Polysiloxane polycarbonate, transparent flame-retardant scratch-resistant polycarbonate material as well as preparation method and application of transparent flame-retardant scratch-resistant polycarbonate material

Abstract

The invention provides polysiloxane polycarbonate, a transparent flame-retardant scratch-resistant polycarbonate material as well as a preparation method and application of the transparent flame-retardant scratch-resistant polycarbonate material. The polysiloxane polycarbonate has a structural formula as shown in a formula (I): # imgabs0 # is prepared from raw materials including polysiloxane, a star-type branching agent, a catalyst A, a phenolic end-capping reagent, phosgene, an organic solvent and a water phase; the water phase comprises diphenol, alkali, an end-capping reagent, a catalyst B and water; the transparent flame-retardant scratch-resistant polycarbonate material comprises polycarbonate, prepared polysiloxane polycarbonate, a flame retardant, a scratch-resistant agent and an antioxidant. The prepared transparent flame-retardant scratch-resistant polycarbonate material is good in scratch resistance and fluidity and high in transparency, and is applicable to various thin-walled transparent materials with complex structures.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials. Further, it relates to a polysiloxane polycarbonate, a transparent flame-retardant and scratch-resistant polycarbonate material, and a preparation method and application thereof. Background Art

[0002] Polycarbonate has excellent impact resistance, thermal properties and processing properties, and at the same time has a high light transmittance comparable to that of glass. It is widely used in parts such as electronic appliances, household appliances, displays, communication equipment, optical lenses, mobile phone casings, goggles and automotive lamp housings. At present, with polycarbonate as the preferred substrate, the injection-molded plastic imitation glass mobile phone back cover solution has become a research and development application hotspot for major mobile phone back cover manufacturers. The imitation glass back cover requires a surface hardness of at least 2H for the plastic, and at the same time requires the material to have transparency and flame retardancy.

[0003] However, the surface hardness of polycarbonate is poor, it is extremely easy to be worn, and it is easy to turn yellow and has poor fluidity. Its hardness is only 2B to 3B, far lower than the application requirements of the imitation glass back cover. Usually, the surface of polycarbonate is subjected to coating modification treatment or additional hardening polymers such as polystyrene, styrene maleic anhydride resin, polyester copolymer, styrene copolymer, etc. (CN102964793A, CN105504751A, CN108976747A), scratch-resistant agents or other modifying aids such as nano-diamond powder, jade powder, microcrystalline stone, silicon dioxide, etc. (CN106009580A, CN109593339A) are used for scratch-resistant performance modification to improve its surface hardness. However, some modifiers will bring unavoidable colors to the polycarbonate material, resulting in a decrease in transparency or the material becoming opaque, thus restricting its application. At the same time, the scratch-resistant performance modification of polycarbonate often leads to a decrease in its mechanical properties, especially the impact toughness. Therefore, it is of great significance to research and develop a transparent polycarbonate material with high hardness, high toughness, flame retardancy and excellent fluidity.

[0004] Chinese Patent CN 112322019A discloses a preparation method of a high-hardness transparent flame-retardant polycarbonate material, which uses surface-modified low-melting-point transparent glass powder to improve the hardness and flame-retardant performance of the material. Chinese Patent CN105504751A discloses a transparent flame-retardant and high-hardness polycarbonate material based on polycarbonate, polymethacrylate and modified polysiloxane. The present invention designs and develops a star-branched polysiloxane polycarbonate, and effectively composes it with polycarbonate, scratch-resistant agent, functional flame retardant, etc. to obtain a transparent flame-retardant and scratch-resistant polycarbonate material.

[0005] The existing polycarbonate materials have problems such as poor scratch resistance, poor fluidity and low transparency, which need to be further solved. Summary of the Invention

[0006] In order to solve the technical problems existing in the prior art, the present invention provides a polysiloxane polycarbonate, a transparent flame-retardant and scratch-resistant polycarbonate material, and a preparation method and application thereof.

[0007] The present invention prepares a star-shaped polysiloxane polycarbonate, which has a main structure similar to that of polycarbonate, good compatibility, and introduces silicone components into the polysiloxane polycarbonate structure from the level of the macromolecular chain structure, which can maintain the dispersion and uniformity at the molecular scale and endow the material with scratch resistance.

[0008] The present invention prepares a transparent flame-retardant and scratch-resistant polycarbonate material, the matrix resin of which is a mixture of the above-prepared polysiloxane polycarbonate and polycarbonate, and is combined with an efficient flame retardant and scratch-resistant agent, further enhancing the flame retardant performance and scratch resistance of the material. By regulating the melt flow index of the polycarbonate substrate, the excellent processing performance of the modified polycarbonate material can be ensured, and it is suitable for the application of various structurally complex and thin-walled transparent materials.

[0009] The present invention solves the problems of poor scratch resistance, poor fluidity and low transparency of polycarbonate materials existing in the prior art. The provided preparation method is simple and easy to implement, and is easy to realize industrial production. The prepared transparent flame-retardant and scratch-resistant polycarbonate material can be used for components such as electronic appliances, instruments, and display screens.

[0010] One of the purposes of the present invention is to provide a polysiloxane polycarbonate, the structural formula of which is shown in formula (I):

[0011]

[0012] In formula (I), R 1 , R 2 , R 3 are each independently selected from at least one of hydrogen, methyl, ethyl, methoxy, ethoxy, phenyl, and siloxanyl; the repeated R 1 , R 2 , R 3 can be the same or different; R 4 is hydrogen or methyl; R 5is hydrogen, methyl, isopropyl, tert-butyl, phenyl, isopropylphenyl or p-tert-butylphenyl; R and R' are each independently selected from cyclohexylene or phenylene; X is methylene, dimethylmethylene, , oxygen atom, sulfur atom, carbonyl or sulfoxide group; m is 0 or 1; n is an integer between 0 and 500, preferably an integer between 25 and 350; p is 0 or 1; q is an integer between 3 and 8; r is 0 or 1; s is an integer between 10 and 1000, preferably an integer between 50 and 800; M is a silyl group, methylsilyl group, phenylsilyl group or cage-type silsesquioxane group, preferably a 3-substituted methylsilyl group, 3-substituted phenylsilyl group, 4-substituted silyl group or 3-8-substituted cage-type silsesquioxane group.

[0013] In a preferred embodiment of the present invention,

[0014] The polysiloxane polycarbonate is prepared from raw materials including polysiloxane, star-shaped branching agent, catalyst A, phenol-terminated agent, phosgene, organic solvent and aqueous phase;

[0015] The aqueous phase includes diphenol, base, terminator, catalyst B and water.

[0016] In a preferred embodiment of the present invention,

[0017] The polysiloxane polycarbonate contains a polysiloxane component with a molar percentage of 0.1-10%, preferably contains a polysiloxane component with a molar percentage of 0.5-7.5%, and more preferably contains a polysiloxane component of 0.5-2%;

[0018] The melt flow rate of the polysiloxane polycarbonate is 5-50 g / 10 min at 300 °C and 1.2 kg, preferably 10-40 g / 10 min, and more preferably 15-30 g / 10 min.

[0019] The second object of the present invention is to provide a method for preparing a polysiloxane polycarbonate, comprising the following steps:

[0020] (1) React the polysiloxane with the star-shaped branching agent in the presence of catalyst A to carry out reaction one, then add the phenol-terminated agent to carry out reaction two, and obtain a phenol-terminated star-shaped polysiloxane after post-treatment one;

[0021] (2) Mix diphenol, base, terminator, catalyst B and water to obtain an aqueous phase;

[0022] (3) Dissolve the phenol-terminated star-shaped polysiloxane and phosgene obtained in step (1) in an organic solvent to obtain an organic phase;

[0023] (4) Add the organic phase obtained in step (3) to the aqueous phase obtained in step (2) to carry out copolymerization reaction, and after post-treatment II, the polysiloxane polycarbonate is obtained;

[0024] Steps (1) to (4) are all carried out under a protective gas atmosphere.

[0025] In a preferred embodiment of the present invention,

[0026] The protective gas is at least one of nitrogen and inert gas; the inert gas is preferably argon; and / or,

[0027] Step (1),

[0028] The structural formula of the polysiloxane is shown in formula (II):

[0029]

[0030] In formula (II), R 1 , R 2 are each independently selected from at least one of hydrogen, methyl, ethyl, methoxy, ethoxy, phenyl, and siloxanyl; n is an integer between 0 and 500, preferably an integer between 25 and 350;

[0031] The star-shaped branching agent is at least one of trivinylmethylsilane, trivinylphenylsilane, triallylmethylsilane, triallylphenylsilane, tetravinylsilane, tetraallylsilane, vinyltriisopropenoxysilane, tetraallyloxysilane, trivinylcage silsesquioxane, tetravinylcage silsesquioxane, pentavinylcage silsesquioxane, hexavinylcage silsesquioxane, heptavinylcage silsesquioxane, and octavinylcage silsesquioxane;

[0032] The catalyst A is at least one of silver catalyst, platinum catalyst, palladium catalyst, ruthenium catalyst, and rhodium catalyst;

[0033] The phenolic end-capping agent is at least one of 2-allylphenol, 3-allylphenol, 4-allylphenol, 2-methoxy-4-allylphenol, 2-methoxy-5-allylphenol, and 2-methoxy-6-allylphenol;

[0034] The structural formula of the phenolic end-capped star-shaped polysiloxane is shown in formula (III):

[0035]

[0036] In formula (III), R 1 , R 2 , R 3independently selected from at least one of hydrogen, methyl, ethyl, methoxy, ethoxy, phenyl, and siloxanyl; repeating R 1 , R 2 , R 3 may be the same or different; R 4 is hydrogen or methyl; m is 0 or 1; n is an integer between 0 and 500, preferably an integer between 25 and 350; p is 0 or 1; q is an integer between 3 and 8; M is a silicon group, methylsilicon group, phenylsilicon group, or cage-type silsesquioxane group, preferably a 3-substituted methylsilicon group, 3-substituted phenylsilicon group, 4-substituted silicon group, or 3- to 8-substituted cage-type silsesquioxane group;

[0037] Step (2),

[0038] The diphenol is at least one of bisphenol A, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 2,2'-bis(4-hydroxycyclohexyl)propane, 2,2'-bis(4-hydroxycyclohexyl)ether, 2,2'-bis(4-hydroxycyclohexyl)sulfide; preferably at least one of bisphenol A, 4,4'-dihydroxydiphenyl ether, 2,2'-bis(4-hydroxycyclohexyl)propane;

[0039] The base is at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide, and ammonia water; preferably at least one of sodium hydroxide and potassium hydroxide;

[0040] The capping agent is at least one of phenol, p-methylphenol, p-isopropylphenol, p-tert-butylphenol, p-phenylphenol, p-cumylphenol, p-tert-butylphenylphenol; preferably p-tert-butylphenol;

[0041] The catalyst B is at least one of triethylamine, triethanolamine, tetramethylammonium chloride, tetramethylammonium bromide, trimethylethylammonium chloride, trimethylethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide, trimethylbenzylammonium chloride, trimethylbenzylammonium bromide, dimethylethylbenzylammonium chloride, dimethylethylbenzylammonium bromide;

[0042] Step (3),

[0043] The organic solvent is at least one of dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane.

[0044] In a preferred embodiment of the present invention,

[0045] Step (1),

[0046] The molar ratio of the polysiloxane to the star-shaped branching agent is (3 to 10):1, preferably (3.05 to 9):1;

[0047] The mass ratio of the catalyst A to the polysiloxane is (0.001 to 1):100, preferably (0.01 to 0.5):100;

[0048] The molar ratio of the phenol-based end-capping agent to the polysiloxane is (1 to 2):1, preferably (1.1 to 1.7):1;

[0049] Step (2),

[0050] In the aqueous phase, the molar ratio of the diphenol, the base, the end-capping agent, the catalyst B to water is (1 to 10):(2 to 50):(0.01 to 0.1):(0.0001 to 0.01):100, preferably (1.5 to 8):(3.5 to 30):(0.05 to 0.08):(0.0005 to 0.008):100, more preferably (4 to 8):(6 to 18):(0.05 to 0.08):(0.0005 to 0.008):100;

[0051] Step (3),

[0052] The molar ratio of the phenol-based end-capped star-shaped polysiloxane, phosgene to the organic solvent is (0.1 to 5):(5 to 50):100, preferably (0.1 to 2.5):(10 to 50):100, more preferably (0.1 to 0.8):(20 to 40):100;

[0053] Step (4),

[0054] The volume ratio of the organic phase to the aqueous phase is (0.1 to 10):1, preferably (0.5 to 5):1, more preferably (0.8 to 1.5):1.

[0055] In a preferred embodiment of the present invention,

[0056] Step (1),

[0057] The temperatures of the first reaction and the second reaction are 40 to 100 °C respectively, preferably 50 to 95 °C, more preferably 50 to 70 °C;

[0058] The first reaction and the second reaction are carried out under stirring, and the stirring rate is 50 to 1000 rpm, preferably 200 to 800 rpm;

[0059] The time of the first reaction is 2 to 24 hours, preferably 3 to 20 hours, more preferably 3 to 10 hours;

[0060] The time of the second reaction is 2 to 24 hours, preferably 3 to 20 hours, and more preferably 8 to 15 hours;

[0061] The first post-treatment is vacuum distillation; the vacuum distillation is preferably carried out at 150 to 250 °C and 0 to 1 kPa, and more preferably at 180 to 230 °C and 0.1 to 0.8 kPa

[0062] Step (4),

[0063] The addition of the organic phase to the aqueous phase is carried out with stirring, and the stirring rate is 200 to 1000 rpm, preferably 300 to 850 rpm, and more preferably 400 to 750 rpm;

[0064] The temperature of the copolymerization reaction is 25 to 80 °C, preferably 30 to 75 °C, and more preferably 35 to 60 °C;

[0065] The time of the copolymerization reaction is 1 to 24 hours, preferably 2 to 20 hours, and more preferably 5 to 16 hours;

[0066] The second post-treatment is precipitation, washing, and drying, and the methods commonly used in the prior art can be adopted.

[0067] The third object of the present invention is to provide a polysiloxane polycarbonate obtained by the above preparation method.

[0068] The fourth object of the present invention is to provide a transparent flame-retardant and scratch-resistant polycarbonate material, which includes polycarbonate, polysiloxane polycarbonate, flame retardant, scratch-resistant agent, and antioxidant; the polysiloxane polycarbonate is the above polysiloxane polycarbonate.

[0069] In a preferred embodiment of the present invention,

[0070] Based on the total weight of polycarbonate and polysiloxane polycarbonate being 100 parts by weight, the transparent flame-retardant and scratch-resistant polycarbonate material includes the following components:

[0071] 100 parts by weight of polycarbonate and polysiloxane polycarbonate;

[0072] 0.1 to 2 parts by weight of flame retardant; preferably 0.25 to 0.75 parts by weight;

[0073] 0.1 to 5 parts by weight of scratch-resistant agent; preferably 0.25 to 3 parts by weight;

[0074] 0.001 to 0.5 parts by weight of antioxidant; preferably 0.005 to 0.25 parts by weight;

[0075] Among them, the polycarbonate and polyorganosiloxane polycarbonate include 20 to 90 parts by weight of polycarbonate and 10 to 80 parts by weight of polyorganosiloxane polycarbonate; preferably, it includes 60 to 85 parts by weight of polycarbonate and 15 to 40 parts by weight of polyorganosiloxane polycarbonate.

[0076] In a preferred embodiment of the present invention,

[0077] The polycarbonate has a melt flow rate of 5 to 50 g / 10 min, preferably 10 to 40 g / 10 min, more preferably 20 to 30 g / 10 min at 300 °C and 1.2 kg;

[0078] The transparent flame-retardant and scratch-resistant polycarbonate material has a melt flow rate of 5 to 50 g / 10 min, preferably 10 to 50 g / 10 min at 300 °C and 1.2 kg;

[0079] The flame retardant is at least one of sodium benzenesulfonylbenzenesulfonate, potassium benzenesulfonylbenzenesulfonate, ammonium benzenesulfonylbenzenesulfonate, sodium perfluorobutanesulfonate, potassium perfluorobutanesulfonate, ammonium perfluorobutanesulfonate, and cage-type polyhedral oligomeric silsesquioxane; preferably, it is a combination of potassium benzenesulfonylbenzenesulfonate and cage-type polyhedral oligomeric silsesquioxane or a combination of potassium perfluorobutanesulfonate and cage-type polyhedral oligomeric silsesquioxane; further preferably, in the combination, the mass ratio of potassium benzenesulfonylbenzenesulfonate to cage-type polyhedral oligomeric silsesquioxane is (1 to 10):1, more preferably (2 to 8):1; in the combination, the mass ratio of potassium perfluorobutanesulfonate to cage-type polyhedral oligomeric silsesquioxane is (1 to 10):1, more preferably (1.5 to 6):1;

[0080] The scratch-resistant agent is at least one of nano-silica, nano-aluminum oxide, nano-titanium dioxide, and nano-silica;

[0081] The antioxidant is at least one of tris(nonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], n-octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and 2,6-di-tert-butyl-4-methylphenol.

[0082] The fifth object of the present invention is to provide a preparation method of a transparent flame-retardant and scratch-resistant polycarbonate material, including:

[0083] After melting and blending the components in the above weight parts, the transparent flame-retardant and scratch-resistant polycarbonate material is obtained; preferably,

[0084] First, the components including the flame retardant, scratch-resistant agent, and antioxidant are mixed to obtain an additive mixture, and then the dried polycarbonate, polyorganosiloxane polycarbonate, and additive mixture are melt-blended.

[0085] In a preferred embodiment of the present invention,

[0086] the temperature of the melt blending is 250 - 320 °C, preferably 260 - 300 °C, more preferably 270 - 280 °C;

[0087] The melt blending is carried out on a twin-screw extruder, the screw speed is 100 - 350 rpm, preferably 200 - 300 rpm, more preferably 220 - 280 rpm;

[0088] The total feeding speed of the components on the twin-screw extruder is 1 - 100 kg / h, preferably 5 - 80 kg / h, more preferably 10 - 75 kg / h.

[0089] The sixth object of the present invention is to provide an application of a polysiloxane polycarbonate and a transparent flame-retardant and scratch-resistant polycarbonate material in electronic appliances, instruments, and display screens.

[0090] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0091] The present invention prepares a star-shaped polysiloxane polycarbonate, which has a main structure similar to that of polycarbonate, good compatibility, and introduces silicone components into the polysiloxane polycarbonate structure at the macromolecular chain structure level, which can maintain the dispersion and uniformity at the molecular scale and endow the material with scratch resistance.

[0092] The present invention prepares a transparent flame-retardant and scratch-resistant polycarbonate material, the matrix resin of which is a mixture of the above-prepared polysiloxane polycarbonate and polycarbonate, and is combined with an efficient flame retardant and scratch-resistant agent, further enhancing the flame retardancy and scratch resistance of the material. By regulating the melt flow index of the polycarbonate substrate, the excellent processing performance of the modified polycarbonate material can be ensured, which is suitable for the application of various complex-structured and thin-walled transparent materials.

[0093] The present invention solves the problems of poor scratch resistance, poor fluidity, and low transparency of polycarbonate materials in the prior art. The provided preparation method is simple and easy to implement, and is easy to realize industrial production, achieving good technical effects. The prepared transparent flame-retardant and scratch-resistant polycarbonate material can be used in components such as electronic appliances, instruments, and display screens. Description of the Drawings

[0094] Figure 1 Infrared spectrum diagram of the polysiloxane polycarbonate A prepared in Example 1. Detailed Embodiments

[0095] The present invention is described in detail below in conjunction with specific embodiments. It is necessary to point out that the following embodiments are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made to the present invention by those skilled in the art based on the contents of the present invention still fall within the scope of protection of the present invention.

[0096] The raw materials used in the examples and comparative examples are all conventional commercially available raw materials.

[0097] Polysiloxane 1 and polysiloxane 2 were purchased from Shanghai Biyang Industrial Co., Ltd.

[0098] Polysiloxane 3: purchased from Wuhan Profo Biotechnology Co., Ltd.;

[0099] Tetravinylsilane, triallylphenylsilane, 4-allylphenol: Zhengzhou Alpha Chemical Company;

[0100] Octavidin cage silsesquioxane: purchased from Beijing Formans Technology Co., Ltd.

[0101] Platinum catalyst: purchased from Wuhan Lanabai Pharmaceutical Chemical Company;

[0102] 2-Methoxy-6-allylphenol: purchased from Wuhan Xinxin Biotechnology Co., Ltd.;

[0103] Bisphenol A: purchased from Xidian Mall;

[0104] 4,4'-Dihydroxydiphenyl ether and p-tert-butylphenol: purchased from Aladdin Company;

[0105] Potassium hydroxide: purchased from Shanghai Aiyan Biotechnology Co., Ltd.;

[0106] Triethylamine: purchased from Sigma-Aldrich;

[0107] Chloroform and dichloromethane: purchased from Sinopharm Group;

[0108] Polycarbonate: melt flow rate 20 g / 10 min, purchased from Covestro;

[0109] Potassium phenylsulfonylbenzenesulfonate: purchased from Wuhan Belleye Biotechnology Co., Ltd.;

[0110] Cage polysilsesquioxane: purchased from Guangzhou Yixin Technology Co., Ltd.

[0111] Nano-silicon dioxide: purchased from Shanghai Xiaohuang Nanotechnology Co., Ltd.

[0112] 2,6-Di-tert-butyl-4-methylphenol: purchased from Nanjing Datang Chemical Company.

[0113] The test instruments and test conditions used in the examples are as follows:

[0114] Melt flow rate test: Determined according to ISO 1133 standard, at a temperature of 300 °C and a load of 1.2 kg.

[0115] Notched impact strength test: Determined according to ASTM D256 standard, with a pendulum energy of 5 J.

[0116] Transparency test: Determined according to ASTM D1003 standard.

[0117] Pencil hardness test: Determined according to GB / T 6739-1996 standard, with a load of 750 g.

[0118] Flame retardancy test: Determined according to UL-94 standard.

[0119]

Example 1

[0120] Synthesis of polysiloxane polycarbonate:

[0121] Step (1): Under stirring at 65 °C and 500 rpm, 6000 g of polysiloxane 1 (2.1 mol) as shown in formula (IV) and 54.4 g of tetravinylsilane (0.4 mol) were reacted for 5 hours under the action of 1.2 g of platinum catalyst, then 422.1 g of 4-allylphenol (3.15 mol) was added, and after continuing the reaction for 10 hours, under reduced pressure distillation at 205 °C and 0.5 kPa, 4-allylphenol-capped tetra-armed star-shaped polysiloxane as shown in formula (V) was obtained, with a yield of 97.8%.

[0122]

[0123] Step (2): Under nitrogen protection, 1140 g of bisphenol A (5 mol), 672 g of potassium hydroxide (12 mol), 7.5 g of p-tert-butylphenol (0.05 mol), 0.505 g of triethylamine (0.005 mol), and 1800 g of water (100 mol) were mixed to obtain an aqueous phase;

[0124] Step (3): 316 g (0.035 mol) of 4-allylphenol-capped tetra-armed star-shaped polysiloxane prepared in (1) and 495 g of phosgene (5 mol) were dissolved in 2380 g of chloroform (20 mol) to obtain an organic phase;

[0125] Step (4): The above organic phase was introduced into the above aqueous phase (volume ratio 1.2:1), and under stirring at 500 rpm, copolymerization reaction was carried out at 55 °C for 10 hours. After precipitation, washing, and drying, polysiloxane polycarbonate A as shown in formula (VI) was obtained, with a melt flow rate of 27.5 g / 10 min, and the molar percentage content of the polysiloxane component was 1.38%. The infrared spectrum is shown in Figure 1 .

[0126]

[0127] Figure 1 In the range of 1080 - 1050 cm -1 is the characteristic peak of the siloxane chain segment Si - O - Si; 1770 cm -1 is the characteristic absorption peak of the carbonate group.

[0128]

Example 2

[0129] Synthesis of polysiloxane polycarbonate:

[0130] Step (1): Under stirring at 65 °C and 500 rpm, 4200 g of polysiloxane 2 (1.7 mol) as shown in formula (VII) and 126.4 g of octavinylcage silsesquioxane (0.2 mol) were reacted for 6 hours under the action of 1.05 g of platinum catalyst, then 273.4 g of 4 - allylphenol (2.04 mol) was added, and after continuing the reaction for 12 hours, octa - armed star - shaped polysiloxane capped with 4 - allylphenol as shown in formula (VIII) was obtained by vacuum distillation at 205 °C and 0.5 kPa, with a yield of 95.9%.

[0131]

[0132] Among them, M is:

[0133] Step (2): Under nitrogen protection, 1200 g of bisphenol A (5.26 mol), 700 g of potassium hydroxide (12.5 mol), 10 g of p - tert - butylphenol (0.067 mol), 0.606 g of triethylamine (0.006 mol), and 1800 g of water (100 mol) were mixed to obtain an aqueous phase;

[0134] Step (3): 400 g (0.097 mol) of octa - armed star - shaped polysiloxane capped with 4 - allylphenol prepared in (1) and 550 g of phosgene (5.56 mol) were dissolved in 2000 g of dichloromethane (23.5 mol) to obtain an organic phase;

[0135] Step (4): The above - mentioned organic phase was introduced into the above - mentioned aqueous phase (volume ratio of 1.3:1), and copolymerization reaction was carried out at 58 °C for 12 hours under stirring at 550 rpm. After precipitation, washing, and drying, polysiloxane polycarbonate B as shown in formula (IX) was obtained, with a melt flow rate of 15.8 g / 10 min and a molar percentage content of the polysiloxane component of 0.89%. The structural formula is:

[0136]

[0137]

Examples 3 - 14, Comparative Examples 1 - 5

[0138] Preparation of a transparent flame - retardant and scratch - resistant polycarbonate material:

[0139] (1) Potassium benzenesulfonylbenzenesulfonate, cage - type polyhedral oligomeric silsesquioxane, nano - silica, and 2,6 - di - tert - butyl - 4 - methylphenol were thoroughly mixed by high - speed stirring to obtain a functional composite additive;

[0140] (2) Polycarbonate and polyorganosiloxane polycarbonate A were respectively dried and then reserved;

[0141] (3) The functional composite additive, polycarbonate, and polyorganosiloxane polycarbonate were respectively introduced into a LABTECH co - rotating twin - screw extruder (screw diameter 16 mm, length - to - diameter ratio 40) through one powder feeder and two pellet feeders. Under the process conditions of a temperature of 275 °C, a rotation speed of 225 rpm, and a feeding rate of 12 kg / h, they were melt - kneaded and extruded, cooled, and pelletized to obtain a transparent flame - retardant and scratch - resistant polycarbonate material.

[0142] The corresponding formulation composition contents and comprehensive performance results are shown in Table 1 and Table 2 respectively.

[0143] Table 1. Raw materials and dosages in Examples 3 - 14 and Comparative Examples 1 - 5

[0144]

[0145] Table 2. Test results of the polycarbonate materials obtained in Examples 3 - 14 and Comparative Examples 1 - 5

[0146]

[0147] Compared with Examples 3 - 6, in Comparative Example 1, there is no polyorganosiloxane polycarbonate A. The test results prove that the addition of star - structured polyorganosiloxane polycarbonate A can not only improve the hardness of the material, but also be beneficial to improving the processing fluidity and impact toughness of the material.

[0148] Compared with Examples 7 - 9, in Comparative Example 2, there is no addition of polyorganosiloxane polycarbonate B. The test results also prove that the addition of star - structured polyorganosiloxane polycarbonate B can not only improve the hardness of the material, but also be beneficial to improving the processing fluidity and impact toughness of the material. The combination of potassium perfluorobutanesulfonate and cage - type polyhedral oligomeric silsesquioxane is beneficial to improving the hardness of the material while ensuring the flame - retardancy and transparency of the material.

[0149] Compared with Example 8, in Comparative Example 3, there is no addition of nano - silica, and both the notched impact strength and hardness decrease significantly, proving that the addition of the scratch - resistant agent enhances the scratch - resistant performance of the material.

[0150] Compared with Example 10, in Comparative Example 4, the commercially available polysiloxane shown in Formula (IV) was used to replace the polysiloxane polycarbonate B in equal mass, and its notched impact strength decreased significantly, proving that the polysiloxane polycarbonate prepared by the present invention is more helpful in improving the toughness of the material.

[0151] Compared with Examples 8 and 10, in Comparative Example 5, not only the commercially available polysiloxane shown in Formula (IV) was used to replace the polysiloxane polycarbonate B in equal mass, but also nano-silica and flame retardant were not added. Its notched impact strength, hardness, transparency, and flame retardancy all decreased significantly. Moreover, compared with Comparative Example 4, all performance indicators of Comparative Example 5 also decreased, proving that the components in the material of the present invention have a synergistic effect, showing more excellent mechanical, hardness, and flame retardant properties. The introduction of various star-shaped polysiloxane polycarbonates can regulate the transparency and mechanical properties of the material at the molecular scale; directly adding silicone materials to the material not only damages its impact toughness but also is not beneficial to the scratch resistance of the material.

[0152]

Example 15

[0153] Synthesis of polysiloxane polycarbonate:

[0154] The following steps (1) to (4) are all carried out under a protective gas atmosphere;

[0155] Step (1): Under the stirring action at 55 °C and 700 rpm, 5600 g of polysiloxane 3 (0.156 mol) shown in Formula (X) and 11.4 g of triallylphenylsilane (0.05 mol) were reacted for 3.5 hours under the action of 27.8 g of platinum catalyst, and then 41 g of 2-methoxy-6-allylphenol (0.25 mol) was added and the reaction was continued for 10 hours. After that, under reduced pressure distillation at 200 °C and 0.35 kPa, the three-arm star-shaped polysiloxane capped with 2-methoxy-6-allylphenol shown in Formula (XI) was obtained, with a yield of 94.4%.

[0156]

[0157] Step (2): 1500 g of 4,4'-dihydroxydiphenyl ether (7.5 mol), 840 g of potassium hydroxide (15 mol), 15 g of p-tert-butylphenol (0.1 mol), 0.0505 g of triethylamine (0.0005 mol), and 2250 g of water (125 mol) were mixed to obtain an aqueous phase;

[0158] Step (3): 2280 g (0.11 mol) of the three-arm star-shaped polysiloxane capped with 2-methoxy-6-allylphenol prepared in (1) and 747.5 g of phosgene (7.55 mol) were dissolved in 1850 g of dichloromethane (21.76 mol) to obtain an organic phase;

[0159] Step (4): The organic phase is introduced into the aqueous phase (volume ratio 0.8:1), and copolymerization is carried out at 60°C for 15 hours under stirring at 600 rpm. After precipitation, washing and drying, a polysiloxane polycarbonate C represented by formula (XII) is obtained, with a melt flow rate of 20.2 g / 10 min and a molar percentage of the polysiloxane component of 1.03%.

[0160]

[0161] [Example 16]

[0162] Preparation of transparent flame retardant and scratch resistant polycarbonate material:

[0163] (1) 60 g of potassium benzenesulfonylbenzenesulfonate, 15 g of potassium perfluorobutylsulfonate, 300 g of nano-silicon dioxide, and 25 g of 2,6-di-tert-butyl-4-methylphenol were fully mixed by high-speed stirring to obtain a functional composite additive;

[0164] (2) 6000 g of polycarbonate and 4000 g of polysiloxane polycarbonate C were dried and set aside;

[0165] (3) The functional composite additive obtained in (1) and polycarbonate, polysiloxane polycarbonate C are introduced into a LABTECH co-rotating twin-screw extruder (screw diameter 16 mm, aspect ratio 40) through a powder feeder and two pellet feeders, respectively, and the processing conditions are controlled to be a temperature of 270° C., a rotation speed of 350 rpm, and a feed rate of 15 kg / hour. Under the process conditions, the extruded materials are melt-kneaded, cooled, and granulated to obtain a transparent flame-retardant and scratch-resistant polycarbonate material with a melt flow rate of 48 g / 10 min, a notched impact strength of 444 J / m, a transparency of 82.9%, a pencil hardness of 2H, and a flame retardant UL94 V0 grade.

[0166] The star-shaped polysiloxane polycarbonate prepared in Examples 1 to 2 and 15 has a main structure similar to that of polycarbonate and good compatibility. The introduction of silicone components into the polysiloxane polycarbonate structure from the macromolecular chain structure level can maintain the dispersion and uniformity at the molecular scale and give the material scratch resistance.

[0167] The transparent flame retardant and scratch resistant polycarbonate materials prepared in Examples 1 to 2 and 15 are used as the base resins, and are combined with high-efficiency flame retardants and scratch resistant agents. They have good flame retardant and scratch resistant properties, as well as good processing properties, and are suitable for the application of various complex structures and thin-walled transparent materials.

Claims

1. A polysiloxane polycarbonate, the structural formula of which is shown in formula (I): In formula (I), R 1 , R 2 , R 3 are each independently selected from at least one of hydrogen, methyl, ethyl, methoxy, ethoxy, phenyl, and siloxanyl; the repeating R 1 , R 2 , R 3 may be the same or different; R 4 is hydrogen or methyl; R 5 is hydrogen, methyl, isopropyl, tert-butyl, phenyl, isopropylphenyl, or p-tert-butylphenyl; R and R' are each independently selected from cyclohexylene or phenylene; X is methylene, dimethylmethylene, oxygen atom, sulfur atom, carbonyl, or sulfoxide group; m is 0 or 1; n is an integer between 0 and 500, preferably an integer between 25 and 350; p is 0 or 1; q is an integer between 3 and 8; r is 0 or 1; s is an integer between 10 and 1000, preferably an integer between 50 and 800; M is a silicon group, methylsilicon group, phenylsilicon group, or cage-type silsesquioxane group, preferably a 3-substituted methylsilicon group, 3-substituted phenylsilicon group, 4-substituted silicon group, or 3- to 8-substituted cage-type silsesquioxane group.

2. The polysiloxane polycarbonate according to claim 1, characterized in that: the polysiloxane polycarbonate is prepared from raw materials including polysiloxane, star-shaped branching agent, catalyst A, phenol-based end-capping agent, phosgene, organic solvent and aqueous phase; the aqueous phase includes diphenol, alkali, end-capping agent, catalyst B and water.

3. The polysiloxane polycarbonate according to claim 1 or 2, characterized in that: the polysiloxane polycarbonate contains a polysiloxane component with a molar percentage content of 0.1-10%, preferably contains a polysiloxane component with a molar percentage content of 0.5-7.5%, and more preferably contains a polysiloxane component of 0.5-2%; and / or, the polysiloxane polycarbonate has a melt flow rate of 5-50 g / 10 min at 300 °C and 1.2 kg, preferably 10-40 g / 10 min, and more preferably 15-30 g / 10 min.

4. A method for preparing the polysiloxane polycarbonate according to any one of claims 1-3, comprising the following steps: (1) React the polysiloxane with the star-shaped branching agent in the presence of catalyst A, then add the phenol-based end-capping agent for reaction two, and obtain the phenol-based end-capped star-shaped polysiloxane after post-treatment one; (2) Mix diphenol, alkali, end-capping agent, catalyst B and water to obtain an aqueous phase; (3) Dissolve the phenol-based end-capped star-shaped polysiloxane and phosgene obtained in step (1) in an organic solvent to obtain an organic phase; (4) Add the organic phase obtained in step (3) to the aqueous phase obtained in step (2) for copolymerization reaction, and obtain the polysiloxane polycarbonate after post-treatment two; Steps (1) to (4) are all carried out under a protective gas atmosphere.

5. The method for preparing the polysiloxane polycarbonate according to claim 4, characterized in that: the protective gas is at least one of nitrogen and inert gas; the inert gas is preferably argon; and / or, Step (1), the structural formula of the polysiloxane is shown in formula (II): In formula (II), R 1 , R 2 are each independently selected from at least one of hydrogen, methyl, ethyl, methoxy, ethoxy, phenyl, and siloxanyl; n is an integer between 0 and 500, preferably an integer between 25 and 350; and / or, the star-shaped branching agent is at least one of trivinylmethylsilane, trivinylphenylsilane, triallylmethylsilane, triallylphenylsilane, tetravinylsilane, tetraallylsilane, vinyltriisopropenyloxysilane, tetraallyloxysilane, trivinylcage silsesquioxane, tetravinylcage silsesquioxane, pentavinylcage silsesquioxane, hexavinylcage silsesquioxane, heptavinylcage silsesquioxane, octavinylcage silsesquioxane; and / or, the catalyst A is at least one of silver catalyst, platinum catalyst, palladium catalyst, ruthenium catalyst, rhodium catalyst; and / or, the phenol-based end-capping agent is at least one of 2-allylphenol, 3-allylphenol, 4-allylphenol, 2-methoxy-4-allylphenol, 2-methoxy-5-allylphenol, 2-methoxy-6-allylphenol; and / or, the structural formula of the phenol-based end-capped star-shaped polysiloxane is shown in formula (III): In formula (III), R 1 , R 2 , R 3 are each independently selected from at least one of hydrogen, methyl, ethyl, methoxy, ethoxy, phenyl, and siloxanyl; the repeating R 1 , R 2 , R 3 may be the same or different; R 4 is hydrogen or methyl; m is 0 or 1; n is an integer between 0 and 500, preferably an integer between 25 and 350; p is 0 or 1; q is an integer between 3 and 8; M is a silyl group, methylsilyl group, phenylsilyl group, or cage-like silsesquioxanyl group, preferably a 3-substituted methylsilyl group, 3-substituted phenylsilyl group, 4-substituted silyl group, or 3- to 8-substituted cage-like silsesquioxanyl group; and / or, Step (2), The diphenol is at least one of bisphenol A, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 2,2'-bis(4-hydroxycyclohexyl)propane, 2,2'-bis(4-hydroxycyclohexyl)ether, 2,2'-bis(4-hydroxycyclohexyl)sulfide; and / or, The base is at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide, ammonia water; and / or, The capping agent is at least one of phenol, p-cresol, p-isopropylphenol, p-tert-butylphenol, p-phenylphenol, p-cumylphenol, p-tert-butylphenylphenol; and / or, The catalyst B is at least one of triethylamine, triethanolamine, tetramethylammonium chloride, tetramethylammonium bromide, trimethylethylammonium chloride, trimethylethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide, trimethylbenzylammonium chloride, trimethylbenzylammonium bromide, dimethylethylbenzylammonium chloride, dimethylethylbenzylammonium bromide; and / or, Step (3), The organic solvent is at least one of dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane.

6. The method for preparing a polysiloxane polycarbonate according to claim 4, characterized in that: Step (1), The molar ratio of the polysiloxane to the star-branching agent is (3 to 10):1, preferably (3.05 to 9):1; and / or, The mass ratio of the catalyst A to the polysiloxane is (0.001 to 1):100, preferably (0.01 to 0.5):100; and / or, The molar ratio of the phenolic capping agent to the polysiloxane is (1 to 2):1, preferably (1.1 to 1.7):1; and / or, Step (2), In the aqueous phase, the molar ratio of the diphenol, the base, the capping agent, the catalyst B to water is (1 to 10):(2 to 50):(0.01 to 0.1):(0.0001 to 0.01):100, preferably (1.5 to 8):(3.5 to 30):(0.05 to 0.08):(0.0005 to 0.008):100, more preferably (4 to 8):(6 to 18):(0.05 to 0.08):(0.0005 to 0.008):100; and / or, Step (3), The molar ratio of the phenolic-capped star polysiloxane, phosgene to the organic solvent is (0.1 to 5):(5 to 50):100, preferably (0.1 to 2.5):(10 to 50):100, more preferably (0.1 to 0.8):(20 to 40):100; and / or, Step (4), The volume ratio of the organic phase to the aqueous phase is (0.1 to 10):1, preferably (0.5 to 5):1, more preferably (0.8 to 1.5):

1.

7. The method for preparing a polysiloxane polycarbonate according to claim 4, characterized in that: Step (1), The temperatures of the first reaction and the second reaction are 40 - 100 °C respectively, preferably 50 - 95 °C, more preferably 50 - 70 °C; and / or, The first reaction and the second reaction are carried out under stirring, and the stirring rate is 50 - 1000 rpm, preferably 200 - 800 rpm; and / or, The time of the first reaction is 2 - 24 hours, preferably 3 - 20 hours, more preferably 3 - 10 hours; and / or, The time of the second reaction is 2 - 24 hours, preferably 3 - 20 hours, more preferably 8 - 15 hours; and / or, The first post-treatment is vacuum distillation; the vacuum distillation is preferably carried out at 150 - 250 °C and 0 - 1 kPa, more preferably at 180 - 230 °C and 0.1 - 0.8 kPa; and / or, Step (4), The addition of the organic phase to the aqueous phase is carried out under stirring, and the stirring rate is 200 - 1000 rpm, preferably 300 - 850 rpm, more preferably 400 - 750 rpm; and / or, The temperature of the copolymerization reaction is 25 - 80 °C, preferably 30 - 75 °C, more preferably 35 - 60 °C; and / or, The time of the copolymerization reaction is 1 - 24 hours, preferably 2 - 20 hours, more preferably 5 - 16 hours; and / or, The second post-treatment is precipitation, washing and drying.

8. A polysiloxane polycarbonate obtained by the preparation method according to any one of claims 4 - 7.

9. A transparent flame-retardant and scratch-resistant polycarbonate material, comprising polycarbonate, polysiloxane polycarbonate, flame retardant, scratch-resistant agent and antioxidant; the polysiloxane polycarbonate is the polysiloxane polycarbonate according to any one of claims 1 - 3, 8.

10. The transparent flame-retardant and scratch-resistant polycarbonate material according to claim 9, characterized in that: Based on the total weight of polycarbonate and polysiloxane polycarbonate being 100 parts by weight, the transparent flame-retardant and scratch-resistant polycarbonate material comprises the following components: Among them, polycarbonate and polysiloxane polycarbonate include 20 - 90 parts by weight of polycarbonate and 10 - 80 parts by weight of polysiloxane polycarbonate; preferably, it includes 60 - 85 parts by weight of polycarbonate and 15 - 40 parts by weight of polysiloxane polycarbonate.

11. The transparent flame-retardant and scratch-resistant polycarbonate material according to claim 9 or 10, characterized in that: The melt flow rate of the polycarbonate at 300 °C and 1.2 kg is 5 - 50 g / 10 min, preferably 10 - 40 g / 10 min, more preferably 20 - 30 g / 10 min; and / or, The melt flow rate of the transparent flame-retardant and scratch-resistant polycarbonate material at 300 °C and 1.2 kg is 5 - 50 g / 10 min, preferably 10 - 50 g / 10 min; and / or, The flame retardant is at least one of sodium benzenesulfonylbenzenesulfonate, potassium benzenesulfonylbenzenesulfonate, ammonium benzenesulfonylbenzenesulfonate, sodium perfluorobutanesulfonate, potassium perfluorobutanesulfonate, ammonium perfluorobutanesulfonate, and cage-like polyhedral oligomeric silsesquioxane, preferably a combination of potassium benzenesulfonylbenzenesulfonate and cage-like polyhedral oligomeric silsesquioxane or a combination of potassium perfluorobutanesulfonate and cage-like polyhedral oligomeric silsesquioxane; further preferably, the mass ratio of potassium benzenesulfonylbenzenesulfonate to cage-like polyhedral oligomeric silsesquioxane in the combination is (1 to 10):1, more preferably (2 to 8):1; and / or, the mass ratio of potassium perfluorobutanesulfonate to cage-like polyhedral oligomeric silsesquioxane in the combination is (1 to 10):1, more preferably (1.5 to 6):1; and / or, The scratch-resistant agent is at least one of nano-silica, nano-aluminum oxide, and nano-titanium dioxide; and / or, The antioxidant is at least one of tris(nonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], n-octadecyl 3,5-di-tert-butyl-4-hydroxyphenylpropionate, and 2,6-di-tert-butyl-4-methylphenol.

12. A method for preparing a transparent flame-retardant and scratch-resistant polycarbonate material according to any one of claims 9 to 11, comprising: obtaining the transparent flame-retardant and scratch-resistant polycarbonate material by melt-blending the components in the weight parts; preferably, first mixing the components including the flame retardant, scratch-resistant agent, and antioxidant to obtain an additive mixture, and then melt-blending the dried polycarbonate, polyorganosiloxane polycarbonate, and additive mixture.

13. The method for preparing a transparent flame-retardant and scratch-resistant polycarbonate material according to claim 12, characterized in that: the temperature of the melt-blending is 250 to 320 °C, preferably 260 to 300 °C, more preferably 270 to 280 °C; the melt-blending is carried out on a twin-screw extruder, the screw speed is 100 to 350 rpm, preferably 200 to 300 rpm, more preferably 220 to 280 rpm; the total feeding speed of the components on the twin-screw extruder is 1 to 100 kg / hour, preferably 5 to 80 kg / hour, more preferably 10 to 75 kg / hour.

14. An application of a polyorganosiloxane polycarbonate according to any one of claims 1 to 3, 8, a transparent flame-retardant and scratch-resistant polycarbonate material according to any one of claims 9 to 11, or a transparent flame-retardant and scratch-resistant polycarbonate material obtained by the preparation method according to claim 12 or 13 in electronic appliances, instruments, and display screens.

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