CN102924896B - Halogen-free intumescent flame retardant polycarbonate composition and preparation method thereof - Google Patents

Halogen-free intumescent flame retardant polycarbonate composition and preparation method thereof Download PDF

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CN102924896B
CN102924896B CN201210472485.5A CN201210472485A CN102924896B CN 102924896 B CN102924896 B CN 102924896B CN 201210472485 A CN201210472485 A CN 201210472485A CN 102924896 B CN102924896 B CN 102924896B
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halogen
flame retardant
polycarbonate
phosphonitrile
preparation
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CN102924896A (en
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郝冬梅
陈涛
许肖丽
林倬仕
尹亮
陈崇伟
吴向阳
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Shanghai Research Institute of Chemical Industry SRICI
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Abstract

The invention relates to a halogen-free intumescent flame retardant polycarbonate composition and a preparation method thereof, wherein the composition comprises polycarbonate, intumescent flame retardant and auxiliary agent; relative to 100 parts by weight of polycarbonate, 15 to 100 parts by weight of intumescent flame retardant and 0.01 to 3 parts by weight of auxiliary agent are provided; the intumescent flame retardant comprises phosphazene derivative and synergistic auxiliary agent by the weight ratio of (80:20) to (100:0). The halogen-free intumescent flame retardant polycarbonate composition disclosed by the invention overcomes the harm to the environment and human bodies caused by adding the halogen flame retardant in the polycarbonate; and the phosphorus-nitrogen synergistic flame retardant effect in the phosphazene derivative improves the flame retardation of the polycarbonate, which can be up to UL-94V-0.

Description

A kind of halogen-free expansion type flame-proof polycarbonate compositions and preparation method thereof
Technical field
The invention belongs to macromolecule modified technical field, especially relate to a kind of halogen-free expansion type flame-proof polycarbonate compositions and preparation method thereof.
Background technology
Polycarbonate (PC) has good light transmission, higher second-order transition temperature and shock strength, the special performance such as electrical insulating property and weathering resistance, now become one of engineering plastics with fastest developing speed, be widely used in building, traffic, electronic electric equipment and optics.The limiting oxygen index(LOI) of polycarbonate itself (LOI) is 28, vertical combustion test (UL94) V-2 level, and in some specific Application Areas, the flame retardant properties of polycarbonate still is apparent not enough, and therefore must carry out flame-retardant modified to it.Due to the environmental issue of halogenated flame retardant, the expansible type flame retardant resistance of exploitation Halogen, low cigarette, low toxic and environment-friendly is the focus of studying at present.
Phosphorus, nitrogen compound are studied widely and are applied as feature of environmental protection fire retardant.In chloro phosphazene compound, on each phosphorus atom, be connected with two active chlorine atoms that easily replace, can make multiple derivative by nucleophilic substitution reaction.Phosphorus in phosphazene derivative, nitrogen content are higher, can give full play to the effect of phosphorus-nitrogen cooperative flame retardant, belong to simple substance type expanding fire retardant.The research that phosphazene derivative adds in epoxy resin as flame retardant synergistic composition has been reported, but open report is not seen in the research that it is applied in polycarbonate as fire retardant main body composition yet.
Summary of the invention
Object of the present invention is exactly in order to overcome the defect of above-mentioned prior art existence, to provide a kind of to add in polycarbonate phosphazene derivative as main body fire retardant, a kind of halogen-free expansion type flame-proof polycarbonate compositions and preparation method thereof is provided, improves the flame retardant properties of polycarbonate.In the present invention, by adding, take homemade phosphazene derivative after the fire retardant that main body is re-dubbed in polycarbonate, flame retardant effect is remarkable.
Object of the present invention can be achieved through the following technical solutions:
A kind of halogen-free expansion type flame-proof polycarbonate compositions, by halogen-free expansion fire retardant, polycarbonate and auxiliary agent, be (15～100) by weight: 100: (0.01～3) forms, wherein, described halogen-free expansion fire retardant is to form for 80: 20～100: 0 by phosphazene derivative and synergistic auxiliary agent by weight.
Described phosphazene derivative is ring-type chloro phosphonitrile or chain chloro phosphonitrile and O-Phenylene Diamine (NH 2phNH 2), o-amino phenol (NH 2there is the compound that nucleophilic substitution reaction obtains in any PhOH) or in pyrocatechol (HOPhOH).
The molecular formula that ring-type chloro phosphonitrile generation nucleophilic substitution reaction obtains compound is:
In formula, the integer that m is 3～25, R 1and R 2for-NH 2or-any or same in OH, Ph represents phenyl, Ph and R 1and R 2ortho position connects;
The molecular formula that chain chloro phosphonitrile generation nucleophilic substitution reaction obtains compound is:
In formula, the integer that n is 3～10000, X 1represent base or base, X 2represent base or base, wherein R 1and R 2for-NH 2or-any or same in OH, Ph represents phenyl, Ph and R 1and R 2ortho position connects.
Described synergistic auxiliary agent is selected from one or more in zinc borate, titanium oxide, zirconium white, silicon oxide, zinc oxide, magnesium oxide, calcium oxide, magnesium hydroxide, brucite, magnesium salt whisker, aluminium hydroxide or aluminum phosphate.
Described auxiliary agent is selected from one or more in antioxidant, thermo-stabilizer or photostabilizer.
Antioxidant in composition is selected from 2,2 '-methylene-bis (4-methyl-6-tertiary butyl) phenol, 4, any in 4 '-thiobis (3-methyl-6-tert butyl) phenol, three lauryl phosphorous acid esters or three isodecyl phosphorous acid esters.
Thermo-stabilizer in composition is selected from 4,4-biphenyl diphosphinic acid four (2,4-di-tert-butyl-phenyl) ester, 5, any in 7-di-t-butyl-3-(3,4-3,5-dimethylphenyl)-3H-benzofuran-2-ones, phenylbenzene phosphorous acid ester in the last of the ten Heavenly stems, barium laurate, triphenyl phosphite, phosphenylic acid dimethyl ester.
Photostabilizer in composition is selected from 2-(4,6-phenylbenzene-1,3,5-triazines-2-yl)-5-[(hexyl)-oxygen base]-phenol, 2-[4,6-two (2,4-xylyl)-2-(1,3,5-triazines base)]-5-phenol octyloxy or 2,4, any in 6-tri-(2 '-hydroxyl-4 '-n-butoxy phenyl)-1,3,5-triazines.
The preparation method of halogen-free expansion type flame-proof polycarbonate compositions, comprises the following steps:
(1) preparation of phosphazene derivative
In rare gas element, by NH 2phNH 2, NH 2phOH or HOPhOH and acid binding agent are uniformly mixed in solvent, drip ring-type chloro phosphonitrile or chain chloro phosphonitrile solution, and temperature reaction obtains phosphazene derivative;
(2) preparation of flame retardant polycarbonate composition
Phosphazene derivative and synergistic auxiliary agent are fully mixed in the high-speed mixer of 4000 revs/min according to part by weight, make expansion type flame retardant; Then this fire retardant and polycarbonate, auxiliary agent are proportionally mixed, extruding pelletization, makes flame retardant polycarbonate composition.
Solvent described in step (1) comprises ether solvents or aromatic hydrocarbon solvent, and described ether solvents comprises tetrahydrofuran (THF) or dioxane, and described aromatic hydrocarbon solvent comprises benzene, toluene or dimethylbenzene.
Acid binding agent described in step (1) is organic bases or mineral alkali, and described organic bases comprises triethylamine or pyridine, and described mineral alkali is sodium carbonate, sodium bicarbonate, sodium hydroxide, salt of wormwood, saleratus or potassium hydroxide.
Ring-type chloro phosphonitrile or chain chloro phosphonitrile and NH in step (1) 2phNH 2, NH 2phOH or HOPhOH are according to Cl atom on phosphonitrile and substituted radical NH 2or the mol ratio of OH mixed at 1: 1～1: 2, on phosphonitrile, the mol ratio of Cl atom and acid binding agent is 1: 1～1: 1.5, by NH 2phNH 2, NH 2phOH or HOPhOH and acid binding agent add in reaction vessel uses dissolution with solvents, slowly drips chloro phosphonitrile solution while being uniformly mixed, temperature rising reflux reaction 6～24h, and product obtains phosphazene derivative after processing the dry 6～10h of final vacuum.
Compared with prior art, the present invention has overcome and in polycarbonate, has added the harm of halogen flame to environment and human body, expansion type flame retardant forms porous foamed char in condensed phase, can effectively stop the exchanges of mass and energy between flame and body material, thereby improve the flame retardant resistance of polymer materials, the flame retardant properties that in phosphonitrile analog derivative, phosphorus-nitrogen cooperative flame retardant effect has improved polycarbonate can reach UL-94V-0.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1
Synthesizing of phosphazene derivative:
Under rare gas element, in the four-hole boiling flask of 500ml, add 10.71g O-Phenylene Diamine and 19.12g triethylamine then to add 200ml toluene to make solvent, fully stir its dissolving is mixed, with constant pressure funnel, slowly drip 100ml and dissolve 10.43g P 3n 3cl 6toluene solution, after dripping, be warming up to 105 ℃, isothermal reaction 14h, suction filtration obtains white precipitate.Throw out first washs suction filtration with tetrahydrofuran (THF), and then washes with water, after suction filtration, puts into vacuum drying oven dry that pale pink crystal is P 3n 3(C 6h 6n 2) 3(A), productive rate is 90.5%, and purity is 99.2%.
Embodiment 2
Synthesizing of phosphazene derivative:
Under rare gas element, in the four-hole boiling flask of 500ml, add 11.56g pyrocatechol and 16.38gNaHCO 3then add 200ml tetrahydrofuran (THF) to make solvent, fully stir its dissolving is mixed, with constant pressure funnel, slowly drip 100ml and dissolve 10.43g P 3n 3cl 6tetrahydrofuran solution, after dripping, be warming up to 70 ℃, isothermal reaction 8h, suction filtration obtains white precipitate.Throw out first washs suction filtration with tetrahydrofuran (THF), and then washes with water, after suction filtration, puts into vacuum drying oven dry that pale pink crystal is P 3n 3(C 6h 6o 2) 3(B), productive rate is 72.7%, and purity is 91.4%.
Embodiment 3
Synthesizing of phosphazene derivative:
Under rare gas element, in the four-hole boiling flask of 1000ml, add 97.33g O-Phenylene Diamine and 142.38g pyridine, then add 500ml tetrahydrofuran solvent, fully stir, make O-Phenylene Diamine and triethylamine dissolving and mixing, with constant pressure funnel, slowly drip and dissolve 92.80g P 8n 8cl 16200ml tetrahydrofuran solution to flask, after dripping, be warming up to 70 ℃, isothermal reaction 16h, suction filtration obtains white precipitate.Throw out first washs suction filtration with tetrahydrofuran (THF), and then washes with water, after suction filtration, puts into vacuum drying oven dry that pale pink crystal is P 8n 8(C 6h 6n 2) 8(C), productive rate is 88.6%, and purity is 93.4%.
Embodiment 4
Synthesizing of phosphazene derivative:
Under rare gas element, in the four-hole boiling flask of 500ml, add 32.44g O-Phenylene Diamine and 41.46gK 2cO 3, then add 300ml dioxane solvent, fully stir, make O-Phenylene Diamine dissolving and mixing, with constant pressure funnel, slowly drip and dissolve 29.12g P 25n 25cl 50100ml dioxane solution to flask, after dripping, be warming up to 100 ℃, isothermal reaction 24h, suction filtration obtains white precipitate.Throw out first washs suction filtration with tetrahydrofuran (THF), and then washes with water, after suction filtration, puts into vacuum drying oven dry that pale pink crystal is P 25n 25(C 6h 6n 2) 25(D), productive rate is 80.4%, and purity is 90.1%.
Embodiment 5
Synthesizing of phosphazene derivative:
Under rare gas element, in the four-hole boiling flask of 250ml, add 9.33g O-Phenylene Diamine and 6.20g K 2cO 3, then add 100ml tetrahydrofuran solvent fully to stir, the 50ml tetrahydrofuran solution that slowly drips dissolving 2g polydichlorophosphazenes with constant pressure funnel, to flask, is warming up to 70 ℃, isothermal reaction 8h after dripping.After reaction finishes, remove solid, concentrated supernatant liquid, with distilled water and sherwood oil, respectively precipitate 3 times respectively, put into vacuum drying oven and be dried to obtain white viscous solid (E), productive rate is 80.4%, purity is 90.1%, and the number-average molecular weight that records product with vapor pressure method is 9272.
Embodiment 6
Synthesizing of phosphazene derivative:
Under rare gas element, in the four-hole boiling flask of 1000ml, add 89.19g pyrocatechol and 118.39g triethylamine, then add 500ml tetrahydrofuran solvent fully to stir, the 200ml tetrahydrofuran solution that slowly drips dissolving 10.12g polydichlorophosphazenes with constant pressure funnel is to flask, after dripping, be warming up to 70 ℃, isothermal reaction 8h.After reaction finishes, remove solid, concentrated supernatant liquid, with distilled water and sherwood oil, respectively precipitate 3 times respectively, put into vacuum drying oven and be dried to obtain white solid (F), productive rate is 78.7%, purity is 93.3%, and the number-average molecular weight that records product with vapor pressure method is 1087.
Embodiment 7-34
Phosphonitrile analog derivative synthetic in embodiment 1-6 and synergistic auxiliary agent are pressed to the amount shown in table 1, join in mixing machine and fully after mixing 5～10min, obtain Halogen phosphonitrile expansion type fire retardant.The fire retardant making is added in polycarbonate in the ratio shown in table 1, be prepared into the polymkeric substance with flame retardant properties, its resistance
Combustion performance index list in table 1, shown in each component addition be all weight percentage.
Table 1

Claims (6)

1. a halogen-free expansion type flame-proof polycarbonate compositions, it is characterized in that, said composition is (15～100) by halogen-free expansion fire retardant, polycarbonate and auxiliary agent by weight: 100:(0.01～3) form, wherein, described halogen-free expansion fire retardant consists of for 80:20～100:0 by weight phosphazene derivative and synergistic auxiliary agent;
Described phosphazene derivative is ring-type chloro phosphonitrile or chain chloro phosphonitrile and O-Phenylene Diamine (NH 2phNH 2), o-amino phenol (NH 2there is the compound that nucleophilic substitution reaction obtains in any PhOH) or in pyrocatechol (HOPhOH),
The molecular formula that ring-type chloro phosphonitrile generation nucleophilic substitution reaction obtains compound is:
In formula, the integer that m is 3～25, R 1and R 2for-NH -or-any or same in O-, Ph represents phenyl, Ph and R 1and R 2ortho position connects;
The molecular formula that chain chloro phosphonitrile generation nucleophilic substitution reaction obtains compound is:
In formula, the integer that n is 3～10000, X 1represent base or base, X 2represent base, R simultaneously that be connected with Ph with P 1and R 2for-NH-or-O-, the R being only connected with Ph 2for-NH 2or-OH, Ph represents phenyl, Ph and R 1and R 2ortho position connects;
Described synergistic auxiliary agent is selected from one or more in zinc borate, titanium oxide, zirconium white, silicon oxide, zinc oxide, magnesium oxide, calcium oxide, magnesium hydroxide, brucite, magnesium salt whisker, aluminium hydroxide or aluminum phosphate.
2. a kind of halogen-free expansion type flame-proof polycarbonate compositions according to claim 1, is characterized in that, described auxiliary agent is selected from one or more in antioxidant, thermo-stabilizer or photostabilizer.
3. the preparation method of the halogen-free expansion type flame-proof polycarbonate compositions as described in claim 1-2 any one, is characterized in that, the method comprises the following steps:
(1) preparation of phosphazene derivative
In rare gas element, by NH 2phNH 2, NH 2phOH or HOPhOH and acid binding agent are uniformly mixed in solvent, drip ring-type chloro phosphonitrile or chain chloro phosphonitrile solution, and temperature reaction obtains phosphazene derivative;
(2) preparation of flame retardant polycarbonate composition
Phosphazene derivative and synergistic auxiliary agent are fully mixed in the high-speed mixer of 4000 revs/min according to part by weight, make expansion type flame retardant; Then this fire retardant and polycarbonate, auxiliary agent are proportionally mixed, extruding pelletization, makes flame retardant polycarbonate composition.
4. the preparation method of a kind of halogen-free expansion type flame-proof polycarbonate compositions according to claim 3, it is characterized in that, solvent described in step (1) comprises ether solvents or aromatic hydrocarbon solvent, described ether solvents comprises tetrahydrofuran (THF) or dioxane, and described aromatic hydrocarbon solvent comprises benzene, toluene or dimethylbenzene.
5. the preparation method of a kind of halogen-free expansion type flame-proof polycarbonate compositions according to claim 3, it is characterized in that, acid binding agent described in step (1) is organic bases or mineral alkali, described organic bases comprises triethylamine or pyridine, and described mineral alkali is sodium carbonate, sodium bicarbonate, sodium hydroxide, salt of wormwood, saleratus or potassium hydroxide.
6. the preparation method of a kind of halogen-free expansion type flame-proof polycarbonate compositions according to claim 3, is characterized in that, ring-type chloro phosphonitrile or chain chloro phosphonitrile and NH in step (1) 2phNH 2, NH 2phOH or HOPhOH are according to Cl atom on phosphonitrile and substituted radical NH 2or the mol ratio of OH mixes at 1:1～1:2, on phosphonitrile, the mol ratio of Cl atom and acid binding agent is 1:1～1:1.5, by NH 2phNH 2, NH 2phOH or HOPhOH and acid binding agent add in reaction vessel uses dissolution with solvents, slowly drips chloro phosphonitrile solution while being uniformly mixed, temperature rising reflux reaction 6～24h, and product obtains phosphazene derivative after processing the dry 6～10h of final vacuum.
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