CN104693770A - Halogen-free expansion type flame-retardant polycarbonate composite material and preparation method thereof - Google Patents
Halogen-free expansion type flame-retardant polycarbonate composite material and preparation method thereof Download PDFInfo
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- CN104693770A CN104693770A CN201510090200.5A CN201510090200A CN104693770A CN 104693770 A CN104693770 A CN 104693770A CN 201510090200 A CN201510090200 A CN 201510090200A CN 104693770 A CN104693770 A CN 104693770A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
Abstract
The invention discloses a halogen-free expansion type flame-retardant polycarbonate composite material. The halogen-free expansion type flame-retardant polycarbonate composite material is prepared from the following raw materials in parts by weight: 100 parts of polycarbonate, 5-100 parts of a halogen-free expansion type flame retardant, 1-5 parts of a compatibilizer and 0.01-3 parts of auxiliaries, wherein the halogen-free expansion type flame retardant comprises nitrogen-phosphor-series flame retardants with mass fraction of 80-99.9% and synergistic auxiliaries with mass fraction of 0.1-20%; the nitrogen-phosphor-series flame retardants are oligomers of N, N'-dimethyl phosphoryl urea or triazine compounds; the synergistic auxiliaries are one or more of zinc borate, titanium oxide, silicon oxide, polysiloxane, magnesium oxide, calcium oxide, magnesium hydroxide, aluminum hydroxide or stearate. The halogen-free expansion type flame-retardant polycarbonate composite material disclosed by the invention effectively improves the flame resistance of the polycarbonate, is green and environmentally friendly, and free of pollution to environment.
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 field of polymer material preparing technology.
Background technology
Along with the continuous expansion of synthesized polymer material range of application, facing mankind is made new fire threat, reason is that such material has inflammable or flammable notable feature, different from natural materials, and synthetic materials produces poisonous and corrosive gas and flue dust in a large number when burning.So in today of environmental requirement increasingly stringent, development of new environment friendly flame retardant seems particularly important.
Polycarbonate is the thermoplastic engineering plastic of a class high comprehensive performance, is widely used in the fields such as mechanical means, construction work, communications and transportation, instrument and electric lighting.Containing phenyl ring on polycarbonate backbone, can be condensed into fragrant charcoal during burning, charring rate is higher, flame retardant rating is UL94V-2, but flammable, the hot melts dripped during burning, easily cause catching fire of neighbouring material, so be difficult to meet the requirement of some field to Flame Retardancy energy.
Current polycarbonate is commonly used environment friendly flame retardant and is comprised phosphate ester flame retardants, reactive phosphorus flame retardant, Sulfonates fire retardant, silicone flame retardant etc.When using phosphate ester flame retardants fire-retardant polycarbonate, easily reduce stability to hydrolysis and the heat-drawn wire of polycarbonate, and occur stress cracking phenomenon; Reactive phosphorus flame retardant adds in polycarbonate building-up process, although can give material permanent flame retardant resistance, there is complex manufacturing, is difficult to industrialized shortcoming; Sulfonates fire retardant addition is few, flame retarding efficiency is high and can maintain the transparent characteristic of material, but is difficult to be used alone, and price is higher
Summary of the invention
For the deficiency that above-mentioned prior art exists, the object of this invention is to provide a kind of halogen-free expansion type flame-proof polycarbonate composite material and preparation method thereof, with nitrogen phosphorus flame retardant for main body fire retardant, compositely be added in polycarbonate, effectively improve the flame retardant properties of polycarbonate, 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 made up of the raw material of following weight part:
Polycarbonate 100 parts, halogen-free expansion fire retardant 5-100 part, expanding material 1-5 part, auxiliary agent 0.01-3 part;
Described halogen-free expansion fire retardant is made up of the synergistic auxiliary agent of massfraction to be the nitrogen phosphorus flame retardant of 80-99.9% and massfraction be 0.1-20%;
Described nitrogen phosphorus flame retardant is oligopolymer or the compound in triazine class of N, N ′ – solutions of dimethyl phosphoryl base ureas.
Wherein, the structural formula of the oligopolymer of N, N ′ – solutions of dimethyl phosphoryl base ureas is:
In formula, m is the integer of 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-triazines;
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 one or more in zinc borate, titanium oxide, silicon oxide, polysiloxane, magnesium oxide, calcium oxide, magnesium hydroxide, aluminium hydroxide or stearate class.
Described expanding material is one or both in ABS grafted maleic anhydride (ABS-g-MAH) or Research of Grafting Malaic Anhydride Onto Polyethylene (PE-g-MAH).
Described auxiliary agent is one or both in oxidation inhibitor or photostabilizer.
Wherein, oxidation inhibitor is three [2,4-di-tert-butyl-phenyl] phosphorous acid ester, β-(3,5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid, four [(2,4-di-tert-butylphenol)-4,4 ' xenyl] one or more in diphosphites or four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester;
Photostabilizer is 2-(2H-benzotriazole-2-base)-4,6-bis-(1-methyl isophthalic acid-styroyl)-phenol, 2'-(the 2'-hydroxyl-3'-tertiary butyl-5'-aminomethyl phenyl)-5-chlorobenzotriazole, 2-[2-hydroxyl-5-(1,1,3,3-tetramethylbutyl) phenyl] benzotriazole, 2,4,6-tri-(2'-hydroxyl-4'-n-butoxyphenyl)-1,3,5-triazine or two (2,2,6,6-tetramethyl--4-piperidyl) one or more in sebate.
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) preparation of the oligopolymer of N, N ′ – solutions of dimethyl phosphoryl base ureas:
With trimethyl phosphite and dimethylolurea for raw material, the weight ratio of trimethyl phosphite, dimethylolurea is (80-85): 20, mixing with 40% (massfraction) of part dimethylolurea first by part trimethyl phosphite, stir and be warming up to 100 DEG C, insulation 1.5-2.5h; Drip remaining trimethyl phosphite, add remaining dimethylolurea, control temperature is 100 DEG C simultaneously in batches, and after reinforced, insulation 30min, is warming up to 140 DEG C, insulation 4-5h, and transparent to reaction solution, stop heating, pressure distillation, to obtain final product;
2) preparation of 2,4,6-tri-AminomethylphosphoniAcid Acid hexichol ester group-1,3,5-triazines
By paraformaldehyde and Virahol mixing, the pH regulating mixing solutions is 10, stirs and is warming up to 70 DEG C, insulation 30-60min, obtains the depolymerization liquid of paraformaldehyde, in depolymerization liquid, add trimeric cyanamide in batches, drip triphenyl phosphite simultaneously, after dropwising, 70 DEG C of insulation 2.5-3.5h, are warming up to 165 DEG C, the phenol of generation is steamed, after question response, underpressure distillation removing byproduct, to obtain final product; The ratio of paraformaldehyde, Virahol, trimeric cyanamide and triphenyl phosphite add-on is 3g:10mL:(12-13) g:(90-92) mL;
3) preparation of 2,4,6-triphosphoric acid diethyl-ester group-1,3,5-triazines
In triethyl-phosphite, add Cynuric Chloride in batches, after adding, be warming up to 100 DEG C, insulation 6-8h, filters, uses petroleum ether filter cake, and with ethyl alcohol recrystallization, to obtain final product; The mass ratio that triethyl-phosphite and Cynuric Chloride add is (140-145): (25-30);
(2), after polycarbonate, nitrogen phosphorus flame retardant, synergistic auxiliary agent, expanding material and auxiliary agent fully being mixed in high-speed mixer, use parallel double-screw extruder granulation, obtain halogen-free expansion type flame-proof polycarbonate composite material.
The preparation of the oligopolymer of N, N ′ – solutions of dimethyl phosphoryl base ureas in step (1), the trimethyl phosphite that first part adds accounts for the 30-35% (massfraction) adding trimethyl phosphite total amount; The dimethylolurea that part adds accounts for 40% (massfraction) adding dimethylolurea total amount.
Beneficial effect of the present invention:
Compared with existing Polycarbonate flame retardant material, the nitrogen phosphorus expanding fire retardant that halogen-free expansion type flame-proof polycarbonate composite material of the present invention uses is environment friendly flame retardant, play a role formation porous carbon layer in condensed phase is fire-retardant, the fire-retardant flame retardant properties that improve polycarbonate of nitrogen-phosphorus synergistic, flame retardant resistance can reach UL-94V-0 level.
Embodiment
Below by specific examples, the present invention will be further elaborated, should be noted that following explanation is only to explain the present invention, not limiting 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 flask of 250mL, add 28.9g trimethyl phosphite and the homemade dimethylolurea of 8g, mechanical stirring is also warming up to 100 DEG C, insulation 2h.In constant pressure funnel, add remaining 53.82g trimethyl phosphite, control drop rate at 1d/5s, meanwhile add remaining 12g dimethylolurea, temperature still controls at 100 DEG C in batches.After reinforced, after insulation 30min, be warming up to 140 DEG C, insulation 4h reaction solution is transparent, stops heating.At 137 DEG C, underpressure distillation under 0.5mmHg vacuum tightness, obtains N, and the oligopolymer of N ′ – solutions of dimethyl phosphoryl base ureas, productive rate 95%, as nitrogen phosphorus flame retardant.
(2) with the 1:1:1 mixing in mass ratio of zinc borate, titanium oxide and magnesium oxide, as synergistic auxiliary agent; ABS grafted maleic anhydride (ABS-g-MAH) is expanding material; With three [2,4-di-tert-butyl-phenyl] phosphorous acid esters and the 1:2 mixing in mass ratio of 2-(2H-benzotriazole-2-base)-4,6-bis-(1-methyl isophthalic acid-styroyl)-phenol, as auxiliary agent; After nitrogen phosphorus flame retardant, 10g synergistic auxiliary agent, 3g expanding material and the 1g auxiliary agent 100g polycarbonate, 40g step (1) prepared fully mix in high-speed mixer, 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 flame retardant properties reaches UL-94V-0 level.
Embodiment 2: the preparation of halogen-free expansion type flame-proof polycarbonate composite material
(1) preparation of nitrogen phosphorus flame retardant:
In the reaction flask that churned mechanically 250mL is housed, add 3.0g paraformaldehyde and 10mL Virahol, regulate pH=10 with 1% sodium hydroxide solution, mechanical stirring is also warming up to 70 DEG C, and insulation 40min, obtains the depolymerization liquid of paraformaldehyde.Add 12.6g trimeric cyanamide in batches, meanwhile drip 91.7mL triphenyl phosphite, after adding.3h is incubated at 70 DEG C.Be warming up to 165 DEG C subsequently, steamed by the phenol of generation, soaking time is determined by the phenol amount generated.Question response is complete, and underpressure distillation removing byproduct, obtain 2,4,6-tri-AminomethylphosphoniAcid Acid hexichol ester group-1,3,5-triazines, productive rate 87%, as nitrogen phosphorus flame retardant.
(2) with the 1:1:1 mixing in mass ratio of silicon oxide, calcium oxide and magnesium hydroxide, as synergistic auxiliary agent; Research of Grafting Malaic Anhydride Onto Polyethylene (PE-g-MAH) is expanding material; With β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid and the 1:2 mixing in mass ratio of 2'-(the 2'-hydroxyl-3'-tertiary butyl-5'-aminomethyl phenyl)-5-chlorobenzotriazole, as auxiliary agent; After nitrogen phosphorus flame retardant, 2g synergistic auxiliary agent, 1g expanding material and the 3g auxiliary agent 100g polycarbonate, 8g step (1) prepared fully mix in high-speed mixer, 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 flame retardant properties reaches UL-94V-0 level.
Embodiment 3: the preparation of halogen-free expansion type flame-proof polycarbonate composite material
(1) preparation of nitrogen phosphorus flame retardant:
Be equipped with agitator, thermometer, bubbler 500mL four-hole bottle in add 143.8g triethyl-phosphite, the Cynuric Chloride of 28.3g is added, after adding in 2h in batches.Slowly be warming up to 100 DEG C, insulation 7h.Filter, use petroleum ether filter 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 flame retardant.
(2) take zinc borate as synergistic auxiliary agent; ABS grafted maleic anhydride (ABS-g-MAH) is expanding material; With four [(2,4-di-tert-butylphenol)-4,4 ' xenyl] diphosphites and the 1:1.5 mixing in mass ratio of 2,4,6-tri-(2'-hydroxyl-4'-n-butoxyphenyl)-1,3,5-triazines, as auxiliary agent; After nitrogen phosphorus flame retardant, 10g synergistic auxiliary agent, 5g expanding material and the 0.1g auxiliary agent 100g polycarbonate, 90g step (1) prepared fully mix in high-speed mixer, 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 flame retardant properties reaches UL-94V-0 level.
The formula composition of embodiment 4-9 is in table 1, and preparation method is with embodiment 1.
The formula composition of table 1 embodiment 4-9
Claims (9)
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 part:
Polycarbonate 100 parts, halogen-free expansion fire retardant 5-100 part, expanding material 1-5 part, auxiliary agent 0.01-3 part;
Described halogen-free expansion fire retardant is made up of the synergistic auxiliary agent of massfraction to be the nitrogen phosphorus flame retardant of 80-99.9% and massfraction be 0.1-20%;
Described nitrogen phosphorus flame retardant is oligopolymer or the compound in triazine class of N, N ′ – solutions of dimethyl phosphoryl base ureas;
Described synergistic auxiliary agent is one or more in zinc borate, titanium oxide, silicon oxide, polysiloxane, magnesium oxide, calcium oxide, magnesium hydroxide, aluminium hydroxide or stearate class.
2. a kind of halogen-free expansion type flame-proof polycarbonate composite material as claimed in claim 1, is characterized in that, the structural formula of the oligopolymer of described N, N ′ – solutions of dimethyl phosphoryl base ureas is:
In formula, m is the integer of 2 ~ 10.
3. a kind of halogen-free expansion type flame-proof polycarbonate composite material as claimed in claim 1, is characterized in that, 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.
4. a kind of halogen-free expansion type flame-proof polycarbonate composite material as claimed in claim 1, is characterized in that, described expanding material is one or both in ABS grafted maleic anhydride or Research of Grafting Malaic Anhydride Onto Polyethylene.
5. a kind of halogen-free expansion type flame-proof polycarbonate composite material as claimed in claim 1, is characterized in that, described auxiliary agent is one or both in oxidation inhibitor or photostabilizer.
6. a kind of halogen-free expansion type flame-proof polycarbonate composite material as claimed in claim 5, it is characterized in that, described oxidation inhibitor is three [2,4-di-tert-butyl-phenyl] phosphorous acid ester, β-(3,5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid, four [(2,4-di-tert-butylphenol)-4,4 ' xenyl] one or more in diphosphites or four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester.
7. a kind of halogen-free expansion type flame-proof polycarbonate composite material as claimed in claim 5, it is characterized in that, described photostabilizer is 2-(2H-benzotriazole-2-base)-4, 6-bis-(1-methyl isophthalic acid-styroyl)-phenol, 2'-(the 2'-hydroxyl-3'-tertiary butyl-5'-aminomethyl phenyl)-5-chlorobenzotriazole, 2-[2-hydroxyl-5-(1, 1, 3, 3-tetramethylbutyl) phenyl] benzotriazole, 2, 4, 6-tri-(2'-hydroxyl-4'-n-butoxyphenyl)-1, 3, 5-triazine or two (2, 2, 6, 6-tetramethyl--4-piperidyl) one or more in sebate.
8. the preparation method of the halogen-free expansion type flame-proof polycarbonate composite material described in any one of claim 1 to 7, it is characterized in that, step is as follows:
(1) preparation of nitrogen phosphorus flame retardant:
1) preparation of the oligopolymer of N, N ′ – solutions of dimethyl phosphoryl base ureas:
With trimethyl phosphite and dimethylolurea for raw material, the weight ratio of trimethyl phosphite, dimethylolurea is (80-85): 20, first by part trimethyl phosphite and the mixing of part dimethylolurea, stir and be warming up to 100 DEG C, insulation 1.5-2.5h; Drip remaining trimethyl phosphite, add remaining dimethylolurea, control temperature is 100 DEG C simultaneously in batches, and after reinforced, insulation 30min, is warming up to 140 DEG C, insulation 4-5h, and transparent to reaction solution, stop heating, pressure distillation, to obtain final product;
2) preparation of 2,4,6-tri-AminomethylphosphoniAcid Acid hexichol ester group-1,3,5-triazines
By paraformaldehyde and Virahol mixing, the pH regulating mixing solutions is 10, stirs and is warming up to 70 DEG C, insulation 30-60min, obtains the depolymerization liquid of paraformaldehyde, in depolymerization liquid, add trimeric cyanamide in batches, drip triphenyl phosphite simultaneously, after dropwising, 70 DEG C of insulation 2.5-3.5h, are warming up to 165 DEG C, the phenol of generation is steamed, after question response, underpressure distillation removing byproduct, to obtain final product; The ratio of paraformaldehyde, Virahol, trimeric cyanamide and triphenyl phosphite add-on is 3g:10mL:(12-13) g:(90-92) mL;
3) preparation of 2,4,6-triphosphoric acid diethyl-ester group-1,3,5-triazines
In triethyl-phosphite, add Cynuric Chloride in batches, after adding, be warming up to 100 DEG C, insulation 6-8h, filters, uses petroleum ether filter cake, and with ethyl alcohol recrystallization, to obtain final product; The mass ratio that triethyl-phosphite and Cynuric Chloride add is (140-145): (25-30);
(2), after polycarbonate, nitrogen phosphorus flame retardant, synergistic auxiliary agent, expanding material and auxiliary agent fully being mixed in high-speed mixer, use parallel double-screw extruder granulation, obtain halogen-free expansion type flame-proof polycarbonate composite material.
9. the preparation method of halogen-free expansion type flame-proof polycarbonate composite material as claimed in claim 8, it is characterized in that, N in step (1), the preparation of the oligopolymer of N ′ – solutions of dimethyl phosphoryl base ureas, the trimethyl phosphite that first part adds accounts for the 30-35% adding trimethyl phosphite total amount; The dimethylolurea that part adds accounts for and adds 40% of dimethylolurea total amount.
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| CN105255132A (en) * | 2015-10-16 | 2016-01-20 | 鲁西化工集团股份有限公司 | ABS (acfylonitrile-butadiene-styrene) modified LMW (low-molecular-weight) PC (polycarbonate) flame retardant material and preparation method of flame retardant material |
| CN106995602A (en) * | 2017-04-07 | 2017-08-01 | 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 |
| KR20180137938A (en) * | 2017-06-20 | 2018-12-28 | (주)엔나노텍 | flame-retardant ester polyol, the manufacturing method thereof and polyisocyanurates including the anti-flame ester polyol |
| 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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| 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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