A modified polycarbonate, its preparation method and application

Abstract

The present invention discloses a modified polycarbonate and its preparation method and application, which include the following components and / or their reaction products: a polycarbonate matrix, an acrylic acid (ester) monomer, and an initiator. The polycarbonate matrix is selected from at least one of aliphatic polycarbonates, alicyclic polycarbonates, aromatic polycarbonates, aliphatic-aromatic copolycarbonates, and polyester-polycarbonate copolymers. The acrylic acid (ester) monomer is a compound containing a -C=C-C(O)- group in its structure. Introducing the acrylic acid (ester) monomer into the polycarbonate matrix can promote the interaction between the modified polycarbonate material and other polymer materials during compounding, improve the wettability of inorganic materials in the polycarbonate and the two-phase interface compatibility, thereby improving the interfacial bonding strength and mechanical properties of the multi-component composite system, and significantly improving the compatibility.

Description

Technical Field

[0001] The present invention belongs to the field of polycarbonates, and particularly relates to modified polycarbonates and their preparation methods and applications. Background Art

[0002] Polycarbonate refers to a polymer containing carbonate groups in the molecular chain, which can be regarded as a polycondensation product of dihydroxy compounds and carbonic acid, and can be divided into aliphatic, alicyclic, aromatic, and aliphatic-aromatic types, etc. Bisphenol A polycarbonate has outstanding impact toughness, excellent insulation properties, a relatively large service temperature range, and stable product dimensions, and is an engineering plastic with good comprehensive properties.

[0003] However, polycarbonate has some defects, such as being prone to stress cracking, sensitive to notches, poor wear resistance, and poor processing fluidity; in addition, when blended and modified with inorganic materials or organic polymer materials, there are often problems of weak interfacial strength and poor compatibility. In this regard, a lot of work has been done on the physical / chemical modification of polycarbonate in the academic and industrial fields.

[0004] Physical blending modification of polycarbonate is the main and simple modification method. The polymer-based modification substances used include polystyrene, ABS, polyolefins, polyesters, polyamides, polyacrylates, fluororesins, polysiloxanes, polyurethanes, etc. (CN110499010A, CN108164984A, CN110256829A, WO0320827A); the inorganic-based modification substances used include minerals, silica, mica, glass fibers, carbon fibers, graphite, graphene, etc. (CN104341754A, CN107312307A, CN107915974A). In most cases, an interfacial compatibilizer also needs to be added to improve the interfacial adhesion performance of the composite system (CN105778464A, CN111087778A, CN109575552A), otherwise, problems such as spots, defects, delamination, phase separation, and peeling are likely to occur.

[0005] In addition, good progress has been made in the chemical modification of polycarbonate molecular chains, including copolymerization modification and post-polymerization modification methods. CN110776640A reports a method for preparing polycarbonate polyorganosiloxane copolymer by copolymerizing end-phenol polyorganosiloxane with bisphenol A. The key point is to first prepare an end-phenol polyorganosiloxane compound with low free phenol content by a complex and cumbersome chemical method. CN110776631A discloses a copolycarbonate obtained by copolymerizing 3a-methyl octahydropentene-2,5-diol prepared from raw materials such as citric acid and concentrated sulfuric acid with aliphatic diols and dibutyl carbonate. This method is green and environmentally friendly, but there is still the problem of a long preparation process flow. CN110256636A discloses a post-modification method for aliphatic polycarbonate, which uses TEMPO functionalization technology to introduce grafted polystyrene chains into polycarbonate, expanding the chemical / biological properties of aliphatic polycarbonate. Summary of the Invention

[0006] In order to overcome the problem of poor compatibility during the blending modification of polycarbonate with organic / inorganic materials in the prior art, the present invention provides a modified polycarbonate, which can significantly improve the interfacial strength and significantly improve the interfacial compatibility when blended with other polymer materials and / or inorganic materials, and can be used in the fields of optics, communication, electronics, automotive, medical, aerospace, etc.

[0007] One of the purposes of the present invention is to provide a modified polycarbonate, which includes the following components and / or their reaction products: (1) polycarbonate matrix, (2) acrylic acid (ester) monomers, (3) initiator.

[0008] In a preferred embodiment, the polycarbonate matrix is selected from at least one of aliphatic polycarbonate, alicyclic polycarbonate, aromatic polycarbonate, aliphatic-aromatic copolycarbonate, and polyester-polycarbonate copolymer, and is preferably aromatic polycarbonate.

[0009] Among them, the polycarbonate in the polyester-polycarbonate copolymer can be at least one of aliphatic polycarbonate, alicyclic polycarbonate, aromatic polycarbonate, and aliphatic-aromatic copolycarbonate.

[0010] In a preferred embodiment, the aromatic polycarbonate is an aromatic polycarbonate formed by the polymerization reaction of a diphenol compound or a polyphenol compound with a carbonate precursor, and is preferably a linear aromatic polycarbonate formed by the polymerization reaction of a diphenol compound with a carbonate precursor.

[0011] In a preferred embodiment, the aliphatic polycarbonate is an aliphatic polycarbonate formed by the polymerization reaction of an aliphatic diol or an aliphatic polyol with a carbonate precursor, and is preferably a linear aromatic polycarbonate formed by the polymerization reaction of an aliphatic diol with a carbonate precursor.

[0012] In a preferred embodiment, the aliphatic-aromatic copolycarbonate is an aliphatic-aromatic copolycarbonate formed by the polymerization reaction of an aliphatic diol or an aliphatic polyol, a diphenolic compound or a polyphenolic compound with a carbonate precursor, preferably a linear aliphatic-aromatic copolycarbonate formed by the polymerization reaction of an aliphatic diol, a diphenolic compound with a carbonate precursor.

[0013] The polyester-polycarbonate copolymer is formed by the polymerization reaction of an aliphatic diol and / or a diphenolic compound, an aromatic diacid and / or an aliphatic diacid with a carbonate precursor.

[0014] In a preferred embodiment, the diphenolic compounds are selected from aromatic diols, preferably selected from at least one of 4,4'-dihydroxybiphenyl, 2,2-bis(4-hydroxyphenyl)propane, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 2,4-bis(3,5-dimethyl-4-hydroxyphenyl)-2-methylbutane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)cyclohexane, 2,2-bis(3-chloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 4,4-bis(4-hydroxyphenyl)heptane, bis(3,5-dimethyl-4-hydroxyphenyl)methane, 2,2-(3,3',5,5'-tetrachloro-4,4'-dihydroxydiphenyl)propane, 2,2-(3,3',5,5'-tetrabromo-4,4'-dihydroxydiphenyl)propane, (3,3'-dichloro-4,4'-dihydroxyphenyl)methane, bis(3,5-dimethyl-4-hydroxyphenyl)sulfone, bis-4-hydroxyphenylsulfone, bis-4-hydroxyphenylsulfide; more preferably selected from at least one of 4,4'-biphenol, 2,2-bis(4-hydroxyphenyl)propane, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(3-chloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane.

[0015] In a preferred embodiment, the polyphenolic compounds are selected from at least one of tris(4-hydroxyphenyl)methane, tris(3,5-dimethyl-4-hydroxyphenyl)methane, 1,3,5-tris(4-hydroxyphenyl)cyclohexane, phloroglucinol.

[0016] Among them, the polyphenolic compound contains more than 2 (excluding 2) phenolic groups.

[0017] In a preferred embodiment, the aliphatic diol is selected from at least one of 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol.

[0018] In a preferred embodiment, the aliphatic polyol is selected from at least one of 1,2,3-propanetriol, 1,3,5-pentanetriol, neopentyl glycol, 1,3,5-cyclohexanetricarbinol, 1,1,4,4-cyclohexanetetramethanol, and 1,2,3,4,5,6-cyclohexanehexamethanol.

[0019] Among them, the aliphatic polyol contains more than 2 (excluding 2) hydroxyl groups.

[0020] In a preferred embodiment, the aromatic dicarboxylic acid is selected from at least one of terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid.

[0021] In a preferred embodiment, the aliphatic dicarboxylic acid is selected from at least one of succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid.

[0022] In a preferred embodiment, the carbonate precursor is selected from at least one of halogen formates, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, dimethylxylene carbonate, bis(chlorophenyl) carbonate, phenyltolyl carbonate, dinaphthyl carbonate, phosgene, carbonyl bromide, trichloromethyl chloroformate, bis(trichloromethyl) carbonate, and dihaloformates.

[0023] In a preferred embodiment, the weight-average molecular weight of the polycarbonate matrix is 5000 g / mol to 120000 g / mol, preferably 15000 g / mol to 100000 g / mol, more preferably 20000 g / mol to 80000 g / mol, and even more preferably 25000 g / mol to 50000 g / mol; and / or the number-average molecular weight of the polycarbonate matrix is 4000 g / mol to 100000 g / mol, preferably 10000 g / mol to 80000 g / mol, more preferably 15000 g / mol to 60000 g / mol, and even more preferably 20000 g / mol to 50000 g / mol.

[0024] The polycarbonate matrix of the present invention may be selected from any polycarbonates disclosed in the prior art, preferably but not limited to the polycarbonates defined above.

[0025] When preparing the polycarbonate of the present invention, a catalyst, an acid acceptor, and a molecular weight regulator are used to control the molecular weight.

[0026] Preferably, the catalyst is selected from at least one of triethylamine, tripropylamine, N-dimethylaniline, N-diethylaniline, tetraethylammonium bromide, and methyltriphenylphosphonium bromide.

[0027] Preferably, the acid acceptor is selected from at least one of pyridine, triethylamine, N-dimethylaniline, hydroxides of alkali metals, hydroxides of alkaline earth metals, carbonates, bicarbonates, and phosphates.

[0028] Preferably, the molecular weight regulator is selected from at least one of phenol, C 1 -C 6 p-phenol, p-halophenol, dimethylamine, methyl ethylamine, diethylamine, dipropylamine, dibutylamine, and dihexylamine.

[0029] The preparation method and preparation conditions of the polycarbonate of the present invention can be those disclosed in the prior art.

[0030] In a preferred embodiment, the acrylic (meth)acrylate monomer is a compound containing a -C=C-C(O)- group in its structure.

[0031] In a further preferred embodiment, the structure of the acrylic (meth)acrylate monomer further contains a silicon element, such as a siloxy group.

[0032] In a preferred embodiment, the acrylic (meth)acrylate monomer is selected from at least one of the acrylic (meth)acrylate monomers represented by Formula (I) to Formula (IV):

[0033]

[0034] Wherein, in Formula (I) to Formula (IV),

[0035] R 1 、R 2 、R 3 、R 7 、R 8 、R 9 、R 10 、R 11 、R 24 、R 25 are each independently selected from hydrogen, an alkyl group having C 1 to C 30 or an aryl group having C 6 to C 40 ; and / or

[0036] R 4 、R 5 、R 6 are each independently selected from hydrogen, an alkyl group having C 1 to C 30 of alkyl, C1 ~C 30 alkoxy groups of C 2 ~C 30 epoxyalkyl groups of C 1 ~C 30 aminoalkyl groups of C 1 ~C 30 hydroxyalkyl groups of C 1 ~C 30 haloalkyl groups of C 6 ~C 40 or aryl groups of C ; and / or

[0037] R 12 , R 22 , R 23 are each independently selected from C 1 ~C 30 alkylene groups of C 6 ~C 40 or arylene groups of C ; and / or

[0038] R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 are each independently selected from hydrogen, C 1 ~C 30 alkyl groups of C 1 ~C 30 alkoxy groups of C 6 ~C 40 aryl groups of C 6 ~C 40 aryloxy groups of C .

[0039] In a further preferred embodiment, in Formulas (I) to (IV),

[0040] R 1 , R 2 , R 3 , R 7 , R 8 , R 9 , R 10 , R 11 , R 24 , R 25 are each independently selected from hydrogen, C 1 ~C 18 alkyl groups of C 6 ~C 24 or aryl groups of C ; and / or

[0041] R4 , R 5 , R 6 are each independently selected from hydrogen, C 1 to C 18 alkyl, C 1 to C 18 alkoxy, C 2 to C 18 epoxyalkyl, C 1 to C 18 aminoalkyl, C 1 to C 18 hydroxyalkyl, C 1 to C 18 haloalkyl or C 6 to C 24 aryl; and / or

[0042] R 12 , R 22 , R 23 are each independently selected from C 1 to C 18 alkylene or C 6 to C 24 arylene; and / or

[0043] R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 are each independently selected from hydrogen, C 1 to C 18 alkyl, C 1 to C 18 alkoxy, C 6 to C 24 aryl, C 6 to C 24 aryloxy.

[0044] In a further preferred embodiment, the acrylic acid (ester) monomer represented by formula (I) is selected from at least one of acrylic acid, methacrylic acid, n-butyl acrylate, methyl methacrylate, and 2-hydroxyethyl methacrylate; and / or, the acrylic acid (ester) monomer represented by formula (II) is selected from at least one of maleic acid, dimethyl maleate, diethyl maleate, and di-n-butyl maleate; and / or, the acrylic acid (ester) monomer represented by formula (III) is selected from at least one of 3-methacryloxypropyltrimethylsilane, 3-methacryloxypropyltriethylsilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, and trimethylsiloxysilylated poly(ethylene glycol) methacrylate; and / or, the acrylic acid (ester) monomer represented by formula (IV) is selected from at least one of bis(trimethylsilylpropyl) maleate, bis(triethylsilylpropyl) maleate, bis(trimethoxysilylpropyl) maleate, bis(triethoxysilylpropyl) maleate, and bis(trimethylsiloxysilylated poly(ethylene glycol)) maleate.

[0045] In a preferred embodiment, the initiator is selected from at least one of alkyl peroxides, alkyl hydroperoxides, diperoxyesters, peroxyacid esters, and diacyl peroxides.

[0046] In a further preferred embodiment:

[0047] The alkyl peroxides are selected from at least one of dicumyl peroxide, di-tert-butyl peroxide, di-tert-amyl peroxide, 2,2-bis(tert-butylperoxy)butane, 1,1-bis(tert-butylperoxy)cyclohexane, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxynonane, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, and 2,5-dimethyl-2,5-bis(tert-butylperoxy)hex-3-yne; and / or

[0048] The alkyl hydroperoxides are selected from at least one of cumene hydroperoxide, tert-butyl hydroperoxide, tert-amyl hydroperoxide, and 2,5-dimethyl-2,5-bis(hydroperoxy)hexane; and / or

[0049] The diperoxyesters are selected from at least one of dicarbonates, ditetradecyl peroxydicarbonate, dihexadecyl peroxydicarbonate, bis(2-ethylhexyl) peroxydicarbonate, bis(4-tert-butylcyclohexyl) peroxydicarbonate, and 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane; and / or

[0050] The peroxy acid ester is selected from at least one of tert-butyl peroxy 2-ethylhexyl carbonate, tert-amyl peroxy 2-ethylhexyl carbonate, tert-butyl peroxyacetate, tert-butyl peroxyisobutyrate, tert-butyl peroxy pivalate, tert-butyl peroxyneodecanoate, tert-amyl peroxyneodecanoate, tert-butyl peroxy 3,5,5-trimethylhexanoate, tert-butyl peroxy 2-ethylhexanoate, tert-amyl peroxy 2-ethylhexanoate, tert-butyl peroxymaleate, tert-butyl peroxybenzoate, and tert-amyl peroxybenzoate; and / or

[0051] The peroxy diacyl is selected from at least one of benzoyl peroxide, bis(3,5,5-trimethylhexanoyl) peroxide, and dilauroyl peroxide.

[0052] In a further preferred embodiment, the initiator is selected from at least one of 1,1-bis(tert-butylperoxy)cyclohexane, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, bis(2-ethylhexyl) peroxydicarbonate, and tert-butyl peroxy 3,5,5-trimethylhexanoate.

[0053] In a preferred embodiment, based on 100 parts by weight of the polycarbonate matrix, the weight of the acrylic acid (ester) monomer is 0.5 to 20 parts, preferably 1 to 15 parts.

[0054] In a preferred embodiment, based on 100 parts by weight of the polycarbonate matrix, the weight of the initiator is 0.01 to 1 part, preferably 0.05 to 0.5 part.

[0055] In a preferred embodiment, the modified polycarbonate optionally further includes an auxiliary agent.

[0056] In a further preferred embodiment, the auxiliary agent is selected from at least one of a plasticizer, a heat stabilizer, an antioxidant, a UV absorber, and a release agent.

[0057] The auxiliary agent described in the present invention is selected from the auxiliary agents commonly used in the prior art, preferably but not limited to the following limitations.

[0058] Preferably, the plasticizer is selected from at least one of phthalate, glyceryl tristearate, and epoxidized soybean oil; and / or, the heat stabilizer is selected from at least one of triphenyl phosphite, tris(2,6-dimethylphenyl) phosphite, trimethyl phosphate, dimethyl phenyl phosphate, and benzotriazole; and / or, the antioxidant is selected from 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; and / or, the UV absorber is selected from at least one of hydroxybenzodiazole, hydroxybenzotriazine, hydroxybenzophenone, benzoxazinone, nanosized titanium dioxide, and zinc oxide; and / or, the mold release agent is selected from at least one of zinc stearate, calcium stearate, barium stearate, magnesium stearate, stearoyl stearate, pentaerythritol tetrastearate, paraffin wax, silicone oil, and white oil.

[0059] A second object of the present invention is to provide a method for preparing the modified polycarbonate according to the first object of the present invention, comprising: melt-blending raw materials including the polycarbonate matrix, the acrylic acid (ester) monomer, and the initiator to obtain the modified polycarbonate.

[0060] In a preferred embodiment, the raw materials optionally further include additives.

[0061] In a further preferred embodiment, the additives are selected from at least one of plasticizers, heat stabilizers, antioxidants, UV absorbers, and mold release agents.

[0062] The additives of the present invention are selected from the additives commonly used in the prior art and are not particularly limited.

[0063] For example, preferably, the antioxidant is selected from one or more of any antioxidants disclosed in the prior art, such as at least one of antioxidant 1010, antioxidant 1076, antioxidant CA, antioxidant NDP, antioxidant DLTP, antioxidant TNP, antioxidant TPP, antioxidant MB, and antioxidant 264.

[0064] Among them, adding antioxidants and other additives during the processing of polymer materials is a commonly used technical means in the art. In the present invention, the antioxidants and other additives are not particularly limited and can be selected from any one or several disclosed in the prior art.

[0065] In a preferred embodiment, the temperature of the melt-blending is 200 to 360 °C, preferably 250 to 300 °C.

[0066] In a further preferred embodiment, the melt blending is carried out in a screw extruder; preferably, the screw speed is 50-350 rpm, more preferably 100-300 rpm.

[0067] In a preferred embodiment, the preparation method comprises the following steps:

[0068] Step 1: Dispersing the acrylic acid (ester) monomer and the initiator in a dispersing oil agent to form Material 1; preferably, the dispersing oil agent is selected from at least one of paraffin, mineral oil, white oil, and silicone oil, such as white oil;

[0069] Step 2: Mixing the polycarbonate matrix and optionally additives to form Material 2;

[0070] Step 3: Separately introducing Material 1 and Material 2 into a screw extruder, and performing melt blending and extrusion to obtain the modified polycarbonate.

[0071] In a preferred embodiment, based on 100 parts by weight of the polycarbonate matrix, the weight of the acrylic acid (ester) monomer is 0.5-20 parts, preferably 1-15 parts.

[0072] In a preferred embodiment, based on 100 parts by weight of the polycarbonate matrix, the weight of the initiator is 0.01-1 part, preferably 0.05-0.5 part.

[0073] In a preferred embodiment, in Step 3, Material 1 is introduced into the liquid feeding port of the screw extruder, and Material 2 is introduced into the pellet feeding port of the screw extruder.

[0074] A third object of the present invention is to provide a composite material, which contains at least one of polyethylene, polypropylene, polyoxymethylene, polymethyl methacrylate, polystyrene, methyl methacrylate / butadiene / styrene copolymer, acrylonitrile / butadiene / styrene copolymer, acrylonitrile / acrylic ester / styrene copolymer, acrylonitrile / styrene copolymer, styrene / maleic anhydride random copolymer, acrylonitrile / styrene / maleic anhydride random copolymer, polyethylene terephthalate, polybutylene terephthalate, polybutylene succinate, polybutylene adipate, polybutylene succinate / polybutylene terephthalate, polybutylene adipate / polybutylene terephthalate, glass fiber, carbon fiber, aramid fiber, graphene, carbon nanotube and the modified polycarbonate according to one of the objects of the present invention or the modified polycarbonate obtained by the preparation method according to the second object of the present invention.

[0075] Preferably, additives are optionally further contained in the composite material.

[0076] More preferably, the auxiliary agent is selected from at least one of a plasticizer, a heat stabilizer, an antioxidant, a UV absorber, and a release agent.

[0077] Among them, adding an auxiliary agent during the processing of polymer materials is a commonly used technical means in the art. In the present invention, the selection of the auxiliary agent is not particularly limited and can be selected from any one or any several disclosed in the prior art.

[0078] The fourth object of the present invention is to provide the application of the modified polycarbonate described in the first object of the present invention or the composite material described in the third object of the present invention in the fields of optics, communication, electronics, automotive, medical, and aerospace.

[0079] Compared with the prior art, the present invention has the following beneficial effects: In the method of the present invention, the acrylic acid (ester) monomer is added to the polycarbonate matrix, and the acrylate group contained therein can have a compatibilizing chain extension or chain change effect with the polycarbonate matrix through chemical bonding; at the same time, the embedded groups such as silicon-based, carboxyl, and ester groups can promote the interaction between the modified polycarbonate material and other polymer materials (such as polyamide, polyester, ABS, silicone resin, etc.) during compounding, and improve the wettability of inorganic materials (such as glass fiber, minerals, etc.) in polycarbonate and the interfacial compatibility of the two-phase structure, thereby improving the interfacial bonding strength and mechanical properties of the multi-component composite system, and significantly improving the compatibility, achieving better technical effects. Description of the Drawings

[0080] Figure 1 The GPC spectrum of the modified polycarbonate obtained in Example 5 is shown. Detailed Embodiments

[0081] The present invention will be specifically described below in conjunction with specific embodiments. It is necessary to point out here that the following embodiments are only for further illustration of the present invention and cannot be construed as limiting the protection scope of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention still fall within the protection scope of the present invention.

[0082] If there is no special limitation on the raw materials used in the examples and comparative examples, they are all disclosed in the prior art. For example, they can be directly purchased or prepared according to the preparation methods disclosed in the prior art.

[0083] Molecular weight test: Determined by a PL-GPC gel permeation chromatograph from Polymer Laboratories Ltd. (UK), with tetrahydrofuran as the mobile phase. Melt index test: Determined according to ISO 1133 standard using a CEAST 50M melt indexer from Intron Corporation (USA), with a load of 1.2 kg and a temperature of 300 °C, or a load of 5 kg and a temperature of 220 °C. Notched Izod impact strength test: Determined according to ISO 179 standard using a pendulum impact tester from Ceast S.p.A. (Italy), with a pendulum energy of 2.75 J. Notched Charpy impact strength test: Determined according to ASTM D256 standard using a pendulum impact tester from Ceast S.p.A. (Italy), with a pendulum energy of 5 J. Chemical coating thickness test: Determined according to ASTM B568 (2009) using an X-ray fluorescence coating thickness gauge Fischerscope from Germany. Crosshatch test: Test the adhesion or cohesion between the metal coating and the substrate according to GB9286-98 standard, with ≥ 4B being qualified.

[0084] The polycarbonate was purchased from Mitsubishi Chemical Corporation (Japan), the white oil was purchased from Hebei Xinrunde Technology Co., Ltd., the pentaerythritol tetrakis [β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] was purchased from Shanghai Kayin Chemical Co., Ltd., the 2-hydroxyethyl methacrylate was purchased from Sinopharm Chemical Reagent Co., Ltd., the 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane was purchased from Jiangsu Qiangsheng Chemical Co., Ltd., the 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane was purchased from Shandong Moore Chemical Co., Ltd., the peroxydicarbonate was purchased from Shandong Moore Chemical Co., Ltd., the dimethyl maleate was purchased from Sinopharm Chemical Reagent Co., Ltd., the bis(trimethylsilylpropyl) maleate was purchased from Sinopharm Chemical Reagent Co., Ltd., the n-butyl acrylate was purchased from Sinopharm Chemical Reagent Co., Ltd., the 3-methacryloxypropyltriethoxysilane was purchased from Sinopharm Chemical Reagent Co., Ltd., the 3-methacryloxypropyltrimethylsilane was purchased from Sinopharm Chemical Reagent Co., Ltd., the high rubber powder was purchased from Kumho Petrochemical Co., Ltd. (South Korea), the long glass fiber was purchased from Jushi Group Co., Ltd., the styrene / maleic anhydride random copolymer was purchased from Cray Valley Company (USA), and the laser laser additive was purchased from MacDermid Alpha Electronics Solutions (USA).

[0085]

Example 1

[0086] The polycarbonate used in Example 1 was a bisphenol A type aromatic polycarbonate.

[0087] Determination of processing parameters for polycarbonate materials (blank experiment): 100 parts of dried polycarbonate (PC, melt index 19.8 g / 10 min, number average molecular weight 25,200 g / mol, weight average molecular weight 43,700 g / mol), 5 parts of white oil, and 1 part of pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] were mixed evenly and introduced into the pellet feeding port of a LABTECH co-rotating twin-screw extruder (screw diameter 16 mm, length-diameter ratio 40). Under the process conditions of 280 °C and 250 rpm, it was melt-extruded, cooled, and pelletized to obtain processed polycarbonate materials (PC’, melt index 18.1 g / 10 min, number average molecular weight 21,020 g / mol, weight average molecular weight 43,920 g / mol).

[0088] Preparation of modified polycarbonate materials: 3 parts of 2-hydroxyethyl methacrylate and 0.015 parts of 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane were evenly dispersed in 5 parts of white oil at room temperature and introduced into the liquid feeding port of a LABTECH co-rotating twin-screw extruder (screw diameter 16 mm, length-diameter ratio 40). At the same time, 97 parts of dried polycarbonate (PC, melt index 19.8 g / 10 min, number average molecular weight 25,200 g / mol, weight average molecular weight 43,700 g / mol at 300 °C and 1.2 kg) and 1 part of pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] were mixed evenly and introduced into the pellet feeding port of the co-rotating twin-screw extruder. Under the process conditions of 280 °C and 250 rpm, it was melt-reaction co-extruded, cooled, and pelletized to obtain modified polycarbonate material A. Its properties are shown in Table 1.

[0089]

Example 2

[0090] The polycarbonate used in Example 2 was bisphenol A type aromatic polycarbonate.

[0091] Preparation of modified polycarbonate materials: 7 parts of 2-hydroxyethyl methacrylate and 0.035 parts of 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane were evenly dispersed in 5 parts of white oil at room temperature and introduced into the liquid feeding port of a LABTECH co-rotating twin-screw extruder (screw diameter 16 mm, length-diameter ratio 40). At the same time, 93 parts of dried polycarbonate (PC, melt index 19.8 g / 10 min, number average molecular weight 25,200 g / mol, weight average molecular weight 43,700 g / mol at 300 °C and 1.2 kg) and 1 part of pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] were mixed evenly and introduced into the pellet feeding port of the co-rotating twin-screw extruder. Under the process conditions of 280 °C and 250 rpm, it was melt-reaction co-extruded, cooled, and pelletized to obtain modified polycarbonate material B. Its properties are shown in Table 1.

[0092]

Example 3

[0093] The polycarbonate used in Example 3 is bisphenol A aromatic polycarbonate.

[0094] Preparation of the modified polycarbonate material: 11 parts of 2-hydroxyethyl methacrylate and 0.055 parts of 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane were uniformly dispersed in 5 parts of white oil at room temperature and introduced into the liquid feeding port of a LABTECH co-rotating twin-screw extruder (screw diameter 16 mm, length-diameter ratio 40); at the same time, 89 parts of dried polycarbonate (PC, 300 °C, melt index 19.8 g / 10 min at 1.2 kg, number-average molecular weight 25,200 g / mol, weight-average molecular weight 43,700 g / mol) and 1 part of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] were mixed evenly and introduced into the pellet feeding port of the co-rotating twin-screw extruder. Under the process conditions of 280 °C and 250 rpm, they were melt-reacted and co-extruded, cooled, and pelletized to obtain the modified polycarbonate material C. Its properties are shown in Table 1.

[0095]

Example 4

[0096] The polycarbonate used in Example 4 is bisphenol A aromatic polycarbonate.

[0097] Preparation of the modified polycarbonate material: 11 parts of 2-hydroxyethyl methacrylate and 0.031 parts of 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane were uniformly dispersed in 5 parts of white oil at room temperature and introduced into the liquid feeding port of a LABTECH co-rotating twin-screw extruder (screw diameter 16 mm, length-diameter ratio 40); at the same time, 89 parts of dried polycarbonate (PC, 300 °C, melt index 19.8 g / 10 min at 1.2 kg, number-average molecular weight 25,200 g / mol, weight-average molecular weight 43,700 g / mol) and 1 part of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] were mixed evenly and introduced into the pellet feeding port of the co-rotating twin-screw extruder. Under the process conditions of 280 °C and 250 rpm, they were melt-reacted and co-extruded, cooled, and pelletized to obtain the modified polycarbonate material D. Its properties are shown in Table 1.

[0098]

Example 5

[0099] The polycarbonate used in Example 5 is bisphenol A aromatic polycarbonate.

[0100] Preparation of modified polycarbonate material: 11 parts of 2-hydroxyethyl methacrylate and 0.082 parts of 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane were uniformly dispersed in 5 parts of white oil at room temperature and introduced into the liquid feeding port of a LABTECH co-rotating twin-screw extruder (screw diameter 16 mm, length-diameter ratio 40); meanwhile, 89 parts of dried polycarbonate (PC, melt index 19.8 g / 10 min at 300 °C, number-average molecular weight 25,200 g / mol, weight-average molecular weight 43,700 g / mol) and 1 part of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] were mixed evenly and introduced into the pellet feeding port of the co-rotating twin-screw extruder. Under the process conditions of 280 °C and 250 rpm, they were melt-reacted and co-extruded, cooled and pelletized to obtain the modified polycarbonate material E. Its properties are shown in Table 1.

[0101]

Example 6

[0102] The polycarbonate used in Example 6 was a bisphenol A type aromatic polycarbonate.

[0103] Preparation of modified polycarbonate material: 7 parts of 2-hydroxyethyl methacrylate, 0.020 parts of 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane and 0.015 parts of dicarbonate peroxide were uniformly dispersed in 5 parts of white oil at room temperature and introduced into the liquid feeding port of a LABTECH co-rotating twin-screw extruder (screw diameter 16 mm, length-diameter ratio 40); meanwhile, 93 parts of dried polycarbonate (PC, melt index 19.8 g / 10 min at 300 °C, number-average molecular weight 25,200 g / mol, weight-average molecular weight 43,700 g / mol) and 1 part of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] were mixed evenly and introduced into the pellet feeding port of the co-rotating twin-screw extruder. Under the process conditions of 280 °C and 250 rpm, they were melt-reacted and co-extruded, cooled and pelletized to obtain the modified polycarbonate material F. Its properties are shown in Table 1.

[0104]

Example 7

[0105] The polycarbonate used in Example 7 was a bisphenol A type aromatic polycarbonate.

[0106] Preparation of modified polycarbonate material: 5 parts of dimethyl maleate and 0.02 part of 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane were uniformly dispersed in 5 parts of white oil at room temperature and introduced into the liquid feeding port of a LABTECH co-rotating twin-screw extruder (screw diameter 16 mm, length-diameter ratio 40); meanwhile, 95 parts of dried polycarbonate (PC, melting index at 300 °C, 1.2 kg is 19.8 g / 10 min, number-average molecular weight 25,200 g / mol, weight-average molecular weight 43,700 g / mol) and 1 part of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] were mixed evenly and introduced into the pellet feeding port of the co-rotating twin-screw extruder. Under the process conditions of 280 °C and 250 rpm, they were melt-reacted and co-extruded, cooled and pelletized to obtain the modified polycarbonate material G. Its properties are shown in Table 1.

[0107]

Example 8

[0108] The polycarbonate used in Example 8 was a bisphenol A type aromatic polycarbonate.

[0109] Preparation of modified polycarbonate material: 5 parts of dimethyl maleate, 2 parts of 3-methacryloxypropyltriethoxysilane and 0.028 part of 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane were uniformly dispersed in 5 parts of white oil at room temperature and introduced into the liquid feeding port of a LABTECH co-rotating twin-screw extruder (screw diameter 16 mm, length-diameter ratio 40); meanwhile, 93 parts of dried polycarbonate (PC, melting index at 300 °C, 1.2 kg is 19.8 g / 10 min, number-average molecular weight 25,200 g / mol, weight-average molecular weight 43,700 g / mol) and 1 part of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] were mixed evenly and introduced into the pellet feeding port of the co-rotating twin-screw extruder. Under the process conditions of 280 °C and 250 rpm, they were melt-reacted and co-extruded, cooled and pelletized to obtain the modified polycarbonate material H. Its properties are shown in Table 1.

[0110]

Example 9

[0111] The polycarbonate used in Example 9 was a bisphenol A type aromatic polycarbonate.

[0112] Preparation of modified polycarbonate material: 1 part of bis(trimethylsilylpropyl) maleate and 0.05 part of 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane were uniformly dispersed in 5 parts of white oil at room temperature and introduced into the liquid feeding port of a LABTECH co-rotating twin-screw extruder (screw diameter 16 mm, length-diameter ratio 40); meanwhile, 99 parts of dried polycarbonate (PC, melting index 30 g / 10 min at 300 °C, number-average molecular weight 11000 g / mol, weight-average molecular weight 19500 g / mol) and 1 part of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] were mixed evenly and introduced into the pellet feeding port of the co-rotating twin-screw extruder. Under the process conditions of 250 °C and 350 rpm, they were melt-reacted and co-extruded, cooled and pelletized to obtain the modified polycarbonate material.

[0113] It was found by GPC detection that: after in-situ reaction treatment, the molecular weight of polycarbonate changed, indicating that the chain-changing effect occurred.

[0114]

Example 10

[0115] The polycarbonate used in Example 10 was bisphenol A type aromatic polycarbonate.

[0116] Preparation of modified polycarbonate material: 10 parts of n-butyl acrylate, 3 parts of 3-methacryloxypropyltrimethylsilane and 0.435 part of 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane were uniformly dispersed in 20 parts of white oil at room temperature and introduced into the liquid feeding port of a LABTECH co-rotating twin-screw extruder (screw diameter 16 mm, length-diameter ratio 40); meanwhile, 87 parts of dried polycarbonate (PC, melting index 2.8 g / 10 min at 300 °C, number-average molecular weight 45600 g / mol, weight-average molecular weight 79800 g / mol) and 1 part of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] were mixed evenly and introduced into the pellet feeding port of the co-rotating twin-screw extruder. Under the process conditions of 300 °C and 200 rpm, they were melt-reacted and co-extruded, cooled and pelletized to obtain the modified polycarbonate material.

[0117] It was found by GPC detection that: after in-situ reaction treatment, the molecular weight of polycarbonate changed, indicating that the chain-changing effect occurred.

[0118]

Comparative Example 1

[0119] The polycarbonate raw material used was the same as that in Example 5.

[0120] Preparation of modified polycarbonate material: 11 parts of 2-hydroxyethyl methacrylate were uniformly dispersed in 5 parts of white oil at room temperature and introduced into the liquid feeding port of a LABTECH co-rotating twin-screw extruder (screw diameter 16 mm, length-diameter ratio 40); meanwhile, 89 parts of dried polycarbonate (PC, melting index 19.8 g / 10 min at 300 °C, number-average molecular weight 25,200 g / mol, weight-average molecular weight 43,700 g / mol) and 1 part of pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] were mixed evenly and introduced into the pellet feeding port of the co-rotating twin-screw extruder. Under the process conditions of 280 °C and 250 rpm, they were melt-reacted and co-extruded, cooled and pelletized to obtain modified polycarbonate material a. Its properties are shown in Table 1.

[0121]

Comparative Example 2

[0122] The polycarbonate raw material used was the same as that in Example 6.

[0123] Preparation of modified polycarbonate material: 0.02 parts of 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane were uniformly dispersed in 5 parts of white oil at room temperature and introduced into the liquid feeding port of a LABTECH co-rotating twin-screw extruder (screw diameter 16 mm, length-diameter ratio 40); meanwhile, 100 parts of dried polycarbonate (PC, melting index 19.8 g / 10 min at 300 °C, number-average molecular weight 25,200 g / mol, weight-average molecular weight 43,700 g / mol) and 1 part of pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] were mixed evenly and introduced into the pellet feeding port of the co-rotating twin-screw extruder. Under the process conditions of 280 °C and 250 rpm, they were melt-reacted and co-extruded, cooled and pelletized to obtain modified polycarbonate material b. Its properties are shown in Table 1.

[0124]

Comparative Example 3

[0125] The polycarbonate raw material used was the same as that in Example 8.

[0126] Preparation of modified polycarbonate material: 2 parts of 3-methacryloxypropyltriethoxysilane were uniformly dispersed in 5 parts of white oil at room temperature and introduced into the liquid feeding port of a LABTECH co-rotating twin-screw extruder (screw diameter 16 mm, length-diameter ratio 40); meanwhile, 98 parts of dried polycarbonate (PC, melting index 19.8 g / 10 min at 300 °C, number-average molecular weight 25,200 g / mol, weight-average molecular weight 43,700 g / mol) and 1 part of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] were mixed evenly and introduced into the pellet feeding port of the co-rotating twin-screw extruder. Under the process conditions of 280 °C and 250 rpm, they were melt-reacted and co-extruded, cooled and pelletized to obtain the modified polycarbonate material c. Its properties are shown in Table 1.

[0127]

Comparative Example 4

[0128] The amounts of each raw material were the same as in Example 6, with the difference that:

[0129] 7 parts of 2-hydroxyethyl methacrylate, 0.020 parts of 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, and 0.015 parts of peroxydicarbonate were uniformly dispersed in 5 parts of white oil at room temperature and reacted at 160 °C for 5 h to obtain a reaction product.

[0130] The obtained reaction product was introduced into the liquid feeding port of a LABTECH co-rotating twin-screw extruder (screw diameter 16 mm, length-diameter ratio 40); meanwhile, 93 parts of dried polycarbonate (PC, melting index 19.8 g / 10 min at 300 °C, number-average molecular weight 25,200 g / mol, weight-average molecular weight 43,700 g / mol) and 1 part of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] were mixed evenly and introduced into the pellet feeding port of the co-rotating twin-screw extruder. Under the process conditions of 280 °C and 250 rpm, they were melt co-extruded, cooled and pelletized to obtain the modified polycarbonate material d. Its properties are shown in Table 1.

[0131] Table 1:

[0132]

[0133] It can be seen from Table 1 that:

[0134] Comparing Examples 1 to 6 with Comparative Example 1, with the change in the content of 2-hydroxyethyl methacrylate, after melt reaction and extrusion, the molecular weight level of polycarbonate can be effectively regulated, and by changing the amount of initiator used, the molecular weight level of the modified polycarbonate material can also be controlled.

[0135] Comparing Examples 7 - 8 with Comparative Examples 2 - 3, by using peroxide initiators or combinations with different thermal decomposition temperatures and half - lives, differential product molecular weight levels can also be obtained.

[0136] Comparing PC’ with Comparative Example 4, it was found that the molecular weight of the polycarbonate in Comparative Example 4 hardly changed, indicating that no in - situ reaction occurred in Comparative Example 4.

[0137] This shows that the melt reaction co - extrusion process proposed in the present invention can effectively achieve the molecular weight level and molecular chain structure of polycarbonate materials, thus providing a basis for their subsequent applications.

[0138]

Example 11

[0139] Application of the modified polycarbonate material: 80 parts of the modified polycarbonate material F prepared in Example 6, 20 parts of high - rubber powder (butadiene content 56%, acrylonitrile content 18%, styrene content 26%), 1 part of pentaerythritol tetrakis [β - (3,5 - di - tert - butyl - 4 - hydroxyphenyl) propionate], and 2 parts of white oil were mixed evenly and introduced into the pellet feeding port of a LABTECH co - rotating twin - screw extruder (screw diameter 16 mm, length - to - diameter ratio 40). Under the process conditions of 280 °C and 250 rpm, through melting, extrusion, cooling, and pelletizing, PC / ABS composite material I was prepared. Its properties are shown in Table 2.

[0140]

Example 12

[0141] Application of the modified polycarbonate material: 64 parts of the modified polycarbonate material F prepared in Example 6, 16 parts of high - rubber powder (butadiene content 56%, acrylonitrile content 18%, styrene content 26%), 1 part of pentaerythritol tetrakis [β - (3,5 - di - tert - butyl - 4 - hydroxyphenyl) propionate], and 2 parts of white oil were mixed evenly and introduced into the pellet feeding port of a LABTECH co - rotating twin - screw extruder (screw diameter 16 mm, length - to - diameter ratio 40). 20 parts of long glass fibers (diameter 13 μm, 1200 tex) were introduced into the middle section of the extruder. Under the process conditions of 280 °C and 250 rpm, through melting, extrusion, cooling, and pelletizing, PC / ABS / GF composite material J was prepared. Its properties are shown in Table 2.

[0142]

Example 13

[0143] Application of the modified polycarbonate material: 80 parts of the modified polycarbonate material H prepared in Example 8, 15 parts of styrene / maleic anhydride random copolymer (SMA, maleic anhydride content 22%, styrene content 78%), 5 parts of laser laser additive (tin content 18%, antimony content 12%, titanium content 8%, the rest is oxygen element), 1 part of pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and 2 parts of white oil are mixed evenly and introduced into the pellet feeding port of a LABTECH co-rotating twin-screw extruder (screw diameter 16 mm, length-diameter ratio 40). Under the process conditions of 280 °C and 250 rpm, through melting, extrusion, cooling, and pelletizing, PC / SMA LDS composite material K is obtained.

[0144] Laser activation: The composite material K is subjected to laser activation treatment using a HAIYI LASER fiber laser. The laser output power is 20 watts, the laser wavelength is 1064 nm, the laser speed is 3000 mm / s, and the pulse frequency is 25 kHz to obtain a laser etching block.

[0145] Electroless copper plating: The surface of the composite material K after laser activation treatment is purged with compressed air and ultrasonically cleaned. The surface of the composite material K is subjected to electroless copper plating using the MacDermid Enthone electroless plating process, and the plating time is 30 min. Its performance is shown in Table 2.

[0146]

Example 14

[0147] Application of the modified polycarbonate material: 55 parts of the modified polycarbonate material H prepared in Example 8, 15 parts of styrene / maleic anhydride random copolymer (SMA, maleic anhydride content 22%, styrene content 78%), 5 parts of laser laser additive (tin content 18%, antimony content 12%, titanium content 8%, the rest is oxygen element), 1 part of pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and 2 parts of white oil are mixed evenly and introduced into the pellet feeding port of a LABTECH co-rotating twin-screw extruder (screw diameter 16 mm, length-diameter ratio 40). 25 parts of long glass fibers (diameter 13 μm, 1200 tex) are introduced into the middle section of the extruder. Under the process conditions of 280 °C and 250 rpm, through melting, extrusion, cooling, and pelletizing, PC / SMA / GF LDS composite material L is obtained.

[0148] Laser activation: The composite material L is subjected to laser activation treatment using a HAIYI LASER fiber laser. The laser output power is 20 watts, the laser wavelength is 1064 nm, the laser speed is 3000 mm / s, and the pulse frequency is 25 kHz to obtain a laser etching block.

[0149] Electroless copper plating: After the surface of the composite material L treated by laser activation is purged with compressed air and ultrasonically cleaned, electroless copper plating is carried out on the surface of the composite material L by using the MacDermid Enthone electroless plating process, and the plating time is 30 min. Its performance is shown in Table 2.

[0150]

Example 15

[0151] Application of the modified polycarbonate material: 100 parts of the modified polycarbonate material prepared in Example 9, 15 - 35 parts of aramid fiber, 0.5 - 1.2 parts of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and 2 - 10 parts of white oil are mixed evenly, and then introduced into the pellet feeding port of a LABTECH co-rotating twin-screw extruder (screw diameter 16 mm, length-diameter ratio 40). Under the process conditions of 275 - 300 °C and 220 - 320 rpm, through melting, extrusion, cooling, and pelletizing, a PC / aramid fiber composite material is prepared.

[0152]

Example 16

[0153] Application of the modified polycarbonate material: 100 parts of the modified polycarbonate material prepared in Example 10, 10 - 40 parts of polyethylene terephthalate, 0.2 - 1 part of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and 4 - 9 parts of white oil are mixed evenly, and then introduced into the pellet feeding port of a LABTECH co-rotating twin-screw extruder (screw diameter 16 mm, length-diameter ratio 40). Under the process conditions of 245 - 275 °C and 150 - 250 rpm, through melting, extrusion, cooling, and pelletizing, a PC / PET composite material is prepared.

[0154]

Comparative Example 5

[0155] 80 parts of dried polycarbonate (PC, melting index 19.8 g / 10 min at 300 °C, number average molecular weight 25200 g / mol, weight average molecular weight 43700 g / mol), 20 parts of high rubber powder (butadiene content 56%, acrylonitrile content 18%, styrene content 26%), 1 part of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and 2 parts of white oil are mixed evenly, and then introduced into the pellet feeding port of a LABTECH co-rotating twin-screw extruder (screw diameter 16 mm, length-diameter ratio 40). Under the process conditions of 280 °C and 250 rpm, through melting, extrusion, cooling, and pelletizing, a PC / ABS composite material e is prepared. Its performance is shown in Table 2.

[0156]

Comparative Example 6

[0157] 64 parts of dried polycarbonate (PC, 300 °C, melt index of 19.8 g / 10 min at 1.2 kg, number-average molecular weight of 25,200 g / mol, weight-average molecular weight of 43,700 g / mol), 16 parts of high rubber powder (butadiene content of 56%, acrylonitrile content of 18%, styrene content of 26%), 1 part of pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and 2 parts of white oil were mixed evenly and introduced into the pellet feeding port of a LABTECH co-rotating twin-screw extruder (screw diameter of 16 mm, length-diameter ratio of 40). 20 parts of long glass fibers (diameter of 13 μm, 1200 tex) were introduced into the middle section of the extruder. Under the process conditions of 280 °C and 250 rpm, through melting, extrusion, cooling, and pelletizing, a PC / ABS / GF composite material f was obtained. Its properties are shown in Table 2.

[0158]

Comparative Example 7

[0159] 80 parts of dried polycarbonate (PC, 300 °C, melt index of 19.8 g / 10 min at 1.2 kg, number-average molecular weight of 25,200 g / mol, weight-average molecular weight of 43,700 g / mol), 15 parts of styrene / maleic anhydride random copolymer (SMA, maleic anhydride content of 22%, styrene content of 78%), 5 parts of laser ablation additive (tin content of 18%, antimony content of 12%, titanium content of 8%, the rest is oxygen element), 1 part of pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and 2 parts of white oil were mixed evenly and introduced into the pellet feeding port of a LABTECH co-rotating twin-screw extruder (screw diameter of 16 mm, length-diameter ratio of 40). Under the process conditions of 280 °C and 250 rpm, through melting, extrusion, cooling, and pelletizing, a PC / SMA LDS composite material g was obtained.

[0160] Laser activation: The composite material g was subjected to laser activation treatment using a HAIYI LASER fiber laser. The laser output power was 20 watts, the laser wavelength was 1064 nm, the laser ablation speed was 3000 mm / s, and the pulse frequency was 25 kHz to obtain a laser etching block.

[0161] Electroless copper plating: The surface of the composite material g after laser activation treatment was purged with compressed air and ultrasonically cleaned. The surface of the composite material g was subjected to electroless copper plating using the MacDermid Enthone electroless plating process, and the plating time was 30 min. Its properties are shown in Table 2.

[0162]

Comparative Example 8

[0163] 55 parts of dried polycarbonate (PC, melt index of 19.8 g / 10 min at 300 °C, number-average molecular weight of 25,200 g / mol, weight-average molecular weight of 43,700 g / mol), 15 parts of styrene / maleic anhydride random copolymer (SMA, maleic anhydride content of 22%, styrene content of 78%), 5 parts of laser laser assistant (tin content of 18%, antimony content of 12%, titanium content of 8%, the rest is oxygen element), 1 part of pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and 2 parts of white oil are mixed evenly and introduced into the pellet feeding port of a LABTECH co-rotating twin-screw extruder (screw diameter of 16 mm, length-diameter ratio of 40). 25 parts of long glass fibers (diameter of 13 μm, 1200 tex) are introduced into the middle section of the extruder. Under the process conditions of 280 °C and 250 rpm, it is melted, extruded, cooled, and pelletized to obtain the PC / SMA / GF LDS composite material h.

[0164] Laser activation: The composite material h is subjected to laser activation treatment using a HAIYI LASER fiber laser. The laser output power is 20 watts, the laser wavelength is 1064 nm, the laser speed is 3000 mm / s, and the pulse frequency is 25 kHz to obtain a laser etching block.

[0165] Electroless copper plating: The surface of the composite material h after laser activation treatment is purged with compressed air and ultrasonically cleaned. The electroless copper plating process of MacDermid Enthone is used to carry out electroless copper plating on the surface of the composite material h, and the plating time is 30 min. Its performance is shown in Table 2.

[0166]

Comparative Example 9

[0167] Application of the modified polycarbonate material: 80 parts of the modified polycarbonate material d prepared in Comparative Example 4, 20 parts of high rubber powder (butadiene content of 56%, acrylonitrile content of 18%, styrene content of 26%), 1 part of pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and 2 parts of white oil are mixed evenly and introduced into the pellet feeding port of a LABTECH co-rotating twin-screw extruder (screw diameter of 16 mm, length-diameter ratio of 40). Under the process conditions of 280 °C and 250 rpm, it is melted, extruded, cooled, and pelletized to obtain the PC / ABS composite material i. Its performance is shown in Table 2.

[0168] Table 2:

[0169]

[0170] It can be seen from Table 2 that:

[0171] Comparing Example 9 with Comparative Example 4 and Comparative Example 9, Example 10 with Comparative Example 5, Example 11 with Comparative Example 6, and Example 12 with Comparative Example 7, the modified polycarbonate material containing silane, carboxyl or ester groups can improve its compatibility with other organic polymers such as high rubber content ABS powder and SMA resin, etc., and can improve the wetting of glass fiber and inorganic additives in the matrix material, thereby improving the adhesion between the modified polycarbonate material and the inorganic material. At the same time, it can improve the distribution of the laser ablation additive inside and on the surface of the modified composite material and improve the adhesion of the coating structure.

Claims

1. A modified polycarbonate, which comprises the following components and / or their reaction products: (1) a polycarbonate matrix, (2) an acrylate monomer, and (3) an initiator; based on 100 parts by weight of the polycarbonate matrix, the weight of the acrylate monomer is 0.5 to 20 parts, and the weight of the initiator is 0.01 to 1 part; the polycarbonate matrix is a bisphenol A type aromatic polycarbonate; the preparation method of the modified polycarbonate comprises: Melting and blending the raw materials including the polycarbonate matrix, the acrylate monomer and the initiator to obtain the modified polycarbonate; The acrylate monomer is selected from at least one of the acrylate monomers represented by formula (III) to formula (IV): Formula (III) Formula (IV) Among them, in Formula (III) to Formula (IV), R 9 , R 10 , R 11 , R 24 , R 25 are each independently selected from hydrogen, an alkyl group having C 1 to C 30 , or an aryl group having C 6 to C 40 , R 12 , R 22 , R 23 are each independently selected from an alkylene group having C 1 to C 30 , or an arylene group having C 6 to C 40 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 are each independently selected from hydrogen, an alkyl group having C 1 to C 30 , an alkoxy group having C 1 to C 30 , an aryl group having C 6 to C 40 , or an aryloxy group having C 6 to C 40 .

2. The modified polycarbonate according to claim 1, wherein, the weight-average molecular weight of the polycarbonate matrix is 5000 g / mol to 120000 g / mol; and / or the number-average molecular weight of the polycarbonate matrix is 4000 g / mol to 100000 g / mol.

3. The modified polycarbonate according to claim 1, wherein, the weight-average molecular weight of the polycarbonate matrix is 15000 g / mol to 100000 g / mol.

4. The modified polycarbonate according to claim 1, wherein, the number-average molecular weight of the polycarbonate matrix is 10000 g / mol to 80000 g / mol.

5. The modified polycarbonate according to claim 1, wherein, in formula (III) to formula (IV), R 9 、R 10 、R 11 、R 24 、R 25 each independently selected from hydrogen, an alkyl group having C 1 ~C 18 or an aryl group having C 6 ~C 24 ; and / or R 12 、R 22 、R 23 are each independently selected from C 1 to C 18 alkylene or C 6 to C 24 arylene; and / or R 13 、R 14 、R 15 、R 16 、R 17 、R 18 、R 19 、R 20 、R 21 each independently selected from hydrogen, C 1 ~C 18 alkyl, C 1 ~C 18 alkoxy, C 6 ~C 24 aryl, C 6 ~C 24 aryloxy.

6. The modified polycarbonate according to claim 1, wherein, the acrylate monomer represented by formula (III) is selected from at least one of 3-methacryloxypropyltrimethylsilane, 3-methacryloxypropyltriethylsilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, and methacrylic acid trimethylsiloxy polyethoxy ester; and / or the acrylate monomer represented by formula (IV) is selected from at least one of bis(trimethylsilylpropyl) maleate, bis(triethylsilylpropyl) maleate, bis(trimethoxysilylpropyl) maleate, bis(triethoxysilylpropyl) maleate, and bis(trimethylsiloxy polyethoxy) maleate.

7. The modified polycarbonate according to claim 1, wherein, the initiator is selected from at least one of alkyl peroxides, alkyl hydroperoxides, diperoxyesters, peroxyacids, and diacyl peroxides.

8. The modified polycarbonate according to claim 7, wherein, The alkyl peroxide is selected from at least one of dicumyl peroxide, di-tert-butyl peroxide, di-tert-amyl peroxide, 2,2-di(tert-butylperoxide)butane, 1,1-di(tert-butylperoxide)cyclohexane, 1,1-di(tert-butylperoxide)-3,3,5-trimethylcyclohexane, 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxynonane, 2,5-dimethyl-2,5-bis(tert-butylperoxide)hexane, and 2,5-dimethyl-2,5-bis(tert-butylperoxide)hexyne-3; and / or The alkyl hydroperoxide is at least one selected from cumene hydroperoxide, tert-butyl hydroperoxide, tert-amyl hydroperoxide, and 2,5-dimethyl-2,5-bis(hydroperoxide)hexane; and / or The peroxy diester is at least one selected from peroxy dicarbonate, ditetradecyl peroxy dicarbonate, dihexadecyl peroxy dicarbonate, bis(2-ethylhexyl) peroxy dicarbonate, bis(4-tert-butylcyclohexyl) peroxy dicarbonate, and 2,5-dimethyl-2,5-bis(2-ethylhexanoic acid peroxy)hexane; and / or The peroxy acid ester is selected from at least one of tert-butyl peroxy-2-ethylhexyl carbonate, tert-amyl peroxy-2-ethylhexyl carbonate, tert-butyl peroxy acetate, tert-butyl peroxy isobutyrate, tert-butyl peroxy tert-valerate, tert-butyl peroxy pivalate, tert-amyl peroxy pivalate, tert-butyl peroxy neodecanoate, tert-amyl peroxy neodecanoate, tert-butyl peroxy 3,5,5-trimethylhexanoate, tert-butyl peroxy 2-ethylhexanoate, tert-amyl peroxy 2-ethylhexanoate, tert-butyl peroxy maleate, tert-butyl peroxy benzoate, and tert-amyl peroxy benzoate; and / or The diacyl peroxide is selected from at least one of dibenzoyl peroxide, di(3,5,5-trimethylhexanoyl) peroxide, and dilauroyl peroxide.

9. The modified polycarbonate according to claim 8, It is characterized in that The initiator is selected from at least one of 1,1-di(tert-butylperoxy)cyclohexane, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, bis(2-ethylhexyl)peroxydicarbonate, and tert-butyl peroxy-3,5,5-trimethylhexanoate.

10. The modified polycarbonate according to any one of claims 1 to 9, It is characterized in that Based on 100 parts by weight of the polycarbonate matrix, the weight of the acrylate monomer is 1 to 15 parts; and / or Based on 100 parts by weight of the polycarbonate matrix, the weight of the initiator is 0.05 to 0.5 parts.

11. The modified polycarbonate according to claim 10, It is characterized in that The modified polycarbonate may further include an auxiliary agent.

12. The modified polycarbonate according to claim 11, It is characterized in that The auxiliary agent is selected from at least one of a plasticizer, a heat stabilizer, an antioxidant, a UV absorber, and a release agent.

13. A method for preparing the modified polycarbonate according to any one of claims 1 to 12, include: The raw materials including the polycarbonate matrix, the acrylate monomer and the initiator are melt-blended to obtain the modified polycarbonate.

14. The preparation method according to claim 13, wherein, the raw materials optionally further include additives.

15. The preparation method according to claim 14, wherein, the additives are selected from at least one of plasticizers, heat stabilizers, antioxidants, UV absorbers, and mold release agents.

16. The preparation method according to any one of claims 13 to 15, wherein, the temperature of the melt-blending is 200 - 360 °C.

17. The preparation method according to claim 16, wherein, the temperature of the melt-blending is 250 - 300 °C.

18. The preparation method according to claim 16, wherein, the melt-blending is carried out in a screw extruder.

19. The preparation method according to claim 18, wherein, the screw rotation speed is 50 - 350 rpm.

20. The preparation method according to claim 18, wherein, the screw rotation speed is 100 - 300 rpm.

21. The preparation method according to claim 16, wherein, the preparation method includes the following steps: Step 1, dispersing the acrylate monomer and the initiator in a dispersing oil agent to form Material 1; Step 2, mixing the polycarbonate matrix and optionally the additives to form Material 2; Step 3, respectively introducing Material 1 and Material 2 into a screw extruder, and performing melt-blending and extrusion to obtain the modified polycarbonate.

22. The preparation method according to claim 21, wherein, the dispersing oil agent is selected from at least one of paraffin, mineral oil, and silicone oil.

23. The preparation method according to claim 22, wherein, the dispersing oil agent is selected from white oil.

24. A composite material, which contains at least one of polyethylene, polypropylene, polyoxymethylene, polymethyl methacrylate, polystyrene, methyl methacrylate / butadiene / styrene copolymer, acrylonitrile / butadiene / styrene copolymer, acrylonitrile / acrylate / styrene copolymer, acrylonitrile / styrene copolymer, styrene / maleic anhydride random copolymer, acrylonitrile / styrene / maleic anhydride random copolymer, polyethylene terephthalate, polybutylene terephthalate, polybutylene succinate, polybutylene adipate, polybutylene succinate / polybutylene terephthalate, polybutylene adipate / polybutylene terephthalate, glass fiber, carbon fiber, aramid fiber, graphene, and carbon nanotube, and the modified polycarbonate according to any one of claims 1 to 12 or the modified polycarbonate obtained by the preparation method according to any one of claims 13 to 23.

25. The application of the modified polycarbonate according to any one of claims 1 to 12 or the composite material according to claim 24 in the fields of optics, communication, electronics, automotive, medical, and aerospace.

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