CN104693770B - A kind of halogen-free expansion type flame-proof polycarbonate composite material and preparation method thereof - Google Patents
A kind of halogen-free expansion type flame-proof polycarbonate composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of halogen-free expansion type flame-proof polycarbonate composite material, is to be made up of the raw material of following weight portion: 100 parts of Merlon, halogen-free expansion fire retardant 5-100 part, bulking agent 1-5 part, auxiliary agent 0.01-3 part; The synergistic auxiliary agent that the nitrogen phosphorus flame retardant that described halogen-free expansion fire retardant is 80-99.9% by mass fraction and mass fraction are 0.1-20% forms; Described nitrogen phosphorus flame retardant is N, oligomer or the compound in triazine class of N ′ – solutions of dimethyl phosphoryl base ureas; Described synergistic auxiliary agent is one or more in Firebrake ZB, titanium oxide, silica, polysiloxanes, magnesia, calcium oxide, magnesium hydroxide, aluminium hydroxide or stearate class. Halogen-free expansion type flame-proof polycarbonate composite material of the present invention has effectively improved the fire resistance of Merlon, and environmental protection, environmentally safe.
Description
Technical field
The present invention relates to a kind of halogen-free expansion type flame-proof polycarbonate composite material and preparation method thereof, belong to Polymer materialspreparationTechnical field.
Background technology
Along with the continuous expansion of synthesized polymer material range of application, make facing mankind new fire threat, reason is suchMaterial has inflammable or flammable notable feature, different from natural material, and synthetic material produces a large amount of poisonous and corrosion in the time of burningGas and the flue dust of property. So in today of environmental requirement increasingly stringent, it is particularly important that development of new environment friendly flame retardant seems.
Merlon is the thermoplastic engineering plastic of a class high comprehensive performance, be widely used in plant equipment, architectural engineering,The fields such as communications and transportation, instrument and electric lighting. On Merlon main chain, contain phenyl ring, when burning, can be condensed into aroma type charcoal,Charring rate is higher, and flame retardant rating is UL94V-2, but flammable, and the hot melt dripping when burning easily causes near catching fire of material,So be difficult to meet the requirement of some field to Flame Retardancy energy.
The conventional environment friendly flame retardant of Merlon comprises phosphoric acid ester fire retardant, reactive phosphorus flame retardant, Sulfonates resistance at presentCombustion agent, silicone flame retardant etc. While using phosphoric acid ester fire retardant Merlon, the hydrolysis that easily reduces Merlon is steadyQualitative and heat distortion temperature, and there is stress cracking phenomenon; Reactive phosphorus flame retardant is to add in Merlon building-up process,Although can give material permanent anti-flammability, there is complex manufacturing, be difficult to industrialized shortcoming; Sulfonates resistanceCombustion agent addition is few, flame retarding efficiency Gao Bingneng maintains the transparent characteristic of material, but is difficult to independent use, and price is higher
Summary of the invention
The deficiency existing for above-mentioned prior art, the object of this invention is to provide a kind of halogen-free expansion type flame-proof Merlon compoundMaterial and preparation method thereof, taking nitrogen phosphorus flame retardant as main body fire retardant, composite being added in Merlon, has effectively improved poly-The fire resistance of carbonic ester, and environmental protection, environmentally safe.
For achieving the above object, the present invention adopts following technical proposals:
A kind of halogen-free expansion type flame-proof polycarbonate composite material is to be made up of the raw material of following weight portion:
100 parts of Merlon, halogen-free expansion fire retardant 5-100 part, bulking agent 1-5 part, auxiliary agent 0.01-3 part;
The nitrogen phosphorus flame retardant that described halogen-free expansion fire retardant is is 80-99.9% by mass fraction and mass fraction are 0.1-20%Synergistic auxiliary agent composition;
Described nitrogen phosphorus flame retardant is N, oligomer or the compound in triazine class of N ′ – solutions of dimethyl phosphoryl base ureas.
Wherein, N, the structural formula of the oligomer of N ′ – solutions of dimethyl phosphoryl base ureas is:
In formula, the integer that m is 2～10.
Compound in triazine class is selected from 2,4,6-, tri-aminomethyl phosphonic acid hexichol ester group-1,3,5-triazines or 2,4,6-triphosphoric acid diethyl-ester group-1,3,5-Triazine;
The structural formula of 2,4,6-, tri-aminomethyl phosphonic acid hexichol ester group-1,3,5-triazines is as follows:
The structural formula of 2,4,6-triphosphoric acid diethyl-ester group-1,3,5-triazines is as follows:
Described synergistic auxiliary agent is Firebrake ZB, titanium oxide, silica, polysiloxanes, magnesia, calcium oxide, magnesium hydroxide, hydrogenOne or more in aluminium oxide or stearate class.
Described bulking agent is in ABS grafted maleic anhydride (ABS-g-MAH) or Research of Grafting Malaic Anhydride Onto Polyethylene (PE-g-MAH)One or both.
Described auxiliary agent is one or both in antioxidant or light stabilizer.
Wherein, antioxidant is three [2,4-di-tert-butyl-phenyl] phosphite ester, β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid positive 18Carbon alcohol ester, four [(2,4-di-tert-butylphenol)-4,4 ' xenyl] diphosphites or four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid]One or more in pentaerythritol ester;
Light stabilizer is 2-(2H-BTA-2-yl)-4,6-bis-(1-methyl isophthalic acid-phenethyl)-phenol, the 2'-(2'-hydroxyl-3'-tert-butyl group-5'-Aminomethyl phenyl)-5-chlorobenzotriazole, 2-[2-hydroxyl-5-(1,1,3,3-tetramethylbutyl) phenyl] BTA, 2,4,6-tri-(2'-hydroxyl-4'-N-butoxy phenyl) one or more in-1,3,5-triazines or two (2,2,6,6-tetramethyl-4-piperidyl) sebacate.
The preparation method of this halogen-free expansion type flame-proof polycarbonate composite material, step is as follows:
(1) preparation of nitrogen phosphorus flame retardant:
1) N, the preparation of the oligomer of N ′ – solutions of dimethyl phosphoryl base ureas:
Taking Trimethyl phosphite and dimethylol urea as raw material, the weight ratio of Trimethyl phosphite, dimethylol urea is (80-85): 20,First mix with 40% (mass fraction) part dimethylol urea part Trimethyl phosphite, stir and be warming up to 100 DEG C,Insulation 1.5-2.5h; Drip remaining Trimethyl phosphite, add remaining dimethylol urea simultaneously in batches, controlling temperature is 100 DEG C,After reinforced, insulation 30min, is warming up to 140 DEG C, and insulation 4-5h is transparent to reactant liquor, stops heating, distillation under pressure,Obtain;
2) 2,4, the preparation of 6-tri-AminomethylphosphoniAcid Acid hexichol ester group-1,3,5-triazines
Paraformaldehyde and isopropyl alcohol are mixed, and regulating the pH of mixed solution is 10, stirs and be warming up to 70 DEG C, insulation 30-60min,The depolymerization liquid that obtains paraformaldehyde adds melamine in depolymerization liquid in batches, drips triphenyl phosphite simultaneously, after dropwising,70 DEG C of insulation 2.5-3.5h, are warming up to 165 DEG C, and the phenol of generation is steamed, and after question response, byproduct is removed in decompression distillation,Obtain; The ratio of paraformaldehyde, isopropyl alcohol, melamine and triphenyl phosphite addition is 3g:10mL:(12-13) g:(90-92)mL；
3) 2,4, the preparation of 6-triphosphoric acid diethyl-ester group-1,3,5-triazines
In triethyl phosphite, add cyanuric trichloride in batches, after adding, be warming up to 100 DEG C, insulation 6-8h, filters,Use petroleum ether filter cake, and with ethyl alcohol recrystallization, to obtain final product; The mass ratio that triethyl phosphite and cyanuric trichloride add is(140-145)：(25-30)；
(2) after Merlon, nitrogen phosphorus flame retardant, synergistic auxiliary agent, bulking agent and auxiliary agent are fully mixed in high-speed mixer,Use parallel double-screw extruder granulation, obtain halogen-free expansion type flame-proof polycarbonate composite material.
N in step (1), the preparation of the oligomer of N ′ – solutions of dimethyl phosphoryl base ureas, the Trimethyl phosphite that first part adds accounts forAdd the 30-35% (mass fraction) of Trimethyl phosphite total amount; The dimethylol urea that part adds accounts for and adds dimethylol urea total40% (mass fraction) of amount.
Beneficial effect of the present invention:
Compared with existing Merlon fire proofing, the nitrogen that halogen-free expansion type flame-proof polycarbonate composite material of the present invention usesPhosphorus expanding fire retardant is environment friendly flame retardant, the formation porous carbon layer that plays a role in condensed phase is fire-retardant, and nitrogen-phosphorus synergistic is fire-retardantImproved the fire resistance of Merlon, anti-flammability can reach UL-94V-0 level.
Detailed description of the invention
Below by instantiation, the present invention will be further elaborated, should be noted that following explanation is only in order to explainThe present invention, does not limit its content.
Embodiment 1: the preparation of halogen-free expansion type flame-proof polycarbonate composite material
(1) preparation of nitrogen phosphorus flame retardant:
In the reaction bulb of 250mL, add the homemade dimethylol urea of 28.9g Trimethyl phosphite and 8g, mechanical agitation also risesTemperature, to 100 DEG C, is incubated 2h. In constant pressure funnel, add remaining 53.82g Trimethyl phosphite, control drop rateAt 1d/5s, meanwhile add remaining 12g dimethylol urea in batches, temperature is still controlled at 100 DEG C. Reinforced completeAfter, after insulation 30min, being warming up to 140 DEG C, insulation 4h reactant liquor is transparent, stops heating. At 137 DEG C, 0.5mmHgDecompression distillation under vacuum, obtains N, the oligomer of N ′ – solutions of dimethyl phosphoryl base ureas, and productive rate 95%, as nitrogen phosphorus flame retardant.
(2) with the 1:1:1 mixing in mass ratio of Firebrake ZB, titanium oxide and magnesia, as synergistic auxiliary agent; ABS grafting maleic acidAcid anhydride (ABS-g-MAH) is bulking agent; With three [2,4-di-tert-butyl-phenyl] phosphite esters and 2-(2H-BTA-2-yl)-4,6-Two (1-methyl isophthalic acid-phenethyl)-phenol in mass ratio 1:2 mixes, as auxiliary agent; By 100g Merlon, 40g step (1) systemStandby nitrogen phosphorus flame retardant, 10g synergistic auxiliary agent, 3g bulking agent and 1g auxiliary agent uses flat after fully mixing in high-speed mixerThe granulation of row double screw extruder, obtains halogen-free expansion type flame-proof polycarbonate composite material.
After tested, halogen-free expansion type flame-proof polycarbonate composite material prepared by the present embodiment, its fire resistance reaches UL-94V-0Level.
Embodiment 2: the preparation of halogen-free expansion type flame-proof polycarbonate composite material
(1) preparation of nitrogen phosphorus flame retardant:
In the reaction bulb that churned mechanically 250mL is housed, add 3.0g paraformaldehyde and 10mL isopropyl alcohol, use 1% hydrogen-oxygenChange sodium solution and regulate pH=10, mechanical agitation is also warming up to 70 DEG C, is incubated 40min, obtains the depolymerization liquid of paraformaldehyde. PointCriticize and add 12.6g melamine, meanwhile drip 91.7mL triphenyl phosphite, after adding. Insulation at 70 DEG C3h. Be warming up to subsequently 165 DEG C, the phenol of generation is steamed, temperature retention time is determined by the phenol amount generating. Question response is complete,Byproduct is removed in decompression distillation, obtains 2,4,6-, tri-AminomethylphosphoniAcid Acid hexichol ester group-1,3,5-triazines, and productive rate 87%, as nitrogen phosphorus isFire retardant.
(2) with the 1:1:1 mixing in mass ratio of silica, calcium oxide and magnesium hydroxide, as synergistic auxiliary agent; Polycthylene grafted horseCarrying out acid anhydrides (PE-g-MAH) is bulking agent; With the β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid and 2'-(2'-hydroxyl-3'-the tert-butyl group-5'-aminomethyl phenyl) the 1:2 mixing in mass ratio of-5-chlorobenzotriazole, as auxiliary agent; By 100g Merlon, 8gNitrogen phosphorus flame retardant, 2g synergistic auxiliary agent, 1g bulking agent and 3g auxiliary agent prepared by step (1) fully mixes in high-speed mixerAfter, use parallel double-screw extruder granulation, obtain halogen-free expansion type flame-proof polycarbonate composite material.
After tested, halogen-free expansion type flame-proof polycarbonate composite material prepared by the present embodiment, its fire resistance reaches UL-94V-0Level.
Embodiment 3: the preparation of halogen-free expansion type flame-proof polycarbonate composite material
(1) preparation of nitrogen phosphorus flame retardant:
In the four-hole bottle of 500mL that agitator, thermometer, bubbler are housed, add 143.8g triethyl phosphite, by 28.3The cyanuric trichloride of g adds in 2h in batches, after adding. Slowly be warming up to 100 DEG C, insulation 7h. Filter, use oilEther washing leaching cake, and with ethyl alcohol recrystallization, obtain 2,4,6-triphosphoric acid diethyl-ester group-1,3,5-triazines, productive rate 90%, as nitrogen phosphorus isFire retardant.
(2) taking Firebrake ZB as synergistic auxiliary agent; ABS grafted maleic anhydride (ABS-g-MAH) is bulking agent; With four [(2,4-Di-tert-butylphenol)-4,4 ' xenyl]-1,3,5-triazines is in mass ratio for diphosphites and 2,4,6-tri-(2'-hydroxyl-4'-n-butoxy phenyl)1:1.5 mixes, as auxiliary agent; Nitrogen phosphorus flame retardant, 10g synergistic prepared by 100g Merlon, 90g step (1) helpAgent, 5g bulking agent and 0.1g auxiliary agent use parallel double-screw extruder granulation after fully mixing in high-speed mixer, obtain nothingHalogen expansion type flame-retarding polycarbonate composite material.
After tested, halogen-free expansion type flame-proof polycarbonate composite material prepared by the present embodiment, its fire resistance reaches UL-94V-0Level.
The formula of embodiment 4-9 forms in table 1, and preparation method is with embodiment 1.
The formula composition of table 1 embodiment 4-9
Claims (7)
1. a halogen-free expansion type flame-proof polycarbonate composite material, is characterized in that, is to be made up of the raw material of following weight portion:
100 parts of Merlon, halogen-free expansion fire retardant 5-100 part, bulking agent 1-5 part, auxiliary agent 0.01-3 part;
The nitrogen phosphorus flame retardant that described halogen-free expansion fire retardant is is 80-99.9% by mass fraction and mass fraction are 0.1-20%Synergistic auxiliary agent composition;
Described nitrogen phosphorus flame retardant is N, oligomer or the compound in triazine class of N ′ – solutions of dimethyl phosphoryl base ureas;
Described synergistic auxiliary agent is Firebrake ZB, titanium oxide, silica, polysiloxanes, magnesia, calcium oxide, magnesium hydroxide, hydrogenOne or more in aluminium oxide or stearate class;
Described N, the structural formula of the oligomer of N ′ – solutions of dimethyl phosphoryl base ureas is:
In formula, the integer that m is 2～10;
Described compound in triazine class is 2,4,6-, tri-aminomethyl phosphonic acid hexichol ester group-1,3,5-triazines or 2,4,6-triphosphoric acid diethyl-ester group-1,3,5-triazines.
2. a kind of halogen-free expansion type flame-proof polycarbonate composite material as claimed in claim 1, is characterized in that described increase-volumeAgent is one or both in ABS grafted maleic anhydride or Research of Grafting Malaic Anhydride Onto Polyethylene.
3. a kind of halogen-free expansion type flame-proof polycarbonate composite material as claimed in claim 1, is characterized in that described auxiliary agentFor one or both in antioxidant or light stabilizer.
4. a kind of halogen-free expansion type flame-proof polycarbonate composite material as claimed in claim 3, is characterized in that described antioxygenAgent is three [2,4-di-tert-butyl-phenyl] phosphite ester, the positive octadecanol ester of β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid, four [(2,4-Di-tert-butylphenol)-4,4 ' xenyl] in diphosphites or four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esterOne or more.
5. a kind of halogen-free expansion type flame-proof polycarbonate composite material as claimed in claim 3, is characterized in that, described light is steadyDetermining agent is 2-(2H-BTA-2-yl)-4,6-bis-(1-methyl isophthalic acid-phenethyl)-phenol, the 2'-(2'-hydroxyl-3'-tert-butyl group-5'-methylbenzeneBase)-5-chlorobenzotriazole, 2-[2-hydroxyl-5-(1,1,3,3-tetramethylbutyl) phenyl] BTA, 2,4,6-tri-(the positive fourth oxygen of 2'-hydroxyl-4'-Base phenyl) one or more in-1,3,5-triazines or two (2,2,6,6-tetramethyl-4-piperidyl) sebacate.
6. the preparation method of the halogen-free expansion type flame-proof polycarbonate composite material described in claim 1 to 5 any one, its feature existsIn, step is as follows:
(1) preparation of nitrogen phosphorus flame retardant:
1) N, the preparation of the oligomer of N ′ – solutions of dimethyl phosphoryl base ureas:
Taking Trimethyl phosphite and dimethylol urea as raw material, the weight ratio of Trimethyl phosphite, dimethylol urea is (80-85): 20,First part Trimethyl phosphite and part dimethylol urea are mixed, stir and be warming up to 100 DEG C, insulation 1.5-2.5h; Drip surplusRemaining Trimethyl phosphite adds remaining dimethylol urea simultaneously in batches, and controlling temperature is 100 DEG C, after feeding in raw material, and insulation30min, is warming up to 140 DEG C, and insulation 4-5h is transparent to reactant liquor, stops heating, and distillation under pressure, to obtain final product;
2) 2,4, the preparation of 6-tri-AminomethylphosphoniAcid Acid hexichol ester group-1,3,5-triazines
Paraformaldehyde and isopropyl alcohol are mixed, and regulating the pH of mixed solution is 10, stirs and be warming up to 70 DEG C, insulation 30-60min,The depolymerization liquid that obtains paraformaldehyde adds melamine in depolymerization liquid in batches, drips triphenyl phosphite simultaneously, after dropwising,70 DEG C of insulation 2.5-3.5h, are warming up to 165 DEG C, and the phenol of generation is steamed, and after question response, byproduct is removed in decompression distillation,Obtain; The ratio of paraformaldehyde, isopropyl alcohol, melamine and triphenyl phosphite addition is 3g:10mL:(12-13) g:(90-92)mL；
3) 2,4, the preparation of 6-triphosphoric acid diethyl-ester group-1,3,5-triazines
In triethyl phosphite, add cyanuric trichloride in batches, after adding, be warming up to 100 DEG C, insulation 6-8h, filters,Use petroleum ether filter cake, and with ethyl alcohol recrystallization, to obtain final product; The mass ratio that triethyl phosphite and cyanuric trichloride add is(140-145)：(25-30)；
(2) after Merlon, nitrogen phosphorus flame retardant, synergistic auxiliary agent, bulking agent and auxiliary agent are fully mixed in high-speed mixer,Use parallel double-screw extruder granulation, obtain halogen-free expansion type flame-proof polycarbonate composite material.
7. the preparation method of halogen-free expansion type flame-proof polycarbonate composite material as claimed in claim 6, is characterized in that, step(1) N in, the preparation of the oligomer of N ′ – solutions of dimethyl phosphoryl base ureas, the Trimethyl phosphite that first part adds accounts for and adds sub-phosphorusThe 30-35% of acid trimethyl total amount; The dimethylol urea that part adds accounts for and adds 40% of dimethylol urea total amount.
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| CN106995602B (en) * | 2017-04-07 | 2019-02-05 | 广州科苑新型材料有限公司 | A kind of high-modulus height flowing halogen-free flame retardant PC/ABS alloy material and preparation method thereof |
| CN109721990A (en) * | 2018-11-29 | 2019-05-07 | 苏州斯英铂聚合材料有限公司 | A kind of PC/ABS alloy of fire-retardant enhancing and preparation method thereof |
| CN115181406A (en) * | 2022-08-10 | 2022-10-14 | 横店集团得邦工程塑料有限公司 | Film-grade halogen-free flame-retardant PC material and preparation method thereof |
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| EP2379643B1 (en) * | 2008-12-17 | 2012-11-14 | Basf Se | Layered silicate flame retardant compositions |
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Inventor after: Zhang Jincheng Inventor after: Zhang Wen Inventor after: Bi Jingli Inventor after: Chen Yunfeng Inventor after: Teng Mouyong Inventor after: Wei Wei Inventor after: Zhang Chao Inventor before: Zhang Jincheng Inventor before: Zhang Wen Inventor before: Chen Yunfeng Inventor before: Teng Mouyong Inventor before: Bi Jingli Inventor before: Wei Wei Inventor before: Zhang Chao |