethyl ester, in 30 DEG C (solvent temperatures), use
The LED light of 410nm is irradiated: radiation intensity 0.6W/m2, irradiation reaction time 5min, by polythene material through deionized water cleaning,
It is modified that surface is not implemented still about 31mN/m in 80 DEG C of heated-air dryings, its final surface tension.
Comparative example 2
This example provides a kind of method that existing conventional polyolefine material surface is modified, it is specific use application No. is
Step in 201610587498.5 Chinese invention patent, partial condition are as follows: 40~60 DEG C at a temperature of be grafted it is anti-
It answers, 10~60min of dip time, it is 0.5~1 part that Osxidation-reduction catalyst, which is up to,.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention, it is all according to the present invention
Equivalent change or modification made by Spirit Essence, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of modified method in polyolefine material surface, which is characterized in that it the following steps are included:
(a) polyolefine material is made to obtain chlorinated polyolefin material containing progress surface chlorination in solutions of chlorine；
(b) the chlorinated polyolefin material is immersed in graft reaction solution, photocatalysis-atom is carried out under light effect of irradiation and is turned
Move radical reaction.
2. the modified method in polyolefine material surface according to claim 1, which is characterized in that described to contain in step (a)
Solutions of chlorine includes the component of following parts by weight:
90 ~ 95 parts of deionized water；
5 ~ 10 parts of sodium hypochlorite；
0.5 ~ 1 part of sodium bicarbonate.
3. the modified method in polyolefine material surface according to claim 1 or 2, which is characterized in that in step (a), institute
State the condition of surface chlorination are as follows: the temperature containing solutions of chlorine is 30 ~ 40 DEG C and UV light irradiates 5 ~ 20min.
4. the modified method in polyolefine material surface according to claim 3, which is characterized in that in step (a), the chlorine
For the surface chlorination degree 30 ~ 50% of polyolefine material.
5. the modified method in polyolefine material surface according to claim 1, which is characterized in that described to connect in step (b)
Branch reaction solution includes the component of following parts by weight:
100 parts of grafted monomers, the grafted monomers are propylene derived species monomer or/and styrene derived species monomer；
0.1 ~ 0.2 part of reducing agent, the reducing agent is organic amine；
0.001 ~ 0.003 part of photochemical catalyst, the photochemical catalyst is transient metal complex.
6. the modified method in polyolefine material surface according to claim 1 or 5, which is characterized in that in step (b), institute
State the condition of light irradiation are as follows: monochromatic light or wave band light source, the 0.3 ~ 0.7W/m of radiation intensity of 400 ~ 500 nm2And normal-temperature reaction 2 ~
10 min。
7. the modified method in polyolefine material surface according to claim 5, it is characterised in that: the grafted monomers are choosing
From (methyl) hydroxy-ethyl acrylate, (methyl) hydroxypropyl acrylate, (methyl) acrylic acid, (methyl) glycidyl acrylate,
Acrylamide, to the mixture of one of carboxyl styrene and 4-Vinyl phenol or a variety of compositions.
8. the modified method in polyolefine material surface according to claim 5, it is characterised in that: the reducing agent be selected from
One of three n-propyl amine, triethylamine, triethanolamine, pentamethyldiethylenetriamine, diethyl acetamide and diethylenetriamine
Or the mixture of a variety of compositions.
9. the modified method in polyolefine material surface according to claim 5, it is characterised in that: the photochemical catalyst was
Cross metal Ru, iridium or/and osmium and ligand bipyridine, union II picoline, union II carboxyl pyridine, union II itrile group pyridine, connection three
Pyridine, connection trimethylpyridine, three carboxyl pyridines of connection and the complex for joining one or more compositions in three itrile group pyridines.
10. the modified method in polyolefine material surface according to claim 1, it is characterised in that: in step (b), into
It also cleaned, dried after row photocatalysis-atom transferred free radical reaction.
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| CN111850832A (en) * | 2020-07-10 | 2020-10-30 | 杭州米娅纺织品有限公司 | Antibacterial low-resistance melt-blown non-woven fabric and preparation method thereof |
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