CN103087247A - POSS acrylate/p-vinylbenzylazide copolymer coat material and its preparation method - Google Patents
POSS acrylate/p-vinylbenzylazide copolymer coat material and its preparation method Download PDFInfo
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- CN103087247A CN103087247A CN2013100469452A CN201310046945A CN103087247A CN 103087247 A CN103087247 A CN 103087247A CN 2013100469452 A CN2013100469452 A CN 2013100469452A CN 201310046945 A CN201310046945 A CN 201310046945A CN 103087247 A CN103087247 A CN 103087247A
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Abstract
The invention relates to a coat material rapidly cross-linking under the irradiation of ultraviolet and simultaneously containing a POSS component and an azide reaction group, and concretely relates to a POSS acrylate/p-vinylbenzylazide copolymer coat material and its preparation method. Free radical copolymerization of a polyhedral oligomeric silsesquioxane-containing (meth)acrylate monomer and an azido group-containing styrene monomer is carried out, the obtained copolymer is dissolved in a solvent to form a dispersion, and ultraviolet irradiation and solvent volatilization are carried out to obtain a coat having a good stability and a high adhesion. According to the invention, the azido group decomposes to a nitrene group having an extremely-high reaction activity under the irradiation of the ultraviolet, and the nitrene group can almost react with any C-H bonds or C=C bonds of an adjacent molecule, and can even be inserted into a O-H bond or an N-H bond, so the chemical modification of the surface of glass and a cotton fiber or a film in covalent bond is realized, and the process is simple and rapid.
Description
Technical field
The invention belongs to coated material and process for modifying surface field, relate to a kind of POSS acrylate/to copolymer coated material of vinyl benzyl nitrine and preparation method thereof, especially a kind of POSS component and can be by the surface modifying material of azido group Quick cross-linking of containing.
Background technology
Polyhedral oligomeric silsesquioxane (Polyhedral Oligomeric Silsesquioxane is called for short POSS) is the hybrid molecule of a cage-like shape structure, has super-hydrophobicity, large steric effect and nanoscale.Rely on the variation of monomer structure and nano-grade size thereof and placed hope on and construct type material, making it possess good thermal characteristics, mechanical property, antioxidant property etc., thereby expand the new capability of POSS in functional materials and new the application.
Azido group is more responsive to heat and UV-light, azido group can generate the nitrene group of high reaction activity under the effect of heat or UV-light, the nitrene group almost can react with any C-H or the C=C key of neighboring molecule, even can insert in O-H or N-H key, therefore can be used as the efficient group of cross-linked material or surface modifying material; In addition, change the comonomer kind, can prepare the macromolecular material of difference in functionality by the reaction of azido group.With respect to common silane coupling agent, azido group has higher reactive behavior, only needs the irradiation of the short period of time of UV-light, just can realize being attached to matrix surface with the form of covalent linkage.
Reversible addition-fracture chain transfer polymerization (Reversible Addition-Fragmentation Chain Transfer Polymerization is called for short the RAFT polymerization) is a kind of of activity/controllable free-radical polymerisation (CRP).RAFT polymerization monomer scope applicatory is wide, and the products therefrom monodispersity is good, extremely is conducive to contain the polyreaction of specific functional groups vinyl monomer, has vital role for functional type POSS synthetic polymer.
In recent years, the research of polymeric coating material is focus always.Chinese patent CN102181218 has reported a kind of Novel polymer anticorrosion painting material, by selecting polyurethane modified epoxy resin and adding other auxiliary agents, prepares the coating that cost is low, have the performances such as excellent anticorrosion antiwear.Chinese patent CN102040901 has reported a kind of polymer wear-resistance coating material, by adding polyurethane modified epoxy resin binding agent bond varigrained silicon carbide, electric smelting sub-white corundum etc., prepare cost low, have the coating of superior abrasion resistance, erosion resistance, cavitation.People (the Surface﹠amp such as Wei-Gang Ji; Coatings Technology, 2007,201:4789-4795) silane coating reagent on the aluminium sheet matrix makes itself and epoxy resin amine hardener generation graft reaction under organotin catalysis, thereby makes that erosion resistance is good, low electric capacity, hydrophobic coating.
At present, take contain the POSS polymkeric substance as the document of coated material actually rare.Chinese patent CN101024751 has reported a kind of coated material of the POSS of containing acrylate copolymer, carry out free-radical polymerized join in resin as properties-correcting agent afterwards by POSS acrylate monomer and (methyl) acrylic ester monomer, obtain having high-intensity coated material through after ultraviolet light polymerization.The people such as Eric Devaux (Fire and Materials, 2002,26:149-154) prepare the multipolymer of urethane and POSS, utilize the excellent properties of POSS polymkeric substance, obtain the high and stable coated material of thermal characteristics of flame retardant properties.And the research of relevant copolymer coated material of POSS that contains azido group and preparation method thereof there is not yet report.
The present invention proposes that a kind of POSS acrylate/to copolymer coated material of vinyl benzyl nitrine and preparation method thereof, this material contains POSS component and azide reaction group simultaneously, but and under ultraviolet lighting Quick cross-linking.At first the synthetic styrene monomer that contains azido group, then make it the methyl with POSS(by the RAFT living polymerisation process) acrylic ester monomer copolymerization obtains POSS acrylate/to vinyl benzyl nitrine multipolymer.The present invention utilizes the reactivity of azido group, namely decompose under the ultraviolet light irradiation condition and generate the nitrene group with high reactive behavior, realize fast with the form of covalent linkage, the POSS component being connected to glass, cotton fibre or film surface, thereby obtain to have the high coated material of certain hydrophobicity and thermostability and sticking power, play the effect to the substrate surface modification.
Summary of the invention
The object of the present invention is to provide a kind of POSS acrylate/to copolymer coated material of vinyl benzyl nitrine and preparation method thereof.
Described POSS acrylate/to the copolymer coated material of vinyl benzyl nitrine is by the POSS(methyl) acrylic ester monomer and contain the azido group styrene monomer and form by the copolymerization of RAFT method, the film forming after crosslinked and solvent evaporates through ultraviolet lighting.
Described POSS acrylate/as follows to the structure iron of vinyl benzyl nitrine multipolymer:
Wherein R is POSS drift angle organic group, and m is the POSS(methyl) polymerization degree of acrylate, n is the polymerization degree of vinylbenzene benzyl nitrine.
Described POSS official can the drift angle group be that (methyl) is acrylate-based, and all the other seven drift angle R bases are isobutyl-or phenyl.
Described POSS acrylate/to the POSS(methyl of vinyl benzyl nitrine multipolymer) polymerization degree scope of acrylate is 15 ~ 25, and the polymerization degree scope of vinylbenzene benzyl nitrine is 80 ~ 100, and molecular weight of copolymer is 25000 ~ 45000g/mol.
Described POSS acrylate/as follows to vinyl benzyl nitrine multipolymer preparation method:
(1) add 25 ~ 50mL solvent and with the vinylbenzene benzyl chlorine of 0.01 ~ 0.04mol, be placed in 60 ℃ of oil baths, add the potassiumiodide of 0.015 ~ 0.08mol sodium azide and 0.0001 ~ 0.0004mol, be warming up to 70 ~ 80 ℃ after the end that feeds intake, reacted 12 ~ 15 hours, and then be cooled to room temperature.Pour in the water of 100 ~ 200mL, remove unnecessary anhydrous diethyl ether with revolving to steam after 25 ~ 50mL anhydrous diethyl ether extraction 2 ~ 3 times, obtain vinylbenzene benzyl triazo-compound, productive rate is Y
1
(2) with the POSS(methyl of 0.1 ~ 2mmol) acrylate, the vinylbenzene benzyl triazo-compound of 2 ~ 40mmol, 0.04 ~ 0.8mmol CDB, 0.01 ~ 0.15mmol initiator is dissolved in solvent, freeze thawing is degassed 3 ~ 6 times continuously, in argon gas atmosphere after 65 ~ 70 ℃ of lower polymerization 40 ~ 60h, the sudden cold stopped reaction of liquid nitrogen.With 10 ~ 80mL precipitation agent repeated precipitation 3 times, vacuum-drying obtains that yellow the POSS acrylate/to vinyl benzyl nitrine multipolymer, productive rate is Y
2
(3) with body material ultrasonic cleaning in the second alcohol and water successively, then 120 ~ 150 ℃ of dryings 1 ~ 2 hour.Body material after cleaning soaks after 1 minute in POSS acrylate/to the solvent dispersions of vinyl benzyl nitrine multipolymer and takes out, and dries by the fire under 70 ~ 80 ℃ 10 ~ 30 minutes, then shines under UV-light 5 ~ 15 minutes.
Described in step (1), solvent is a kind of of DMF, DMSO, THF.
Initiator described in step (2) is a kind of in AIBN, BPO/DMA, BPO.
Described in step (2), solvent is a kind of of toluene, THF.
Precipitation agent described in step (2) is a kind of in methyl alcohol, acetonitrile.
Described in step (3), solvent is THF, CHCl
3A kind of.
Described in step (3), body material is a kind of of glass, cotton fibre.
The prepared POSS acrylate of the present invention/material modifiedly show good thermostability and high sticking power to the vinyl benzyl nitrine is copolymer coated, and have certain hydrophobicity.Add the coating system of silane coupling agent than routine, the present invention need not to add in addition coupling agent, by ultra violet lamp, utilizes azide reaction group on multipolymer to realize bonding between coating and substrate, played the effect of surface modification, and preparation and operating process simple and convenient.
Description of drawings
Fig. 1 is 4-vinylbenzene benzyl nitrine
1The HNMR nuclear magnetic spectrogram
Fig. 2 is POSS acrylate/to vinyl benzyl nitrine multipolymer IR spectrogram
Fig. 3 is water droplet contact angle photo
Embodiment
The present invention will be further described below by embodiment
(1) azide of vinylbenzene benzyl chlorine
Add 25mL DMSO and 2mL4-vinylbenzene benzyl chlorine in 50mL twoport flask, bottle with two necks is put into 60 ℃ of oil baths, add 1.7g sodium azide and 0.215g potassiumiodide, after reinforced the end, oil bath temperature is risen to 80 ℃, vacuumize, logical argon gas, third-order reaction is 12 hours repeatedly, stopped reaction, reaction solution is poured in 100mL water after being cooled to room temperature, use the anhydrous diethyl ether extracting twice, obtain the product of yellow liquid, productive rate Y
1Be 85%.
(2) POSS acrylate/to the preparation of vinyl benzyl nitrine multipolymer
With 0.667g styryl benzyl nitrine; 0.1187g the POSS(methyl) acrylate; 0.0136g CDB; 0.00164g be dissolved in the THF of 1.5mL; continuously after degassed 3 ~ 5 times of freeze thawing under argon shield 65 ℃ of polymerizations, react the sudden cold stopped reaction of liquid nitrogen after 48 hours, selection methyl alcohol volume ratio is 1:20 repeated precipitation 3 times; vacuum-drying obtains yellow product, productive rate Y
2Be 72%.
(3) surface modification of base material
With substrate (glass or cotton) ultrasonic cleaning in the second alcohol and water successively, then in 120 ℃ of vacuum drying ovens dry 1 hour.Body material after cleaning soaks after 1 minute in POSS acrylate/to the THF dispersion liquid of vinyl benzyl nitrine multipolymer and takes out, and prior to baking under 80 ℃ 10 minutes, then uses UV-irradiation 9 minutes.
(4) material modified performance characterization
Adopt the thermostability of TGA mensuration manufactured coating material, by its hydrophobicity of water contact angle measurement.Measure sticking power by drawing the circle method.
The δ of Fig. 1
H/ppmBe that 5.29 and 6.78 spectrum peaks are characteristic peaks of the two keys of C=C, δ
HBe that 4.35 spectrum peak is the peak that connects the methylene radical of azido group.2097cm in Fig. 2 infrared spectrum
-1Be the stretching vibration of azido group, 822cm
-1Be the flexural vibration of phenyl ring contraposition, the successful preparation of target compound is described.Fig. 3 demonstration, POSS acrylate of the present invention/be 125 ° to the copolymer-modified cotton fibre contact angle of vinyl benzyl nitrine.The TGA test chart decomposition temperature (T that begins from tomorrow
5%, lower same) be 195 ℃.Sticking power reaches 1 grade of sticking power.
Add 25mLDMSO and 1.5mL pentadiene acyl chlorides in 50mL twoport flask, bottle with two necks is put into 60 ℃ of oil baths, add 1.9g sodium azide and 0.215g potassiumiodide, after reinforced the end, oil bath temperature is risen to 80 ℃, vacuumize, logical argon gas, third-order reaction is 12 hours repeatedly, stopped reaction, reaction solution is poured in 110mL water after being cooled to room temperature, use the anhydrous diethyl ether extracting twice, obtain the product of yellow liquid, productive rate Y
1Be 88%.With 0.8g pentadiene acylazide; 0.1187g the POSS(methyl) acrylate; 0.0136g CDB; 0.00164g be dissolved in the THF of 1.5mL; continuously after degassed 3 ~ 5 times of freeze thawing under argon shield 65 ℃ of polymerizations, react the sudden cold stopped reaction of liquid nitrogen after 48 hours, selection methyl alcohol volume ratio is 1:20 repeated precipitation 3 times; vacuum-drying obtains yellow product, productive rate Y
2Be 73%.With substrate (glass or cotton) ultrasonic cleaning in the second alcohol and water successively, then in 120 ℃ of vacuum drying ovens dry 1 hour.Body material after cleaning soaks after 1 minute in POSS acrylate/to the THF dispersion liquid of vinyl benzyl nitrine multipolymer and takes out, and baking is 10 minutes under 80 ℃, then irradiation 10 minutes under UV-light.
Add 25mL DMSO and 1.8mL methacrylic acid-4-chlorobenzene ester in 50mL twoport flask, bottle with two necks is put into 60 ℃ of oil baths, add 2.1g sodium azide and 0.21g potassiumiodide, after reinforced the end, oil bath temperature is risen to 80 ℃, vacuumize, logical argon gas, third-order reaction is 12 hours repeatedly, stopped reaction, reaction solution is poured in 120mL water after being cooled to room temperature, use the anhydrous diethyl ether extracting twice, obtain the product of yellow liquid, productive rate Y
1Be 85%.With 1g methacrylic acid-4-nitrine phenyl ester; 0.1187gPOSS(methyl) acrylate; 0.0136g CDB; 0.00164g be dissolved in the THF of 1.5mL; continuously after degassed 3 ~ 5 times of freeze thawing under argon shield 65 ℃ of polymerizations, react the sudden cold stopped reaction of liquid nitrogen after 48 hours, selection methyl alcohol volume ratio is 1:20 repeated precipitation 3 times; vacuum-drying obtains yellow product, productive rate Y
2Be 70%.With substrate (glass or cotton) ultrasonic cleaning in the second alcohol and water successively, then in 120 ℃ of vacuum drying ovens dry 1 hour.Body material after cleaning soaks after 1 minute in POSS acrylate/to the THF dispersion liquid of vinyl benzyl nitrine multipolymer and takes out, and baking is 12 minutes under 80 ℃, then irradiation 12 minutes under UV-light.
Embodiment 4
Add 25mL DMSO and 2mL methacrylic-2-chloroethyl ether in 50mL twoport flask, bottle with two necks is put into 60 ℃ of oil baths, add 2.3g sodium azide and 0.23g potassiumiodide, after reinforced the end, oil bath temperature is risen to 80 ℃, vacuumize, logical argon gas, third-order reaction is 12 hours repeatedly, stopped reaction, reaction solution is poured in 120mL water after being cooled to room temperature, use the anhydrous diethyl ether extracting twice, obtain the product of yellow liquid, productive rate Y
1Be 83%.With 0.9g methacrylic-2-azidoethyl ether; 0.1187g the POSS(methyl) acrylate; 0.0136g CDB; 0.00164g be dissolved in the THF of 1.5mL; continuously after degassed 3 ~ 5 times of freeze thawing under argon shield 65 ℃ of polymerizations, react the sudden cold stopped reaction of liquid nitrogen after 48 hours, selection methyl alcohol volume ratio is 1:20 repeated precipitation 3 times; vacuum-drying obtains yellow product, productive rate Y
2Be 68%.With substrate (glass or cotton) ultrasonic cleaning in the second alcohol and water successively, then in 120 ℃ of vacuum drying ovens dry 1.5 hours.Body material after cleaning soaks after 1 minute in POSS acrylate/to the THF dispersion liquid of vinyl benzyl nitrine multipolymer and takes out, and baking is 15 minutes under 80 ℃, then irradiation 15 minutes under UV-light.
The transformation efficiency of embodiment 2 ~ 4, contact angle, thermostability result are as shown in table 1.
Table 1
Claims (9)
1. a POSS acrylate/to the copolymer coated material of vinyl benzyl nitrine, by the POSS(methyl) acrylic ester monomer and contain the azido group styrene monomer and form by the copolymerization of RAFT method, the film forming after crosslinked and solvent evaporates through ultraviolet lighting.
2. a kind of POSS acrylate according to claim 1/to the copolymer coated material of vinyl benzyl nitrine is characterized in that described POSS acrylate/as follows to the structure of vinyl benzyl nitrine multipolymer:
Wherein R is POSS drift angle organic group, and m is the POSS(methyl) polymerization degree of acrylate, n is the polymerization degree of vinylbenzene benzyl nitrine;
Described POSS official can the drift angle group be that (methyl) is acrylate-based, and all the other seven drift angle R bases are isobutyl-or phenyl.
3. a kind of POSS acrylate according to claim 2/to the copolymer coated material of vinyl benzyl nitrine, it is characterized in that described POSS acrylate/to the POSS(methyl of vinyl benzyl nitrine multipolymer) polymerization degree scope of acrylate is 15 ~ 25, the polymerization degree scope of vinylbenzene benzyl nitrine is 80 ~ 100, and molecular weight of copolymer is 25000 ~ 45000g/mol.
4. a POSS acrylate/to the copolymer coated material preparation method of vinyl benzyl nitrine is characterized in that POSS acrylate/vinyl benzyl nitrine multipolymer is prepared as follows:
(1) add 25 ~ 50mL solvent and with the vinylbenzene benzyl chlorine of 0.01 ~ 0.04mol, be placed in 60 ℃ of oil baths, add the potassiumiodide of 0.015 ~ 0.08mol sodium azide and 0.0001 ~ 0.0004mol, be warming up to 70 ~ 80 ℃ after the end that feeds intake, reacted 12 ~ 15 hours, and then be cooled to room temperature; Pour in the water of 100 ~ 200mL, remove unnecessary anhydrous diethyl ether with revolving to steam after 25 ~ 50mL anhydrous diethyl ether extraction 2 ~ 3 times, obtain vinylbenzene benzyl triazo-compound;
(2) with the POSS(methyl of 0.1 ~ 2mmol) acrylate, the vinylbenzene benzyl triazo-compound of 2 ~ 40mmol, 0.04 ~ 0.8mmol CDB, 0.01 ~ 0.15mmol initiator is dissolved in solvent, freeze thawing is degassed 3 ~ 6 times continuously, in argon gas atmosphere after 65 ~ 70 ℃ of lower polymerization 40 ~ 60h, the sudden cold stopped reaction of liquid nitrogen; With 10 ~ 80mL precipitation agent repeated precipitation 3 times, vacuum-drying obtains yellow POSS acrylate/to vinyl benzyl nitrine multipolymer;
(3) with body material ultrasonic cleaning in the second alcohol and water successively, then 120 ~ 150 ℃ of dryings 1 ~ 2 hour; Body material after cleaning soaks after 1 minute in POSS acrylate/to the solvent dispersions of vinyl benzyl nitrine multipolymer and takes out, and dries by the fire under 70 ~ 80 ℃ 10 ~ 30 minutes, then shines under UV-light 5 ~ 15 minutes.
5. a kind of POSS acrylate according to claim 4/to the copolymer coated material of vinyl benzyl nitrine, its feature is described is that described in step (1), solvent is a kind of of DMF, DMSO, THF.
6. a kind of POSS acrylate according to claim 4/to the copolymer coated material of vinyl benzyl nitrine is characterized in that initiator described in described step (2) is a kind of in AIBN, BPO/DMA, BPO.
7. a kind of POSS acrylate according to claim 4/to the copolymer coated material of vinyl benzyl nitrine, it is characterized in that described in described step (2), solvent is a kind of of toluene, THF.
8. a kind of POSS acrylate according to claim 4/to the copolymer coated material of vinyl benzyl nitrine, it is characterized in that precipitation agent described in step (2) is a kind of in methyl alcohol, acetonitrile, described in described step (3), solvent is a kind of of THF, CHCl3.
9. a kind of POSS acrylate according to claim 4/to the copolymer coated material of vinyl benzyl nitrine, it is characterized in that described in described step (3), body material is a kind of of glass, cotton fibre.
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Cited By (3)
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| WO2019082105A1 (en) * | 2017-10-26 | 2019-05-02 | Sabic Global Technologies B.V. | Cross-linked polymer/polyhedral oligomeric silsesquioxane (poss) composite material; methods of making; and uses thereof |
| CN113276490A (en) * | 2021-04-26 | 2021-08-20 | 杭州诗蓝过滤科技有限公司 | Fluffy modified polypropylene sound-absorbing cotton and preparation method thereof |
| CN113279139A (en) * | 2021-04-26 | 2021-08-20 | 杭州诗蓝过滤科技有限公司 | Preparation method of high-strength fluffy melt-blown fabric |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019082105A1 (en) * | 2017-10-26 | 2019-05-02 | Sabic Global Technologies B.V. | Cross-linked polymer/polyhedral oligomeric silsesquioxane (poss) composite material; methods of making; and uses thereof |
| CN113276490A (en) * | 2021-04-26 | 2021-08-20 | 杭州诗蓝过滤科技有限公司 | Fluffy modified polypropylene sound-absorbing cotton and preparation method thereof |
| CN113279139A (en) * | 2021-04-26 | 2021-08-20 | 杭州诗蓝过滤科技有限公司 | Preparation method of high-strength fluffy melt-blown fabric |
| CN113279139B (en) * | 2021-04-26 | 2022-06-17 | 杭州诗蓝过滤科技有限公司 | Preparation method of high-strength fluffy melt-blown fabric |
| CN113276490B (en) * | 2021-04-26 | 2022-06-17 | 杭州诗蓝过滤科技有限公司 | Fluffy modified polypropylene sound-absorbing cotton and preparation method thereof |
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Application publication date: 20130508 |