CN115612084B - Chemical-resistant polycarbonate material and preparation method thereof - Google Patents

Chemical-resistant polycarbonate material and preparation method thereof Download PDF

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CN115612084B
CN115612084B CN202110796484.5A CN202110796484A CN115612084B CN 115612084 B CN115612084 B CN 115612084B CN 202110796484 A CN202110796484 A CN 202110796484A CN 115612084 B CN115612084 B CN 115612084B
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titanium dioxide
polycarbonate material
chemical
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CN115612084A (en
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任志刚
王伟林
卢锦生
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Shenzhen Yuanchuang Chemical Technology Co ltd
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Shenzhen Yuanchuang Chemical Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/22—General preparatory processes using carbonyl halides
    • C08G64/24—General preparatory processes using carbonyl halides and phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/04—Aromatic polycarbonates
    • C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
    • C08G64/08—Aromatic polycarbonates not containing aliphatic unsaturation containing atoms other than carbon, hydrogen or oxygen
    • C08G64/085—Aromatic polycarbonates not containing aliphatic unsaturation containing atoms other than carbon, hydrogen or oxygen containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide

Abstract

The application discloses a chemical-resistant polycarbonate material, which comprises the following raw materials: bisphenol A, dihydric phenol, alkaline agent, catalyst, halogenated alkane, auxiliary agent, siloxane, organic sodium salt, ionic liquid, phosgene and deionized water. According to the application, through accurate raw material selection, compounding and proportion adjustment, and simple melt mixing, the polycarbonate material with good chemical resistance, photoyellowing resistance and mechanical strength is prepared, the overall comprehensive performance of the polycarbonate material is further enhanced, the applicability of the polycarbonate material is improved, and the application field and environment of the polycarbonate material are expanded.

Description

Chemical-resistant polycarbonate material and preparation method thereof
Technical Field
The application relates to the field of IPC classified C08L69, in particular to a chemical-resistant polycarbonate material and a preparation method thereof.
Background
Polycarbonates (PC) are a high molecular polymer containing carbonate groups in the molecular chain, and can be classified into various types depending on the ester groups. Polycarbonate is used as one of amorphous engineering plastics, and has the characteristics of good heat resistance, good transparency and the like, so that the polycarbonate is widely applied to the fields of automobiles, electric appliances and medical care products. At the same time, however, polycarbonate materials also suffer from a number of performance problems, such as notch sensitivity, poor chemical resistance, poor light and yellowing resistance, and susceptibility to cracking, limiting their further application, especially in the healthcare field, where numerous healthcare devices are often in the environment of various medical and medical chemicals, and therefore, higher demands are placed on the corresponding chemical resistance properties of polycarbonate materials.
The prior art (CN 201611178739.7) provides a chemical resistant flame retardant polycarbonate material, which is prepared by simply mixing polycarbonate, oligomeric silsesquioxane, a flame retardant, an anti-dripping agent, a toughening agent and an antioxidant, and is claimed to have good chemical resistance and flame retardant performance, but a simple mixing preparation method is easy to cause problems of additive precipitation and compatibility when adding excessive amounts of functional additives. Meanwhile, the chemical resistance, flame retardance and other properties of the polycarbonate are mainly improved, and the change and improvement of other important characteristic properties such as light resistance, yellowing resistance and hydrophobicity are less.
The prior art (CN 201180063799.3) provides a polycarbonate resin composition having excellent chemical resistance, which mainly adopts aromatic polycarbonate and siloxane-based polycarbonate and syndiotactic polystyrene, and claims to have good chemical resistance and fluidity, but the raw materials of the chemical-resistant polycarbonate material prepared by the composition do not have obvious raw materials capable of inhibiting yellowing and oxidation of the material, which makes the material extremely easy to undergo yellowing and oxidation phenomena under the condition of illumination ultraviolet rays, and simultaneously affects the quality and service life of the polycarbonate material.
It is therefore a significant task to develop a polycarbonate material which has good chemical resistance, and at the same time also has good resistance to light yellowing and hydrophobicity.
Disclosure of Invention
In order to solve the above problems, the first aspect of the present application provides a chemical-resistant polycarbonate material, which comprises the following raw materials: bisphenol A, dihydric phenol, alkaline agent, catalyst, halogenated alkane, auxiliary agent, siloxane, organic sodium salt, ionic liquid, phosgene and deionized water.
In some preferred embodiments, the raw materials comprise at least the following parts by weight: 80-100 parts of bisphenol A, 40-55 parts of dihydric phenol, 30-60 parts of alkaline agent, 1-2 parts of catalyst, 15-25 parts of halogenated alkane, 1-10 parts of auxiliary agent, 40-60 parts of siloxane, 0.1-1 part of organic sodium salt, 1-5 parts of ionic liquid, 110-140 parts of phosgene and 300-500 parts of deionized water.
In some preferred embodiments, the dihydric phenol is at least one of 2,2 '-biphenol, 4' -biphenol, hydroquinone, 2, 6-dihydroxynaphthalene.
In some preferred embodiments, the mass ratio of dihydric phenol to bisphenol a is from 4 to 5: 8-9.
In some preferred embodiments, the dihydric phenol to bisphenol a mass ratio is 4.6:8.5.
in some preferred embodiments, the dihydric phenol is 4,4' -biphenol.
In the application, the chemical resistance of the polycarbonate material is further improved by adding 4,4' -biphenol as a synthesis raw material. The inventors speculate that: the addition of 4,4' -biphenol can cooperate with the process of synthesizing polycarbonate by using o-allylphenol-terminated dimethyl silicone oil and phosgene to form a three-dimensional network structure in order to replace the original straight structure, and the addition of the multi-benzene ring can further improve entanglement strength of long chains and benzene rings in the polycarbonate material, improve crosslinking property and crosslinking density, reduce the number of movable groups in the material and inhibit the flow of internal electrons; meanwhile, the addition of the 4,4' -biphenol can generate stronger connecting force through intermolecular acting force between hydroxyl groups and the surfaces of the titanium dioxide particles, so as to inhibit precipitation of modified particles in the material, wherein the mass ratio of the crosslinking and the titanium dioxide particles to bisphenol A is 4.6: the best is achieved at 8.5; too low an amount of addition significantly reduces the chemical resistance and stability of the polycarbonate material.
In some preferred embodiments, the alkaline agent is at least one of 50wt% aqueous sodium hydroxide solution, 50wt% aqueous sodium bicarbonate solution.
In some preferred embodiments, the alkaline agent is 50wt% aqueous sodium hydroxide.
In some preferred embodiments, the catalyst is triethylamine.
In some preferred embodiments, the haloalkane is at least one of dichloromethane, chloroform.
In some preferred embodiments, the haloalkane is dichloromethane.
In some preferred embodiments, the adjunct is at least one of titanium dioxide, zinc oxide, antimony dioxide, modified titanium dioxide, and modified zinc oxide.
In some preferred embodiments, the adjunct is modified titanium dioxide.
In some preferred embodiments, the modified titanium dioxide has an average fineness of 60 to 80nm.
In some preferred embodiments, the mass ratio of the modified titanium dioxide to bisphenol a is 4 to 8: 80-90.
In some preferred embodiments, the mass ratio of the modified titanium dioxide to bisphenol a is 5:85.
in the application of the application, the mechanical property and the light resistance and yellowing resistance of the polycarbonate material are effectively improved by adding the modified titanium dioxide as an auxiliary agent. The inventors speculate that: the modified titanium dioxide is connected through a metal coordination bond to form an electron flow path with a special PN junction structure, and can gather carriers and electron holes in a valence band and a conduction band of the composite particles under the illumination of visible light, so that the forbidden band distance of the composite ions is reduced, the absorption wavelength of the composite particles under the visible light is improved, the ultraviolet light absorption capacity is further improved, and especially when the mass ratio of the modified titanium dioxide to bisphenol A is 5: at 85, the light resistance of the polycarbonate material is optimal; meanwhile, when the fineness of the modified titanium dioxide is 60-80 nm, the modified titanium dioxide can be most effectively present under the action of external stress, the inside of the generated microscopic crack structure is in filiform tight connection with the polycarbonate material through the active surface and the surface group, and when the modified titanium dioxide is subjected to strong external stress, the modified titanium dioxide can convert cracks into silver cracks, so that microscopic notch formation of the polycarbonate material is prevented, and the penetration of a chemical solvent is further reduced.
In some preferred embodiments, the method of preparing the modified titanium dioxide comprises the steps of: (1) Dissolving succinic anhydride in DMF solution, adding a certain amount of silane coupling agent, heating and stirring for 1 hour at the water bath temperature of 60 ℃; (2) Dropwise adding DMF solution containing titanium dioxide into the reaction solution, and continuously stirring and reacting for 2 hours to obtain pretreated titanium dioxide particles; (3) Dispersing pretreated titanium dioxide particles in deionized water, then adding dimethyl imidazole, cetyl trimethyl ammonium bromide, zinc nitrate and a proper amount of deionized water, rapidly mixing and stirring for 10 minutes, then adding the mixture into a 120 ℃ hydrothermal kettle for reaction for 2-2.5 hours, and after the reaction is completed, vacuum drying at 60 ℃ and grinding to obtain the titanium dioxide.
In some preferred embodiments, the siloxane is at least one of a dimethicone, a hydroxy silicone oil, a hydrogen containing silicone oil.
In some preferred embodiments, the siloxane is an ortho allylphenol terminated dimethicone.
In some preferred embodiments, the weight ratio of the o-allylphenol-terminated simethicone to bisphenol A is from 5 to 6: 8-9.
In some preferred embodiments, the weight ratio of o-allylphenol-terminated simethicone to bisphenol a is 5.8:8.5.
in some preferred embodiments, the ortho allylphenol end capped simethicone has an average molecular weight of 3000 to 3800.
In the application of the application, the chemical solvent resistance and the corresponding mechanical properties of the polycarbonate material are effectively improved by adding the dimethyl silicone oil capped by the o-allylphenol in the synthesis process of the polycarbonate material. The inventors speculate that: adding o-allylphenol-terminated dimethyl silicone oil in the synthesis process, and particularly when the average molecular weight is 3000-3800, and the mass ratio is 5.8:8.5, the o-allylphenol-terminated dimethyl silicone oil can cooperate with bisphenol A and phosgene in the raw materials to form an optimal cyclic low-aggregation structure, so that further condensation reaction is carried out to form a high-molecular-weight polymer material, larger molecular long chains are formed in the polymer material, more internal entanglement points are increased, and disentanglement resistance is improved; in addition, the number of microscopic stress concentration points existing at the low end group in the polycarbonate material can be obviously reduced, and microscopic defects are reduced, so that the formation number of microscopic cracks is greatly reduced when external stress is applied, and the total penetration amount of chemical solvents is reduced.
In some preferred embodiments, the organic sodium salt is sodium gluconate.
In some preferred embodiments, the ionic liquid is at least one of trifluoroethanol, methyltriazabicycloundecane, methylimidazolium.
In some preferred embodiments, the ionic liquid is trifluoroethanol.
In some preferred embodiments, at least one of a flame retardant, an inorganic filler, an organic filler, an anti-drip agent, a heat stabilizer, an antioxidant, and an ultraviolet light absorber may be further added to the chemical-resistant polycarbonate material.
In the application of the application, the modified titanium dioxide is converted from a pure hydrophilic state with 4 hydroxyl groups on the surface into a hydrophobic state with a rough skeleton surface, and then the modified titanium dioxide is synergistic with the dimethyl silicone oil blocked by the o-allylphenol in the raw material, so that the hydrophobic property of the surface of the polycarbonate material is obviously enhanced. When the polycarbonate material is specifically used, the residual time of the chemical water solvent on the surface of the polycarbonate is greatly shortened, so that the cleaning condition of the chemical solvent on the surface of the polycarbonate is improved, and the chemical resistance and environmental applicability of the polycarbonate material are further improved.
In some preferred embodiments, the chemical resistant polycarbonate material is substantially free of non-nanostructured fluoropolymers encapsulated by an encapsulating polymer, preferably substantially free of styrene-acrylonitrile encapsulated non-nanostructured poly (tetrafluoroethylene).
The second aspect of the present application provides a method for preparing the chemical-resistant polycarbonate material, comprising the steps of: (1) Adding deionized water and dihydric phenol into a six-neck flask with a stirrer, a pH meter and a condenser tube, stirring and purging with nitrogen for 5-10 minutes, then adding an alkaline agent, and stirring for 10-15 minutes to dissolve the dihydric phenol; (2) Adding a catalyst and halogenated alkane into another container, and shaking uniformly to prepare a uniform solution; (3) Adding bisphenol A, siloxane, ionic liquid and organic sodium salt into a six-neck flask, then introducing a certain amount of phosgene at a constant speed, simultaneously adding an alkaline agent again to adjust the pH to 9.8-10.2, and continuously stirring for 10-15 minutes; (4) Adding a catalyst and a uniform solution of halogenated alkane into a flask, adding an alkaline agent again in an appropriate amount to keep the pH of the solution at 10-11, and then introducing phosgene at 2-2.4 g/min for 10-12 min, wherein the pH of the solution is kept at 8.7-9.3 continuously by adding the alkaline agent during the process, and adjusting the pH to 8.5 after the introduction of the phosgene is completed; (5) And (3) standing the solution for layering, taking the lower layer of oil phase, adding 0.1N hydrochloric acid with the same volume for washing once, washing with deionized water for four times, adding methanol into the oil phase to precipitate and separate out a product, placing the product in a 100-DEG oven for 6-8 hours for drying, and then adding an auxiliary agent for granulating after melt mixing to obtain the chemical-resistant polycarbonate material.
The third aspect of the present application provides an application of the chemical-resistant polycarbonate material, which is characterized in that: the use of the chemical resistant polycarbonate materials in molded articles, thermoformed articles, extruded films, extruded sheets, substrates for coated articles, and substrates for metallized articles is included.
Further, the chemical resistant polycarbonate material is included in the electronic housing of a game console, game controller, portable game device, cellular telephone, television, personal computer, tablet, laptop, personal digital assistant, portable media player, digital camera, portable music player, appliance, power tool, robot, toy, greeting card, home entertainment system, active speaker, bar-form box, adapter, cell phone, smart phone, GPS device, laptop, tablet, electronic reader, copier or solar device, or the article is an electrical junction box, electrical connector, electric automobile charger, outdoor electrical housing, smart meter housing, smart grid power node, photovoltaic frame, automobile, scooter, and motorcycle exterior or interior components, preferably a panel, rear roof side panel, rocker panel, plaque, fender, battery cover, door, trunk deck lid, trunk lid, engine cover, roof, bumper, fascia, headlights, rear mirror housing, pillar trim, cladding, body side molding, wheel covers, door handles, window covers, tail lights, window frames, roof light, roof side frames, license plates, roof side frames, roof mirror housings, license plates, roof frames, roof light, roof frames.
The beneficial effects are that:
1. according to the application, through accurate raw material selection, compounding and proportion adjustment, and simple melt mixing, the polycarbonate material with good chemical resistance, photoyellowing resistance and mechanical strength is prepared, the overall comprehensive performance of the polycarbonate material is further enhanced, the applicability of the polycarbonate material is improved, and the application field and environment of the polycarbonate material are expanded.
2. In the application of the application, the polycarbonate material with high molecular weight and good crosslinking degree is effectively synthesized by reasonably selecting and preparing the dosage ratio of bisphenol A, the dimethyl silicone oil capped by the o-allylphenol and the biphenol, and the chemical strength and the mechanical property of the polycarbonate material are effectively improved.
3. According to the application, by simply adding the modified titanium dioxide, the light resistance and yellowing resistance of the polycarbonate under visible light are effectively improved, the polycarbonate material has good hydrophobic performance, the tolerance of a chemical solvent is further improved, and the application field and the application environment of the polycarbonate material are widened.
Detailed Description
The following describes the technical solution of the present application in detail by examples, but the scope of protection of the present application is not limited to all the examples described. The raw materials of the present application are all commercially available unless otherwise specified.
Example 1
Example 1 in a first aspect, a chemical resistant polycarbonate material is provided, the raw materials comprising, by weight: 85 parts of bisphenol A, 46 parts of 4,4' -biphenol, 39.3 parts of 50wt% sodium hydroxide aqueous solution, 1.2 parts of triethylamine, 20 parts of methylene dichloride, 5 parts of modified titanium dioxide (average fineness of 75 nm), 58 parts of dimethyl silicone oil (average molecular weight of 3500) capped with o-allylphenol, 0.5 part of sodium alginate, 2 parts of trifluoroethanol, 129.6 parts of phosgene and 400 parts of deionized water.
In this example, the preparation method of the modified titanium dioxide comprises the following steps: (1) 5 parts of succinic anhydride are dissolved in 50 parts of DMF solution, 10 parts of (3-aminopropyl) triethoxysilane are added, and the mixture is heated and stirred for 1 hour at a water bath temperature of 60 ℃; (2) Dropwise adding 50 parts of DMF solution containing 2 parts of titanium dioxide into the reaction solution, and continuously stirring and reacting for 2 hours to obtain pretreated titanium dioxide particles; (3) 1 part of pretreated titanium dioxide particles are dispersed in deionized water, then 10 parts of dimethyl imidazole, 15 parts of 0.01wt% of cetyltrimethylammonium bromide, 2 parts of zinc nitrate and 50 parts of deionized water are added, the mixture is rapidly mixed and stirred for 10 minutes, then the mixture is added into a 120 ℃ hydrothermal kettle for reaction for 2.25 hours, and after the reaction is completed, the mixture is dried in vacuum at 60 ℃ and ground to obtain the titanium dioxide.
In this example, succinic anhydride CAS 108-30-5, (3-aminopropyl) triethoxysilane CAS 919-30-2, dimethylimidazole CAS 693-98-1, cetyl trimethylammonium bromide CAS 57-09-0.
In this example, the titanium dioxide is a model P25 titanium dioxide product sold by Shanghai Michlin corporation.
In this example, bisphenol A is a bisphenol A product sold by Shandong North chemical Co., ltd.
In this example, 4 '-biphenol is a 4,4' -biphenol product sold by Jiangsu Qingquan chemical Co., ltd.
In this example, the o-allylphenol-terminated simethicone was an o-allylphenol-terminated simethicone product sold by Jinan silicon harbor chemical Co.
The second aspect of the present embodiment provides a method for preparing a chemical-resistant polycarbonate material, comprising the steps of: (1) Into a six-neck flask with a stirrer, a pH meter and a condenser tube, 400 parts of deionized water and 46 parts of 4,4 '-biphenol are added, stirred and purged with nitrogen for 8 minutes, then 39.3 parts of 50wt% aqueous sodium hydroxide solution is added, and stirred for 12 minutes to dissolve the 4,4' -biphenol; (2) Adding 1.2 parts of triethylamine and 20 parts of dichloromethane into another container, and shaking uniformly to prepare a uniform solution; (3) 85 parts of bisphenol A, 58 parts of dimethyl silicone oil capped by o-allylphenol, 2 parts of trifluoroethanol and 0.5 part of sodium alginate are added into a six-neck flask, 108 parts of phosgene is introduced at a constant speed, and simultaneously sodium hydroxide solution is added again to adjust the pH to 10, and stirring is continued for 12 minutes; (4) Adding a uniform solution of triethylamine and dichloromethane into a flask, adding a proper amount of sodium hydroxide solution again to keep the pH of the solution at 10.5, and then introducing phosgene at 2.16 parts/min for 10 min, continuously keeping the pH at 9 by adding the sodium hydroxide solution during the period, and adjusting the pH at 8.5 after the phosgene is introduced; (5) And (3) after the solution is still layered, taking the lower layer of oil phase, adding 0.1N hydrochloric acid with the same volume for washing once, washing four times by using deionized water, adding 20 parts of methanol into the oil phase to precipitate a product, placing the product in a 100-DEG C oven for 8 hours for drying, and then adding 5 parts of modified titanium dioxide for granulating by melt mixing to obtain the chemical-resistant polycarbonate material.
Example 2
The specific implementation of this example is the same as example 1, except that: 40 parts of 4,4' -biphenol.
Example 3
The specific implementation of this example is the same as example 1, except that: the modified titanium dioxide is reacted in a hydrothermal kettle for 2.5 hours, and the average fineness of the modified titanium dioxide is 80nm.
Example 4
The specific implementation of this example is the same as example 1, except that: the average molecular weight of the o-allylphenol-terminated simethicone was 3000 and 50 parts by weight.
Comparative example 1
The specific embodiment of this comparative example is the same as example 1, except that: 20 parts of 4,4' -biphenol.
Comparative example 2
The specific embodiment of this comparative example is the same as example 1, except that: the 4,4' -biphenol was 65 parts.
Comparative example 3
The specific embodiment of this comparative example is the same as example 1, except that: the modified titanium dioxide is reacted in a hydrothermal kettle for 4.5 hours, and the average fineness of the modified titanium dioxide is 150nm.
Comparative example 4
The specific embodiment of this comparative example is the same as example 1, except that: 2 parts of modified titanium dioxide.
Comparative example 5
The specific embodiment of this comparative example is the same as example 1, except that: the modified titanium dioxide is replaced by the common P25 type titanium dioxide.
Comparative example 6
The specific embodiment of this comparative example is the same as example 1, except that: the weight of the o-allylphenol-terminated simethicone is 20 parts.
Evaluation of Performance
Spline test: the polycarbonate materials prepared in each example and comparative example were prepared into corresponding ASTM test bars, the surface of the bars was coated with a chemical agent (Banana BOAT Ultra Sport SPF) when a tensile test was performed, the angle of the fixed curved surface stretching was 20 °, and after 15 days, the number of cracks on the surface of the bars was observed to be 3 or less, 6 or less, and 6 or more, C.
Light fastness test: all the polycarbonate materials prepared in examples and comparative examples were prepared into sheets of 3cm x 1cm, sun-dried for 8 hours a day with sufficient sunlight, the yellowing and morphology of the sheets were observed, and the sheets were judged to be unacceptable if there was a significant yellowing, 50 samples were tested in each example and comparative example, 5 or less samples were marked as failed A, 5 or less samples were marked as failed B, 15 or more samples were marked as failed C, and the results of the observations were recorded in Table 1.
Hydrophilicity test: all polycarbonate materials prepared in examples and comparative examples were prepared into 3cm x 1cm flakes, after which the hydrophilic angle of the corresponding flakes was tested by the sitting-drop method, 5 samples were tested in each example comparative example, and the average of the measured values is reported in table 1.
TABLE 1
Examples Chemical resistance Light resistance Hydrophilic (°)
Example 1 A A 121
Example 2 A A 119
Example 3 A A 120
Example 4 A A 118
Comparative example 1 B B 109
Comparative example 2 B B 105
Comparative example 3 C B 107
Comparative example 4 C C 84
Comparative example 5 B C 85
Comparative example 6 C B 104
It can be known from examples 1 to 4, comparative examples 1 to 6 and table 1 that the chemical-resistant polycarbonate material provided by the application has good chemical solvent resistance, mechanical properties, light resistance and hydrophobicity, effectively widens the application field and environment of the polycarbonate material, is suitable for popularization in the field of engineering plastics, and has wide development prospect. Wherein example 1 obtained the best performance index with the best raw material ratio and preparation process.
Finally, it should be understood that the foregoing embodiments are merely preferred embodiments of the present application, and are not intended to limit the application, but are intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the application.

Claims (2)

1. A preparation method of a chemical-resistant polycarbonate material is characterized by comprising the following steps: the method comprises the following steps: (1) Into a six-neck flask with a stirrer, a pH meter and a condenser tube, 400 parts of deionized water and 46 parts of 4,4 '-biphenol are added, stirred and purged with nitrogen for 8 minutes, then 39.3 parts of 50wt% aqueous sodium hydroxide solution is added, and stirred for 12 minutes to dissolve the 4,4' -biphenol; (2) Adding 1.2 parts of triethylamine and 20 parts of dichloromethane into another container, and shaking uniformly to prepare a uniform solution; (3) 85 parts of bisphenol A, 58 parts of dimethyl silicone oil capped by o-allylphenol, 2 parts of trifluoroethanol and 0.5 part of sodium alginate are added into a six-neck flask, 108 parts of phosgene is introduced at a constant speed, and simultaneously sodium hydroxide solution is added again to adjust the pH to 10, and stirring is continued for 12 minutes; (4) Adding a uniform solution of triethylamine and dichloromethane into a flask, adding a proper amount of sodium hydroxide solution again to keep the pH of the solution at 10.5, and then introducing phosgene at 2.16 parts/min for 10 min, continuously keeping the pH at 9 by adding the sodium hydroxide solution during the period, and adjusting the pH at 8.5 after the phosgene is introduced; (5) After the solution is static and layered, taking the lower layer of oil phase, adding 0.1N hydrochloric acid with the same volume for washing once, then washing with deionized water for four times, adding 20 parts of methanol into the oil phase to precipitate a product, placing the product in a 100-DEG oven for 8 hours for drying, and then adding 5 parts of modified titanium dioxide for granulating by melt mixing to obtain the chemical-resistant polycarbonate material;
the preparation method of the modified titanium dioxide comprises the following steps: (1) 5 parts of succinic anhydride are dissolved in 50 parts of DMF solution, 10 parts of (3-aminopropyl) triethoxysilane are added, and the mixture is heated and stirred for 1 hour at a water bath temperature of 60 ℃; (2) Dropwise adding 50 parts of DMF solution containing 2 parts of titanium dioxide into the reaction solution, and continuously stirring and reacting for 2 hours to obtain pretreated titanium dioxide particles; (3) Dispersing 1 part of pretreated titanium dioxide particles in deionized water, then adding 10 parts of dimethyl imidazole, 15 parts of 0.01wt% of cetyltrimethylammonium bromide, 2 parts of zinc nitrate and 50 parts of deionized water, rapidly mixing and stirring for 10 minutes, then adding the mixture into a 120 ℃ hydrothermal kettle for reaction for 2.25 hours, and after the reaction is completed, vacuum drying at 60 ℃ and grinding to obtain the titanium dioxide;
the average fineness of the modified titanium dioxide is 75nm;
the average molecular weight of the o-allylphenol end-capped simethicone is 3500;
the titanium dioxide is a P25 titanium dioxide product sold by Shanghai microphone company.
2. Use of a material prepared by the process for the preparation of a chemical resistant polycarbonate according to claim 1, characterized in that: the use of the chemical resistant polycarbonate materials in molded articles, thermoformed articles, extruded films, extruded sheets, substrates for coated articles, and substrates for metallized articles is included.
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CN1103079A (en) * 1993-07-09 1995-05-31 通用电气公司 Compositions of siloxane polycarbonate block copolymers and high heat polycarbonates
CN1784468A (en) * 2003-03-10 2006-06-07 拜尔材料科学股份公司 polycarbonate-based composition
CN1863846A (en) * 2003-08-08 2006-11-15 通用电气公司 Method for preparation of copolyorganosiloxanecarbonates of high clarity
CN101087828A (en) * 2004-12-22 2007-12-12 通用电气公司 Polycarbonates with fluoroalkylene carbonate end groups
CN103189450A (en) * 2010-11-08 2013-07-03 出光兴产株式会社 Polycarbonate resin composition, molded article, and structural member for solar power generation
CN104755530A (en) * 2012-10-12 2015-07-01 出光兴产株式会社 Method for continuously producing polycarbonate-polyorganosiloxane copolymer

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0524731A1 (en) * 1991-07-01 1993-01-27 General Electric Company Polymer blends of polycarbonate-polysiloxane block copolymers with polycarbonates and polyestercarbonate copolymers
CN1103079A (en) * 1993-07-09 1995-05-31 通用电气公司 Compositions of siloxane polycarbonate block copolymers and high heat polycarbonates
CN1784468A (en) * 2003-03-10 2006-06-07 拜尔材料科学股份公司 polycarbonate-based composition
CN1863846A (en) * 2003-08-08 2006-11-15 通用电气公司 Method for preparation of copolyorganosiloxanecarbonates of high clarity
CN101087828A (en) * 2004-12-22 2007-12-12 通用电气公司 Polycarbonates with fluoroalkylene carbonate end groups
CN103189450A (en) * 2010-11-08 2013-07-03 出光兴产株式会社 Polycarbonate resin composition, molded article, and structural member for solar power generation
CN104755530A (en) * 2012-10-12 2015-07-01 出光兴产株式会社 Method for continuously producing polycarbonate-polyorganosiloxane copolymer

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