CN1970606A - Preparation method for dialysis-resistant composite halogen-free flame-proof agent - Google Patents
Preparation method for dialysis-resistant composite halogen-free flame-proof agent Download PDFInfo
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- CN1970606A CN1970606A CN 200610154608 CN200610154608A CN1970606A CN 1970606 A CN1970606 A CN 1970606A CN 200610154608 CN200610154608 CN 200610154608 CN 200610154608 A CN200610154608 A CN 200610154608A CN 1970606 A CN1970606 A CN 1970606A
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Abstract
The invention discloses a making method of dialysis-proof composite non-halogen fire retardant, which comprises the following steps: decorating bulking-typed non-halogen fire retardant through coupling agent; blending with monomer with aldehyde group, initiator, anti-oxidant and dispersing dielectric suspension evenly; reacting at 150-220 deg.c completely; acting monomer with aldehyde group and composite non-halogen fire retardant completely; drying to obtain the smooth fire retardant polypropylene material without releasing toxic smoke.
Description
Technical field
The present invention relates to a kind of preparation method of dialysis-resistant composite halogen-free flame-proof agent, especially be specifically designed to the preparation method of the dialysis-resistant composite halogen-free flame-proof agent of producing halogen-free flame retardant polypropylene composite material.
Background technology
Polypropylene has excellent comprehensive performances, is widely used in civilian and engineering plastics field.But polypropylene easily burning and combustion heating amount is big, and the molten drop of generation is propagating flame very easily again, thereby polypropylene fire retardant technology, particularly Non-halogen Flame Retardant Technology become the inexorable trend of flame-retardant polypropylene composite material development because compliance with environmental protection requirements
Add organic, inorganic no-halogen fire retardant and have simple to operately with the method that realizes the polypropylene halogen-free flameproof in polypropylene, the production efficiency height, is easy to characteristics such as industrialization at environment-friendly high-efficiency, is widely adopted.Wherein, the halogen-free expansion fire retardant that comprises acid source (as ammonium polyphosphate), carbon source (polyol compound), three basal components in foaming source (nitrogenous many carbon compounds), its fire retardant mechanism is to promote that polymkeric substance becomes charcoal, form one deck expansion porous homogeneous charcoal layer at material surface, play heat insulation, oxygen barrier, press down cigarette, prevent the effect of molten drop, reach fire-retardant purpose.Comparing with inorganic no-halogen fire retardant that to have an addition little, to advantages such as the matrix polymer performance impact are little, is to develop class nitrogen-phosphorus composite flame-retardant agent faster now.But shortcomings such as water absorbability is big, poor with the matrix polymer consistency, poor heat stability that this based flame retardant has simultaneously, make after adding polymkeric substance easily to polymer surfaces migration dialysis, easily decompose in the material processing etc., have a strong impact on material mechanical performance, anti-flaming function, processing characteristics and product surface performance, its application is restricted.
Summary of the invention
The objective of the invention is to give expanding halide-free fire-retardant special function of surface, for producing the preparation method that halogen-free flame retardant polypropylene composite material provides a kind of dialysis-resistant composite halogen-free flame-proof agent in conjunction with the expanding halide-free fire-retardant advantage.
The preparation method of dialysis-resistant composite halogen-free flame-proof agent of the present invention may further comprise the steps:
1) 100 parts of expanding halide-free fire-retardants are dry in 50～80 ℃ vacuum drying oven, the coupling agent that adds 0.5-2 part then mixes under 80～150 ℃, obtains active composite flame-retardant agent;
2) monomer, 0.01～0.1 part of initiator, 0.02～0.5 part of oxidation inhibitor and 10～100 parts of dispersion medium with 1～10 part of band aldehyde radical mix, and form suspension system;
3) get 100 parts of the active composite flame-retardant agents that step 1) makes, stir down and be warming up to 150～220 ℃, add step 2 then) suspension system that makes, 150～220 ℃ of fully reactions,, get dialysis-resistant composite halogen-free flame-proof agent through cooling, drying.
Among the present invention, it is ammonium polyphosphate that used expanding halide-free fire-retardant can adopt by mass ratio: tetramethylolmethane: trimeric cyanamide=40～80: 15～35: 5～25 compound systems that are mixed with.
Among the present invention; said coupling agent is silane coupling agent or phthalate ester coupling agent, comprises γ-An Bingjisanyiyangjiguiwan, γ-Racemic glycidol acyl-oxygen propyl trimethoxy silicane, sec.-propyl three (dioctylphyrophosphoric acid ester) ethene phthalate or sec.-propyl three (isostearate acyl group) phthalate etc.
Among the present invention, the monomer of said band aldehyde radical is oxalic dialdehyde or glutaraldehyde etc.; Said initiator is a superoxide, comprises dicumyl peroxide or benzoyl peroxide etc.; Said dispersion medium can be ethanol or ethylene glycol etc.
The particle diameter of the dialysis-resistant composite halogen-free flame-proof agent of the present invention's preparation is 20～100 μ m.When being used to prepare halogen-free flame retardant polypropylene composite material, by weight, with respect to 100 parts of polypropylene, with 25～30 parts dialysis-resistant composite halogen-free flame-proof agent.
Dialysis-resistant composite halogen-free flame-proof agent of the present invention is according to the actual requirement of producing halogen-free flame retardant polypropylene composite material, general filler, anti UV agent, dispersion agent, lubricant can be added, so that matrix material has good dimensional stability, processibility, uviolresistance in the material preparation process.
The invention has the beneficial effects as follows: after expanding halide-free fire-retardant is handled by the coupling agent finishing, fully act on the monomer of being with aldehyde radical, thereby make fire retardant surface-functionalized.The dialysis-resistant composite halogen-free flame-proof agent of the inventive method preparation can be directly and polypropylene to carry out fusion compound, have with the polymeric matrix consistency well, not to material surface migration dialysis, interpolation is convenient, simple to operate, production efficiency is high, cost is low, pollution is little, be easy to advantage such as suitability for industrialized production, with this anti-flaming polypropylene material any surface finish that makes, flame retardant properties reaches the requirement of UL 94 V-0 levels, no fusion drippage behind the material combustion, no poison gas discharges, and the mechanical property of body material is not impaired substantially.
Embodiment
Embodiment 1
1) be ammonium polyphosphate with mass ratio: tetramethylolmethane: the compound system of trimeric cyanamide=be mixed with at 65: 20: 15, dry 4h in 80 ℃ vacuum drying oven, add 1 part of γ-An Bingjisanyiyangjiguiwan then, under 100 ℃, mix, obtain active composite flame-retardant agent;
Will by 1 part of oxalic dialdehyde, the suspension system formed of 0.01 part of dicumyl peroxide, 0.08 part of oxidation inhibitor and 10 parts of ethanol joins in 100 parts of active composite flame-retardant agents, at 150 ℃ of following stirring reaction 60min, through cooling, drying, getting particle diameter is the dialysis-resistant composite halogen-free flame-proof agent of 20～100 μ m.
2) with above-mentioned dialysis-resistant composite halogen-free flame-proof agent and polypropylene by quality than fire retardant: polypropylene=30: 100 high-speed stirring 5min, being 150～180 ℃ through twin screw extruder at barrel temperature then melt extrudes, and injection moulding must be tested batten, injecting machine material tube temperature: 180～200 ℃, 60～80 ℃ of mould temperature, test halogen-free flame retardant polypropylene composite material performance.And make comparisons through the batten of same process preparation with polypropylene matrix, the results are shown in following table:
| Project | Testing standard | Unit | Index | |
| Polypropylene flame redardant | Polypropylene matrix | |||
| Density | GB1033 | g/cm 3 | 1.0 | 0.92 |
| Melting index | GB3682 | g/10min | 7 | 5 |
| Tensile strength | GB1040 | Mpa | 27 | 29 |
| Flexural strength | GB9341 | Mpa | 40 | 38 |
| 23 ℃ of simply supported beam notched Izod impact strength | GB1043 | KJ/m 2 | 8 | 6.5 |
| Heat-drawn wire (0.46Mpa) | GB1634 | ℃ | 128 | 130 |
| Incendivity | UL-94 (1.6mm) | V-0 | Burning | |
| Outward appearance | Bright and clean, dry and comfortable | |||
Embodiment 2
1) be ammonium polyphosphate with mass ratio: tetramethylolmethane: the compound system of trimeric cyanamide=be mixed with at 40: 35: 25, dry 4h in 80 ℃ vacuum drying oven, add 0.5 part of γ-Racemic glycidol acyl-oxygen propyl trimethoxy silicane then, under 150 ℃, mix, obtain active composite flame-retardant agent;
To join in 100 parts of active composite flame-retardant agents by the suspension system that 3 parts of glutaraldehyde, 0.08 part of dicumyl peroxide, 0.5 part of oxidation inhibitor and 50 parts of ethanol are formed, at 150 ℃ of following stirring reaction 30min, through cooling, drying, getting particle diameter is the dialysis-resistant composite halogen-free flame-proof agent of 20～100 μ m.
2) above-mentioned dialysis-resistant composite halogen-free flame-proof agent and polypropylene are pressed quality proportioning fire retardant: polypropylene=30: 100 high-speed stirring 5min, being 150～180 ℃ through twin screw extruder at barrel temperature then melt extrudes, and injection moulding must be tested batten, injecting machine material tube temperature: 180～200 ℃, 60～80 ℃ of mould temperature, test halogen-free flame retardant polypropylene composite material performance.And make comparisons according to the material of same recipe, prepared with using the composite halogen-free fire retardant without above-mentioned surface-functionalized same composition, the results are shown in following table:
| Project | Testing standard | Unit | The result | |
| Add the polypropylene flame redardant of functionalization fire retardant | Add the not polypropylene flame redardant of functionalization fire retardant | |||
| Tensile strength | GB1040 | Mpa | 27 | 18 |
| 23 ℃ of simply supported beam notched Izod impact strength | GB1043 | KJ/m 2 | 8 | 5 |
| Incendivity | UL-94 (1.6mm) | V-0 | Burning | |
| Outward appearance | Bright and clean, dry and comfortable | The surface has oily matter to ooze out | ||
Embodiment 3
1) be ammonium polyphosphate with mass ratio: tetramethylolmethane: the compound system of trimeric cyanamide=be mixed with at 80: 15: 5, dry 4hr in 80 ℃ vacuum drying oven, add 2 parts of sec.-propyls three (isostearate acyl group) phthalate then, under 80 ℃, mix, obtain active composite flame-retardant agent;
To join in 100 parts of active composite flame-retardant agents by the suspension system that 10 parts of glutaraldehyde, 0.1 part of benzoyl peroxide, 0.02 part of oxidation inhibitor and 100 parts of ethanol are formed, at 220 ℃ of following stirring reaction 30min, through cooling, drying, getting particle diameter is the dialysis-resistant composite halogen-free flame-proof agent of 20～100 μ m.
2) with above-mentioned dialysis-resistant composite halogen-free flame-proof agent and polypropylene by quality than fire retardant: polypropylene: talcum powder=30: 100: 30 high-speed stirring 5min, being 150～200 ℃ through twin screw extruder at barrel temperature then melt extrudes, and injection moulding must be tested batten, injecting machine material tube temperature: 180～200 ℃, 60～80 ℃ of mould temperature, test halogen-free flame retardant polypropylene composite material performance.And make comparisons according to the material of same recipe, prepared with using the composite halogen-free fire retardant without above-mentioned surface-functionalized same composition, the results are shown in following table:
| Project | Testing standard | Unit | The result | |
| Polypropylene flame redardant with the functionalization fire retardant | With the polypropylene flame redardant of functionalization fire retardant not | |||
| Tensile strength | GB1040 | Mpa | 25 | 15 |
| 23 ℃ of simply supported beam notched Izod impact strength | GB1043 | KJ/m 2 | 6.5 | 4 |
| Incendivity | UL-94 (1.6mm) | V-0 | Burning | |
| Outward appearance | Bright and clean, dry and comfortable | The surface has oily matter to ooze out | ||
Above-mentioned test shows, adopts the present invention not losing the matrix polymer tensile property substantially, on the basis that crooked, impact property are slightly improved, gives polypropylene good flame retardancy and outward appearance simultaneously, makes fire retardant material be able to fine application.
Claims (7)
1, a kind of preparation method of dialysis-resistant composite halogen-free flame-proof agent is characterized in that may further comprise the steps:
1) 100 parts of expanding halide-free fire-retardants are dry in 50～80 ℃ vacuum drying oven, the coupling agent that adds 0.5-2 part then mixes under 80～150 ℃, obtains active composite flame-retardant agent;
2) monomer, 0.01～0.1 part of initiator, 0.02～0.5 part of oxidation inhibitor and 10～100 parts of dispersion medium with 1～10 part of band aldehyde radical mix, and form suspension system;
3) get 100 parts of the active composite flame-retardant agents that step 1) makes, stir down and be warming up to 150～220 ℃, add step 2 then) suspension system that makes, 150～220 ℃ of fully reactions,, get dialysis-resistant composite halogen-free flame-proof agent through cooling, drying.
2. the preparation method of dialysis-resistant composite halogen-free flame-proof agent according to claim 1 is characterized in that said expanding halide-free fire-retardant is is ammonium polyphosphate by mass ratio: tetramethylolmethane: trimeric cyanamide=40～80: 15～35: 5～25 compound systems that are mixed with.
3, the preparation method of dialysis-resistant composite halogen-free flame-proof agent according to claim 1 is characterized in that the dialysis-resistant composite halogen-free flame-proof agent particle diameter is 20～100 μ m.
4, the preparation method of dialysis-resistant composite halogen-free flame-proof agent according to claim 1 is characterized in that said coupling agent is γ-An Bingjisanyiyangjiguiwan, γ-Racemic glycidol acyl-oxygen propyl trimethoxy silicane, sec.-propyl three (dioctylphyrophosphoric acid ester) ethene phthalate or sec.-propyl three (isostearate acyl group) phthalate.
5. the preparation method of dialysis-resistant composite halogen-free flame-proof agent according to claim 1, the monomer that it is characterized in that said band aldehyde radical is oxalic dialdehyde or glutaraldehyde.
6, the preparation method of dialysis-resistant composite halogen-free flame-proof agent according to claim 1 is characterized in that said initiator is dicumyl peroxide or benzoyl peroxide.
7, the preparation method of dialysis-resistant composite halogen-free flame-proof agent according to claim 1 is characterized in that said dispersion medium is ethanol or ethylene glycol.
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| CNB2006101546085A CN100400578C (en) | 2006-11-10 | 2006-11-10 | Preparation method for dialysis-resistant composite halogen-free flame-proof agent |
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| CNB2006101546085A CN100400578C (en) | 2006-11-10 | 2006-11-10 | Preparation method for dialysis-resistant composite halogen-free flame-proof agent |
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| CN1970606A true CN1970606A (en) | 2007-05-30 |
| CN100400578C CN100400578C (en) | 2008-07-09 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102975252A (en) * | 2012-11-22 | 2013-03-20 | 北京林业大学 | Wood treatment agent and preparation method thereof |
| CN104842620A (en) * | 2014-02-18 | 2015-08-19 | 常州百佳薄膜科技有限公司 | Precipitation-resistant halogen-free flame retardation polypropylene cast sheet and production method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1247694C (en) * | 1999-08-03 | 2006-03-29 | 国碳科技股份有限公司 | Composition of expansible flame-retarding adhesive and expansible fire retardent |
| CN1309772C (en) * | 1999-08-03 | 2007-04-11 | 国碳科技股份有限公司 | Halogen-free flame-retarding composition of foamed plastics |
| US6492444B1 (en) * | 2000-11-27 | 2002-12-10 | David H. Blount | Organic phosphorus-phosphorus oxyacid compounds |
| DE10112155A1 (en) * | 2001-03-14 | 2002-09-19 | Budenheim Rud A Oetker Chemie | Derivative of phosphoric acid ester substitute or adduct or mixtures thereof, process for their preparation and their use |
| CN1159373C (en) * | 2001-08-28 | 2004-07-28 | 中国石化集团巴陵石油化工有限责任公司 | Expanding fire retardant composition without halide for polyolefine |
| CN1311019C (en) * | 2002-12-18 | 2007-04-18 | 西巴特殊化学品控股有限公司 | Method for preparing five retardant agent based on cyanurotriamide and polymer composition |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102975252A (en) * | 2012-11-22 | 2013-03-20 | 北京林业大学 | Wood treatment agent and preparation method thereof |
| CN102975252B (en) * | 2012-11-22 | 2015-06-24 | 北京林业大学 | Wood treatment agent and preparation method thereof |
| CN104842620A (en) * | 2014-02-18 | 2015-08-19 | 常州百佳薄膜科技有限公司 | Precipitation-resistant halogen-free flame retardation polypropylene cast sheet and production method thereof |
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| CN100400578C (en) | 2008-07-09 |
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Assignee: Zhejiang Kexiang Wallpaper Manufacturing Co., Ltd. Assignor: Zhejiang University Contract record no.: 2011330000094 Denomination of invention: Preparation method for dialysis-resistant composite halogen-free flame-proof agent Granted publication date: 20080709 License type: Exclusive License Open date: 20070530 Record date: 20110314 |
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Granted publication date: 20080709 Termination date: 20151110 |
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