CN104193999A - Method for preparing fluorine-silicon-containing benzoxazine copolymer - Google Patents
Method for preparing fluorine-silicon-containing benzoxazine copolymer Download PDFInfo
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- CN104193999A CN104193999A CN201410454287.5A CN201410454287A CN104193999A CN 104193999 A CN104193999 A CN 104193999A CN 201410454287 A CN201410454287 A CN 201410454287A CN 104193999 A CN104193999 A CN 104193999A
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Abstract
The invention relates to a method for preparing a fluorine-silicon-containing benzoxazine copolymer, belonging to the technical field of macromolecule compound preparation. According to method for preparing the fluorine-silicon-containing benzoxazine copolymer, benzoxazine containing unsaturated bonds and double-hydrogen-terminated polysiloxane are adopted as monomers, a platinum catalyst or/and chloroplatinic acid is/are adopted as catalysts, and the reaction is performed at 60-110 DEG C. The invention discloses the method for preparing the fluorine-silicon-containing benzoxazine copolymer which can be used for oil-water separation for the first time. The fluorine-silicon-containing benzoxazine copolymer which is prepared by using the method provided by the invention is relatively in surface energy and excellent in hydrophobic property and oleophylic property after being prepared into an oil-water separation membrane, the water content angle is greater than 155 degrees, and the content angle with oil in air is proximate to 0 degree.
Description
Technical field
The preparation method who the present invention relates to a kind of fluorine silicon benzoxazine multipolymer, belongs to macromolecular compound preparing technical field.
Background technology
In oil plant, contain free-water, have a strong impact on the quality of oil plant.In addition, the oily(waste)water that city and industrial production are discharged is the severe contamination source of environment, thereby, find economy and durability, oil-water separation method that efficiency is good and be industrial production, urban life and need badly and solve to obtain problem.At present, in oily water separation technique field, applying more is the water-and-oil separator that equipment is complicated, energy consumption is higher.Conventionally adopt to there is special infiltrating separatory membrane it is processed, but realize oil and sewage to separate oily water separation membrane technique also immature, there is less selectivity for separable oil.And the condition deficiency of suitability for industrialized production.Therefore look for suitable method and prepare the important topic that oily water separation film is whole chemical production field and resource environment field.But benzoxazine was as a kind of novel thermosetting resin in recent years, have when curing without small molecules discharge, the cure shrinkage of goods is little, porosity is low, thermotolerance and the advantage such as flame retardant resistance is high, machining property is good, be subject to the favor of industrial community and academia, part kind has been applied to Aeronautics and Astronautics and the field such as electric.The research that the present invention prepares fluorine silicon benzoxazine segmented copolymer with end hydrogen polysiloxanes and unsaturated of bonding benzoxazine by the method for silicon hydrogen addition there is not yet relevant report in the literature.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of the fluorine silicon benzoxazine segmented copolymer that can be used for oily water separation.
Technical scheme:
A preparation method for fluorine silicon benzoxazine multipolymer, be taking containing unsaturated of bonding benzoxazine and both-end hydrogen polysiloxanes as monomer, using platinum catalyst or/and Platinic chloride as catalyzer, in 60-110 DEG C of reaction;
The chemical structural formula of described fluorine silicon benzoxazine multipolymer suc as formula 1 or formula 2 shown in, its number-average molecular weight is 2000-30000; In formula 1 and formula 2, A is CF
3or CH
3, R is CH
3or CH
2cH
2cF
3;
Formula 1
Formula 2.
Above-mentioned preparation method, preferred, monomer reacts with after dissolution with solvents again; Solvent for use is one or more in toluene, phenylfluoroform and benzene; Reaction times is more than 12 hours.Can obtain with this understanding higher yields.
Experimental study shows, reacts the productive rate that can effectively improve product under nitrogen protection; So, above-mentioned preparation method, preferred, reaction is carried out under nitrogen protection condition.
Above-mentioned preparation method,
Wherein, containing the mol ratio of unsaturated of bonding benzoxazine and both-end hydrogen polysiloxanes, can determine according to the structure of target product, preferred, be 1:1-3:0.000021-0.000048 containing the mol ratio of unsaturated of bonding benzoxazine, both-end hydrogen polysiloxanes and catalyzer.The consumption of solvent is preferably 1/ (2-30) of monomer total mass.
Above-mentioned preparation method, usedly containing unsaturated of bonding benzoxazine can be: allylamine type benzoxazine or propargylamine type benzoxazine; Can adopt any means that can realize to be prepared from.In the present invention, be to be prepared from taking allylamine, dihydroxyphenyl propane/bisphenol AF and paraformaldehyde as raw material.In the time that temperature of reaction is 70 DEG C, obtain allylamine type benzoxazine; In the time that temperature of reaction is 80-90 DEG C, obtain propargylamine type benzoxazine.
Wherein, the structural formula of allylamine type benzoxazine is as shown in Equation 3:
Formula 3
The structural formula of propargylamine type benzoxazine is as shown in Equation 4:
Formula 4
In formula 3 and formula 4, A is CH
3or CF
3.
Above-mentioned preparation method, both-end hydrogen polysiloxanes used, its number-average molecular weight is 100-3000; What the present invention specifically adopted is the poly-methyl trifluoro propyl siloxanes of both-end hydrogen polydimethylsiloxane (being 1,1,3,3-tetramethyl disiloxane in the time that molecular weight is 134) and both-end hydrogen.
Above-mentioned preparation method, preferred, its concrete steps are: first under the condition of 10-40 DEG C, by both-end hydrogen polysiloxanes, containing unsaturated of bonding benzoxazine and catalyzer dissolution with solvents; Then be warming up to 60-110 DEG C, after isothermal reaction 12-72 hour, except desolventizing, obtain fluorine silicon benzoxazine multipolymer.Adopt this concrete operation step, can obtain more high yield.
The present invention discloses a kind of preparation method of the fluorine silicon benzoxazine multipolymer that can be used in oily water separation first.The fluorine silicon benzoxazine multipolymer that adopts method of the present invention to prepare, after being prepared into oily water separation film, its surface has lower surface energy, has excellent hydrophobic performance and oleophylic performance; Water contact angle is greater than 155 °, in air, oily contact angle is approached to 0 °.
Those skilled in the art, the fluorine silicon benzoxazine multipolymer of preparing taking the present invention is main raw material, can adopt the method that can realize arbitrarily, is prepared into oily water separation film.The given a kind of preparation method of the present invention is: the silicon-dioxide that is 10-500nm by fluorine silicon benzoxazine polymkeric substance of the present invention and particle diameter is dissolved in solvent, is mixed with massfraction by the mass ratio of 1:0.5-8 is 1-30% solution, then by this solution spraying in 80-300 object fabric web, utilize after gradient heating dry solidification, make oily water separation film.Solvent for use is one or more in toluene, tetrahydrofuran (THF) and benzene.First described gradient heating dry solidification specifically refers at 0-100 DEG C of dry 1-3 hour, and then 120-150 DEG C of dry 0.5-2 hour, and then 180-200 DEG C of dry 0.5-2 hour, finally at 220-240 DEG C of dry 0.5-3 hour.The oily water separation film that adopts gradient heating dry solidification method to obtain is more durable, and its access times are more than 50 times; And the oily water separation membrane durability that adopts other dry solidification methods to obtain is poor, its access times are below 10 times.
Oily water separation film of the present invention, strong to oily penetrating power, oil is had to lower adhesivity, not only separating but also can be used for separating of polar oil and water for non-polar oil and water mixture.
Embodiment
embodiment 1
the preparation of allylamine type benzoxazine:under ice-water bath condition, in four-hole bottle, add 11.4g allylamine (being the amino propylene of 3-, No. CAS: 107-11-9), then add slowly 33.6g bisphenol AF, after stirring makes it to dissolve completely in batches; Then, under nitrogen protection, slowly add paraformaldehyde (CAS 30525-89-4) 12g in batches, make it completely to dissolve and mix.Temperature is slowly risen to 70 DEG C, and isothermal reaction was down to room temperature after 8 hours, purified with ether and sodium hydroxide washing, obtained allylamine type benzoxazine after anhydrous sodium sulfate drying.
the preparation of fluorine silicon benzoxazine multipolymer:under room temperature condition, add 2.12g 1,1,3 in four-hole bottle, 3-tetramethyl disiloxane (No. CAS: 3277-26-7) and 60g toluene, add the platinum catalyst of 80 microlitres with liquid-transfering gun; Then the allylamine type benzoxazine 7.47g that adds step to prepare.Then be slowly warming up to 80 DEG C, isothermal reaction 12 hours, is down to room temperature, and except desolventizing obtains product, yield is 87%.
the preparation of fluorine silicon benzoxazine oily water separation film and oily water separation experiment: the silicon-dioxide of fluorine silicon benzoxazine multipolymer prepared by upper step and particle diameter 100 nanometers is dissolved in toluene with the quality proportioning of 3:7, is made into 10% solution.Solution spraying, on 140 clean order copper mesh, by being cooled to room temperature after gradient heating crosslinking curing, is obtained to fluorine silicon benzoxazine oily water separation film.The water contact angle of oily water separation film is 161.6 °, and in air, the contact angle of oil is less than 1 °.When gradient heating crosslinking curing, be raised to 80 DEG C with 20 minutes from room temperature, be then incubated 2 hours; Then be raised to 140 DEG C with 10 minutes from 80 DEG C, be incubated 1 hour; Be raised to 200 DEG C with 10 minutes from 140 DEG C again, be incubated 1 hour; Finally be raised to 240 DEG C with 20 minutes from 200 DEG C, be incubated 2 hours.By the oily water separation film obtaining, (area is 12cm
2) be fixed on easy oily-water seperating equipment, water is dyed to red and tetracol phenixin 1:1 mixing and stirring by volume with red ink, obtain mixed solution; At 5s, 50ml mixed solution is poured in oily-water seperating equipment, tetracol phenixin also in 5s by separatory membrane, be penetrated into and connect in liquid bottle, and water (redness) is stayed the top of separatory membrane, has reached oil-water separation.
embodiment 2
the preparation of propargylamine type benzoxazine:under ice-water bath condition, in four-hole bottle, add 11.4g allylamine; Then add slowly 22.8g dihydroxyphenyl propane in batches, after stirring makes it to dissolve completely, under nitrogen protection, slowly add paraformaldehyde 12g in batches; Stir at ambient temperature 40 minutes, make it completely to dissolve and mix.Then temperature is slowly risen to 80 DEG C, isothermal reaction was purified with ether and sodium hydroxide washing after 4 hours, obtained propargylamine type benzoxazine after anhydrous sodium sulfate drying.
the preparation of fluorine silicon benzoxazine multipolymer:under room temperature condition, in four-hole bottle, add 16.95g both-end hydrogen to gather methyl trifluoro propyl siloxanes (relative molecular weight is 1700) and 40g benzene, pass into nitrogen protection, stir 40 minutes; Then add the chloroplatinic acid catalyst of 60 microlitres with liquid-transfering gun, then drip propargylamine type benzoxazine 3.9g prepared by upper step that 40g benzene dissolved; After being added dropwise to complete, at room temperature react 30 minutes, be then slowly warming up to 60 DEG C, isothermal reaction and be down to room temperature after 72 hours, revolve steaming, vacuum-drying, obtains product; Yield is 79%.
the preparation of fluorine silicon benzoxazine oily water separation film and oily water separation experiment:the silicon-dioxide of fluorine silicon benzoxazine multipolymer prepared by upper step and particle diameter 200 nanometers is dissolved in benzene with 1:1 quality proportioning, is made into 20% solution; Solution spraying, on 80 clean object stainless (steel) wires, is then put into stainless (steel) wire to tube furnace by gradient heating crosslinking curing, and then cool to room temperature obtains fluorine silicon benzoxazine oily water separation film.The water contact angle of oily water separation film is 155.2 °, and in air, the contact angle of oil is less than 1 °.When gradient heating crosslinking curing, be raised to 80 DEG C with 30 minutes from room temperature, be incubated 3 hours; Then be raised to 150 DEG C with 30 minutes from 100 DEG C, be incubated 1 hour, then be raised to 200 DEG C with 20 minutes from 150, be incubated 2 hours.(area is 12cm to the oily water separation film obtaining
2) be fixed on easy oily-water seperating equipment, water is dyed to red and ethyl acetate 1:1 mixing and stirring by volume with red ink, obtain mixed solution; 50ml mixed solution is poured in oily-water seperating equipment, and ethyl acetate is also penetrated into and is connect in liquid bottle by separatory membrane in 5s, and water (redness) is stayed the top of separatory membrane, has reached oil-water separation.
embodiment 3
the preparation of allylamine type benzoxazine:under ice-water bath condition, in four-hole bottle, add 22.8g allylamine; Then add slowly 67.2g bisphenol AF, after stirring makes it to dissolve completely in batches; Under nitrogen protection, slowly add paraformaldehyde 24g in batches, under room temperature condition, stir 40 minutes, make it completely to dissolve and mix; Temperature is slowly risen to 90 DEG C, and isothermal reaction was purified with ether and sodium hydroxide washing after 4 hours, obtained propargylamine type benzoxazine after anhydrous sodium sulfate drying.
the preparation of fluorine silicon benzoxazine multipolymer:under room temperature condition, in four-hole bottle, add 30g polydimethylsiloxane (relative molecular weight is 3000) and 30g tetrahydrofuran (THF), pass into nitrogen protection, stir 50 minutes; Then add the chloroplatinic acid catalyst of 70 microlitres with liquid-transfering gun, more then drip propargylamine type benzoxazine 3.9g prepared by upper step that 30g tetrahydrofuran (THF) dissolved.After being added dropwise to complete, at room temperature react 40 minutes.Then be slowly warming up to 80 DEG C.Isothermal reaction 48 hours, is down to room temperature, revolves steaming, and vacuum-drying, obtains product; Yield 89%.
the preparation of fluorine silicon benzoxazine oily water separation film and oily water separation experiment:the silicon-dioxide of fluorine silicon benzoxazine prepared by upper step and particle diameter 500 nanometers is dissolved in tetrahydrofuran (THF) with the quality proportioning of 4:6, is made into 2% solution, then solution is sprayed on respectively on 200 clean object stainless (steel) wires; Obtain fluorine silicon benzoxazine oily water separation film by gradient heating crosslinking curing, cool to room temperature again.The water contact angle of oily water separation film is 159.4 °, and in air, the contact angle of oil is less than 1 °.When gradient heating crosslinking curing, be raised to 100 DEG C with 20 minutes from room temperature, be incubated 2 hours; Then be raised to 120 DEG C with 10 minutes from 100 DEG C, be incubated 1 hour; Be raised to 200 DEG C with 20 minutes from 120 DEG C again, be incubated 2 hours, be finally raised to 230 DEG C with 20 minutes from 200 DEG C, be incubated 3 hours.By oily water separation film (the area 12cm obtaining
2) be fixed on easy oily-water seperating equipment, water is dyed to red and n-Hexadecane 1:1 mixing and stirring by volume with red ink, obtain mixed solution; In 5s, 50ml mixed solution is poured in oily-water seperating equipment, n-Hexadecane is also penetrated into and is connect in liquid bottle by separatory membrane in 5s, and water (redness) is stayed the top of separatory membrane, has reached oil-water separation.
Claims (9)
1. a preparation method for fluorine silicon benzoxazine multipolymer, be taking containing unsaturated of bonding benzoxazine and both-end hydrogen polysiloxanes as monomer, using platinum catalyst or/and Platinic chloride as catalyzer, in 60-110 DEG C of reaction;
The chemical structural formula of described fluorine silicon benzoxazine multipolymer suc as formula 1 or formula 2 shown in, its number-average molecular weight is 2000-30000; In formula 1 and formula 2, A is CF
3or CH
3, R is CH
3or CH
2cH
2cF
3;
Formula 1
Formula 2.
2. preparation method according to claim 1, is characterized in that, monomer reacts with after dissolution with solvents again; Solvent for use is one or more in toluene, phenylfluoroform and benzene; Reaction times is more than 12 hours.
3. preparation method according to claim 1, is characterized in that, reaction is carried out under nitrogen protection condition.
4. preparation method according to claim 1, is characterized in that,
Mol ratio containing unsaturated of bonding benzoxazine, both-end hydrogen polysiloxanes and catalyzer is 1:1-3:0.000021-0.000048.
5. preparation method according to claim 1, is characterized in that, the consumption of solvent is 1/ (2-30) of monomer total mass.
6. according to the preparation method described in any one in claim 1-5, it is characterized in that, usedly containing unsaturated of bonding benzoxazine be: allylamine type benzoxazine or propargylamine type benzoxazine.
7. according to the preparation method described in any one in claim 1-5, it is characterized in that, both-end hydrogen polysiloxanes used, its number-average molecular weight is 100-3000.
8. preparation method according to claim 7, is characterized in that, both-end hydrogen polysiloxanes used is the poly-methyl trifluoro propyl siloxanes of both-end hydrogen polydimethylsiloxane or both-end hydrogen.
9. according to the preparation method described in any one in claim 1-5, it is characterized in that, its concrete steps are: first under the condition of 10-40 DEG C, by both-end hydrogen polysiloxanes, containing unsaturated of bonding benzoxazine and catalyzer dissolution with solvents; Then be warming up to 60-110 DEG C, after isothermal reaction 12-72 hour, except desolventizing, obtain fluorine silicon benzoxazine multipolymer.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105801875A (en) * | 2016-05-24 | 2016-07-27 | 济南大学 | Fluorine-silicon segmented copolymer with side chain containing benzoxazine ring, preparation method and application |
| CN106139647A (en) * | 2016-07-18 | 2016-11-23 | 华中农业大学 | Metal ion polybenzoxazine micro-nano ball is as the purposes of oil-water separation material |
| CN107602867A (en) * | 2017-09-06 | 2018-01-19 | 济南大学 | A kind of fluorine-containing and/or silicon polyolefin polyarylate copolymer and preparation method and application |
| CN109867792A (en) * | 2019-01-16 | 2019-06-11 | 江苏大学 | Poly- (benzoxazine-siloxanes) copolymer of one kind and preparation method thereof |
| CN111361245A (en) * | 2020-03-11 | 2020-07-03 | 宁波东旭成新材料科技有限公司 | Barrier film |
| CN111848959A (en) * | 2019-04-29 | 2020-10-30 | 华东理工大学 | Benzoxazine modified organic silicon resin and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101585917A (en) * | 2009-06-19 | 2009-11-25 | 南京大学 | Polybenzoxazine precursor and preparing method thereof |
| CN102083890A (en) * | 2008-07-09 | 2011-06-01 | 汉高股份有限及两合公司 | Polymerizable composition |
| CN102584884A (en) * | 2011-12-19 | 2012-07-18 | 中科院广州化学有限公司 | Benzoxazine monomer, benzoxazine precursor and low-dielectric benzoxazine resin |
| US20130053529A1 (en) * | 2011-08-31 | 2013-02-28 | Chung-Shan Institute of Science and Technology, Armaments, Bureau, Ministry of National Defense | Bridged Bis(Alkoxysilane) or Silsesquioxane Compound Having Benzoxazine-Containing Group |
-
2014
- 2014-09-09 CN CN201410454287.5A patent/CN104193999B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102083890A (en) * | 2008-07-09 | 2011-06-01 | 汉高股份有限及两合公司 | Polymerizable composition |
| CN101585917A (en) * | 2009-06-19 | 2009-11-25 | 南京大学 | Polybenzoxazine precursor and preparing method thereof |
| US20130053529A1 (en) * | 2011-08-31 | 2013-02-28 | Chung-Shan Institute of Science and Technology, Armaments, Bureau, Ministry of National Defense | Bridged Bis(Alkoxysilane) or Silsesquioxane Compound Having Benzoxazine-Containing Group |
| CN102584884A (en) * | 2011-12-19 | 2012-07-18 | 中科院广州化学有限公司 | Benzoxazine monomer, benzoxazine precursor and low-dielectric benzoxazine resin |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105801875A (en) * | 2016-05-24 | 2016-07-27 | 济南大学 | Fluorine-silicon segmented copolymer with side chain containing benzoxazine ring, preparation method and application |
| CN105801875B (en) * | 2016-05-24 | 2018-07-17 | 济南大学 | The fluorosilicic block copolymer and preparation method and application of side chain ring containing benzoxazine |
| CN106139647A (en) * | 2016-07-18 | 2016-11-23 | 华中农业大学 | Metal ion polybenzoxazine micro-nano ball is as the purposes of oil-water separation material |
| CN106139647B (en) * | 2016-07-18 | 2018-09-21 | 华中农业大学 | Metal ion-purposes of the Polybenzoxazine micro-nano ball as water-oil separating material |
| CN107602867A (en) * | 2017-09-06 | 2018-01-19 | 济南大学 | A kind of fluorine-containing and/or silicon polyolefin polyarylate copolymer and preparation method and application |
| CN107602867B (en) * | 2017-09-06 | 2020-07-07 | 济南大学 | Polyolefin-polyarylate copolymer containing fluorine and/or silicon, preparation method and application thereof |
| CN109867792A (en) * | 2019-01-16 | 2019-06-11 | 江苏大学 | Poly- (benzoxazine-siloxanes) copolymer of one kind and preparation method thereof |
| CN111848959A (en) * | 2019-04-29 | 2020-10-30 | 华东理工大学 | Benzoxazine modified organic silicon resin and preparation method and application thereof |
| CN111361245A (en) * | 2020-03-11 | 2020-07-03 | 宁波东旭成新材料科技有限公司 | Barrier film |
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