CN101412843A - Flame-retardant polycarbonate and acrylonitrile-butadiene-styrene resin compositions - Google Patents

Flame-retardant polycarbonate and acrylonitrile-butadiene-styrene resin compositions Download PDF

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Publication number
CN101412843A
CN101412843A CNA2007100470539A CN200710047053A CN101412843A CN 101412843 A CN101412843 A CN 101412843A CN A2007100470539 A CNA2007100470539 A CN A2007100470539A CN 200710047053 A CN200710047053 A CN 200710047053A CN 101412843 A CN101412843 A CN 101412843A
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Prior art keywords
retardant
flame retardant
combination
fire
butadiene
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尹亮
刘彦明
郝冬梅
陈崇伟
陈涛
林倬仕
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Shanghai Research Institute of Chemical Industry SRICI
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Shanghai Research Institute of Chemical Industry SRICI
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Abstract

The invention provides a composition of flame-retardant polycarbonate and acrylonitrile-butadiene-styrene resin. The composition comprises the following components and weight percentage (based on the total weight of the composition): 40 to 80 percent of polycarbonate, 5 to 45 percent of acrylonitrile-butadiene-styrene resin, 5 to 40 percent of halogen-free main flame retardant and 1 to 5 percent of boron-containing auxiliary flame retardant. The composition of flame-retardant polycarbonate and acrylonitrile-butadiene-styrene resin can not emit a large amount of dense smoke, corrosive gas or toxic gas during combustion, and improves the processability of materials.

Description

A kind of fire-retardant polycarbonate and acrylonitrile-butadiene-styrene resin composition
Technical field
The invention belongs to macromolecule modified field, specifically is a kind of fire-retardant polycarbonate and acrylonitrile-butadiene-styrene (ABS) thermoplastic resin composition.
Background technology
Polycarbonate (PC) is a kind of armorphous thermoplastic engineering plastic, has the machinery of excellent combination property, electric and resistance toheat, and resistance to impact shock and the creep resistant with excellence is celebrated especially.Polycarbonate itself and be widely used in numerous areas such as electronics, electric, mechanical, automobile, space flight and aviation, building, office with the composition of mixture (or alloy), particularly acrylonitrile-butadiene-styrene (ABS) of other superpolymer.
Household electrical appliances and office appliance have heat-resisting and fire-retardant requirement, and it is fire-retardant in addition to add halogenated flame retardant usually.A kind of fire retardant thermoplastic combinations that aromatic polycarbonate, acrylonitrile-butadiene-styrene (ABS) connect branched copolymer, styrene-acrylonitrile copolymer, halogenide, retardant synergist and tetrafluoroethylene that comprises is disclosed as US4810739; And for example CN1978528A discloses a kind of low-smoke and flame retardant PC alloy plate special material, mainly is to have added triphenylphosphate, decabromodiphenyl oxide and activation zinc borate to be prepared from.But the adding halogenated flame retardant, material can discharge a large amount of toxic gases and dense smoke when burning, unfriendly to environment, and can produce secondary disaster.
" the RoHS instruction " that European Union announces requires since requirement on July 1 in 2006, the exit electronic electric equipment products of rendering to market must not contain Polybrominated biphenyl (PBB) and Poly Brominated Diphenyl Ethers objectionable impuritiess such as (PBDE), the product of outlet European Union of enterprise all need meet the above requirement of limiting the quantity of, so the use of halogenated flame retardant is restricted day by day.In above-mentioned field,, will turn on feature of environmental protection halogen-free flameproof gradually from now on along with the growth of fire retardant and fire retardant material consumption.
Some patent documentations have also been reported the method for halogen-free and flame-retardant polycarbonate/acrylonitrile-butadiene-styrene (ABS) alloy, disclose a kind of halogen-free and flame-retardant polycarbonate/styren-based resin composition as CN1435445.The PC alloy time can produce a large amount of smog in burning, and fire-retardant polycarbonate/acrylonitrile-butadiene-styrene (ABS) is more like this, in case with this product presence of fire of making, the life security that a large amount of toxic smogs will threaten people.And single use phosphor nitrogen combustion inhibitor, but flame retardant effect is not best and can not well solves the cigarette problem.In sum, this area lacks a kind of polycarbonate and acrylonitrile-butadiene-styrene resin composition of environment friendly halogen-free fireproof.Therefore, this area presses for the polycarbonate and the acrylonitrile-butadiene-styrene resin composition of a kind of environment friendly halogen-free fireproof of exploitation, can not emit a large amount of dense smoke, corrosive gases, toxic gas during burning, and improve Drawing abillity.
Summary of the invention
The objective of the invention is to obtain a kind of polycarbonate and acrylonitrile-butadiene-styrene resin composition of environment friendly halogen-free fireproof, can not emit a large amount of dense smoke, corrosive gases, toxic gas during burning, and improved Drawing abillity.
Another purpose of the present invention is to obtain the fire retardant material that a kind of described composition makes, and can not emit a large amount of dense smoke, corrosive gases, toxic gas during burning, and improve Drawing abillity.
A further object of the invention is to obtain a kind of purposes of composite flame-retardant agent, makes fire retardant material can not emit a large amount of dense smoke, corrosive gases, toxic gas when burning, and has improved Drawing abillity.
In a first aspect of the present invention, a kind of fire-retardant polycarbonate and acrylonitrile-butadiene-styrene resin composition are provided, it comprises:
40-80 weight % polycarbonate,
5-45 weight % acrylonitrile-butadiene-styrene resin,
5-40 weight % without halide main flame retardant and
The auxilliary fire retardant of 1-5 weight % boron system.
In a specific embodiment of the present invention,
Described without halide main flame retardant is made up of phosphorus flame retardant and nitrogen flame retardant,
The weight proportion of described phosphorus flame retardant and nitrogen flame retardant is 0.4:1~4:1.
In a specific embodiment of the present invention, the weight proportion of described without halide main flame retardant and boron flame retardant is 2:1~30:1.
In a specific embodiment of the present invention, described phosphorus flame retardant is selected from phosplate, biphosphonate or its combination.
Preferably, described phosplate is selected from triphen phosphoric acid ester, tricresyl phosphate ethyl ester, tricresyl phosphate butyl ester or its combination.
Preferably, described biphosphonate is selected from Resorcinol bisphosphonate, dihydroxyphenyl propane bisphosphonates, bisphosphate diphenyl pentaerythritol or its combination.
In a specific embodiment of the present invention, described nitrogen flame retardant is to be selected from Dyhard RU 100, trimeric cyanamide, melamine salt, trimeric cyanamide isocyanic ester or its combination.
In a specific embodiment of the present invention, the auxilliary fire retardant of described boron system is selected from zinc borate, borax, phenyl-boron dihydroxide compound or its combination.
The auxilliary fire retardant of preferably described boron system is phenyl-boron dihydroxide compound, borax or its combination.
More preferably, described phenyl-boron dihydroxide compound is to benzene hypoboric acid, a benzene three boric acid or its combination.
In a specific embodiment of the present invention, composition also comprises following component: acceptable assistant or its combination in 0.1-5% oxidation inhibitor, 1-10% impact modifier, 0.1-5% expanding material, fire-retardant of 0.1-5%.
In a specific embodiment of the present invention, described oxidation inhibitor is selected from four β-(3,5-di-tert-butyl-hydroxy phenyl propionic acid) pentaerythritol ester, 2,6-di-tert-butyl-4-methy phenol, β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester, tetramethylolmethane diphosphite two (2,4-di-tert-butyl phenyl) ester, 2,2 '-methylene radical-two (4-methyl-6 tert.-butyl phenols), three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) three isocyanuric acid esters, (2,4 di-tert-butyl-phenyl) tris phosphite or its combination.
In a specific embodiment of the present invention, described impact modifier is selected from acrylate copolymer resin (ACR resin), methyl methacrylate/butadiene/styrene copolymers, chlorinated polyethylene resin, ethene-acetate ethylene copolymer, acrylonitrile-butadiene-styrene (ABS) high glue powder or its combination.
In a specific embodiment of the present invention, described expanding material is selected from polycarbonate graft phenylethene/propylene cyanogen multipolymer, polycthylene grafted maleic anhydride, polymethylmethacrylate, ethylene-methyl methacrylate-methacrylic acid sodium ion aggressiveness, styrene-butadiene copolymer or its combination.
In a specific embodiment of the present invention, acceptable assistant is selected from lubricant, stablizer, static inhibitor or its combination in described other fire-retardant.
The fire retardant material that the present invention provides a kind of described composition to make on the other hand; And the fire-retardant product that makes of described fire retardant material.
Preferably, described fire-retardant product is the electronic apparatus material; More preferably, be printed circuit board (PCB).
A further aspect of the invention provides a kind of purposes of composite flame-retardant agent, and it is used to prepare fire-retardant polycarbonate and acrylonitrile-butadiene-styrene resin material;
Wherein,
Described composite flame-retardant agent is made up of without halide main flame retardant and boron flame retardant,
The weight proportion of described without halide main flame retardant and boron flame retardant is 2:1~30:1;
Described without halide main flame retardant is made up of phosphorus flame retardant and nitrogen flame retardant, and the weight proportion of described phosphorus flame retardant and nitrogen flame retardant is 0.4:1~4:1.
Embodiment
The inventor is through extensive and deep research, by improving preparation technology, obtained a kind of composite flame-retardant agent that is applicable to polycarbonate and acrylonitrile-butadiene-styrene resin composition, and can not emit a large amount of dense smoke, corrosive gases, toxic gas when finding burning, and improved Drawing abillity.So be particularly suitable as the flame-retardant additive of polycarbonate and acrylonitrile-butadiene-styrene resin composition.Finished the present invention on this basis.
As used herein, described " alkyl " except as otherwise noted, refers to the straight or branched alkane that contains 2-20 carbon atom.The alkane that preferably contains 2-10 carbon atom, for example, alkyl includes but not limited to methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl.
As used herein, described " aryl " except as otherwise noted, refers to the mononuclear aromatics that contains 6 carbon atoms, the double ring arene of 10 carbon atoms, and the thrcylic aromatic hydrocarbon of 14 carbon atoms, and on each ring 1-4 substituting group can be arranged, for example be 1-4 alkyl.For example, aryl includes but not limited to phenyl, naphthyl, anthryl.
Below describe in detail to various aspects of the present invention:
Polycarbonate and acrylonitrile-butadiene-styrene resin composition
Polycarbonate of the present invention is not particularly limited.The aromatic polycarbonate that the transesterification reaction gained of the aromatic polycarbonate of for example various dihydroxyl aryl compounds and phosgene reaction gained or dihydroxyl aryl compound and diphenyl carbonate is specifically arranged.For example be the bisphenol A-type aromatic copolycarbonate particularly.
Particularly, the dihydroxyl aryl compound is the bis-phenol based on formula (III)
Wherein:
A represents singly-bound, C1-C5 alkylidene group, C2-C5 alkylidene, the C5-C6 cycloalkyl ,-S-,-SO 2-,-O-,-CO-or C6-C12 arylidene, described group can randomly contain heteroatomic aromatic ring with other and carry out condensation,
B represents C1-C8 alkylidene group, C6-C10 aryl independently of one another, preferred phenyl, C7-C12 cycloalkyl,
Y represents 0,1 or 2 independently of one another,
P represents 1 or 0.
Suitable binary phenol can be two (4-hydroxyphenyl) methane, 1,1 '-two (4-hydroxyphenyl) ethane, 2,2 '-two (4-hydroxyphenyl) propane (" dihydroxyphenyl propane "), 2,2 '-two (4-hydroxyphenyl) butane, 2,2 '-two (4-hydroxyl-3-aminomethyl phenyl) propane, 2,2 '-two (4-hydroxyl-3-p-methoxy-phenyl) propane, 2,2 '-two (4-hydroxyl-3-tert-butyl phenyl) propane, 2,2 '-two (4-hydroxyl-3-cyclohexyl phenyl) propane, 1,1 '-two (4-hydroxyphenyl) pentamethylene, 1,1 '-two (4-hydroxyphenyl) cyclohexane, 1,1 '-two (4-hydroxyphenyl) cyclododecane, 4,4 '-dihydroxy phenyl ether, 4,4 '-dihydroxyl diphenyl sulfoxide, 4,4 '-dihydroxy-diphenyl sulfone, two (4-hydroxy phenyl) ketone, 2,6-dihydroxy naphthlene etc.
Preferred two (4-hydroxyphenyl) methane, 2,2 '-two (4-hydroxyphenyl) propane (" dihydroxyphenyl propane "), 2,2 '-two (4-hydroxyl-3-aminomethyl phenyl) propane.Preferred especially dihydroxyphenyl propane.
The production method of polycarbonate of the present invention is not particularly limited, can be according to known method production in the document, and can obtain from a plurality of commercial source.For example transesterify particularly, interface polymerization, solution polymerization, mass polymerization.
Acrylonitrile-butadiene-styrene resin of the present invention (ABS) is not particularly limited, as long as it reaches required use properties.By changing three kinds of monomeric ratios and adopting different polymerization processs, can make the product of all size, its structure has with the elastomerics to be the graft copolymer of main chain and to be the graft copolymer of main chain with the resin.For example three kinds of monomeric part by weight scope vinyl cyanide 25%--35%, divinyl 25%--30% and vinylbenzene 40%--50% particularly.
The production method of acrylonitrile-butadiene-styrene resin of the present invention (ABS) is not particularly limited, can be according to known method production in the document, and can obtain from a plurality of commercial source.
Polycarbonate content is 40-80 weight % in the present composition, preferably 50~70 weight %.
Acrylonitrile-butadiene-styrene resin content is 5-45 weight % in the present composition, preferably 5~40 weight %.
The Halogen main flame retardant
Phosphorus flame retardant
Phosphorus flame retardant of the present invention is suc as formula organo phosphorous compounds shown in (I):
Wherein said R 1, R 2, R 3, R 4Represent the C1-C8 alkyl independently of one another, or C5-C6 cycloalkyl, C6-C20 aryl or C7-C12 aralkyl, each group is optional can be replaced by the C1-C4 alkyl, preferred phenyl, tolyl, xylyl, C1-C4-alkyl, cyclohexane, preferred especially phenyl.
N represents 0 or 1 independently of one another, and preferred 1.
N is 0-30, preferred 0-10, preferred especially 0-5.
X representative contains the monocycle or the Ppolynuclear aromatic group of 6-30 carbon atom, and it can be to phenyl, a phenyl, dihydroxyphenyl propane, quinhydrones etc., preferably between phenyl, dihydroxyphenyl propane.
Preferably, described phosphorus flame retardant is selected from phosplate, biphosphonate or its combination.The example of corresponding formula (I) organo phosphorous compounds comprises: Triphenyl phosphate (also being the triphen phosphoric acid ester), tricresyl phosphate ethyl ester, tricresyl phosphate butyl ester, trimethylphenyl phosphoric acid ester, three (2, the 4-3,5-dimethylphenyl) phosphoric acid ester, two idol-(diphenyl phosphates) of Resorcinol, the two idols of dihydroxyphenyl propane-(diphenyl phosphate) or its combination.
More preferably, described phosplate is selected from Triphenyl phosphate, tricresyl phosphate ethyl ester, tricresyl phosphate butyl ester or its combination; Described biphosphonate is selected from Resorcinol bisphosphonate, dihydroxyphenyl propane bisphosphonates, bisphosphate diphenyl pentaerythritol or its combination.
The nitrogen flame retardant
The compound that nitrogen flame retardant of the present invention is represented by general formula (II),
R wherein 5, R 6, R 7Be selected from the alkoxyl group that hydrogen atom, amino, aryl or carbonatoms are 1-3, R 5, R 6, R 7Identical differently all can.
As described R 5, R 6, R 7When being selected from amino, described nitrogenous compound also comprises amino and sour salt that forms or the condenses that forms with aldehydes.
Described acid is not specifically limited, only otherwise goal of the invention of the present invention is produced restriction to get final product.For example be uric acid, phosphoric acid particularly.
Described aldehydes is not specifically limited, only otherwise goal of the invention of the present invention is produced restriction to get final product.For example be formaldehyde particularly.
Preferably, the R in described formula (II) compound 7Be selected from amino and salt thereof.
More preferably be the R in described formula (II) compound 6, R 7Be amino and salt thereof.
Most preferably be that described nitrogen flame retardant is to be selected from Dyhard RU 100, trimeric cyanamide, melamine salt, trimeric cyanamide isocyanic ester or its combination.
Without halide main flame retardant of the present invention is generally 5-40 weight %, and preferred 10 ± 3 weight % are in fire-retardant polycarbonate and acrylonitrile-butadiene-styrene resin composition.
In the halogen-free flame retardants of the present invention, phosphonium flame retardant is generally (1:10)~(10:1) with the weight ratio that contains nitrogen combustion inhibitor in mixture, preferred 0.4:1~4:1, more preferably 0.5:1~2:1, more preferably 1.5:1.
The auxilliary fire retardant of boron system of the present invention
The auxilliary fire retardant of described boron system is selected from zinc borate, borax, phenyl-boron dihydroxide compound or its combination.
The object lesson of described phenyl-boron dihydroxide compound is to benzene hypoboric acid, a benzene three boric acid or its combination, preferred between benzene three boric acid.
The content of the auxilliary fire retardant of boron system is 1-5 weight %, in composition total weight.
The weight proportion of described without halide main flame retardant and boron flame retardant is 2:1~30:1, usually 2:1~15:1, most preferably 3:1~10:1.
The present inventor finds, in the composition of polycarbonate and acrylonitrile-butadiene-styrene (ABS) system, adds the auxilliary fire retardant of halogen-free flame retardants and boron system of specific proportioning, can obtain synergy and reaches good flame-retardant effect.After two kinds of fire retardants were composite in proportion, dehydration formed network structure under processing temperature, when material combustion decomposes; form layer protective layer at material surface; play the heat insulation oxygen effect that presses down, stop material to burn away, because being added in of boron flame retardant presses down cigarette aspect better effects if.When particularly adopting the phenyl-boron dihydroxide compound, smoke suppressing effect is better.
Oxidation inhibitor
Can add oxidation inhibitor in the composition of the present invention.Usually, described oxidation inhibitor is selected from four β-(3,5-di-tert-butyl-hydroxy phenyl propionic acid) pentaerythritol ester, 2,6-di-tert-butyl-4-methy phenol, β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester, tetramethylolmethane diphosphite two (2,4-di-tert-butyl phenyl) ester, 2,2 '-methylene radical-two (4-methyl-6 tert.-butyl phenols), three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) three isocyanuric acid esters, (2,4 di-tert-butyl-phenyl) tris phosphite or its combination.
Oxidation inhibitor consumption of the present invention is generally 0.1-5%, calculates with composition total weight.
Impact modifier
Can add impact modifier in the composition of the present invention.Usually, impact modifier of the present invention is selected from acrylate copolymer (ACR resin), methyl methacrylate/butadiene/styrene copolymers (MBS resin), chlorinated polyethylene resin (CPE resin), ethene-acetate ethylene copolymer (EVA resin), acrylonitrile-butadiene-styrene (ABS) high glue powder or its combination.
The model or the trade mark of described resin are not particularly limited, only otherwise goal of the invention of the present invention is produced restriction to get final product.
The consumption of impact modifier of the present invention is 1-10%, calculates with composition total weight.
Expanding material
Can add expanding material in the composition of the present invention.Usually, described expanding material is selected from polycarbonate graft phenylethene/propylene cyanogen multipolymer (PC-g-SAN), polycthylene grafted maleic anhydride (PE-g-MAH), polymethylmethacrylate (PMMA), ethylene-methyl methacrylate-methacrylic acid sodium ion aggressiveness, styrene-butadiene copolymer or its combination.
The polymerization degree of described expanding material, molecular weight distribution, segment distribute (as being multipolymer) be not particularly limited, only otherwise goal of the invention of the present invention is produced restriction to get final product.
The consumption of expanding material of the present invention is 0.1-5%, with the total weight of composition.
Other auxiliary agent that is suitable for
Composition of the present invention can also be chosen any one kind of them or multiple other suitable auxiliary agent, and the kind of described auxiliary agent is not particularly limited, only otherwise goal of the invention of the present invention is produced restriction to get final product.For example be in particular the additive of thermo-stabilizer, photostabilizer, pigment, releasing agent, lubricant, flow improver additive, inorganic reinforcement, carbon fiber, small-particle and/or static inhibitor.
Preferably, described other auxiliary agents are selected from lubricant, stablizer, static inhibitor or its combination.
The consumption of suitable other auxiliary agent of the present invention is not particularly limited, only otherwise goal of the invention of the present invention is produced restriction to get final product.For example be 0.1-5 weight % particularly, in composition total weight.
Fire retardant material or fire-retardant product
Fire-retardant combination of the present invention can adopt this area method commonly used to make fire retardant material.
The fire-retardant product that the present invention also provides described fire retardant material to make.
For example, polycarbonate, acrylonitrile-butadiene-styrene resin, phosphorus nitrogen main flame retardant, the auxilliary fire retardant of boron system, oxidation inhibitor, impact modifier, expanding material and other auxiliary agents are mixed through high-speed mixer by a certain percentage, mix with twin screw extruder and to extrude, granulation get final product fire retardant material.
Described fire retardant material can adopt this area method commonly used to make fire-retardant product.Preferably, described fire-retardant product is the electronic apparatus material; More preferably, be printed circuit board (PCB).
Purposes
The present invention also provides a kind of purposes of composite flame-retardant agent, and it is used to prepare fire-retardant polycarbonate and acrylonitrile-butadiene-styrene resin material.
Preferably, described composite flame-retardant agent comprises phosphorus owner fire retardant, nitrogen owner fire retardant, the auxilliary fire retardant of boron system, its part by weight is: phosphorus owner fire retardant: nitrogen owner fire retardant: the auxilliary fire retardant of boron system=(2-20): (2-20): (1-5), and the gross weight of phosphorus owner fire retardant and nitrogen owner fire retardant accounts for the 5-40 weight % of described composition.
Preferably, the part by weight of carbonic ether in described polycarbonate and the acrylonitrile-butadiene-styrene resin material and acrylonitrile-butadiene-styrene resin is (40-80): (5~45).
The invention has the advantages that:
(1) composition of the present invention has the excellent fire retardant smoke suppressing effect, and environment is not produced harm, can reach the UL941.6V-0 grade standard, has good physicals simultaneously, and has improved Drawing abillity.
Compound provided by the present invention can be synthetic by marketable material and traditional chemical transform mode.
Other aspects of the present invention are because the disclosure of this paper is conspicuous to those skilled in the art.
Below in conjunction with specific embodiment, further illustrate the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example usually according to normal condition, for example is " condition in the smooth organic chemistry handbook of Bel Si (Chemical Industry Press, 1996), or the condition of advising according to manufacturer.Ratio and per-cent are based on weight, unless stated otherwise.
Unless otherwise defined or explanation, same meanings of being familiar with of all specialties used herein and scientific words and those skilled in the art.Any in addition method similar or impartial to described content and material all can be applicable in the inventive method.
Embodiment 1~18
Polycarbonate, acrylonitrile-butadiene-styrene resin, phosphorus nitrogen main flame retardant, the auxilliary fire retardant of boron system, oxidation inhibitor, impact modifier, expanding material and other auxiliary agents are obtained said composition in following ratio through the high-speed mixer mixing, mix with twin screw extruder and to extrude (210~240 ℃), granulation get final product fire retardant material.The injection moulding sample preparation can test performance.
Adopt following measuring method among the present invention:
Combustible measuring method: UL-94 standard.UL-the 94th, testing vertical flammability: carry out V level fire prevention test by UL94 " the plastic material inflammability test of equipment and device component " standard.
The measuring method of tensile strength: GB/T1040-1992
The measuring method of shock strength: GB/T1843-1996
The measuring method of smoke density: GB/T8323-87 embodiment 1 is as shown in table 1 to the results of property of example 9
Table 1: embodiment specifies performance test with material
Annotate:
1. the polycarbonate of the foregoing description 1~9 and Comparative Examples 1~2 employing is the polycarbonate 3103 that Bayer A.G produces.
2. aforesaid propylene nitrile-butadiene styrene resin (ABS resin) part by weight scope is vinyl cyanide 25~35%, divinyl 25~30% and vinylbenzene 40~50%, with the acrylonitrile-butadiene-styrene resin total weight.
3. being commonly called as of oxidation inhibitor of the foregoing description 1~9 and Comparative Examples 1~2 employing is respectively antioxidant 1010 and oxidation inhibitor 168.
4. the impact modifier that adopts of the foregoing description 1~9 and Comparative Examples 1~2 is the A1218 that the ACR-401 resin (acrylate copolymer) of the poly-rich Science and Technology Ltd. in Zhuhai and Guangdong Huizhou are praised general chemical industry company limited.
5. other auxiliary agents of the foregoing description 1~9 and Comparative Examples 1~2 employing are the equivalent combination of the KJD-730 of Haining benefit chemical industry company limited on favour chemistry photostabilizer EH-770 of Science and Technology Ltd. of last Haier and the static inhibitor.
Polycarbonate, acrylonitrile-butadiene-styrene resin, phosphorus nitrogen main flame retardant, the auxilliary fire retardant of boron system, oxidation inhibitor, impact modifier, expanding material and other auxiliary agents are mixed through high-speed mixer in following ratio, mix with twin screw extruder and to extrude (210~240 ℃), through granulation get final product said composition.The injection moulding sample preparation can test performance.Embodiment 10 is to the results of property such as the table 2 of example 18.
Table 2: example specify performance test with material
Annotate:
1. the polycarbonate of the foregoing description 10~18 employings is the polycarbonate 3103 that Bayer A.G produces.
2. aforesaid propylene nitrile-butadiene styrene resin part by weight scope is vinyl cyanide 25~35%, divinyl 25~30% and vinylbenzene 40~50%, with the acrylonitrile-butadiene-styrene resin total weight.
3. the oxidation inhibitor of the foregoing description 10~18 employings is 1076.
4. the impact modifier that adopts of the foregoing description 10~18: methyl methacrylate/butadiene/styrene copolymers (MBS resin) LB-22 is available from Shanghai well bamboo chemical industry company limited, and described ethene-acetate ethylene copolymer (EVA) 4260 is available from the general chemical novel material of Wuhan luxuriant growth company limited.
5. other auxiliary agents of the foregoing description 10~18 employings are the balanced mix of the KJD-730 of Haining benefit chemical industry company limited on favour chemistry photostabilizer EH-770 of Science and Technology Ltd. of last Haier and the static inhibitor.
All quote in this application as a reference at all documents that the present invention mentions, just quoted as a reference separately as each piece document.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after having read above-mentioned teachings of the present invention, these equivalent form of values fall within the application's appended claims institute restricted portion equally.

Claims (10)

1. fire-retardant polycarbonate and acrylonitrile-butadiene-styrene resin composition, it comprises:
40-80 weight % polycarbonate,
5-45 weight % acrylonitrile-butadiene-styrene resin,
5-40 weight % without halide main flame retardant and
The auxilliary fire retardant of 1-5 weight % boron system.
2. composition as claimed in claim 1 is characterized in that,
Described without halide main flame retardant is made up of phosphorus flame retardant and nitrogen flame retardant,
The weight proportion of described phosphorus flame retardant and nitrogen flame retardant is 0.4:1~4:1.
3. composition as claimed in claim 1 is characterized in that, the weight proportion of described without halide main flame retardant and boron flame retardant is 2:1~30:1.
4. composition as claimed in claim 2 is characterized in that, described phosphorus flame retardant is selected from phosplate, biphosphonate or its combination;
Preferably, described phosplate is selected from triphen phosphoric acid ester, tricresyl phosphate ethyl ester, tricresyl phosphate butyl ester or its combination;
Preferably, described biphosphonate is selected from Resorcinol bisphosphonate, dihydroxyphenyl propane bisphosphonates, bisphosphate diphenyl pentaerythritol or its combination.
5. composition as claimed in claim 2 is characterized in that, described nitrogen flame retardant is to be selected from Dyhard RU 100, trimeric cyanamide, melamine salt, trimeric cyanamide isocyanic ester or its combination.
6. composition as claimed in claim 1 is characterized in that,
The auxilliary fire retardant of described boron system is selected from zinc borate, borax, phenyl-boron dihydroxide compound or its combination;
Be preferably phenyl-boron dihydroxide compound, borax or its combination;
More preferably, described phenyl-boron dihydroxide compound is to benzene hypoboric acid, a benzene three boric acid or its combination.
7. composition as claimed in claim 1 is characterized in that, also comprises following component: acceptable assistant or its combination in 0.1-5% oxidation inhibitor, 1-10% impact modifier, 0.1-5% expanding material, fire-retardant of 0.1-5%.
8. composition as claimed in claim 7 is characterized in that,
Preferably, described oxidation inhibitor is selected from four β-(3,5-di-tert-butyl-hydroxy phenyl propionic acid) pentaerythritol ester, 2,6-di-tert-butyl-4-methy phenol, β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester, tetramethylolmethane diphosphite two (2,4-di-tert-butyl phenyl) ester, 2,2 '-methylene radical-two (4-methyl-6 tert.-butyl phenols), three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) three isocyanuric acid esters, (2,4 di-tert-butyl-phenyl) tris phosphite or its combination;
Preferably, described impact modifier is selected from acrylate copolymer resin (ACR resin), methyl methacrylate/butadiene/styrene copolymers, chlorinated polyethylene resin, ethene-acetate ethylene copolymer, acrylonitrile-butadiene-styrene (ABS) high glue powder or its combination;
Preferably, described expanding material is selected from polycarbonate graft phenylethene/propylene cyanogen multipolymer, polycthylene grafted maleic anhydride, polymethylmethacrylate, ethylene-methyl methacrylate-methacrylic acid sodium ion aggressiveness, styrene-butadiene copolymer or its combination;
Preferably, acceptable assistant is selected from lubricant, stablizer, static inhibitor or its combination in described other fire-retardant.
9. fire retardant material that makes as each described composition of claim 1~8; And the fire-retardant product that makes of described fire retardant material;
Preferably, described fire-retardant product is the electronic apparatus material; More preferably, be printed circuit board (PCB).
10, a kind of purposes of composite flame-retardant agent is characterized in that, is used to prepare fire-retardant polycarbonate and acrylonitrile-butadiene-styrene resin material;
Wherein,
Described composite flame-retardant agent is made up of without halide main flame retardant and boron flame retardant,
The weight proportion of described without halide main flame retardant and boron flame retardant is 2:1~30:1;
Described without halide main flame retardant is made up of phosphorus flame retardant and nitrogen flame retardant, and the weight proportion of described phosphorus flame retardant and nitrogen flame retardant is 0.4:1~4:1.
CNA2007100470539A 2007-10-16 2007-10-16 Flame-retardant polycarbonate and acrylonitrile-butadiene-styrene resin compositions Pending CN101412843A (en)

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CN101967274A (en) * 2010-10-11 2011-02-09 余林华 Permanent antistatic polycarbonate (PC)/acrylonitrile-butadiene-styrene (ABS) composite material and preparation method thereof
CN102093690A (en) * 2010-12-30 2011-06-15 佛山市顺德区圆融新材料有限公司 Cold-resistant flame-retardant polycarbonate alloy material and preparation method thereof
CN102241881A (en) * 2010-11-30 2011-11-16 深圳市科聚新材料有限公司 Halogen-free, flame-retarding and high glowing filament resistant PC/ABS alloy and preparation method thereof
CN102382436A (en) * 2010-09-02 2012-03-21 天津大沽化工股份有限公司 Preparation method for polycarbonate/acrylonitrile-butadiene-styrene alloy
CN102516732A (en) * 2011-12-02 2012-06-27 四川长虹电器股份有限公司 Polycarbonate (PC) resin/acrylonitrile-butadiene-styrene (ABS) alloy and preparation method thereof
CN103087495A (en) * 2013-01-24 2013-05-08 李顺平 Alloy plastic particle
CN103333481A (en) * 2013-07-19 2013-10-02 上海锦湖日丽塑料有限公司 Wear-resisting PC/ABS alloy material and preparation method thereof
CN103525059A (en) * 2013-10-25 2014-01-22 安徽省富光实业股份有限公司 ABS (acrylonitrile-butadiene-styrene)-modified composite polycarbonate material for water cup shell and preparation method of ABS-modified composite polycarbonate material
CN110358278A (en) * 2019-07-01 2019-10-22 武汉市太行冶金材料有限公司 A kind of packaging steel coils flame retardant type plastic sheet PP Pipe Compound and preparation method thereof

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102382436A (en) * 2010-09-02 2012-03-21 天津大沽化工股份有限公司 Preparation method for polycarbonate/acrylonitrile-butadiene-styrene alloy
CN101967274A (en) * 2010-10-11 2011-02-09 余林华 Permanent antistatic polycarbonate (PC)/acrylonitrile-butadiene-styrene (ABS) composite material and preparation method thereof
CN102241881A (en) * 2010-11-30 2011-11-16 深圳市科聚新材料有限公司 Halogen-free, flame-retarding and high glowing filament resistant PC/ABS alloy and preparation method thereof
CN102093690A (en) * 2010-12-30 2011-06-15 佛山市顺德区圆融新材料有限公司 Cold-resistant flame-retardant polycarbonate alloy material and preparation method thereof
CN102516732A (en) * 2011-12-02 2012-06-27 四川长虹电器股份有限公司 Polycarbonate (PC) resin/acrylonitrile-butadiene-styrene (ABS) alloy and preparation method thereof
CN103087495A (en) * 2013-01-24 2013-05-08 李顺平 Alloy plastic particle
CN103333481A (en) * 2013-07-19 2013-10-02 上海锦湖日丽塑料有限公司 Wear-resisting PC/ABS alloy material and preparation method thereof
CN103333481B (en) * 2013-07-19 2015-10-28 上海锦湖日丽塑料有限公司 A kind of wear-resisting PC/ABS alloy material and preparation method thereof
CN103525059A (en) * 2013-10-25 2014-01-22 安徽省富光实业股份有限公司 ABS (acrylonitrile-butadiene-styrene)-modified composite polycarbonate material for water cup shell and preparation method of ABS-modified composite polycarbonate material
CN110358278A (en) * 2019-07-01 2019-10-22 武汉市太行冶金材料有限公司 A kind of packaging steel coils flame retardant type plastic sheet PP Pipe Compound and preparation method thereof

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