CN113683734A - Preparation method of novel notch impact resistant photosensitive PC and application of novel notch impact resistant photosensitive PC in sun protection - Google Patents
Preparation method of novel notch impact resistant photosensitive PC and application of novel notch impact resistant photosensitive PC in sun protection Download PDFInfo
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- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
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Abstract
The invention provides a novel notch impact resistant photosensitive PC, and azobenzene and VDT monomers are introduced in the preparation processThe notch impact resistant photosensitive PC prepared by the invention overcomes the defects that a PC material is easy to generate stress cracking and has high notch impact sensitivity, and the notch impact strength of a cantilever beam is improved to 20-60 kJ/m2. In addition, when the polymer is combined with an ultraviolet light filter membrane for use, the azobenzene unit can be changed from a trans-form to a cis-form under illumination, a regularly arranged crystal structure is formed in PC, the azobenzene unit is not transparent any more, the ray injection is effectively prevented, and after the illumination disappears, the cis-form structure of the azobenzene can be spontaneously changed into the trans-form structure, and the transparency of the azobenzene unit is recovered.
Description
Technical Field
The invention relates to a novel notch impact resistant photosensitive PC device, in particular to a preparation method of a novel notch impact resistant photosensitive PC and application thereof in the field of sun protection, and belongs to the technical field of high polymer materials.
Background
Polycarbonate (PC) is an engineering plastic widely used in the fields of electronics, automobiles, construction, and the like, and polycarbonate itself has good mechanical properties such as elongation, and excellent optical properties. However, the PC has high notch sensitivity and weak notch impact resistance in the long-term use process, so that the PC is limited in practical application.
In general, the prior art makes up for the deficiency in PC performance by modification means, and the commonly used modification methods include: copolymerization, filling, reinforcement, alloying, and the like. Overall, the modification method is mainly divided into physical modification and chemical modification. The chemical modification is mainly realized through the change of the structure of a main chain, a branched chain or a side chain of a macromolecule, and the physical modification is mainly realized through filling modification and polymer blending, and the optimization of the performance is realized by fully utilizing the actions of physical adsorption, complexation or hydrogen bonds and the like.
In order to better meet the needs of real life, the multifunctionalization of PC materials is also an important development direction. Azobenzene is a photoresponsive molecule which can show a trans-structure under the condition of no external stimulation, but can change from a trans-structure to a cis-structure after being irradiated by ultraviolet light, and can spontaneously recover to the trans-structure after the ultraviolet light disappears.
Meanwhile, in order to further enhance the notch impact resistance of the PC, a third monomer with 3 degrees of functionality or multiple degrees of functionality can be added in the polycarbonate polymerization process to enable molecular chains of the third monomer to be crosslinked, so that the notch impact resistance of the PC is greatly improved.
The notch impact strength can be greatly improved by PC crosslinking, but too high crosslinking degree or too dense crosslinking points can limit molecular chain movement and influence the transformation of a cis-structure and a trans-structure of azobenzene.
Disclosure of Invention
The invention aims to provide a novel notch impact resistant photosensitive PC and a preparation method thereof, and also provides application of the novel notch impact resistant photosensitive PC in a sun-proof material.
The technical scheme adopted by the invention is as follows:
a novel notch impact resistant photosensitive PC material has the following structural formula:
wherein-R is of the structure
—R1The end-capping group may be a monophenol compound such as phenol or p-tert-butylphenol, n is preferably 30 to 50, and m is preferably 2 to 5.
A preparation method of novel notch impact resistant photosensitive PC comprises the following steps:
1) stirring bisphenol A, azobenzene, alkali liquor and a certain amount of sodium hydrosulfite to react in an inert gas atmosphere at a certain temperature to obtain a homogeneous phase aqueous solution a;
2) adding a certain amount of oil-soluble solvent into the aqueous solution a to obtain an oil-water mixture b;
3) adding 2-vinyl-4, 6-diamino-1, 3, 5-triazine (VDT) into the oil-water mixture b under the condition of stirring to obtain a mixture c;
4) continuously introducing phosgene and alkali liquor in a certain proportion into the mixture c under the condition of stirring for reaction, and controlling the reaction temperature to be a certain equilibrium temperature
5) Adding a certain proportion of end capping agent and a small amount of catalyst, continuously introducing a certain amount of alkali liquor, controlling a certain reaction temperature, and continuously reacting for a period of time to obtain a PC-VDT-azobenzene copolymer reaction solution;
6) taking the reaction liquid oil phase, carrying out acid washing and water washing, and then removing the oil-soluble solvent to obtain a PC-VDT-azobenzene copolymer solid;
7) crushing the solid, and adding a certain amount of VDT monomer and an initiator to obtain a mixture d;
8) and (3) placing a certain amount of the mixture d into a high-temperature mould for a certain time to obtain the novel notch impact resistant photosensitive PC.
Further, in the step 1), the molar ratio of azobenzene to bisphenol A is 0.01-0.1;
the alkali can be strong alkali such as NaOH, KOH and the like, preferably NaOH, and the concentration of the alkali in the aqueous solution a is 4-7 wt%;
the concentration of bisphenol A in the aqueous solution a is 10 to 20 weight percent;
the concentration of the sodium hydrosulfite in the aqueous solution a is 0.1-1 wt%;
the temperature is 20-40 ℃, and the reaction time is 10-40 min.
In the step 2), the oil-soluble solvent may be chloroform, tetrachloroethane, dichloromethane, chlorobenzene, tetrahydrofuran, dioxane, pyridine, etc., preferably dichloromethane, and the mass ratio of the aqueous solution a to the oil-soluble solvent is 0.5-1.5, preferably 0.9-1.1.
In the step 3), the molar ratio of VDT to bisphenol A is 0.01-0.1.
In the step 4), the molar ratio of phosgene to (the total molar amount of bisphenol A + azobenzene + VDT) is 1-1.5;
the temperature is 15-36 ℃, and the reaction time is 5-10 min;
the alkali can be strong alkali such as NaOH, KOH, etc., preferably NaOH, the concentration is 5 wt% -50 wt%, preferably 32%, and the alkali is introduced at the flow rate of 1-10g/min in the reaction process.
In the step 5), preferably, the catalyst is triethylamine or quaternary ammonium salts, such as N, N, N, N-trimethyl benzyl ammonium chloride, N, N-dimethyl ethyl octadecyl ammonium sulfate, more preferably triethylamine, and the content of the catalyst in the reaction solution in the step (4) is 50-500 ppm;
preferably, the end-capping agent is phenol or monophenols such as p-tert-butylphenol, preferably p-tert-butylphenol, and the molar ratio of the end-capping agent to bisphenol A is 0.03-0.06;
the alkali can be strong alkali such as NaOH, KOH, and the like, preferably NaOH, the concentration is 5 wt% -50 wt%, preferably 32%, and the alkali is introduced at the flow rate of 0.1-1g/min in the reaction process;
preferably, the temperature control range is 25-36 ℃; preferably, the reaction time is 5-40 min.
In the step 6), the acid used for acid washing can be strong acid substances such as hydrochloric acid, sulfuric acid, nitric acid and the like, preferably hydrochloric acid, and the concentration can be 0.5 wt% -10 wt%, preferably 1 wt%;
the content of the catalyst in the solid product is less than 0.3ppm, the content of chloride ions is less than 10ppm, and the content of the oil-soluble solvent is less than 100 ppm.
In the step 7), the addition amount of VDT is 3-10 wt% of the mass of the crushed solid;
the initiator may be azo initiators such as Azobisisobutyronitrile (AIBN) and Azobisisoheptonitrile (ABVN), or organic peroxide initiators such as Benzoyl Peroxide (BPO), benzoyl peroxide tert-butyl peroxide and methyl ethyl ketone peroxide, preferably AIBN, and its amount is 0.5-3% of VDT by mass;
in the step 8), preferably, the temperature of the mold is 250-350 ℃, and the heat preservation time is 10-120 min.
The invention also provides application of the notch impact resistant photosensitive PC in a sun-proof material.
A novel notch impact resistant photosensitive PC combined device for a sun-proof material is formed by combining an ultraviolet light filter membrane and photosensitive PC through an adhesive, wherein the ultraviolet light filter membrane only allows ultraviolet light to pass through.
The notch impact resistant photosensitive PC has a photoresponse azobenzene structure, is combined with an ultraviolet light filter membrane for use, an azobenzene unit can be changed from a trans-form to a cis-form under illumination, a regularly arranged crystal structure is formed in the photosensitive PC and is not transparent any more, the incidence of light rays is effectively prevented, and after illumination disappears, the cis-form structure of azobenzene can be spontaneously changed into the trans-form structure, and the transparency of the azobenzene is recovered.
Compared with the prior art, the invention has the following advantages:
1) VDT is used as a cross-linking agent, so that the VDT is subjected to polycondensation reaction with phosgene in the polymerization process by virtue of amino, and is subjected to free radical polymerization reaction in the processing process by virtue of carbon-carbon double bonds, so that the notch impact strength of a cantilever beam is improved to 20-60 kJ/m under the condition of cross-linking without influencing the processing performance of PC2And simultaneously obtains stronger notch impact resistance.
2) The azobenzene in the material is opaque under strong light irradiation and has better light transmission without strong light;
3) the azobenzene film is combined with the ultraviolet film to form a device, so that the structural change of azobenzene can be effectively controlled, and a sun-screening effect is better achieved;
4) compared with the prior art, the novel notch impact resistant photosensitive PC device is used for sunscreen for the first time, and the notch impact resistance is greatly improved.
Drawings
FIG. 1 is a schematic diagram of a photosensitive PC composite device of the present invention.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be illustrative of the invention and are not to be construed as limiting the scope of the invention.
Notched Izod impact Strength in the examples was tested in accordance with GB/T1843-2008.
[ example 1 ]
540g of deionized water was added to a 2L jacketed kettle under nitrogen, after which 31g of solid NaOH was added and dissolved with stirring. After the temperature is adjusted to 32 ℃, 1g of sodium hydrosulfite, 80g of bisphenol A solid and 1.5g of azobenzene solid (the molar ratio of azobenzene to BPA is 0.02) are added and stirred for 30min until the bisphenol A and the azobenzene solid are completely dissolved, so as to obtain homogeneous phase water solution;
adding 650g of dichloromethane into the reaction kettle, and adjusting the rotating speed to 300r/min to uniformly mix the water phase and the oil phase;
2.5g of VDT (VDT/BPA molar ratio 0.05) are added to the oil-water mixture;
introducing 9.4L of phosgene gas into the reaction kettle at the speed of 0.94L/min, and simultaneously adding 32 wt% of NaOH alkali liquor into the reaction kettle at the speed of 1.9g/min, wherein the reaction temperature is controlled to be 35 ℃;
adding 18.6g of p-tert-butylphenol dichloromethane solution with the concentration of 10 percent and 78ppm triethylamine into a reaction kettle, simultaneously adding 32 weight percent NaOH alkali liquor into the reaction kettle at the speed of 0.28g/min, continuously stirring for 30min, and stopping, wherein the reaction temperature is controlled to be 28 ℃;
after separation of the water and oil phases, the oil phase was first washed with 1.5% HCl solution, and then the oil phase was washed with deionized water until the water was neutral after washing. Then removing MC and drying to obtain a solid PC-VDT-azobenzene copolymer;
crushing the solid PC-VDT-azobenzene copolymer, adding VDT accounting for 8 wt% of the solid mass and azobisisobutyronitrile accounting for 0.8 wt% of the VDT mass, and uniformly mixing;
pressing into 3mm plate at 300 deg.C with plate vulcanizer, and keeping the temperature for 40 min.
And attaching an ultraviolet light filter membrane on the surface of the plate.
The light transmittance measured under the irradiation of ultraviolet light at 254nm was 98%, and the light transmittance measured under the condition of no irradiation of ultraviolet light was 99.8%. Meanwhile, the notch impact strength of the cantilever beam is 32kJ/m2。
[ example 2 ]
540g of deionized water was added to a 2L jacketed kettle under nitrogen, after which 31g of solid NaOH was added and dissolved with stirring. After the temperature is adjusted to 35 ℃, 1g of sodium hydrosulfite, 80g of bisphenol A solid and 3.8g of azobenzene solid (the molar ratio of azobenzene to BPA is 0.05) are added and stirred for 30min until the bisphenol A and the azobenzene solid are completely dissolved, so as to obtain homogeneous phase water solution;
adding 650g of dichloromethane into the reaction kettle, and adjusting the rotating speed to 300r/min to uniformly mix the water phase and the oil phase;
4.1g of VDT (VDT/BPA molar ratio 0.08) are added to the oil-water mixture;
introducing 9.4L of phosgene gas into the reaction kettle at the speed of 0.94L/min, and simultaneously adding 32 wt% of NaOH alkali liquor into the reaction kettle at the speed of 1.9g/min, wherein the reaction temperature is controlled to be 35 ℃;
adding 18.6g of p-tert-butylphenol dichloromethane solution with the concentration of 10 percent and 100ppm of N, N, N, N-trimethyl benzyl ammonium chloride into a reaction kettle, simultaneously adding 32wt percent of NaOH alkali liquor into the reaction kettle at the speed of 0.28g/min, continuously stirring for 30min, and stopping, wherein the reaction temperature is controlled to be 28 ℃;
after separation of the water and oil phases, the oil phase was first washed with 1.5% HCl solution, and then the oil phase was washed with deionized water until the water was neutral after washing. Then removing MC and drying to obtain a solid PC-VDT-azobenzene copolymer;
crushing the solid PC-VDT-azobenzene copolymer, adding VDT accounting for 6 wt% of the solid mass and azobisisobutyronitrile accounting for 1.2 wt% of the VDT mass, and uniformly mixing;
pressing into 3mm plate at 300 deg.C with plate vulcanizer, and keeping the temperature for 40 min.
And attaching an ultraviolet light filter membrane on the surface of the plate.
The transmittance was measured to be 76% under irradiation with UV light at 254nm and 99.5% without UV light. Meanwhile, the notch impact strength of the cantilever beam is 41kJ/m2。
[ example 3 ]
540g of deionized water was added to a 2L jacketed kettle under nitrogen, after which 31g of solid NaOH was added and dissolved with stirring. After the temperature is adjusted to 32 ℃, 1g of sodium hydrosulfite, 80g of bisphenol A solid and 6.8g of azobenzene solid (the molar ratio of azobenzene to BPA is 0.09) are added and stirred for 30min until the bisphenol A and the azobenzene solid are completely dissolved, so as to obtain homogeneous phase water solution;
adding 650g of dichloromethane into the reaction kettle, and adjusting the rotating speed to 300r/min to uniformly mix the water phase and the oil phase;
1.6g of VDT (VDT/BPA molar ratio 0.03) are added to the oil-water mixture;
introducing 11L of phosgene gas into the reaction kettle at the speed of 1.1L/min, and simultaneously adding 32 wt% of NaOH alkali liquor into the reaction kettle at the speed of 1.9g/min, wherein the reaction temperature is controlled to be 30 ℃;
adding 18.6g of p-tert-butylphenol dichloromethane solution with the concentration of 10 percent and 78ppm triethylamine into a reaction kettle, simultaneously adding 32 weight percent NaOH alkali liquor into the reaction kettle at the speed of 0.28g/min, continuously stirring for 30min, and stopping, wherein the reaction temperature is controlled to be 30 ℃;
after separation of the water and oil phases, the oil phase was first washed with 1.5% HCl solution, and then the oil phase was washed with deionized water until the water was neutral after washing. Then removing MC and drying to obtain a solid PC-VDT-azobenzene copolymer;
crushing the solid PC-VDT-azobenzene copolymer, adding VDT accounting for 6 wt% of the solid mass and azobisisobutyronitrile accounting for 0.8 wt% of the VDT mass, and uniformly mixing;
pressing into 3mm plate at 300 deg.C with plate vulcanizer, and keeping the temperature for 40 min.
And attaching an ultraviolet light filter membrane on the surface of the plate.
The transmittance was measured to be 53% under irradiation with UV light at 254nm and 99.2% without UV light. Meanwhile, the notch impact strength of the cantilever beam is 20kJ/m2。
[ example 4 ]
540g of deionized water was added to a 2L jacketed kettle under nitrogen, after which 31g of solid NaOH was added and dissolved with stirring. After the temperature is adjusted to 32 ℃, 1g of sodium hydrosulfite, 80g of bisphenol A solid and 6.7g of azobenzene solid (the molar ratio of azobenzene to BPA is 0.09) are added and stirred for 30min until the bisphenol A and the azobenzene solid are completely dissolved, so as to obtain homogeneous phase water solution;
adding 650g of dichloromethane into the reaction kettle, and adjusting the rotating speed to 300r/min to uniformly mix the water phase and the oil phase;
4.1g of VDT (VDT/BPA molar ratio 0.08) are added to the oil-water mixture;
introducing 9.4L of phosgene into the reaction kettle at the speed of 0.94L/min, and simultaneously adding 32 wt% of NaOH alkali liquor into the reaction kettle at the speed of 1.9g/min, wherein the reaction temperature is controlled to be 35 ℃;
adding 18.6g of p-tert-butylphenol dichloromethane solution with the concentration of 10 percent and 78ppm triethylamine into a reaction kettle, simultaneously adding 32 weight percent NaOH alkali liquor into the reaction kettle at the speed of 0.28g/min, continuously stirring for 30min, and stopping, wherein the reaction temperature is controlled to be 28 ℃;
after separation of the water and oil phases, the oil phase was first washed with 1.5% HCl solution, and then the oil phase was washed with deionized water until the water was neutral after washing. Then removing MC and drying to obtain a solid PC-VDT-azobenzene copolymer;
crushing the solid PC-VDT-azobenzene copolymer, adding VDT accounting for 4 wt% of the solid mass and azobisisobutyronitrile accounting for 3 wt% of the VDT mass, and uniformly mixing;
pressing into 3mm plate at 300 deg.C with plate vulcanizer, and keeping the temperature for 40 min.
And attaching an ultraviolet light filter membrane on the surface of the plate.
The light transmittance was measured to be 73% under irradiation with ultraviolet light of 254nm and 99.6% under the condition of no irradiation with ultraviolet light. Meanwhile, the impact strength of the gap of the cantilever beam is 56kJ/m2。
Claims (10)
1. A notch impact resistant photosensitive PC having the following structural formula:
wherein-R is of the structure
R1 is a terminal group, is a monophenol, and is preferably selected fromFrom phenol, p-tert-butylphenol; n is preferably 30 to 50, and m is preferably 2 to 5.
2. A preparation method of notch impact resistant photosensitive PC comprises the following steps:
1) mixing bisphenol A, azobenzene and alkali liquor to obtain homogeneous phase aqueous solution a;
2) adding a certain amount of oil-soluble solvent into the aqueous solution a to obtain an oil-water mixture b;
3) adding 2-vinyl-4, 6-diamino-1, 3, 5-triazine (VDT) into the oil-water mixture b to obtain a mixture c;
4) continuously introducing phosgene and alkali liquor into the mixture c for reaction;
5) adding a terminating agent and a catalyst, continuously introducing a certain amount of alkali liquor, and continuously reacting for a period of time to obtain a PC-VDT-azobenzene copolymer reaction solution;
6) taking the reaction liquid oil phase, removing the oil-soluble solvent after acid washing and water washing to obtain a PC-VDT-azobenzene copolymer solid;
7) crushing the solid, and adding a certain amount of VDT and an initiator to obtain a mixture d;
8) and (3) placing a certain amount of the mixture d into a high-temperature mould for a certain time to obtain the notch impact resistant photosensitive PC.
3. The process according to claim 2, wherein in step 1), the molar ratio of azobenzene to bisphenol a is from 0.01 to 0.1;
the concentration of bisphenol A in the aqueous solution a is 10-20 wt%;
the alkali is NaOH and/or KOH, and the concentration of the alkali in the aqueous solution a is 4-7 wt%.
4. The method according to any one of claims 2 to 3, wherein in the step 2), the oil-soluble solvent is one or more of chloroform, tetrachloroethane, dichloromethane, chlorobenzene, tetrahydrofuran, dioxane and pyridine, and the mass ratio of the aqueous solution a to the oil-soluble solvent is 0.5 to 1.5.
5. The process according to any one of claims 2 to 4, wherein in step 3), the molar ratio of 2-vinyl-4, 6-diamino-1, 3, 5-triazine to bisphenol A is from 0.01 to 0.1.
6. The process according to any one of claims 2 to 5, wherein in step 4) the molar ratio of phosgene to (total molar amount of bisphenol A + azobenzene + 2-vinyl-4, 6-diamino-1, 3, 5-triazine) is from 1 to 1.5;
the reaction time is 5-10 min;
the concentration of the alkali liquor is 5 wt% -50 wt%, and the alkali liquor is introduced at the flow rate of 1-10g/min in the reaction process.
7. The method according to any one of claims 2 to 6, wherein in the step 5), the catalyst is triethylamine and/or quaternary ammonium salt, and the addition amount is 50 to 500ppm of the mass of the reaction solution in the step 4);
the end capping agent is monophenolic substance, preferably phenol and/or p-tert-butylphenol, and the molar ratio of the end capping agent to the bisphenol A is 0.03-0.06;
the concentration of the alkali liquor is 5 wt% -50 wt%, and the alkali liquor is introduced at the flow rate of 0.1-1g/min in the reaction process;
the reaction time is 5-40 min.
8. The process according to any one of claims 2 to 7, wherein in step 7) 2-vinyl-4, 6-diamino-1, 3, 5-triazine is added in an amount of 3% to 10% by weight of the mass of the solids after comminution;
the initiator is azo initiator and/or organic peroxide initiator, and the amount of the initiator is 0.5-3% of the mass of the 2-vinyl-4, 6-diamino-1, 3, 5-triazine.
9. The method according to any one of claims 2 to 8, wherein in step 8), the mold temperature is 250 ℃ to 350 ℃ and the holding time is 10min to 120 min.
10. Use of a notch impact resistant photosensitive PC according to any one of claims 1-9 in a sunscreen material.
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| JP2009057444A (en) * | 2007-08-31 | 2009-03-19 | Jsr Corp | Thermoplastic resin composition, method for producing the same and optical actuator material |
| CN102675562A (en) * | 2012-05-16 | 2012-09-19 | 天津大学 | Polyethylene glycol macromonomer cross-linked high-strength hydrogel and photo-initiation radical polymerization process thereof |
| CN103172802A (en) * | 2013-04-10 | 2013-06-26 | 天津大学 | Diamino triazine hydrogen bond enhanced hydrogel based on cyclodextrin crosslinking and preparation method and application thereof |
| JP2015163598A (en) * | 2014-01-31 | 2015-09-10 | 株式会社デンソー | Azobenzene compound and heat pump system using the same |
| CN107556729A (en) * | 2017-09-19 | 2018-01-09 | 深圳市科聚新材料有限公司 | Polycarbonate composite material, PC sunlight plate and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009057444A (en) * | 2007-08-31 | 2009-03-19 | Jsr Corp | Thermoplastic resin composition, method for producing the same and optical actuator material |
| CN102675562A (en) * | 2012-05-16 | 2012-09-19 | 天津大学 | Polyethylene glycol macromonomer cross-linked high-strength hydrogel and photo-initiation radical polymerization process thereof |
| CN103172802A (en) * | 2013-04-10 | 2013-06-26 | 天津大学 | Diamino triazine hydrogen bond enhanced hydrogel based on cyclodextrin crosslinking and preparation method and application thereof |
| JP2015163598A (en) * | 2014-01-31 | 2015-09-10 | 株式会社デンソー | Azobenzene compound and heat pump system using the same |
| CN107556729A (en) * | 2017-09-19 | 2018-01-09 | 深圳市科聚新材料有限公司 | Polycarbonate composite material, PC sunlight plate and preparation method thereof |
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