Polycarbonate-polysiloxane copolymer as well as preparation method and application thereof

Abstract

The invention provides a polycarbonate-polysiloxane copolymer as well as a preparation method and application thereof, and belongs to the technical field of polycarbonate material preparation. The polycarbonate-polyorganosiloxane copolymer comprises a polycarbonate block and a polyorganosiloxane block, and the polycarbonate-polyorganosiloxane copolymer comprises a polycarbonate block and a polyorganosiloxane block. A high-boiling-point solvent capable of simultaneously dissolving polysiloxane and polycarbonate is added, and a high-boiling-point cosolvent capable of improving intersolubility of polysiloxane and other monomers (an aromatic bisphenol compound and / or an aliphatic diol compound and diester carbonate) is introduced into a melt transesterification polycondensation method; in the ester exchange stage, the intersolubility of reaction monomers is improved, the conversion rate of polysiloxane is improved, and the transparency and molecular weight of the copolymer are improved.

Description

Technical Field

[0001] The invention belongs to the technical field of polycarbonate material preparation, and specifically relates to a polycarbonate-polyorganosiloxane copolymer and a preparation method and application thereof. Background Art

[0002] Polycarbonate has excellent optical transparency, impact toughness, dimensional stability, creep resistance and other properties, and is widely used. However, the main chain of bisphenol A polycarbonate contains rigid benzene rings and carbonate bonds that are easily attacked by nucleophilic reagents. The melt viscosity is relatively high, and the processing fluidity is poor, making it difficult to obtain thin-walled and large-sized products. In addition, the solvent resistance and weather resistance are poor, and stress cracking is prone to occur in the environment, which limits the use of polycarbonate under certain special conditions. Polysiloxane is non-toxic and safe, and is good for the environment. The flexible long siloxane chain and side chain methyl groups can bring excellent lubrication and anti-fouling, low-temperature impact resistance and melt fluidity to the polymer, which can effectively make up for the defects of polycarbonate.

[0003] In many cases, the phosgene method is used to manufacture polycarbonate-polyorganosiloxane copolymers. Although the polycarbonate-polyorganosiloxane prepared by the phosgene method has excellent transparency and mechanical properties, the phosgene method requires the use of highly toxic carbonyl chloride (phosgene) as a carbonate source, and the use of dichloromethane, which has a large environmental burden, as a solvent in the reaction. A large amount of water is required in the post-treatment, which is disadvantageous in terms of economy and environment.

[0004] In order to avoid the above problems, studies have been conducted to produce polycarbonate-polyorganosiloxane copolymers by production methods other than the phosgene method, such as melt polymerization. However, since the solubility parameter of polyorganosiloxane is 7.3 cal 1 / 2 cm 3 / 2 , the solubility parameter of polycarbonate is 9.5cal 1 / 2 cm 3 / 2 , the phase difference is large, which belongs to a thermodynamically incompatible system, resulting in microphase separation of the copolymer system. During melt polycondensation, polyorganosiloxane and other monomers (such as carbonate monomers) are not completely miscible. Therefore, there is a problem of low polyorganosiloxane conversion rate (60-82%), which not only affects the surface properties (such as hydrophobicity) and optical transparency of the copolymer (the transmittance of a 3mm film of a polycarbonate-polyorganosiloxane copolymer prepared by the melt ester exchange method is less than 50%), but also the free polyorganosiloxane during the processing will cause mold contamination. Summary of the invention

[0005] In view of this, the object of the present invention is to provide a polycarbonate-polyorganosiloxane (PC-PDMS) copolymer and a preparation method and application thereof. The method provided by the present invention has a high polyorganosiloxane conversion rate, and the prepared polycarbonate-polyorganosiloxane copolymer has a high molecular weight, a small color difference, and a high heat resistance temperature.

[0006] In order to achieve the above object, the present invention provides the following scheme:

[0007] The present invention provides a polycarbonate-polyorganosiloxane copolymer, comprising a polycarbonate block and a polyorganosiloxane block; the polycarbonate block has a repeating unit of a structure shown in formula A; the polyorganosiloxane block has a repeating unit of a structure shown in formula B;

[0008]

[0009] In formula A, R1 is an aliphatic alkylene group having 2 to 40 carbon atoms, an alicyclic alkylene group having 3 to 40 carbon atoms, or a hydroxy-substituted arylene group having 6 to 20 carbon atoms;

[0010] In formula B, R2 has the structure shown in formula 1:

[0011]

[0012] In Formula 1, n is 5 to 60; m is 1 to 20; a, a1, b and b1 are independently 0 or 1;

[0013] R3 to R6 are independently -H, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 6 to 10 carbon atoms;

[0014] R7 and R8 are independently an arylene group having 6 to 20 carbon atoms, a linear alkylene group having 1 to 10 carbon atoms, or an alkyl-substituted arylene group;

[0015] R9 and R 10 are independently an arylene group having 6 to 20 carbon atoms, a straight-chain alkylene group having 2 to 10 carbon atoms, a branched-chain alkylene group having 3 to 10 carbon atoms, or an alkyl-substituted arylene group;

[0016] The light transmittance of the polycarbonate-polyorganosiloxane copolymer is greater than 50%.

[0017] Preferably, R1 is an aliphatic alkylene group having 2 to 40 main chain carbon atoms, an alicyclic alkylene group having 3 to 40 main chain carbon atoms, or a hydroxy-substituted arylene group having 6 to 20 main chain carbon atoms.

[0018] Preferably, the mass of the polyorganosiloxane block is 0.5 to 20% of the total mass of the polycarbonate-polyorganosiloxane copolymer.

[0019] The present invention provides a method for preparing the polycarbonate-polyorganosiloxane copolymer described in the above scheme, comprising the following steps:

[0020] In a protective atmosphere, carbonic acid diester, diol monomer, co-solvent and catalyst are mixed to carry out ester exchange reaction to obtain polycarbonate prepolymer; the boiling point of the co-solvent is 200-400°C;

[0021] The diol monomer comprises a first component and a second component, the first component is an aromatic bisphenol compound and / or an aliphatic diol compound, and the second component is a polyorganosiloxane; the polyorganosiloxane has a structure shown in Formula 2;

[0022]

[0023] The polycarbonate prepolymer is subjected to polycondensation reaction to obtain the polycarbonate-polyorganosiloxane copolymer.

[0024] Preferably, the co-solvent includes one or more of cyclohexylbenzene, isophorone, sulfolane, N-methylpyrrolidone, dimethyl sulfoxide, 2,2-diphenylpropane, dodecane, tridecane, 1-dodecene, 1-tetradecene, bicyclohexane, 1,2,3-tribromopropane, biphenyl, naphthalene and α-methylnaphthalene.

[0025] Preferably, the transesterification reaction comprises: heating from 160° C. to 180° C., keeping the temperature for 1 to 3 hours, then heating to 210° C., and keeping the temperature for 1 to 3 hours.

[0026] Preferably, the polycondensation reaction comprises: heating from 210° C. to 275° C., reducing the pressure to ≤50 Pa, and then maintaining the temperature and pressure for 0.5 to 5 hours.

[0027] Preferably, the carbonic acid diester includes diphenyl carbonate or dimethyl carbonate.

[0028] Preferably, the aromatic bisphenol compound includes one or more of 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3-methylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and 1,1-bis(4-hydroxyphenyl)cyclododecene;

[0029] The aliphatic diol compound includes one or more of isosorbide, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,3-propylene glycol and 1,4-butanediol.

[0030] The present invention provides the use of the polycarbonate-polyorganosiloxane copolymer described in the above scheme or the polycarbonate-polyorganosiloxane copolymer prepared by the preparation method described in the above scheme in engineering plastics.

[0031] The present invention provides a polycarbonate-polyorganosiloxane copolymer, comprising a polycarbonate block and a polyorganosiloxane block; the polycarbonate block has a repeating unit of a structure shown in formula A; the polyorganosiloxane block has a repeating unit of a structure shown in formula B;

[0032]

[0033] In formula A, R1 is an aliphatic alkylene group having 2 to 40 carbon atoms, an alicyclic alkylene group having 3 to 40 carbon atoms, or a hydroxy-substituted arylene group having 6 to 20 carbon atoms;

[0034] In formula B, R2 has the structure shown in formula 1:

[0035]

[0036] In Formula 1, n is 5 to 60; m is 1 to 20; a, a1, b and b1 are independently 0 or 1;

[0037] R3 to R6 are independently -H, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 6 to 10 carbon atoms; R7 and R8 are independently an arylene group having 6 to 20 carbon atoms, a linear alkylene group having 1 to 10 carbon atoms, or an alkyl-substituted arylene group; R9 and R 10 The polycarbonate-polyorganosiloxane copolymer is independently an arylene group having 6 to 20 carbon atoms, a linear alkylene group having 2 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, or an alkyl-substituted arylene group. The light transmittance of the polycarbonate-polyorganosiloxane copolymer is greater than 50%.

[0038] The reason why the conversion rate of polyorganosiloxane is not high is that the compatibility of polyorganosiloxane with carbonic acid diester and other diol monomers is poor. Therefore, during the reaction process, polyorganosiloxane cannot fully contact with other monomers to react. The present invention adds a high boiling point solvent that can dissolve polyorganosiloxane and polycarbonate at the same time, introduces a high boiling point co-solvent that improves the mutual solubility of polyorganosiloxane and other monomers (aromatic bisphenol compounds and / or aliphatic diol compounds and carbonic acid diester) in the melt transesterification polycondensation method, helps to improve the mutual solubility of the reaction monomers in the transesterification stage, improves the conversion rate of polyorganosiloxane, and improves the transparency and molecular weight of the copolymer.

[0039] The method provided by the present invention has a higher polyorganosiloxane conversion rate (i.e., lower free polysiloxane residue), and the polyorganosiloxane conversion rate can reach more than 95%. The prepared polycarbonate-polyorganosiloxane copolymer has a high molecular weight, small color difference, and a higher heat resistance temperature.

[0040] Furthermore, the polycondensation reaction of the present invention is carried out under high temperature and high vacuum conditions, and the solvent can be completely removed.

[0041] The preparation method provided by the invention has little pollution. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative labor.

[0043] Figure 1 The structure and hydrogen spectrum of the polycarbonate-polyorganosiloxane copolymer obtained in Example 1 of the present invention;

[0044] Figure 2 The structure and hydrogen spectrum of the polycarbonate-polyorganosiloxane copolymer obtained in Example 5 of the present invention;

[0045] Figure 3 The structure and hydrogen spectrum of the polycarbonate-polyorganosiloxane copolymer obtained in Example 6 of the present invention;

[0046] Figure 4 The structure and hydrogen spectrum of the polycarbonate-polyorganosiloxane copolymer obtained in Example 10 of the present invention;

[0047] Figure 5 The structure and hydrogen spectrum of the polycarbonate-polyorganosiloxane copolymer obtained in Example 11 of the present invention. DETAILED DESCRIPTION

[0048] The present invention provides a polycarbonate-polyorganosiloxane copolymer, comprising a polycarbonate block and a polyorganosiloxane block; the polycarbonate block has a repeating unit of a structure shown in formula A; the polyorganosiloxane block has a repeating unit of a structure shown in formula B;

[0049]

[0050] In formula A, R1 is an aliphatic alkylene group having 2 to 40 carbon atoms, an alicyclic alkylene group having 3 to 40 carbon atoms, or a hydroxy-substituted arylene group having 6 to 20 carbon atoms.

[0051] In the present invention, R1 is preferably an aliphatic alkylene group having 2 to 40 main chain carbon atoms, an alicyclic alkylene group having 3 to 40 main chain carbon atoms, or a hydroxy-substituted arylene group having 6 to 20 main chain carbon atoms.

[0052] In formula B, R2 has the structure shown in formula 1:

[0053]

[0054] In Formula 1, n is 5 to 60; m is 1 to 20; a, a1, b and b1 are independently 0 or 1;

[0055] R3 to R6 are independently -H, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 6 to 10 carbon atoms;

[0056] R7 and R8 are independently an arylene group having 6 to 20 carbon atoms, a straight-chain alkylene group having 1 to 10 carbon atoms, or an alkyl-substituted arylene group; the carbon number of the alkyl group in the alkyl-substituted arylene group is preferably 1 to 10, further preferably a dimethylene group, a methyl-substituted dimethylene group or a trimethylene group, and more preferably a trimethylene group (-(CH2)3).

[0057] R9 and R 10 It is independently an arylene group having 6 to 20 carbon atoms, a straight-chain alkylene group having 2 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, or an alkyl-substituted arylene group; the carbon number of the alkyl group in the alkyl-substituted arylene group is preferably 1 to 10, and is further preferably phenyl, dimethylene (-(CH2)2-), methyl-substituted dimethylene (-CH2CHMe-), trimethylene (-(CH2)3-) or tetramethylene (-(CH2)4-), and is more preferably trimethylene (-(CH2)3-).

[0058] In the present invention, the selection of the polyorganosiloxane structure can improve its affinity with other diol monomers, thereby achieving uniform polymerization.

[0059] In the present invention, the mass of the polyorganosiloxane block is preferably 0.5 to 20% of the total mass of the polycarbonate-polyorganosiloxane copolymer, more preferably 3 to 15%, and even more preferably 5 to 10%.

[0060] In the present invention, the structure of the polycarbonate-polyorganosiloxane copolymer preferably has a structure shown in formula a to formula:

[0061]

[0062] In formula a, n=18, m=12.

[0063]

[0064] In formula b, n=30.

[0065]

[0066] In formula c, n=30.

[0067]

[0068] In formula d, n=31.

[0069]

[0070] In formula e, n=30.

[0071] In the present invention, the light transmittance of the polycarbonate-polyorganosiloxane copolymer is 50% or more, preferably 55 to 100%, and more preferably 60 to 85%.

[0072] The present invention provides a method for preparing the polycarbonate-polyorganosiloxane copolymer described in the above scheme, comprising the following steps:

[0073] Under a protective atmosphere, carbonic acid diester, diol monomer, co-solvent and catalyst are mixed to carry out ester exchange reaction to obtain polycarbonate prepolymer;

[0074] The polycarbonate prepolymer is subjected to polycondensation reaction to obtain the polycarbonate-polyorganosiloxane copolymer.

[0075] Unless otherwise specified, the materials and equipment used in the present invention are commercially available products.

[0076] The present invention mixes carbonic acid diester, diol monomer, co-solvent and catalyst under protective atmosphere, performs ester exchange reaction and obtains polycarbonate prepolymer.

[0077] In the present invention, the protective atmosphere preferably includes nitrogen. In the present invention, the carbonic acid diester preferably includes diphenyl carbonate or dimethyl carbonate; the diol monomer includes a first component and a second component, the first component is an aromatic bisphenol compound and / or an aliphatic diol compound, and the second component is a polyorganosiloxane; in the present invention, the aromatic bisphenol compound preferably includes 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)cyclohexane, The aliphatic diol compound preferably includes one or more of isosorbide, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,3-propylene glycol and 1,4-butanediol.

[0078] In the present invention, the polyorganosiloxane has a structure shown in Formula 2;

[0079]

[0080] In the present invention, the polyorganosiloxane preferably includes one or more of phenolic hydroxy silicone oil, alcoholic hydroxy silicone oil and polyether silicone oil.

[0081] In the present invention, the preparation of the polyorganosiloxane preferably comprises the following steps:

[0082] Under a protective atmosphere, polysiloxane, an allyl-hydroxyl compound and a catalyst are mixed and polymerized to obtain the polyorganosiloxane.

[0083] In the present invention, the protective atmosphere preferably includes nitrogen; the polysiloxane preferably has a structure shown in Formula I;

[0084]

[0085] In the present invention, the polysiloxane of the structure shown in Formula I preferably includes polysiloxane with an average siloxane chain length of 18, polysiloxane with an average siloxane chain length of 30, polysiloxane with an average siloxane chain length of 42, or polysiloxane with an average siloxane chain length of 31.

[0086] In the present invention, the allyl-hydroxyl compound preferably includes a compound having a structure shown in Formula II, 2-allylphenol or eugenol.

[0087]

[0088] In the present invention, the compound of the structure shown in Formula II preferably includes allyl polyethylene glycol or ethylene glycol monoallyl ether having an average oxyethylene chain length of 12. In the present invention, the catalyst preferably includes H2PtCl6. In the present invention, the molar ratio of the polysiloxane to the allyl-hydroxyl-containing compound is preferably 1:2.2; the molar amount of the catalyst is preferably 5ppm of the molar amount of the polysiloxane. In the present invention, the temperature of the polymerization reaction is preferably 110°C and the time is preferably 5h.

[0089] In the present invention, the molar ratio of the carbonic acid diester to the diol monomer is preferably (0.9-1.2):1, more preferably (0.95-1.2):1, and more preferably (1-1.1):1. In the present invention, if the molar ratio is less than 0.9, the terminal -OH groups of the obtained polycarbonate-polyorganosiloxane copolymer increase, and the thermal stability and water resistance of the polymer are poor; if the molar ratio is greater than 1.2, the transesterification reaction rate decreases under the same conditions, or the polycarbonate-polyorganosiloxane of the desired molecular weight cannot be obtained, and the residual carbonic acid diester in the manufactured polycarbonate-polyorganosiloxane increases.

[0090] In the present invention, the mass of the polyorganosiloxane is preferably 6% of the total mass of the diol monomer. In the present invention, the boiling point of the co-solvent is 200-400°C; the co-solvent preferably includes one or more of cyclohexylbenzene, isophorone, sulfolane, N-methylpyrrolidone, dimethyl sulfoxide, 2,2-diphenylpropane, dodecane, tridecane, 1-dodecene, 1-tetradecene, bicyclohexane, 1,2,3-tribromopropane, biphenyl, naphthalene and α-methylnaphthalene. In the present invention, the molar ratio of the co-solvent to the diol monomer is preferably (0-10):1, and is not 0, further preferably (2-8:1), and more preferably (3-6):1.

[0091] The invention adds a high boiling point solvent capable of dissolving polyorganosiloxane and polycarbonate at the same time, introduces a high boiling point co-solvent in the melt transesterification polycondensation method, improves the mutual solubility of polyorganosiloxane and other monomers (aromatic bisphenol compounds and / or aliphatic diol compounds and carbonic acid diesters), helps to improve the mutual solubility of reaction monomers in the transesterification stage, improves the conversion rate of polyorganosiloxane, and improves the transparency and molecular weight of the copolymer.

[0092] The present invention controls the molar ratio of the co-solvent to the diol monomer within the above range, which can improve the affinity between the co-solvent and the diol monomer, thereby achieving uniform polymerization and having the advantage of economic efficiency.

[0093] In the present invention, the catalyst preferably includes one or more of a Group IA metal compound, a Group IIA metal compound, a Group IB metal compound or a Group IIB metal compound, an alkaline boron compound, an alkaline phosphorus compound, an alkaline ammonium compound, an organic amine compound and an ionic liquid compound.

[0094] In the present invention, the Group IA metal compound preferably includes sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, cesium bicarbonate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, sodium acetate, potassium acetate, lithium acetate, cesium acetate, sodium stearate, potassium stearate, lithium stearate, cesium stearate, sodium borohydride, potassium borohydride, lithium borohydride, cesium borohydride, sodium phenyl borohydride, potassium phenyl borohydride , lithium phenyl borate, cesium phenyl borate, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, dicesium hydrogen phosphate, disodium phenyl phosphate, dipotassium phenyl phosphate, dilithium phenyl phosphate, dicesium phenyl phosphate, sodium alkoxide, potassium alkoxide, lithium alkoxide, cesium alkoxide, sodium phenoxide, potassium phenoxide, lithium phenoxide, cesium phenoxide, one or more of the disodium salt, dipotassium salt, dilithium salt and dicesium salt of bisphenol A.

[0095] In the present invention, the Group IIA metal compound preferably includes one or more of calcium acetate, calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium bicarbonate, barium bicarbonate, magnesium bicarbonate, strontium bicarbonate, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium chloride, magnesium chloride, zinc chloride, calcium stearate, barium stearate, magnesium stearate and strontium stearate.

[0096] In the present invention, the Group IB metal compound preferably includes one or more of copper hydroxide, copper oxide, copper chloride, copper nitrate, copper stearate, copper sulfate, copper sulfite, copper benzoate, copper carbonate, copper bicarbonate, copper fluoride, copper bromide, copper iodide, copper acetate, copper acetylacetonate, copper oxalate and copper phosphate.

[0097] In the present invention, the Group IIB metal compound preferably includes one or more of zinc hydroxide, zinc oxide, zinc chloride, zinc nitrate, zinc stearate, zinc sulfate, zinc sulfite, zinc benzoate, zinc carbonate, zinc bicarbonate, zinc fluoride, zinc bromide, zinc iodide, zinc acetate, zinc acetylacetonate, zinc oxalate and zinc phosphate.

[0098] In the present invention, the alkaline boron compound preferably includes one or more of sodium salt, potassium salt, lithium salt, calcium salt, magnesium salt, barium salt and strontium salt of boron compound; the boron compound preferably includes one or more of tetramethyl boron, tetraethyl boron, tetrapropyl boron, tetrabutyl boron, trimethyl ethyl boron, trimethyl benzyl boron, trimethyl phenyl boron, triethyl methyl boron, triethyl benzyl boron, triethyl phenyl boron, tributyl benzyl boron, tributyl phenyl boron, tetraphenyl boron, benzyl triphenyl boron, methyl triphenyl boron and butyl triphenyl boron.

[0099] In the present invention, the basic phosphorus compound preferably includes one or more of triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine and a quaternary phosphonium salt, and more preferably a quaternary phosphonium salt.

[0100] In the present invention, the alkaline ammonium compound preferably includes one or more of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide and butyltriphenylammonium hydroxide. From the perspective of reaction activity and the color of the obtained polycarbonate resin, tetramethylammonium hydroxide is more preferred.

[0101] In the present invention, the organic amine compound preferably includes one or more of 4-aminopyridine, 2-aminopyridine, N,N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2-dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, aminoquinoline and guanidine.

[0102] In the present invention, the anion of the ionic liquid compound is preferably an amino acid anion or an amide anion.

[0103] In the present invention, the amino acid anion is preferably a lysine anion, a threonine anion, a valine anion, an alanine anion, a serine anion, a histidine anion or an aspartic acid anion.

[0104] In the present invention, the amide anion is preferably N-methylacetamide, N-ethylacetamide, acetanilide, 2-pyrrolidone, 2-nitrohexyl cyclopentane, 1,8-naphthalimide, 1,2-cyclopentanedicarboximide, 3,3-pentamethyleneglutarimide, 3,3-tetramethyleneglutarimide, 1,2,3,6-tetrahydrophthalimide, hexahydrophthalimide, diethylamide, succinimide, glutarimide, adipic imide, maleimide, succinimide, phthalimide or bistrifluoroacetamide.

[0105] In the present invention, the cation of the ionic liquid compound is preferably a quaternary ammonium cation, a quaternary phosphine cation, an imidazolium cation, a pyridinium cation or a piperidine cation.

[0106] In the present invention, the quaternary ammonium cation is preferably a tetraethylammonium cation, a tetrabutylammonium cation or a choline cation; the quaternary phosphine cation is preferably a tetrabutylphosphine cation or a trihexyl (tetradecyl)phosphine cation; the imidazolium cation is preferably a 1-ethyl-3-methylimidazolium cation, a 1-propyl-3-methylimidazolium cation, a 1-butyl-3-methylimidazolium cation, a 1-pentyl-3-methylimidazolium cation, a 1-hexyl-3-methylimidazolium cation, a 1-benzyl-3-methylimidazolium cation, a 1-ethyl acetate-3-methylimidazolium cation, a 1-allyl-3-methylimidazolium cation or a 1-2 (hydroxyethyl)-3-methylimidazolium cation; the pyridinium cation is preferably an N-ethylpyridinium cation; the piperidine cation is preferably an N-butyl-N-methylpiperidinium cation.

[0107] In the present invention, when the catalyst comprises a metal compound of Group IA, Group IIA, Group IB or Group IIB, the molar amount of the catalyst is preferably 0.1 to 50 ppm of the total molar amount of the carbonic acid diester and diol monomers, more preferably 3 to 40 ppm, and more preferably 10 to 30 ppm; when the catalyst comprises an alkaline phosphorus compound, an alkaline ammonium compound, an organic amine compound or an ionic liquid compound, the molar amount of the catalyst is preferably 1 to 1500 ppm of the total molar amount of the carbonic acid diester and diol monomers, more preferably 50 to 1000 ppm, and more preferably 100 to 500 ppm. 。

[0108] In the present invention, the transesterification reaction preferably includes: heating from 160°C to 180°C, keeping warm for 1 to 3 hours, and then heating to 210°C, keeping warm for 1 to 3 hours. In an embodiment of the present invention, it can be specifically heating from 160°C to 180°C, keeping warm for 1.5 hours, and then heating to 210°C, keeping warm for 1 hour; the pressure of the transesterification reaction is preferably normal pressure.

[0109] After obtaining the polycarbonate prepolymer, the present invention performs polycondensation reaction on the polycarbonate prepolymer to obtain the polycarbonate-polyorganosiloxane copolymer.

[0110] In the present invention, the polycondensation reaction preferably includes: heating from 210°C to 275°C, reducing pressure to ≤50Pa, and then maintaining the temperature and pressure for 0.5 to 5h. In an embodiment of the present invention, specifically, the temperature can be raised from 210°C to 275°C, reducing pressure to ≤50Pa, and then maintaining the temperature and pressure for 0.5h.

[0111] After the polycondensation reaction is completed, the present invention preferably dissolves the obtained copolymer in dichloromethane, slowly drips into ethanol after sufficient dissolution to remove unreacted polyorganosiloxane monomers and oligomers, and then repeatedly washes three times, and the obtained precipitate is filtered and dried to obtain the polycarbonate-polyorganosiloxane copolymer. In the present invention, the drying temperature is preferably 100° C. and the drying time is preferably 24 hours.

[0112] In the present invention, since the copolymer is insoluble in ethanol, while the oligomer and the polyorganosiloxane monomer are soluble in ethanol, the oligomer and the polyorganosiloxane monomer can be removed by separating the copolymer from the ethanol solution.

[0113] In the transesterification reaction of the present invention, in a molten state, diol monomers, such as polyorganosiloxane, bisphenol A, isosorbide, etc., react with carbonic acid diesters, such as diphenyl carbonate, and the diol monomers lose a hydrogen and diphenyl carbonate loses a phenoxy group, so that the diol monomers obtain a carbonate bond, and the by-product is phenol. The reaction continues until the monomers react completely.

[0114] In the present invention, in order to prevent yellowing and thermal deterioration, additives may be added to the reaction system during polymerization, at the end of polymerization or in the later stage of polymerization; the additives preferably include one or more of hindered phenol antioxidant stabilizers, phosphite antioxidant stabilizers, heat stabilizers, catalytic activity quenchers, UV absorbers, light stabilizers, release agents and hue regulators. In the present invention, the hindered phenol antioxidant stabilizer preferably includes antioxidant 1010; the phosphite antioxidant stabilizer preferably includes one or more of antioxidant 36, antioxidant 168 and bisphenol A phosphite; the heat stabilizer preferably includes phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, triphenyl phosphate, tris(nonylphenyl) phosphate, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl ester, monophenyl phosphate, dioctyl monophenyl phosphate, diisopropyl monophenyl phosphate, monobutyl diphenyl phosphate, monodecyl diphenyl phosphate, monooctyl diphenyl phosphate, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, 2,2-methylenebis(4,6-di-tert-butylphenyl) octyl phosphate, bis(nonylphenyl) pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) ) one or more of pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, trimethyl phosphate, trimethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, dimethyl phenylphosphate, diethyl phenylphosphate and dipropyl phenylphosphate; the catalytic activity quencher preferably includes n-butyl p-toluenesulfonate; the UV absorber preferably includes one or more of phenyl salicylate, ultraviolet absorber UV-P and ultraviolet absorber UV-O; the light stabilizer preferably includes one or more of light stabilizer UV-3346, light stabilizer 944 and light temperature agent BW-10LD; the release agent preferably includes one or more of E-1338, E-3149 and E-3161; the hue adjuster preferably includes one or more of bluing agent, ultramarine, permanent violet, phthalocyanine violet and cobalt violet.

[0115] The present invention has no special requirements for the method of adding the above-mentioned additives, and the additives can be added in a manner well known in the art. In the embodiments of the present invention, specifically: when adding during polymerization, the additives are added together with the reaction monomers before the reaction starts (i.e., added at the beginning of the transesterification reaction); when adding at the end of polymerization or at a later stage, the operation is performed in a twin-screw extruder, that is, the obtained material is mixed with the additives and then added to the twin-screw extruder for extrusion.

[0116] The present invention has no special requirements on the amount of the additives added, and it can be adjusted according to the type of additives.

[0117] The method provided by the present invention has a higher polyorganosiloxane conversion rate (i.e., lower free polysiloxane residue), and the polyorganosiloxane conversion rate can reach more than 95%. The prepared polycarbonate-polyorganosiloxane copolymer has a high molecular weight, small color difference, and a higher heat resistance temperature.

[0118] The present invention provides the use of the polycarbonate-polyorganosiloxane copolymer described in the above scheme or the polycarbonate-polyorganosiloxane copolymer prepared by the preparation method described in the above scheme in engineering plastics.

[0119] In order to further illustrate the present invention, a polycarbonate-polyorganosiloxane copolymer provided by the present invention and its preparation method and application are described in detail below in combination with embodiments and drawings, but they should not be construed as limiting the scope of protection of the present invention.

[0120] The structural formulas of PDMS-1 to PDMS-6 involved in Examples 1 to 6 of the present invention are shown in Table 1.

[0121] Table 1 Structural formula of PDMS-1 to PDMS-6

[0122]

[0123]

[0124] Preparation 1: Preparation of PDMS-1 (polyorganosiloxane-1):

[0125] Under nitrogen atmosphere, to the polysiloxane (80 g) of which the average siloxane chain length is 18 (i.e., n is 18 in Formula I), add allyl polyethylene glycol (100.2 g) of which the average oxyethylene chain length is 12 (i.e., m is 12 in Formula II) of the structure shown in Formula I, and the added amount is 2.2 times the molar amount of the polysiloxane. An H2PtCl6 catalyst is added in an amount of 5 ppm relative to the molar amount of the siloxane. The temperature of the mixture is controlled at 110°C and stirred for 5 hours to obtain colorless and transparent polyether modified polysiloxane PDMS-1.

[0126]

[0127] Preparation 2: Preparation of PDMS-2:

[0128] The only difference from Preparation 1 is that "polysiloxane with an average siloxane chain length of 18 shown in Formula I" is replaced by "polysiloxane with an average siloxane chain length of 30 shown in Formula I (ie, n is 30 in Formula I)".

[0129] Preparation 3: Preparation of PDMS-3:

[0130] The only difference from Preparation 1 is that "polysiloxane with an average siloxane chain length of 18 as shown in Formula I" is replaced by "polysiloxane with an average siloxane chain length of 42 as shown in Formula I (ie, n is 42 in Formula I)".

[0131] Preparation 4: Preparation of PDMS-4:

[0132] The only difference from Preparation 1 is that: "polysiloxane with an average siloxane chain length of 18 as shown in formula I" is replaced by "polysiloxane with an average siloxane chain length of 31 as shown in formula I (i.e., n is 31 in formula I)", and "allyl polyethylene glycol with an average oxyethylene chain length of 12 in the structure shown in formula II" is replaced by "ethylene glycol monoallyl ether (CH2=CHCH2-O-CH2CH2-OH) (i.e., m is 1 in formula II)".

[0133] Preparation 5: Preparation of PDMS-5:

[0134] The only difference from Preparation 1 is that: "polysiloxane with an average siloxane chain length of 18 shown in formula I" is replaced by "polysiloxane with an average siloxane chain length of 30 shown in formula I (i.e., n is 30 in formula I)", and "allyl polyethylene glycol with an average oxyethylene chain length of 12 in the structure shown in formula II" is replaced by "2-allylphenol".

[0135] Preparation 6: Preparation of PDMS-6:

[0136] The only difference from Preparation 1 is that the "polysiloxane with an average siloxane chain length of 18 shown in formula I" is replaced by "polysiloxane with an average siloxane chain length of 30 shown in formula I (i.e., n is 30 in formula I)", and the "allyl polyethylene glycol with an average oxyethylene chain length of 12 in the structure shown in formula II" is replaced by "eugenol".

[0137] Example 1

[0138] At room temperature, 7.583 g of diphenyl carbonate, 8.002 g of bisphenol A (BPA), 0.569 g of PDMS-1 (polyorganosiloxane), 5.608 g of cyclohexylbenzene (co-solvent), 10 ppm of cesium carbonate and 100 ppm of tetramethylammonium hydroxide were added to a 100 mL three-necked flask, and an ester exchange reaction was carried out under the protection of a nitrogen atmosphere: the temperature was raised to 160° C. and stirred for 20 min to melt, then the temperature was raised to 180° C. (20 min from 160° C. to 180° C.) and kept warm for 1.5 h, and then the temperature was raised to 210° C. and kept warm for 1 h (30 min from 180° C. to 210° C.), to obtain a polycarbonate prepolymer;

[0139] The polycarbonate prepolymer is subjected to a condensation reaction, the temperature is raised from 210°C to 275°C (2h from 210°C to 275°C), and the pressure is reduced to ≤50Pa while the temperature is raised. After the temperature and pressure meet the requirements (i.e., the temperature is raised to 275°C and the pressure is reduced to ≤50Pa), the temperature and pressure are maintained for 0.5h, and the reaction is completed to obtain a copolymer.

[0140] The obtained copolymer was dissolved in 50 mL of dichloromethane, and after being fully dissolved, it was slowly dripped into 500 mL of ethanol to remove unreacted polyorganosiloxane monomers and oligomers (the copolymer is insoluble in ethanol, while the oligomers and polyorganosiloxane monomers are soluble in ethanol. The oligomers and polyorganosiloxane monomers can be removed by separating the copolymer from the ethanol solution), and washed repeatedly three times. The obtained precipitate was filtered and vacuum dried at 100° C. for 24 hours to obtain the polycarbonate-polyorganosiloxane copolymer. The evaluation results are shown in Table 2.

[0141] like Figure 1 As shown, the structure and hydrogen spectrum of the polycarbonate-polyorganosiloxane copolymer obtained in Example 1 are shown. Figure 1 Where n = 18, m = 12. The hydrogen spectrum data are as follows:

[0142] Among them, 0ppm is the chemical shift of (Si-CH3) on the main chain of the polyorganosiloxane repeating unit, 0.45ppm is the first methylene group close to the Si-O-Si bond of the polyorganosiloxane repeating unit, 1.45ppm is the chemical shift of -CH3 on the BPA repeating unit and the second methylene group close to the Si-O-Si bond of the polyorganosiloxane repeating unit, 3.6ppm is the chemical shift of the third methylene group close to the Si-O-Si bond of the polyorganosiloxane and the polyether group, and 7.1 and 7.2ppm are the chemical shifts of the four protons of the benzene ring on the BPA repeating unit, respectively.

[0143] According to the above data and spectrum analysis, the obtained product is Figure 1 The target product carbonate-polyorganosiloxane copolymer with the structure shown.

[0144] Example 2

[0145] The preparation steps are the same as those in Example 1, except that, at room temperature, 7.617 g of diphenyl carbonate, 8.002 g of BPA, 0.569 g of PDMS-2, 5.608 g of cyclohexylbenzene, 10 ppm of potassium carbonate and 100 ppm of tetraethylammonium hydroxide are added to a 100 mL three-necked flask, and the reaction is completed to obtain a polycarbonate-polyorganosiloxane copolymer. The evaluation results are shown in Table 2.

[0146] The structure of the polycarbonate-polyorganosiloxane copolymer obtained in Example 2 is similar to that in Example 1, except that the chain length of the PDMS-2 portion is different, i.e. Figure 1 The height of the peak in a is different.

[0147] Example 3

[0148] The preparation steps are the same as those in Example 1, except that, at room temperature, 7.609 g of diphenyl carbonate, 8.002 g of BPA, 0.569 g of PDMS-3, 5.608 g of cyclohexylbenzene, 10 ppm of potassium hydroxide and 100 ppm of tetrabutylammonium hydroxide are added to a 100 mL three-necked flask, and the reaction is completed to obtain a polycarbonate-polyorganosiloxane copolymer. The evaluation results are shown in Table 2.

[0149] The structure of the polycarbonate-polyorganosiloxane copolymer obtained in Example 3 is similar to that in Example 1, except that the chain length of the PDMS-3 portion is different, i.e. Figure 1 The height of the peak in a is different.

[0150] Example 4

[0151] The preparation steps are the same as those in Example 1, except that, at room temperature, 7.616 g of diphenyl carbonate, 8.002 g of BPA, 0.569 g of PDMS-4, 5.608 g of cyclohexylbenzene, 5 ppm of cesium hydroxide and 150 ppm of tetramethylammonium hydroxide are added to a 100 mL three-necked flask, and the reaction is completed to obtain a polycarbonate-polyorganosiloxane copolymer. The evaluation results are shown in Table 2.

[0152] The structure of the polycarbonate-polyorganosiloxane copolymer obtained in Example 4 is similar to that in Example 1, except that the chain length of the PDMS-3 portion is different, i.e. Figure 1 The height of the a peak is different, and the e+f peak becomes smaller.

[0153] Example 5

[0154] The preparation steps are the same as those in Example 1, except that, at room temperature, 7.637 g of diphenyl carbonate, 8.002 g of BPA, 0.569 g of PDMS-5, 5.608 g of cyclohexylbenzene, 15 ppm of cesium carbonate and 50 ppm of tetramethylammonium hydroxide are added to a 100 mL three-necked flask, and the reaction is completed to obtain a polycarbonate-polyorganosiloxane copolymer. The evaluation results are shown in Table 2.

[0155] like Figure 2 As shown, the structure and hydrogen spectrum of the polycarbonate-polyorganosiloxane copolymer obtained in Example 5 are shown. Figure 2 Where n = 30. The hydrogen spectrum data are as follows:

[0156] Among them, 0ppm is the chemical shift of (Si-CH3) on the main chain of the polyorganosiloxane repeating unit, 0.45ppm is the first methylene group close to the Si-O-Si bond of the polyorganosiloxane repeating unit, 1.45ppm is the chemical shift of -CH3 on the BPA repeating unit and the second methylene group close to the Si-O-Si bond of the polyorganosiloxane repeating unit, 2.6ppm is the chemical shift of the third methylene group close to the Si-O-Si bond of the polyorganosiloxane repeating unit, and 7.1 and 7.2ppm are the chemical shifts of the four protons of the benzene ring on the BPA repeating unit and the four protons of the benzene ring in the polyorganosiloxane repeating unit, respectively.

[0157] According to the above data and spectrum analysis, the obtained product is Figure 2 The target product carbonate-polyorganosiloxane copolymer with the structure shown.

[0158] Example 6

[0159] The preparation steps are the same as those in Example 1, except that, at room temperature, 7.636 g of diphenyl carbonate, 8.002 g of BPA, 0.569 g of PDMS-6, 5.608 g of cyclohexylbenzene, 2 ppm of cesium hydroxide and 100 ppm of tetramethylammonium hydroxide are added to a 100 mL three-necked flask, and the reaction is completed to obtain a polycarbonate-polyorganosiloxane copolymer. The evaluation results are shown in Table 2.

[0160] like Figure 3 As shown, the structure and hydrogen spectrum of the polycarbonate-polyorganosiloxane copolymer obtained in Example 6 of the present invention are shown. Figure 3 Where n=30.

[0161] The hydrogen spectrum data are as follows:

[0162] Among them, 0ppm is the chemical shift of (Si-CH3) on the main chain of the polyorganosiloxane repeating unit, 0.45ppm is the first methylene group near the Si-O-Si bond of the polyorganosiloxane repeating unit, 1.45ppm is the chemical shift of -CH3 on the BPA repeating unit and the second methylene group near the Si-O-Si bond of the polyorganosiloxane repeating unit, 2.6ppm is the chemical shift of the third methylene group near the Si-O-Si bond of the polyorganosiloxane repeating unit, and 3.8ppm is the chemical shift of -CH3 on the polyorganosiloxane repeating unit. 7.1 and 7.2ppm are the chemical shifts of the four protons of the benzene ring on the BPA repeating unit and the three protons of the benzene ring in the polyorganosiloxane repeating unit, respectively.

[0163] According to the above data and spectrum analysis, the obtained product is Figure 3 The target product carbonate-polyorganosiloxane copolymer with the structure shown.

[0164] Example 7

[0165] The preparation steps were the same as those in Example 1, except that, at room temperature, 7.616 g of diphenyl carbonate, 8.002 g of BPA, 0.569 g of PDMS-4, 4.844 g of isophorone and 10 ppm of cesium carbonate were added to a 100 mL three-necked flask, and the reaction was completed to obtain a polycarbonate-polyorganosiloxane copolymer. The evaluation results are shown in Table 2.

[0166] Example 8

[0167] The preparation steps are the same as those in Example 1, except that, at room temperature, 7.616 g of diphenyl carbonate, 8.002 g of BPA, 0.569 g of PDMS-4, 4.206 g of cyclopentane sulfone and 5 ppm of cesium hydroxide are added to a 100 mL three-necked flask, and the reaction is completed to obtain a polycarbonate-polyorganosiloxane copolymer. The evaluation results are shown in Table 2.

[0168] Example 9

[0169] The preparation steps are the same as those in Example 1, except that, at room temperature, 7.603 g of diphenyl carbonate, 4.547 g of isosorbide (ISB), 0.505 g of 1,4-cyclohexanedimethanol (CHDM), 0.569 g of PDMS-3, 4.206 g of cyclohexylbenzene and 10 ppm of potassium hydroxide are added to a 100 mL three-necked flask, and the reaction is completed to obtain a polycarbonate-polyorganosiloxane copolymer. The evaluation results are shown in Table 3.

[0170] Example 10

[0171] The preparation steps are the same as those in Example 1, except that, at room temperature, 7.616 g of diphenyl carbonate, 4.547 g of ISB, 0.505 g of CHDM, 0.569 g of PDMS-4, 4.206 g of cyclohexylbenzene and 1000 ppm of tetramethylammonium hydroxide are added to a 100 mL three-necked flask, and the reaction is completed to obtain a polycarbonate-polyorganosiloxane copolymer. The evaluation results are shown in Table 3.

[0172] like Figure 4 As shown, the structure and hydrogen spectrum of the polycarbonate-polyorganosiloxane copolymer obtained in Example 10 of the present invention are shown. Figure 4 Where n=31.

[0173] The hydrogen spectrum data are as follows:

[0174] Among them, 0ppm is the chemical shift of (Si-CH3) on the main chain of the polyorganosiloxane repeating unit, 0.45ppm is the chemical shift of the first methylene group of the polyorganosiloxane repeating unit close to the Si-O-Si bond, 1.45ppm is the chemical shift of the second methylene group of the polyorganosiloxane repeating unit close to the Si-O-Si bond, 1 and 1.5ppm are the cis and trans chemical shifts of -CH2- on CHDM, the three NMR peaks between 3-4ppm are the chemical shifts of the three -CH2- on the polyorganosiloxane repeating unit, 4ppm is the chemical shift of -CH2- on isosorbide, 4.85 and 4.5ppm are the two H proton peaks on isosorbide, and 5ppm is the H proton peak of isosorbide close to the ether bond.

[0175] According to the above data and spectrum analysis, the obtained product is Figure 4 The target product carbonate-polyorganosiloxane copolymer with the structure shown.

[0176] Embodiment 11

[0177] The preparation steps are the same as those in Example 1, except that, at room temperature, 7.637 g of diphenyl carbonate, 4.547 g of ISB, 0.505 g of CHDM, 0.569 g of PDMS-5, 4.206 g of cyclohexylbenzene, 10 ppm of calcium chloride and 100 ppm of tetramethylammonium hydroxide are added to a 100 mL three-necked flask, and the reaction is completed to obtain a polycarbonate-polyorganosiloxane copolymer. The evaluation results are shown in Table 3.

[0178] like Figure 5 Shown are the structure and hydrogen spectrum of the polycarbonate-polyorganosiloxane copolymer obtained in Example 11 of the present invention.

[0179] The hydrogen spectrum data are as follows:

[0180] Among them, 0ppm is the chemical shift of (Si-CH3) on the main chain of the polyorganosiloxane repeating unit, 0.45ppm is the first methylene of the polyorganosiloxane repeating unit close to the Si-O-Si bond, 1.45ppm is the chemical shift of the second methylene of the polyorganosiloxane repeating unit close to the Si-O-Si bond, 1 and 1.5ppm are the cis and trans chemical shifts of -CH2- on CHDM, 2.6ppm is the chemical shift of the third -CH2- on the polyorganosiloxane repeating unit, 4ppm is the chemical shift of -CH2- on isosorbide, 4.85 and 4.5ppm are the two H proton peaks on isosorbide. 5ppm is the H proton peak of isosorbide close to the ether bond. Near 7ppm is the chemical shift of the benzene ring proton on the polyorganosiloxane.

[0181] According to the above data and spectrum analysis, the obtained product is Figure 5The target product carbonate-polyorganosiloxane copolymer with the structure shown.

[0182] Example 12

[0183] The preparation steps are the same as those in Example 1, except that, at room temperature, 7.616 g of diphenyl carbonate, 3.586 g of ISB, 1.516 g of CHDM, 0.569 g of PDMS-4, 4.837 g of isophorone, and 10 ppm of sodium hydroxide and 100 ppm of tetramethylammonium hydroxide are added to a 100 mL three-necked flask, and the reaction is completed to obtain a polycarbonate-polyorganosiloxane copolymer. The evaluation results are shown in Table 3.

[0184] Example 13

[0185] The preparation steps are the same as those in Example 1, except that, at room temperature, 7.616 g of diphenyl carbonate, 3.586 g of ISB, 1.516 g of CHDM, 0.569 g of PDMS-4, 4.212 g of cyclopentane sulfone, 10 ppm of calcium acetate and 100 ppm of tetramethylammonium hydroxide are added to a 100 mL three-necked flask, and the reaction is completed to obtain a polycarbonate-polyorganosiloxane copolymer. The evaluation results are shown in Table 3.

[0186] Embodiment 14

[0187] The preparation steps are the same as those in Example 1, except that, at room temperature, 7.616 g of diphenyl carbonate, 3.586 g of ISB, 1.516 g of CHDM, 0.569 g of PDMS-4, 4.212 g of N-methylpyrrolidone, 10 ppm of potassium carbonate and 100 ppm of tetrabutylammonium hydroxide are added to a 100 mL three-necked flask, and the reaction is completed to obtain a polycarbonate-polyorganosiloxane copolymer. The evaluation results are shown in Table 3.

[0188] Table 2 Properties of polycarbonate-polyorganosiloxane copolymers prepared in Examples 1 to 8

[0189]

[0190]

[0191] Table 3 Properties of polycarbonate-polyorganosiloxane copolymers prepared in Examples 9 to 14

[0192]

[0193]

[0194] In Tables 2 and 3, *wt% of polyorganosiloxane (B) represents the amount of charged polyorganosiloxane (B) contained in the mass (theoretical value) of the obtained polycarbonate-polyorganosiloxane copolymer, and this value is calculated by the following formula.

[0195] The mass of the polycarbonate-polyorganosiloxane copolymer (theoretical value) = the mass of all diol monomers + the mass of the carbonate diester - the mass of the generated phenol (twice the molar number of phenol as the carbonate diester), and the unit is g.

[0196] The amount of polyorganosiloxane (B) = mass of polyorganosiloxane (ie, the amount charged, in g) / [mass of the polycarbonate-polyorganosiloxane copolymer (theoretical value)].

[0197] Comparative Example 1

[0198] The preparation steps were the same as those in Example 1, except that no co-solvent was added to obtain a polycarbonate-polyorganosiloxane copolymer. The evaluation results are shown in Table 4.

[0199] Comparative Example 2

[0200] The preparation steps are the same as those in Example 2, except that no co-solvent is added to obtain a polycarbonate-polyorganosiloxane copolymer. The evaluation results are shown in Table 4.

[0201] Comparative Example 3

[0202] The preparation steps are the same as those in Example 3, except that no co-solvent is added to obtain a polycarbonate-polyorganosiloxane copolymer. The evaluation results are shown in Table 4.

[0203] Comparative Example 4

[0204] The preparation steps are the same as those in Example 4, except that no co-solvent is added to obtain a polycarbonate-polyorganosiloxane copolymer. The results are shown in Table 4.

[0205] Comparative Example 5

[0206] The preparation steps are the same as those in Example 5, except that no co-solvent is added to obtain a polycarbonate-polyorganosiloxane copolymer. The evaluation results are shown in Table 4.

[0207] Comparative Example 6

[0208] The preparation steps are the same as those in Example 6, except that no co-solvent is added to obtain a polycarbonate-polyorganosiloxane copolymer. The evaluation results are shown in Table 4.

[0209] Comparative Example 7

[0210] The preparation steps were the same as those in Example 9, except that no co-solvent was added to obtain a polycarbonate-polyorganosiloxane copolymer. The evaluation results are shown in Table 4.

[0211] Comparative Example 8

[0212] The preparation steps were the same as those in Example 10, except that no co-solvent was added to obtain a polycarbonate-polyorganosiloxane copolymer. The evaluation results are shown in Table 4.

[0213] Comparative Example 9

[0214] The preparation steps were the same as those in Example 11, except that no co-solvent was added to obtain a polycarbonate-polyorganosiloxane copolymer. The evaluation results are shown in Table 4.

[0215] Comparative Example 10

[0216] The preparation steps are the same as those in Example 12, except that no co-solvent is added to obtain a polycarbonate-polyorganosiloxane copolymer. The evaluation results are shown in Table 4.

[0217] Table 4 Properties of polycarbonate-polyorganosiloxane copolymers prepared in Comparative Examples 1 to 10

[0218]

[0219] In Table 4, *wt% of polyorganosiloxane (B) represents the amount of charged polyorganosiloxane (B) contained in the mass (theoretical value) of the obtained polycarbonate-polyorganosiloxane copolymer, and this value is calculated by the following formula.

[0220] The mass of the polycarbonate-polyorganosiloxane copolymer (theoretical value) = the mass of all diol monomers + the mass of the carbonate diester - the mass of the generated phenol (twice the molar number of phenol as the carbonate diester), and the unit is g.

[0221] The amount of polyorganosiloxane (B) = mass of polyorganosiloxane (ie, the amount charged, in g) / [mass of the polycarbonate-polyorganosiloxane copolymer (theoretical value)].

[0222] The performance testing methods in the embodiments of the present invention and the comparative examples are as follows:

[0223] (1) Intrinsic viscosity

[0224] The polycarbonate-polyorganosiloxane copolymer was dissolved in chloroform to a concentration c of 0.01 g / mL and measured using an Ubbelohde viscometer at a temperature of 25°C ± 0.5°C. The intrinsic viscosity [η] was calculated according to the following formula.

[0225]

[0226] Here, t is the flow time of the solution and t0 is the flow time of the solvent alone.

[0227] (2) Light transmittance

[0228] The transmittance of a 0.1 mm thick polycarbonate-polyorganosiloxane copolymer film was measured in the range of 380-780 nm using an ultraviolet / visible spectrophotometer (UV1900, Youke Instrument), and the total transmittance T of the copolymer film in the visible light region was calculated by the following formula: total (%).

[0229]

[0230] Wherein, T(λ) represents the transmittance of the corresponding wavelength, and 780nm and 380nm both represent wavelengths.

[0231] (3) Color difference

[0232] 0.1 g of polycarbonate-polyorganosiloxane copolymer was fully dissolved in 10 mL of chloroform, and the solution was measured using an ultraviolet / visible spectrophotometer (UV1900, Youke Instrument), and the color difference (ΔC) was calculated according to the following formula.

[0233]

[0234] Among them, T 600 、T 555 and T 445 Represent the transmittance of the solution at 600, 555, and 445 nm, respectively, and T = T 600 +T 555 +T 445 .

[0235] (4) Quantitative method for polyorganosiloxane conversion rate

[0236] Example: A method for quantifying the amount of polydimethylsiloxane contained in the polycarbonate-polyorganosiloxane copolymer obtained in Example 1 and undergoing ester exchange reaction.

[0237] A: integrated value of the methyl group of the dimethylsiloxane moiety observed near δ-0.02-0.3;

[0238] B: integrated value of H protons in the ISB part observed around δ4.3-4.6;

[0239] C: integrated value of the methylene group at the terminal of dimethylsiloxane observed near δ0.4-0.6;

[0240] D: integrated value of the methylene group in the CHDM part observed around δ0.8-1.5;

[0241] E: integrated value of the methylene group of the PEG part observed around δ 3.3-3.8;

[0242] a=a / 6b=B c=C / 4d=D / 4e=E / 4;

[0243] T = a + b + c + d + e;

[0244] f=a / T×100g=b / T×100h=c / T×100i=d / T×100j=e / T×100;

[0245] TW=f×74.1+g×172+h×116+i×170+j×44;

[0246] The mass proportion of polyorganosiloxane block in the copolymer is W PDMS =g×74.1 / TW×100;

[0247] Conversion rate (%) = W PDMS / W0, W0 is the mass ratio of diol monomer:polyorganosiloxane (B) in Tables 2 to 4.

[0248] In summary, compared with the polycarbonate-polyorganosiloxane copolymer without the addition of a co-solvent, the polycarbonate-polyorganosiloxane copolymer of the present invention has a higher molecular weight (expressed as intrinsic viscosity) and a higher heat resistance temperature (expressed as glass transition temperature), and the polyorganosiloxane conversion rate is increased by 2 to 20%. In particular, the use of cyclohexylbenzene as a co-solvent has the best effect on improving the conversion rate, and the polyorganosiloxane conversion rate in some polycarbonate-polyorganosiloxane copolymers can reach more than 95%; and the transparency (expressed as light transmittance) and light resistance (expressed as color difference) are also improved due to the addition of the co-solvent, so it is useful in the field of engineering plastics as a molding material used in various injection molding, extrusion molding, compression molding, etc.

[0249] Although the above embodiment describes the present invention in detail, it is only a part of the embodiments of the present invention, not all of the embodiments. People can also obtain other embodiments based on this embodiment without creativity, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A polycarbonate-polyorganosiloxane copolymer, comprising a polycarbonate block and a polyorganosiloxane block; the polycarbonate block has a repeating unit of a structure represented by formula A; the polyorganosiloxane block has a repeating unit of a structure represented by formula B; In formula A, R1 is an aliphatic alkylene group having 2 to 40 carbon atoms, an alicyclic alkylene group having 3 to 40 carbon atoms, or a hydroxy-substituted arylene group having 6 to 20 carbon atoms; In formula B, R2 has the structure shown in formula 1: In Formula 1, n is 5 to 60; m is 1 to 20; a, a1, b and b1 are independently 0 or 1; R3 to R6 are independently -H, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 6 to 10 carbon atoms; R7 and R8 are independently an arylene group having 6 to 20 carbon atoms, a linear alkylene group having 1 to 10 carbon atoms, or an alkyl-substituted arylene group; R9 and R 10 are independently an arylene group having 6 to 20 carbon atoms, a straight-chain alkylene group having 2 to 10 carbon atoms, a branched-chain alkylene group having 3 to 10 carbon atoms, or an alkyl-substituted arylene group; The light transmittance of the polycarbonate-polyorganosiloxane copolymer is greater than 50%.

2. The polycarbonate-polyorganosiloxane copolymer according to claim 1, characterized in that: The R1 is an aliphatic alkylene group having 2 to 40 carbon atoms in the main chain, an alicyclic alkylene group having 3 to 40 carbon atoms in the main chain, or a hydroxy-substituted arylene group having 6 to 20 carbon atoms in the main chain.

3. The polycarbonate-polyorganosiloxane copolymer according to claim 1 or 2, characterized in that: The mass of the polyorganosiloxane block is 0.5 to 20% of the total mass of the polycarbonate-polyorganosiloxane copolymer.

4. The method for preparing the polycarbonate-polyorganosiloxane copolymer according to any one of claims 1 to 3, comprising the following steps: In a protective atmosphere, carbonic acid diester, diol monomer, co-solvent and catalyst are mixed to carry out ester exchange reaction to obtain polycarbonate prepolymer; the boiling point of the co-solvent is 200-400°C; The diol monomer comprises a first component and a second component, the first component is an aromatic bisphenol compound and / or an aliphatic diol compound, and the second component is a polyorganosiloxane; the polyorganosiloxane has a structure shown in Formula 2; The polycarbonate prepolymer is subjected to polycondensation reaction to obtain the polycarbonate-polyorganosiloxane copolymer.

5. The preparation method according to claim 4, characterized in that: The co-solvent includes one or more of cyclohexylbenzene, isophorone, sulfolane, N-methylpyrrolidone, dimethyl sulfoxide, 2,2-diphenylpropane, dodecane, tridecane, 1-dodecene, 1-tetradecene, bicyclohexane, 1,2,3-tribromopropane, biphenyl, naphthalene and α-methylnaphthalene.

6. The preparation method according to claim 4 or 5, characterized in that: The transesterification reaction comprises: heating from 160° C. to 180° C., keeping the temperature for 1 to 3 hours, and then heating to 210° C., keeping the temperature for 1 to 3 hours.

7. The preparation method according to claim 4, characterized in that: The polycondensation reaction comprises: heating from 210° C. to 275° C., reducing the pressure to ≤50 Pa, and then maintaining the temperature and pressure for 0.5 to 5 hours.

8. The preparation method according to claim 4 or 5, characterized in that: The carbonic acid diester includes diphenyl carbonate or dimethyl carbonate.

9. The preparation method according to claim 4 or 5, characterized in that: The aromatic bisphenol compound includes one or more of 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3-methylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and 1,1-bis(4-hydroxyphenyl)cyclododecene; The aliphatic diol compound includes one or more of isosorbide, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,3-propylene glycol and 1,4-butanediol.

10. Use of the polycarbonate-polyorganosiloxane copolymer according to any one of claims 1 to 3 or the polycarbonate-polyorganosiloxane copolymer prepared by the preparation method according to any one of claims 4 to 9 in engineering plastics.

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