CN113880995A - Modified polycarbonate and preparation method and application thereof - Google Patents

Modified polycarbonate and preparation method and application thereof Download PDF

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CN113880995A
CN113880995A CN202010619862.8A CN202010619862A CN113880995A CN 113880995 A CN113880995 A CN 113880995A CN 202010619862 A CN202010619862 A CN 202010619862A CN 113880995 A CN113880995 A CN 113880995A
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polycarbonate
tert
bis
butyl
modified polycarbonate
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于志省
白瑜
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/02—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils

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Abstract

The invention discloses a modified polycarbonate and a preparation method and application thereof, wherein the modified polycarbonate comprises the following components and/or reaction products thereof: polycarbonate matrix, olefine acid (ester) monomer and initiator. The polycarbonate substrate is at least one selected from aliphatic polycarbonate, alicyclic polycarbonate, aromatic polycarbonate, aliphatic-aromatic copolycarbonate and polyester-polycarbonate copolymer, and the acrylic acid (ester) monomer is a compound containing a-C (O) -group in the structure. The olefine acid (ester) monomer is introduced into the polycarbonate matrix, so that the interaction of the modified polycarbonate material and other polymer materials during compounding can be promoted, the wettability of an inorganic material in the polycarbonate and the compatibility of two-phase interfaces are improved, the interface bonding strength and the mechanical property of a multi-component composite system are improved, and the compatibility is obviously improved.

Description

Modified polycarbonate and preparation method and application thereof
Technical Field
The invention belongs to the field of polycarbonate, and particularly relates to modified polycarbonate, and a preparation method and application thereof.
Background
Polycarbonate is a polymer containing a carbonate group in its molecular chain, and can be considered as a polycondensation product of a dihydroxy compound and carbonic acid, and can be classified into aliphatic, alicyclic, aromatic, aliphatic-aromatic and the like types. The bisphenol A polycarbonate has outstanding impact toughness, excellent insulativity, large use temperature range and stable product size, and is an engineering plastic with better comprehensive performance.
However, polycarbonate has some defects, such as easy stress cracking, notch sensitivity, poor wear resistance, poor processing fluidity and the like; in addition, when the modified polymer is blended with an inorganic material or an organic polymer material, the interfacial strength is weak and the compatibility is poor. In this regard, there has been a great deal of work in the academic and industrial world on the physical/chemical modification of polycarbonates.
The physical blending modification of polycarbonate is a main and convenient modification method. Polymer-based modified substances employed include polystyrene, ABS, polyolefin, polyester, polyamide, polyacrylate, fluororesin, polysiloxane, polyurethane, and the like (CN110499010A, CN108164984A, CN110256829A, WO 0320827A); the inorganic modifying substances include minerals, silica, mica, glass fiber, carbon fiber, graphite, graphene, etc. (CN104341754A, CN107312307A, CN 107915974A). In most cases, an interface compatilizer is required to be added to improve the interface bonding performance of the composite system (CN105778464A, CN111087778A and CN109575552A), otherwise, problems such as spots, flaws, delamination, phase separation, peeling and the like are easily caused.
In addition, the chemical modification of the polycarbonate molecular chain is also well developed, and the method comprises copolymerization modification and polymer post-modification. CN110776640A reports a method for preparing a polycarbonate polyorganosiloxane copolymer by copolymerization of a terminal phenol polysiloxane and bisphenol a, which is characterized in that a terminal phenol polysiloxane compound with low content of free phenol is prepared by a complicated chemical method. CN110776631A discloses a copolycarbonate obtained by copolymerization of 3 a-methyl octahydro pentene-2, 5-diol prepared from raw materials such as citric acid and concentrated sulfuric acid with aliphatic diol and dibutyl carbonate. CN110256636A discloses a post-modification method of aliphatic polycarbonate, which adopts TEMPO functionalization technology to introduce grafted polystyrene chains to the polycarbonate, expanding the chemical/biological properties of the aliphatic polycarbonate.
Disclosure of Invention
In order to overcome the problem of poor compatibility when polycarbonate is blended and modified with organic/inorganic materials in the prior art, the invention provides modified polycarbonate which can be obviously improved in interface strength and interface compatibility when being blended with other polymer materials and/or inorganic materials and can be used in the fields of optics, communication, electronics, automobiles, medical treatment, aerospace and the like.
One of the objects of the present invention is to provide a modified polycarbonate comprising the following components and/or reaction products thereof: (1) polycarbonate matrix, (2) olefine acid (ester) monomer, and (3) initiator.
In a preferred embodiment, the polycarbonate substrate is at least one selected from the group consisting of aliphatic polycarbonate, alicyclic polycarbonate, aromatic polycarbonate, aliphatic-aromatic copolycarbonate, and polyester-polycarbonate copolymer, and is preferably aromatic polycarbonate.
The polycarbonate in the polyester-polycarbonate copolymer may be at least one of aliphatic polycarbonate, alicyclic polycarbonate, aromatic polycarbonate, and aliphatic-aromatic copolycarbonate.
In a preferred embodiment, the aromatic polycarbonate is an aromatic polycarbonate obtained by polymerizing a diphenolic compound or a polyphenol compound with a carbonate precursor, and is preferably a linear aromatic polycarbonate obtained by polymerizing a diphenolic compound with a carbonate precursor.
In a preferred embodiment, the aliphatic polycarbonate is an aliphatic polycarbonate obtained by polymerizing an aliphatic diol or an aliphatic polyol with a carbonate precursor, and is preferably a linear aromatic polycarbonate obtained by polymerizing an aliphatic diol with a carbonate precursor.
In a preferred embodiment, the aliphatic-aromatic copolycarbonate is an aliphatic diol or aliphatic polyol, an aliphatic-aromatic copolycarbonate formed by polymerization of a diphenolic compound or a polyphenol compound with a carbonate precursor, and is preferably a linear aliphatic-aromatic copolycarbonate formed by polymerization of an aliphatic diol or a diphenolic compound with a carbonate precursor.
The polyester-polycarbonate copolymer is formed by the polymerization reaction of aliphatic diol and/or diphenol, aromatic diacid and/or aliphatic diacid and a carbonate precursor.
In a preferred embodiment, the diphenols are selected from the group consisting of aromatic diols, preferably from the group consisting of 4, 4' -dihydroxydiphenyl, 2-bis (4-hydroxyphenyl) propane, 2, 4-bis (4-hydroxyphenyl) -2-methylbutane, 2, 4-bis (3, 5-dimethyl-4-hydroxyphenyl) -2-methylbutane, 1-bis (4-hydroxyphenyl) cyclohexane, 1-bis (3, 5-dimethyl-4-hydroxyphenyl) cyclohexane, 2-bis (3-chloro-4-hydroxyphenyl) propane, 2-bis (3, 5-dichloro-4-hydroxyphenyl) propane, 2-bis (3-methyl-4-hydroxyphenyl) propane, mixtures thereof, At least one of 2, 2-bis (3, 5-dimethyl-4-hydroxyphenyl) propane, 4-bis (4-hydroxyphenyl) heptane, bis (3, 5-dimethyl-4-hydroxyphenyl) methane, 2- (3,3 ', 5, 5' -tetrachloro-4, 4 '-dihydroxydiphenyl) propane, 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-hydroxyphenyl sulfide; more preferably at least one selected from the group consisting of 4, 4' -biphenol, 2-bis (4-hydroxyphenyl) propane, 2, 4-bis (4-hydroxyphenyl) -2-methylbutane, 1-bis (4-hydroxyphenyl) cyclohexane, 2-bis (3-chloro-4-hydroxyphenyl) propane, 2-bis (3, 5-dichloro-4-hydroxyphenyl) propane, 2-bis (3-methyl-4-hydroxyphenyl) propane and 2, 2-bis (3, 5-dimethyl-4-hydroxyphenyl) propane.
In a preferred embodiment, the polyphenolic compound is 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.
Wherein the polyphenol compound contains more than 2 (not including 2) phenol groups.
In a preferred embodiment, the aliphatic diol is selected from at least one of 1, 4-cyclohexyldimethanol, 1, 3-cyclohexyldimethanol, 1, 2-ethanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol.
In a preferred embodiment, the aliphatic polyol is selected from at least one of 1,2, 3-glycerol, 1,3, 5-pentanetriol, neopentyltetraol, 1,3, 5-cyclohexyltrimethanol, 1,4, 4-cyclohexyltetramol, 1,2,3,4,5, 6-cyclohexylhexanemethanol.
Wherein the aliphatic polyol contains 2 or more (not containing 2) hydroxyl groups.
In a preferred embodiment, the aromatic diacid is selected from at least one of terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid.
In a preferred embodiment, the aliphatic diacid is selected from at least one of succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid.
In a preferred embodiment, the carbonate precursor is selected from at least one of haloformate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, phenyl cresyl carbonate, dinaphthyl carbonate, phosgene, carbonyl bromide, trichloromethyl chloroformate, bis (trichloromethyl) carbonate, and bis-haloformate.
In a preferred embodiment, the weight average molecular weight of the polycarbonate matrix is from 5000g/mol to 120000g/mol, preferably from 15000g/mol to 100000g/mol, preferably from 20000g/mol to 80000g/mol, more preferably from 25000g/mol to 50000 g/mol; and/or the number average molecular weight of the polycarbonate matrix is 4000g/mol to 100000g/mol, preferably 10000g/mol to 80000g/mol, preferably 15000g/mol to 60000g/mol, more preferably 20000g/mol to 50000 g/mol.
The polycarbonate substrate according to the present invention may be selected from any of the polycarbonates disclosed in the prior art, preferably but not limited to the polycarbonates defined above.
In the preparation of the polycarbonate of the present invention, a catalyst, an acid acceptor, a molecular weight regulator are used to control the molecular weight.
Preferably, the catalyst is selected from at least one of triethylamine, tripropylamine, N-dimethylaniline, N-diethylaniline, tetraethylammonium bromide and methyltriphenylphosphonium bromide.
Preferably, the acid acceptor is selected from at least one of pyridine, triethylamine, N-dimethylaniline, alkali metal hydroxide, alkaline earth metal hydroxide, carbonate, bicarbonate and phosphate.
Preferably, the molecular weight regulator is selected from phenol and C1-C6At least one of para-phenol, para-halophenol, dimethylamine, methylethylamine, diethylamine, dipropylamine, dibutylamine and dihexylamine.
The preparation method and the preparation conditions of the polycarbonate disclosed by the invention can be realized by adopting the methods disclosed in the prior art.
In a preferred embodiment, the acrylic monomer is a compound having a structure containing a group of-C ═ C-C (o) -.
In a more preferred embodiment, the acrylic monomer further contains a silicon element in its structure, for example, contains a siloxy group.
In a preferred embodiment, the alkenoic acid (ester) monomer is selected from at least one of the alkenoic acid (ester) monomers of formula (I) to formula (IV):
Figure BDA0002564811250000051
wherein, in the formulae (I) to (IV),
R1、R2、R3、R7、R8、R9、R10、R11、R24、R25each independently selected from hydrogen and C1～C30Alkyl or C6～C40An aromatic hydrocarbon group of (1); and/or
R4、R5、R6Each independently selected from hydrogen and C1～C30Alkyl of (C)1～C30Alkoxy group of (C)2～C30Epoxyalkyl group of (1), C1～C30Aminoalkyl radical of (2)1～C30Hydroxyalkyl of (C)1～C30Haloalkyl or C6～C40An aromatic hydrocarbon group of (1); and/or
R12、R22、R23Each independently selected from C1～C30Alkylene or C6～C40An arylene group of (a); and/or
R13、R14、R15、R16、R17、R18、R19、R20、R21Each independently selected from hydrogen and C1～C30Alkyl of (C)1～C30Alkoxy group of (C)6～C40An aromatic hydrocarbon group of6～C40An aralkyloxy group of (2).
In a further preferred embodiment, in the formulae (I) to (IV),
R1、R2、R3、R7、R8、R9、R10、R11、R24、R25each independently selected from hydrogen and C1～C18Alkyl or C6～C24An aromatic hydrocarbon group of (1); and/or
R4、R5、R6Each independently selected from hydrogen and C1～C18Alkyl of (C)1～C18Alkoxy group of (C)2～C18Epoxyalkyl group of (1), C1～C18Aminoalkyl radical of (2)1～C18Hydroxyalkyl of (C)1～C18Haloalkyl or C6～C24An aromatic hydrocarbon group of (1); and/or
R12、R22、R23Each independently selected from C1～C18Alkylene or C6～C24An arylene group of (a); and/or
R13、R14、R15、R16、R17、R18、R19、R20、R21Each independently selected from hydrogen and C1～C18Alkyl of (C)1～C18Alkoxy group of (C)6～C24An aromatic hydrocarbon group of6～C24An aralkyloxy group of (2).
In a further preferred embodiment, the alkenoic acid (ester) monomer represented by the formula (I) is at least one selected from the group consisting of acrylic acid, methacrylic acid, n-butyl acrylate, methyl methacrylate and hydroxyethyl methacrylate; and/or the olefine acid (ester) monomer shown in the formula (II) is selected from at least one of maleic acid, dimethyl maleate, diethyl maleate and di-n-butyl maleate; and/or the olefine acid (ester) monomer shown in the formula (III) is selected from at least one of 3-methacryloxypropyltrimethylsilane, 3-methacryloxypropyltriethylsilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane and trimethylsiloxypolymethacrylate; and/or the olefine acid (ester) monomer shown in the formula (IV) is selected from at least one of maleic acid bis (trimethylsilylpropyl) ester, maleic acid bis (triethylsilylpropyl) ester, maleic acid bis (trimethoxysilylpropyl) ester, maleic acid bis (triethoxysilylpropyl) ester and maleic acid bis (trimethylsiloxypolyethoxy) ester.
In a preferred embodiment, the initiator is selected from at least one of alkyl peroxides, alkyl hydroperoxides, peroxydiesters, peroxyesters, diacyl peroxides.
In a further preferred embodiment:
the alkyl peroxide is selected from at least one of dicumyl peroxide, di-tert-butyl peroxide, di-tert-amyl peroxide, 2-di (tert-butylperoxy) butane, 1-di (tert-butylperoxy) cyclohexane, 1-di (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) 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 peroxydiester is at least one selected from peroxydicarbonate, peroxydimyristyl dicarbonate, dicetyl peroxydicarbonate, bis (2-ethylhexyl) peroxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate and 2, 5-dimethyl-2, 5-bis (2-ethylhexanoic acid peroxy) hexane; and/or
The peroxyester 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 peroxypivalate, tert-amyl peroxypivalate, 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
The diacyl peroxide is at least one selected from dibenzoyl peroxide, bis (3,5, 5-trimethylhexanoyl) peroxide and dilauroyl peroxide.
In a still further preferred embodiment, the initiator is selected from at least one of 1, 1-di (t-butylperoxy) cyclohexane, 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane, bis (2-ethylhexyl) peroxydicarbonate, t-butyl peroxy-3, 5, 5-trimethylhexanoate.
In a preferred embodiment, the weight of the olefinic acid (ester) monomer is 0.5 to 20 parts, preferably 1 to 15 parts, based on 100 parts by weight of the polycarbonate substrate.
In a preferred embodiment, the initiator is present in an amount of 0.01 to 1 part by weight, preferably 0.05 to 0.5 part by weight, based on 100 parts by weight of the polycarbonate matrix.
In a preferred embodiment, an auxiliary is optionally further included in the modified polycarbonate.
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 mold release agent.
The auxiliary agent of the present invention is selected from the auxiliary agents commonly used in the prior art, and is preferably, but not limited to, the following limitations.
Preferably, the plasticizer is selected from at least one of phthalate, glyceryl tristearate and epoxidized soybean oil; and/or the heat stabilizer is at least one selected from triphenyl phosphite, tris- (2, 6-dimethylphenyl) phosphite, trimethyl phosphate, dimethylphenyl phosphate and benzotriazole; and/or the antioxidant is selected from at least one of tris (nonylphenyl) phosphite, tris (2, 4-di-tert-butylphenyl) phosphite, pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, and 2, 6-di-tert-butyl-4-methylphenol; and/or the UV absorbent is selected from at least one of hydroxybenzodiazole, hydroxybenzotriazine, hydroxybenzophenone, benzoxazinone, nano-sized titanium dioxide and zinc oxide; and/or the release agent is at least one selected from zinc stearate, calcium stearate, barium stearate, magnesium stearate, stearyl stearate, pentaerythritol tetrastearate, paraffin, silicone oil and white oil.
Another object of the present invention is to provide a process for producing a modified polycarbonate, which comprises: and (3) carrying out melt blending on raw materials comprising the polycarbonate matrix, the olefine acid (ester) monomer and the initiator to obtain the modified polycarbonate.
In a preferred embodiment, the feedstock optionally further comprises an adjuvant.
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 mold release agent.
The auxiliary agent of the present invention is selected from conventional auxiliary agents in the prior art, and is not particularly limited.
For example, preferably, the antioxidant is selected from one or more of any of the antioxidants disclosed in the prior art, such as at least one selected from the group consisting of antioxidant 1010, antioxidant 1076, antioxidant CA, antioxidant NDP, antioxidant DLTP, antioxidant TNP, antioxidant TPP, antioxidant MB, and antioxidant 264.
The addition of the antioxidant and other additives during the processing of the polymer material is a common technical means in the art, and the antioxidant and other additives are not particularly limited in the present invention and may be selected from any one or more of those disclosed in the prior art.
In a preferred embodiment, the melt blending temperature is 200 to 360 ℃, preferably 250 to 300 ℃.
In a further preferred embodiment, the melt blending is carried out in a screw extruder; preferably, the rotation speed of the screw is 50-350 rpm, preferably 100-300 rpm.
In a preferred embodiment, the preparation method comprises the following steps:
step 1, dispersing the olefine acid (ester) monomer and an initiator in a dispersible oil agent to form a material I; preferably, the dispersible oil agent is selected from at least one of paraffin, mineral oil, white oil and silicone oil, such as white oil;
step 2, mixing the polycarbonate matrix and an optional auxiliary agent to form a material II;
and 3, respectively introducing the first material and the second material into a screw extruder, and performing melt blending extrusion to obtain the modified polycarbonate.
In a preferred embodiment, the weight of the olefinic acid (ester) monomer is 0.5 to 20 parts, preferably 1 to 15 parts, based on 100 parts by weight of the polycarbonate substrate.
In a preferred embodiment, the initiator is present in an amount of 0.01 to 1 part by weight, preferably 0.05 to 0.5 part by weight, based on 100 parts by weight of the polycarbonate matrix.
In a preferred embodiment, in step 3, the first material is introduced into the screw extruder liquid feed port and the second material is introduced into the screw extruder pellet feed port.
The third object of the present invention is to provide a composite material comprising polyethylene, polypropylene, polyoxymethylene, polymethyl methacrylate, polystyrene, methyl methacrylate/butadiene/styrene copolymer, acrylonitrile/acrylate/styrene copolymer, acrylonitrile/styrene copolymer, styrene/maleic anhydride random copolymer, acrylonitrile/styrene/maleic anhydride random copolymer, polyethylene terephthalate, polybutylene succinate, polybutylene adipate, polybutylene succinate/butylene terephthalate, glass fiber, carbon fiber, aramid fiber, polyethylene terephthalate, and polyethylene terephthalate, polyethylene terephthalate, and polyethylene terephthalate, polyethylene, Graphene, carbon nanotubes and the modified polycarbonate of the first aspect of the invention or the modified polycarbonate obtained by the preparation method of the second aspect of the invention.
Preferably, an auxiliary agent is optionally further contained in the composite material.
More preferably, the auxiliary agent is at least one selected from the group consisting of a plasticizer, a heat stabilizer, an antioxidant, a UV absorber, and a mold release agent.
The addition of the auxiliary agent during the processing of the polymer material is a technical means commonly used in the art, and the selection of the auxiliary agent in the present invention is not particularly limited, and may be any one or any several of those disclosed in the prior art.
The fourth object of the present invention is to provide the use of the modified polycarbonate of one of the objects of the present invention or the composite material of the third object of the present invention in the fields of optics, communications, electronics, automobiles, medical treatment, and aerospace.
Compared with the prior art, the invention has the following beneficial effects: in the method, the olefine acid (ester) monomer is added into a polycarbonate matrix, wherein the contained acrylate group can generate compatibilization chain extension or chain change effect with the polycarbonate matrix through chemical bonding; meanwhile, the embedded silicon-based, carboxyl, ester-based and other groups can promote the interaction of the modified polycarbonate material and other polymer (such as polyamide, polyester, ABS, organic silicon resin and the like) materials during compounding, and improve the wettability and two-phase structure interface compatibility of inorganic materials (such as glass fibers, mineral substances and the like) in the polycarbonate, so that the interface bonding strength and the mechanical property of a multi-component composite system are improved, the compatibility is obviously improved, and a better technical effect is achieved.
Drawings
FIG. 1 shows the GPC chart of the modified polycarbonate obtained in example 5.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
The raw materials used in the examples and comparative examples are disclosed in the prior art if not particularly limited, and may be, for example, directly purchased or prepared according to the preparation methods disclosed in the prior art.
And (3) testing molecular weight: tetrahydrofuran was used as a mobile phase as measured by PL-GPC gel permeation chromatography, Inc. of British PL. Melt index test: measured according to ISO 1133 using a melt index apparatus of type CEAST 50M from Intron corporation, USA, with a load of 1.2kg and a temperature of 300 ℃ or 5kg and a temperature of 220 ℃. And (3) testing the impact strength of the notch of the simply supported beam: the pendulum energy was 2.75J as determined by ISO 179 standard using a pendulum impact machine, Ceast Italy. Testing the notch impact strength of the cantilever beam: pendulum energy was 5J as measured by ASTM D256 using a pendulum impact machine, Ceast, Italy. And (3) testing the thickness of the chemical plating layer: measured according to ASTM B568(2009) using a Fischer Tropsch X-ray fluorescence coating thickness gauge, Germany. And (3) testing the grids: the adhesive force or adhesive force between the metal coating and the base material is tested according to the GB9286-98 standard, and the condition that the adhesive force or the adhesive force is more than or equal to 4B is qualified.
Polycarbonate was purchased from Mitsubishi chemical company, white oil was purchased from Xinrundcondu company, tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propanoic acid ] pentaerythritol ester was purchased from Shanghai Kai chemical company, hydroxyethyl methacrylate was purchased from national drug group company, 1-bis (tert-butylperoxy) -3,3, 5-trimethylcyclohexane was purchased from Jiangsu Qiangsheng chemical company, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane was purchased from Shandong Moore chemical company, peroxydicarbonate was purchased from Shandong Moore chemical company, dimethyl maleate was purchased from national drug group company, bis (trimethylsilylpropyl) maleate was purchased from national drug group company, n-butyl acrylate was purchased from national drug group company, 3-methacryloxypropyltriethoxysilane was purchased from national drug group company, 3-methacryloxypropyltrimethylsilane was purchased from national pharmaceutical group, high rubber powder from Korea Jinhu petrochemical company, long glass fiber from Jushi group, styrene/maleic anhydride random copolymer from Kley corporation, and laser assistant from Maide-Less corporation.
[ example 1 ]
The polycarbonate used in example 1 was a bisphenol A aromatic polycarbonate.
Determination of processing parameters for polycarbonate materials (blank experiment): 100 parts of dried polycarbonate (PC, melt index 19.8g/10min, number average molecular weight 25200g/mol, weight average molecular weight 43700g/mol), 5 parts of white oil and 1 part of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] are uniformly mixed, introduced into a feed port of a LABTECH co-rotating twin-screw extruder (screw diameter 16mm, length-diameter ratio 40) pellet, and subjected to melt extrusion, cooling and granulation at 280 ℃ and 250rpm to prepare a processed polycarbonate material (PC', melt index 18.1g/10min, number average molecular weight 21020g/mol, weight average molecular weight 43920 g/mol).
Preparation of modified polycarbonate material: uniformly dispersing 3 parts of hydroxyethyl methacrylate and 0.015 part of 1, 1-di (tert-butylperoxy) -3,3, 5-trimethylcyclohexane in 5 parts of white oil at room temperature, and introducing into a liquid feeding port of a LABTECH co-rotating twin-screw extruder (the diameter of a screw is 16mm, and the length-diameter ratio is 40); meanwhile, 97 parts of dried polycarbonate (PC, 300 ℃, 1.2kg melt index 19.8g/10min, number average molecular weight 25200g/mol, weight average molecular weight 43700g/mol) and 1 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester are uniformly mixed, introduced into a pellet feeding port of a co-rotating double-screw extruder, and subjected to melt reaction, co-extrusion, cooling and granulation under the process conditions of 280 ℃ and 250rpm to prepare the modified polycarbonate material A. The properties are shown in Table 1.
[ example 2 ]
The polycarbonate used in example 2 was a bisphenol A aromatic polycarbonate.
Preparation of modified polycarbonate material: uniformly dispersing 7 parts of hydroxyethyl methacrylate and 0.035 part of 1, 1-di (tert-butylperoxy) -3,3, 5-trimethylcyclohexane in 5 parts of white oil at room temperature, and introducing the mixture into a liquid feeding port of a LABTECH co-rotating twin-screw extruder (the diameter of a screw is 16mm, the length-diameter ratio is 40); meanwhile, 93 parts of dried polycarbonate (PC, 300 ℃, 1.2kg melt index 19.8g/10min, number average molecular weight 25200g/mol, weight average molecular weight 43700g/mol) and 1 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester are uniformly mixed, introduced into a pellet feeding port of a co-rotating double-screw extruder, and subjected to melt reaction, co-extrusion, cooling and granulation under the process conditions of 280 ℃ and 250rpm to prepare the modified polycarbonate material B. The properties are shown in Table 1.
[ example 3 ]
The polycarbonate used in example 3 was a bisphenol A aromatic polycarbonate.
Preparation of modified polycarbonate material: uniformly dispersing 11 parts of hydroxyethyl methacrylate and 0.055 part of 1, 1-di (tert-butylperoxy) -3,3, 5-trimethylcyclohexane in 5 parts of white oil at room temperature, and introducing into a liquid feeding port of a LABTECH co-rotating twin-screw extruder (the diameter of a screw is 16mm, and the length-diameter ratio is 40); meanwhile, 89 parts of dried polycarbonate (PC, 300 ℃, 1.2kg melt index 19.8g/10min, number average molecular weight 25200g/mol, weight average molecular weight 43700g/mol) and 1 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester are uniformly mixed, introduced into a pellet feeding port of a co-rotating double-screw extruder, and subjected to melt reaction, co-extrusion, cooling and granulation under the process conditions of 280 ℃ and 250rpm to prepare the modified polycarbonate material C. The properties are shown in Table 1.
[ example 4 ]
The polycarbonate used in example 4 was a bisphenol A aromatic polycarbonate.
Preparation of modified polycarbonate material: uniformly dispersing 11 parts of hydroxyethyl methacrylate and 0.031 part of 1, 1-di (tert-butylperoxy) -3,3, 5-trimethylcyclohexane in 5 parts of white oil at room temperature, and introducing into a liquid feeding port of a LABTECH co-rotating twin-screw extruder (the diameter of a screw is 16mm, and the length-diameter ratio is 40); meanwhile, 89 parts of dried polycarbonate (PC, 300 ℃, 1.2kg melt index 19.8g/10min, number average molecular weight 25200g/mol, weight average molecular weight 43700g/mol) and 1 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester are uniformly mixed, introduced into a pellet feeding port of a co-rotating twin-screw extruder, and subjected to melt reaction, co-extrusion, cooling and granulation under the process conditions of 280 ℃ and 250rpm to prepare a modified polycarbonate material D. The properties are shown in Table 1.
[ example 5 ]
The polycarbonate used in example 5 was a bisphenol A aromatic polycarbonate.
Preparation of modified polycarbonate material: uniformly dispersing 11 parts of hydroxyethyl methacrylate and 0.082 part of 1, 1-di (tert-butylperoxy) -3,3, 5-trimethylcyclohexane in 5 parts of white oil at room temperature, and introducing into a liquid feeding port of a LABTECH co-rotating twin-screw extruder (the diameter of a screw is 16mm, and the length-diameter ratio is 40); meanwhile, 89 parts of dried polycarbonate (PC, 300 ℃, 1.2kg melt index 19.8g/10min, number average molecular weight 25200g/mol, weight average molecular weight 43700g/mol) and 1 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester are uniformly mixed, introduced into a pellet feeding port of a co-rotating double-screw extruder, and subjected to melt reaction, co-extrusion, cooling and granulation under the process conditions of 280 ℃ and 250rpm to prepare the modified polycarbonate material E. The properties are shown in Table 1.
[ example 6 ]
The polycarbonate used in example 6 was a bisphenol A aromatic polycarbonate.
Preparation of modified polycarbonate material: uniformly dispersing 7 parts of hydroxyethyl methacrylate, 0.020 part of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane and 0.015 part of peroxydicarbonate in 5 parts of white oil at room temperature, and introducing the mixture into a liquid feeding port of a LABTECH co-rotating twin-screw extruder (the diameter of a screw is 16mm, and the length-diameter ratio of the screw is 40); meanwhile, 93 parts of dried polycarbonate (PC, 300 ℃, 1.2kg melt index 19.8g/10min, number average molecular weight 25200g/mol, weight average molecular weight 43700g/mol) and 1 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester are uniformly mixed, introduced into a pellet feeding port of a co-rotating twin-screw extruder, and subjected to melt reaction, co-extrusion, cooling and granulation under the process conditions of 280 ℃ and 250rpm to prepare the modified polycarbonate material F. The properties are shown in Table 1.
[ example 7 ]
The polycarbonate used in example 7 was a bisphenol A aromatic polycarbonate.
Preparation of modified polycarbonate material: uniformly dispersing 5 parts of dimethyl maleate and 0.02 part of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane in 5 parts of white oil at room temperature, and introducing into a liquid feeding port of a LABTECH co-rotating twin-screw extruder (the diameter of a screw is 16mm, the length-diameter ratio is 40); meanwhile, 95 parts of dried polycarbonate (PC, 300 ℃, 1.2kg melt index 19.8G/10min, number average molecular weight 25200G/mol, weight average molecular weight 43700G/mol) and 1 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester are uniformly mixed, introduced into a pellet feeding port of a co-rotating twin-screw extruder, and subjected to melt reaction, co-extrusion, cooling and granulation under the process conditions of 280 ℃ and 250rpm to prepare the modified polycarbonate material G. The properties are shown in Table 1.
[ example 8 ]
The polycarbonate used in example 8 was a bisphenol A aromatic polycarbonate.
Preparation of modified polycarbonate material: uniformly dispersing 5 parts of dimethyl maleate, 2 parts of 3-methacryloxypropyltriethoxysilane and 0.028 part of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane in 5 parts of white oil at room temperature, and introducing the mixture into a liquid feeding port of a LABTECH co-rotating twin-screw extruder (the diameter of a screw is 16mm, and the length-diameter ratio is 40); meanwhile, 93 parts of dried polycarbonate (PC, 300 ℃, 1.2kg melt index 19.8g/10min, number average molecular weight 25200g/mol, weight average molecular weight 43700g/mol) and 1 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester are uniformly mixed, introduced into a pellet feeding port of a co-rotating double-screw extruder, and subjected to melt reaction, co-extrusion, cooling and granulation under the process conditions of 280 ℃ and 250rpm to prepare the modified polycarbonate material H. The properties are shown in Table 1.
[ example 9 ]
The polycarbonate used in example 9 was a bisphenol A aromatic polycarbonate.
Preparation of modified polycarbonate material: uniformly dispersing 1 part of bis (trimethylsilylpropyl) maleate and 0.05 part of 1, 1-bis (tert-butylperoxy) -3,3, 5-trimethylcyclohexane in 5 parts of white oil at room temperature, and introducing the mixture into a liquid feeding port of a LABTECH co-rotating twin-screw extruder (the diameter of a screw is 16mm, and the length-diameter ratio of the screw is 40); simultaneously, 99 parts of dried polycarbonate (PC, 300 ℃, 1.2kg melt index 30g/10min, number average molecular weight 11000g/mol, weight average molecular weight 19500g/mol) and 1 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester are uniformly mixed, introduced into a granule feeding port of a co-rotating twin-screw extruder, and subjected to melt reaction co-extrusion, cooling and granulation under the process conditions of 250 ℃ and 350rpm to prepare the modified polycarbonate material.
Through GPC detection, the following results were found: after the in-situ reaction treatment, the molecular weight of the polycarbonate is changed, which indicates that the chain-changing effect is generated.
[ example 10 ]
The polycarbonate used in example 10 was a bisphenol A aromatic polycarbonate.
Preparation of modified polycarbonate material: uniformly dispersing 10 parts of n-butyl acrylate, 3 parts of 3-methacryloxypropyltrimethylsilane and 0.435 part of 1, 1-di (tert-butylperoxy) -3,3, 5-trimethylcyclohexane in 20 parts of white oil at room temperature, and introducing the white oil into a liquid feeding port of a LABTECH (screw diameter is 16mm, and length-diameter ratio is 40) co-rotating twin-screw extruder; meanwhile, 87 parts of dried polycarbonate (PC, 300 ℃, 1.2kg melt index 2.8g/10min, number average molecular weight 45600g/mol and weight average molecular weight 79800g/mol) and 1 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester are uniformly mixed, introduced into a pellet feeding port of a co-rotating twin-screw extruder, and subjected to melt reaction, co-extrusion, cooling and granulation under the process conditions of 300 ℃ and 200rpm to prepare the modified polycarbonate material.
Through GPC detection, the following results were found: after the in-situ reaction treatment, the molecular weight of the polycarbonate is changed, which indicates that the chain-changing effect is generated.
Comparative example 1
The polycarbonate starting material used was the same as in example 5.
Preparation of modified polycarbonate material: uniformly dispersing 11 parts of hydroxyethyl methacrylate in 5 parts of white oil at room temperature, and introducing into a liquid feeding port of a LABTECH co-rotating twin-screw extruder (the diameter of a screw is 16mm, and the length-diameter ratio is 40); meanwhile, 89 parts of dried polycarbonate (PC, 300 ℃, 1.2kg melt index 19.8g/10min, number average molecular weight 25200g/mol, weight average molecular weight 43700g/mol) and 1 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester are uniformly mixed, introduced into a pellet feeding port of a co-rotating twin-screw extruder, and subjected to melt reaction, co-extrusion, cooling and granulation under the process conditions of 280 ℃ and 250rpm to prepare the modified polycarbonate material a. The properties are shown in Table 1.
Comparative example 2
The polycarbonate starting material used was the same as in example 6.
Preparation of modified polycarbonate material: uniformly dispersing 0.02 part of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane in 5 parts of white oil at room temperature, and introducing into a liquid feeding port of a LABTECH co-rotating twin-screw extruder (the diameter of a screw is 16mm, and the length-diameter ratio is 40); meanwhile, 100 parts of dried polycarbonate (PC, 300 ℃, 1.2kg melt index 19.8g/10min, number average molecular weight 25200g/mol, weight average molecular weight 43700g/mol) and 1 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester are uniformly mixed, introduced into a pellet feeding port of a co-rotating twin-screw extruder, and subjected to melt reaction, co-extrusion, cooling and granulation under the process conditions of 280 ℃ and 250rpm to prepare a modified polycarbonate material b. The properties are shown in Table 1.
Comparative example 3
The polycarbonate starting material used was the same as in example 8.
Preparation of modified polycarbonate material: uniformly dispersing 2 parts of 3-methacryloxypropyltriethoxysilane in 5 parts of white oil at room temperature, and introducing into a liquid feeding port of a LABTECH co-rotating twin-screw extruder (the diameter of a screw is 16mm, the length-diameter ratio is 40); meanwhile, 98 parts of dried polycarbonate (PC, 300 ℃, 1.2kg melt index 19.8g/10min, number average molecular weight 25200g/mol, weight average molecular weight 43700g/mol) and 1 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester are uniformly mixed, introduced into a pellet feeding port of a co-rotating twin-screw extruder, and subjected to melt reaction, co-extrusion, cooling and granulation under the process conditions of 280 ℃ and 250rpm to prepare the modified polycarbonate material c. The properties are shown in Table 1.
Comparative example 4
The raw materials are used in the same amount as in example 6, except that:
uniformly dispersing 7 parts of hydroxyethyl methacrylate, 0.020 part of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane and 0.015 part of peroxydicarbonate in 5 parts of white oil at room temperature, and reacting for 5 hours at 160 ℃ to obtain a reaction product.
Introducing the obtained reaction product into a liquid feeding port of a LABTECH co-rotating double-screw extruder (the diameter of a screw is 16mm, and the length-diameter ratio is 40); meanwhile, 93 parts of dried polycarbonate (PC, 300 ℃, 1.2kg melt index 19.8g/10min, number average molecular weight 25200g/mol, weight average molecular weight 43700g/mol) and 1 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester are uniformly mixed, introduced into a pellet feeding port of a co-rotating twin-screw extruder, and subjected to melt co-extrusion, cooling and granulation under the process conditions of 280 ℃ and 250rpm to prepare a modified polycarbonate material d. The properties are shown in Table 1.
Table 1:
Figure BDA0002564811250000181
as can be seen from table 1:
in comparison with comparative example 1, the content of hydroxyethyl methacrylate is changed, and after the melt reaction extrusion, the molecular weight level of the polycarbonate can be effectively controlled, and the amount of the initiator can be changed, and the molecular weight level of the modified polycarbonate material can also be controlled.
In comparison with examples 7-8 and comparative examples 2-3, different product molecular weight levels were obtained using peroxide initiators or combinations with different thermal decomposition temperatures and half-lives.
Comparison of PC' with comparative example 4 revealed that the molecular weight of the polycarbonate in comparative example 4 was hardly changed, indicating that no in situ reaction occurred in comparative example 4.
The melt reaction coextrusion process provided by the invention can effectively realize the molecular weight level and the molecular chain structure of the polycarbonate material, thereby providing a foundation for the subsequent application of the polycarbonate material.
[ example 11 ]
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 tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 2 parts of white oil were mixed uniformly, introduced into a pellet feed port of a LABTECH co-rotating twin-screw extruder (screw diameter 16mm, length-diameter ratio 40), and subjected to melting, extrusion, cooling and granulation at 280 ℃ and 250rpm to prepare a PC/ABS composite material I. The properties are shown in Table 2.
[ example 12 ]
Application of the modified polycarbonate material: 64 parts of the modified polycarbonate material F prepared in the example 6, 16 parts of high rubber powder (the butadiene content is 56%, the acrylonitrile content is 18%, and the styrene content is 26%), 1 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 2 parts of white oil are uniformly mixed, introduced into a material feeding port of a LABTECH co-rotating twin-screw extruder (the screw diameter is 16mm and the length-diameter ratio is 40), 20 parts of long glass fiber (the diameter is 13 mu m and the length is 1200tex) is introduced into the middle section of the extruder, and under the process conditions of 280 ℃ and 250rpm, the PC/ABS/GF composite material J is prepared through melting, extrusion, cooling and granulation. The properties are shown in Table 2.
[ example 13 ]
Application of the modified polycarbonate material: the modified polycarbonate material H80 parts prepared in example 8, styrene/maleic anhydride random copolymer (SMA, maleic anhydride content 22%, styrene content 78%), laser auxiliary agent (tin content 18%, antimony content 12%, titanium content 8%, others are oxygen elements) 5 parts, tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester 1 part, white oil 2 parts were mixed uniformly, introduced into a LABTECH co-rotating twin-screw extruder (screw diameter 16mm, aspect ratio 40) pellet feed port, and subjected to melting, extrusion, cooling, and granulation at 280 ℃ and 250rpm to obtain PC/SMA LDS composite material K.
Laser activation: and (3) carrying out laser activation treatment on the composite material K by adopting an HAIYI LASER optical fiber laser, wherein the laser output power is 20W, the laser wavelength is 1064 nm, the laser speed is 3000 mm/s, and the pulse frequency is 25 kHz, so that a laser etching block is obtained.
Chemical copper plating: and (3) carrying out compressed air blowing and ultrasonic cleaning on the surface of the composite material K subjected to laser activation treatment, and carrying out chemical copper plating on the surface of the composite material K by adopting a Madmaleshi chemical plating process for 30 min. The properties are shown in Table 2.
[ example 14 ]
Application of the modified polycarbonate material: the modified polycarbonate material H55 parts prepared in example 8, styrene/maleic anhydride random copolymer (SMA, maleic anhydride content 22%, styrene content 78%), laser auxiliary agent (tin content 18%, antimony content 12%, titanium content 8%, other elements are oxygen) 5 parts, pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] 1 part, white oil 2 parts were mixed uniformly, introduced into a LABTECH co-rotating twin-screw extruder (screw diameter 16mm, length-diameter ratio 40) pellet feed port, and long glass fiber (diameter 13 μm, 1200tex)25 parts were introduced into the middle section of the extruder, and subjected to melting, extrusion, cooling, and granulation under the process conditions of 280 ℃ and 250rpm to obtain PC/SMA/GF LDS composite material L.
Laser activation: and (3) performing laser activation treatment on the composite material L by adopting an HAIYI LASER optical fiber laser, wherein the laser output power is 20W, 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.
Chemical copper plating: and (3) performing compressed air blowing and ultrasonic cleaning on the surface of the composite material L subjected to laser activation treatment, and performing chemical copper plating on the surface of the composite material L by adopting a Madmaleshi chemical plating process for 30 min. The properties are shown in Table 2.
[ example 15 ]
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 tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 2-10 parts of white oil are uniformly mixed, introduced into a pellet feeding port of a LABTECH co-rotating twin-screw extruder (the diameter of a screw is 16mm and the length-diameter ratio is 40), and subjected to melting, extrusion, cooling and granulation under the process conditions of 275-300 ℃ and 220-320 rpm to prepare the PC/aramid fiber composite material.
[ example 16 ]
Application of the modified polycarbonate material: 100 parts of the modified polycarbonate material prepared in the example 10, 10-40 parts of polyethylene terephthalate, 0.2-1 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 4-9 parts of white oil are uniformly mixed, introduced into a particle feeding port of a LABTECH co-rotating twin-screw extruder (the diameter of a screw is 16mm and the length-diameter ratio is 40), and subjected to melting, extrusion, cooling and granulation under the process conditions of 245-275 ℃ and 150-250 rpm to prepare the PC/PET composite material.
Comparative example 5
80 parts of dried polycarbonate (PC, 300 ℃, 1.2kg melt index 19.8g/10min, number average molecular weight 25200g/mol, weight average molecular weight 43700g/mol), 20 parts of high rubber powder (butadiene content 56%, acrylonitrile content 18%, styrene content 26%), 1 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 2 parts of white oil are uniformly mixed, introduced into a feeding port of a LABTECH co-rotating twin-screw extruder (screw diameter is 16mm, length-diameter ratio is 40) granule, and subjected to melting, extrusion, cooling and granulation under the process conditions of 280 ℃ and 250rpm to prepare the PC/ABS composite material e. The properties are shown in Table 2.
Comparative example 6
64 parts of dried polycarbonate (PC, 300 ℃, 1.2kg melt index 19.8g/10min, number average molecular weight 25200g/mol, weight average molecular weight 43700g/mol), 16 parts of high rubber powder (butadiene content 56%, acrylonitrile content 18%, styrene content 26%), 1 part of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and 2 parts of white oil are uniformly mixed, introduced into a LABTECH co-rotating twin-screw extruder (screw diameter 16mm, length-diameter ratio 40) granule feeding port, and 20 parts of long glass fiber (diameter 13 mu m, 1200tex) are introduced into the middle section of the extruder, and are melted, extruded, cooled and granulated under the process conditions of 280 ℃ and 250rpm to prepare the PC/ABS/GF composite material f. The properties are shown in Table 2.
Comparative example 7
80 parts of dried polycarbonate (PC, 300 ℃, 1.2kg melt index 19.8g/10min, 25200g/mol of number average molecular weight, 43700g/mol of weight average molecular weight), 15 parts of styrene/maleic anhydride random copolymer (SMA, the content of maleic anhydride is 22 percent, the content of styrene is 78 percent), 5 parts of laser auxiliary agent (the content of tin is 18 percent, the content of antimony is 12 percent, the content of titanium is 8 percent, and the rest is oxygen), 1 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 2 parts of white oil are uniformly mixed, introduced into a feeding port of a LABTECH homodromous double-screw extruder (the diameter of a screw is 16mm, the length-diameter ratio is 40) granule, and subjected to melting, extrusion, cooling and granulation under the process conditions of 280 ℃ and 250rpm to prepare the PC/SMA LDS composite material g.
Laser activation: and (3) performing laser activation treatment on the composite material g by adopting an HAIYI LASER optical fiber laser, wherein the laser output power is 20W, 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.
Chemical copper plating: and (3) blowing compressed air and cleaning the surface of the composite material g subjected to laser activation treatment by ultrasonic waves, and carrying out chemical copper plating on the surface of the composite material g by adopting a Madmaleshi chemical plating process for 30 min. The properties are shown in Table 2.
Comparative example 8
Uniformly mixing 55 parts of dried polycarbonate (PC, 300 ℃, 1.2kg melt index 19.8g/10min, number average molecular weight 25200g/mol and weight average molecular weight 43700g/mol), 15 parts of styrene/maleic anhydride random copolymer (SMA, the content of maleic anhydride is 22 percent and the content of styrene is 78 percent), 5 parts of laser auxiliary agent (the content of tin is 18 percent, the content of antimony is 12 percent, the content of titanium is 8 percent and the balance is oxygen), 1 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 2 parts of white oil, introducing the mixture into a feeding port of a LABTECH co-rotating twin-screw extruder (the diameter of a screw is 16mm and the length-diameter ratio is 40) granule, introducing 25 parts of long glass fiber (the diameter of 13 mu m and the diameter of 1200tex) into the middle section of the extruder, and melting, extruding, cooling and granulating under the process conditions of 280 ℃ and 250rpm, and preparing the PC/SMA/GF LDS composite material h.
Laser activation: and (3) performing laser activation treatment on the composite material h by adopting an HAIYI LASER optical fiber laser, wherein the laser output power is 20W, 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.
Chemical copper plating: and (3) performing compressed air blowing and ultrasonic cleaning on the surface of the composite material h subjected to laser activation treatment, and performing chemical copper plating on the surface of the composite material h by adopting a Madmaleshi chemical plating process for 30 min. The properties are shown in Table 2.
Comparative example 9
Application of the modified polycarbonate material: the modified polycarbonate material d80 parts, the high rubber powder (butadiene content 56%, acrylonitrile content 18%, styrene content 26%) 20 parts, the tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester 1 part, and the white oil 2 parts, which were prepared in comparative example 4, were mixed uniformly, introduced into a pellet feed port of a LABTECH co-rotating twin-screw extruder (screw diameter 16mm, aspect ratio 40), and subjected to melting, extrusion, cooling, and granulation at 280 ℃ and 250rpm to prepare a PC/ABS composite material i. The properties are shown in Table 2.
Table 2:
Figure BDA0002564811250000231
as can be seen from table 2:
compared with the comparative examples 4 and 9, 10 and 5, 11 and 6, and 12 and 7, the modified polycarbonate material containing silane, carboxyl or ester groups can improve the compatibility with other organic polymers such as ABS high-adhesive powder, SMA resin and the like, and can improve the infiltration of glass fibers and inorganic additives in the matrix material, thereby improving the adhesive force between the modified polycarbonate material and the inorganic material, and simultaneously improving the distribution of the laser additive in the interior and the surface of the modified composite material and improving the adhesive force of the coating structure.

Claims (16)

1. A modified polycarbonate comprising the following components and/or reaction products thereof: (1) polycarbonate matrix, (2) olefine acid (ester) monomer, and (3) initiator.
2. The modified polycarbonate according to claim 1,
the polycarbonate substrate is at least one selected from aliphatic polycarbonate, alicyclic polycarbonate, aromatic polycarbonate, aliphatic-aromatic copolycarbonate and polyester-polycarbonate copolymer, preferably aromatic polycarbonate; and/or
The weight average molecular weight of the polycarbonate matrix is 5000 g/mol-120000 g/mol, preferably 15000 g/mol-100000 g/mol; and/or
The number average molecular weight of the polycarbonate matrix is 4000g/mol to 100000g/mol, preferably 10000g/mol to 80000 g/mol.
3. The modified polycarbonate according to claim 1, wherein the acrylic monomer is a compound having a group-C (o) -in the structure; preferably, the silicon element is further contained, for example, a silicon oxy group is contained.
4. The modified polycarbonate of claim 3, wherein the olefinic acid (ester) monomer is selected from at least one olefinic acid (ester) monomer of formula (I) to formula (IV):
Figure FDA0002564811240000011
Figure FDA0002564811240000021
wherein, in the formulae (I) to (IV),
R1、R2、R3、R7、R8、R9、R10、R11、R24、R25each independently selected from hydrogen and C1～C30Alkyl or C6～C40An aromatic hydrocarbon group of (1); and/or
R4、R5、R6Each independently selected from hydrogen and C1～C30Alkyl of (C)1～C30Alkoxy group of (C)2～C30Epoxyalkyl group of (1), C1～C30Aminoalkyl radical of (2)1～C30Hydroxyalkyl of (C)1～C30Haloalkyl or C6～C40An aromatic hydrocarbon group of (1); and/or
R12、R22、R23Each independently selected from C1～C30Alkylene or C6～C40An arylene group of (a); and/or
R13、R14、R15、R16、R17、R18、R19、R20、R21Each independently selected from hydrogen and C1～C30Alkyl of (C)1～C30Alkoxy group of (C)6～C40An aromatic hydrocarbon group of6～C40An aralkyloxy group of (2).
5. The modified polycarbonate of claim 4, wherein, in the formulae (I) to (IV),
R1、R2、R3、R7、R8、R9、R10、R11、R24、R25each independently selected from hydrogen and C1～C18Alkyl or C6～C24An aromatic hydrocarbon group of (1); and/or
R4、R5、R6Each independently selected from hydrogen and C1～C18Alkyl of (C)1～C18Alkoxy group of (C)2～C18Epoxyalkyl group of (1), C1～C18Aminoalkyl radical of (2)1～C18Hydroxyalkyl of (C)1～C18Haloalkyl or C6～C24An aromatic hydrocarbon group of (1); and/or
R12、R22、R23Each independently selected from C1～C18Alkylene or C6～C24An arylene group of (a); and/or
R13、R14、R15、R16、R17、R18、R19、R20、R21Each independently selected from hydrogen and C1～C18Alkyl of (C)1～C18Alkoxy group of (C)6～C24An aromatic hydrocarbon group of6～C24An aralkyloxy group of (2).
6. The modified polycarbonate according to claim 4,
the olefine acid (ester) monomer shown in the formula (I) is at least one of acrylic acid, methacrylic acid, n-butyl acrylate, methyl methacrylate and hydroxyethyl methacrylate; and/or
The olefine acid (ester) monomer shown in the formula (II) is at least one selected from maleic acid, dimethyl maleate, diethyl maleate and di-n-butyl maleate; and/or
The olefine acid (ester) monomer shown in the formula (III) is at least one selected from 3-methacryloxypropyltrimethylsilane, 3-methacryloxypropyltriethylsilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane and trimethylsiloxypolymethacrylate; and/or
The olefine acid (ester) monomer shown in the formula (IV) is at least one selected from the group consisting of bis (trimethylsilylpropyl) maleate, bis (triethylsilylpropyl) maleate, bis (trimethoxysilylpropyl) maleate, bis (triethoxysilylpropyl) maleate and bis (trimethylsiloxypolyethoxy) maleate.
7. The modified polycarbonate of claim 1, wherein the initiator is selected from at least one of alkyl peroxides, alkyl hydroperoxides, peroxydiesters, peroxyesters, diacyl peroxides; preferably, the first and second electrodes are formed of a metal,
the alkyl peroxide is selected from at least one of dicumyl peroxide, di-tert-butyl peroxide, di-tert-amyl peroxide, 2-di (tert-butylperoxy) butane, 1-di (tert-butylperoxy) cyclohexane, 1-di (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) 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 peroxydiester is at least one selected from peroxydicarbonate, peroxydimyristyl dicarbonate, dicetyl peroxydicarbonate, bis (2-ethylhexyl) peroxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate and 2, 5-dimethyl-2, 5-bis (2-ethylhexanoic acid peroxy) hexane; and/or
The peroxyester 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 peroxypivalate, tert-amyl peroxypivalate, 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
The diacyl peroxide is at least one selected from dibenzoyl peroxide, bis (3,5, 5-trimethylhexanoyl) peroxide and dilauroyl peroxide.
8. The modified polycarbonate of claim 7, wherein the initiator is selected from at least one of 1, 1-bis (t-butylperoxy) cyclohexane, 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane, bis (2-ethylhexyl) peroxydicarbonate, and t-butyl peroxy-3, 5, 5-trimethylhexanoate.
9. The modified polycarbonate according to any one of claims 1 to 8,
the weight of the olefine acid (ester) monomer is 0.5-20 parts, preferably 1-15 parts, based on 100 parts by weight of the polycarbonate substrate; and/or
The initiator is used in an amount of 0.01 to 1 part by weight, preferably 0.05 to 0.5 part by weight, based on 100 parts by weight of the polycarbonate substrate.
10. The modified polycarbonate according to claim 9, wherein the modified polycarbonate optionally further comprises an auxiliary agent, preferably the auxiliary agent is at least one selected from the group consisting of a plasticizer, a heat stabilizer, an antioxidant, a UV absorber, and a mold release agent.
11. A method for preparing the modified polycarbonate of any one of claims 1 to 10, comprising: and (3) carrying out melt blending on raw materials comprising the polycarbonate matrix, the olefine acid (ester) monomer and the initiator to obtain the modified polycarbonate.
12. The method according to claim 11, wherein the raw material optionally further comprises an auxiliary agent, preferably the auxiliary agent is at least one selected from a plasticizer, a heat stabilizer, an antioxidant, a UV absorber and a mold release agent.
13. The method of claim 11 or 12, wherein the melt blending temperature is 200 to 360 ℃, preferably 250 to 300 ℃;
preferably, the melt blending is carried out in a screw extruder, preferably: the rotation speed of the screw is 50 to 350rpm, preferably 100 to 300 rpm.
14. The method of manufacturing according to claim 13, comprising the steps of:
step 1, dispersing the olefine acid (ester) monomer and an initiator in a dispersible oil agent to form a material I; preferably, the dispersible oil agent is at least one selected from paraffin, mineral oil, white oil and silicone oil;
step 2, mixing the polycarbonate matrix and an optional auxiliary agent to form a material II;
and 3, respectively introducing the first material and the second material into a screw extruder, and performing melt blending extrusion to obtain the modified polycarbonate.
15. A composite material comprising at least one of polyethylene, polypropylene, polyoxymethylene, polymethyl methacrylate, polystyrene, methyl methacrylate/butadiene/styrene copolymer, acrylonitrile/acrylate/styrene copolymer, acrylonitrile/styrene copolymer, styrene/maleic anhydride random copolymer, acrylonitrile/styrene/maleic anhydride random copolymer, polyethylene terephthalate, polybutylene succinate, polybutylene adipate, polybutylene succinate/butylene terephthalate, polybutylene adipate/butylene terephthalate, glass fiber, carbon fiber, aramid fiber, graphene, carbon nanotube, and the modified polycarbonate of any one of claims 1 to 10 or the modified polycarbonate of any one of claims 11 to 14 A modified polycarbonate obtained by the preparation method.
16. Use of the modified polycarbonate of any of claims 1 to 10 or the composite material of claim 15 in the fields of optics, communications, electronics, automotive, medical, aerospace.
CN202010619862.8A 2020-07-01 2020-07-01 Modified polycarbonate and preparation method and application thereof Pending CN113880995A (en)

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EP0520506A1 (en) * 1991-06-27 1992-12-30 Mitsubishi Gas Chemical Company, Inc. Process for producing grafted polycarbonate resin
JP2000319483A (en) * 1999-05-12 2000-11-21 Kanegafuchi Chem Ind Co Ltd Graft polycarbonate resin and its production
CN101747476A (en) * 2008-12-15 2010-06-23 山东省意可曼科技有限公司 Polyhydroxy alkanoates graft polymer and preparation method thereof
CN107118309A (en) * 2017-06-26 2017-09-01 浙江海轩科技有限公司 A kind of biodegradable polyesters alloy and preparation method thereof
CN107936444A (en) * 2016-10-13 2018-04-20 中国石油化工股份有限公司 The thermoplastic cellulose of graft modification and Aliphatic Polyester Blends and preparation method
CN109517113A (en) * 2018-11-16 2019-03-26 广州市聚赛龙工程塑料股份有限公司 A kind of polycarbonate composite material and the preparation method and application thereof that Surface hardened layer is modified
CN111087797A (en) * 2018-10-23 2020-05-01 中国石油化工股份有限公司 Laser direct forming resin composition with improved impact resistance, preparation method and application thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0520506A1 (en) * 1991-06-27 1992-12-30 Mitsubishi Gas Chemical Company, Inc. Process for producing grafted polycarbonate resin
JP2000319483A (en) * 1999-05-12 2000-11-21 Kanegafuchi Chem Ind Co Ltd Graft polycarbonate resin and its production
CN101747476A (en) * 2008-12-15 2010-06-23 山东省意可曼科技有限公司 Polyhydroxy alkanoates graft polymer and preparation method thereof
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