CN102675650A - Organic silicon-modified phosphorus-containing halogen-free expansion flame retardant and preparation method thereof - Google Patents
Organic silicon-modified phosphorus-containing halogen-free expansion flame retardant and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an organic silicon-modified phosphorus-containing halogen-free expansion flame retardant and a preparation method thereof. The flame retardant is prepared by performing condensation polymerization on a foaming agent, a char-forming agent or a compound mixture of the foaming agent and the char-forming agent which are adopted for phosphorus oxychloride, methyl trichlorosilane and an ordinary halogen-free expansion flame retardant, wherein the foaming agent is consists of melamine and a derivative thereof; and the char-forming agent is a polyhydric compound selected from pentaerythritol, a derivative thereof and the like. The method comprises the following steps of: adding phosphorus oxychloride into the foaming agent and the char-forming agent, and reacting at the temperature of 50-100 DEG C for 2-8 hours; and cooling, adding methyl trichlorosilane, reacting at the temperature of 40-100 DEG C for 2-6 hours, and purifying and drying the reactant to obtain the organic silicon-modified phosphorus-containing halogen-free expansion flame retardant. The method has a simple process, and is easy to operate. A phosphorus element and an organic silicon group are introduced into a general foaming agent and char-forming agent, so that a better synergistic flame retarding effect can be brought into play, high hydrophilic performance is achieved, the compatibility between the type of flame retardant and a high molecular substrate is greatly increased, and the mechanical property and processing property of a high molecular material can be improved remarkably; and the organic silicon-modified phosphorus-containing halogen-free expansion flame retardant can be widely applied to high molecular materials such as polyolefins and the like.
Description
Technical field
The invention belongs to the fire retardant synthesis technical field, be specifically related to one type of organic-silicon-modified phosphor-containing halogen-free expansion type flame retardant and preparation method thereof.
Background technology
Along with the widespread use of synthesized polymer material, the application quantity of fire retardant is also increasing.According to estimates, global fire retardant demand will reach 2,300,000,000 tons in 2012, and the fire retardant of addition type is easy to use because of it, good flame retardation effect and being used widely.Traditional halogen containing flame-retardant is few because of its addition, and good flame retardation effect once occupied the dominant position of additive flame retardant.But can emit a large amount of toxic gases and smog when the synthetic materials that uses this based flame retardant is burnt by high heat, serious environment pollution is made in threat people's life security.Along with the issue of WEEE of European Union and ROHS indication, people are constantly exploring new and effective halogen-free flame retardants.Expanding halide-free fire-retardant (IFR) is to be the compound flame retardant of core element with phosphorus, nitrogen, carbon.When this type fire retardant material receives high heat burning, can form one deck dense char layer foam on the surface, play heat insulation, oxygen barrier, press down the effect of cigarette, anti-molten drop, have good flame retardancy.But this based flame retardant because of be rich in-OH ,-NH
2,-HN
4 +Deng hydrophilic group because of, relatively poor with the macromolecule matrix consistency, also can produce moisture absorption phenomenon at the fire retardant material product surface, so its application is had certain influence.Silicone flame retardant is a kind of novel halogen-free flame retardants, have good one-tenth charcoal property, smoke-suppressing, dispersed and with the consistency of body material, also have nontoxic, low cigarette, advantage such as pollution-free simultaneously.But this based flame retardant price is more expensive, to having applied certain influence.
For the friendly new and effective fire retardant of development environment, people explore with organosilicon with phosphorous, contain nitrogen combustion inhibitor etc. and combine, utilize the synergistic effect between phosphorus, nitrogen, the silicon, in the hope of the better fire retardant of acquisition flame retardant properties.As: " a kind of phosphosilicate containing fire retardant and preparation method thereof " (Chinese patent publication number CN1706912A); " organic silicon fibre retardant of a kind of phosphorous and epoxy group(ing) and preparation method thereof " (Chinese patent publication number CN1724591A), " a kind of heat-proof combustion-resistant epoxy type electronic polymer material all has report with phosphorus-and silicon-containing hybridization because of changing in agent and preparation method thereof the patent documentations such as (CN101274998A).But it is rareer that above-mentioned patent prepares the raw material ratio that phosphorous silicon fire retardant selects for use, and comparatively expensive, applies being restricted.
Summary of the invention
In order to solve the problem of above-mentioned existence, the invention provides the one type of organic-silicon-modified phosphor-containing halogen-free expansion type flame retardant and the preparation method of this based flame retardant thereof.
The present invention adopts the METHYL TRICHLORO SILANE (being called for short a first) of by-product cheapness in the production of an organosilane monomer methyl chlorosilane as organosilicon modifier; With POCl3 is phosphorous introducing agent; With whipping agent trimeric cyanamide (MEL) and verivate thereof commonly used among the IFR; Also have char-forming agent tetramethylolmethane and verivate thereof commonly used, perhaps the composite mixture of the two carries out chemical reaction, generates organic-silicon-modified phosphor-containing halogen-free expansion type flame retardant.
All contain-NH in the triazine structure of trimeric cyanamide (MEL) and verivate melamine cyanurate (MCA) thereof, melamine phosphate (MP), melamine polyphosphate compounds such as (MPOP)
2,-NH
2On active Hydrogen Energy and POCl3 and METHYL TRICHLORO SILANE play polycondensation, emit HCl gas, generate the organic-silicon-modified trimeric cyanamide base polymer of phosphorated.
Tetramethylolmethane and verivate NSC 65881 thereof, tripentaerythritol; Also has trihydroxyethyl isocyanuric salt etc. as the char-forming agent among the IFR; In its molecule, all be rich in-OH; Reactive hydrogen among the-OH also can play polycondensation with POCl3 and METHYL TRICHLORO SILANE, emits HCl gas, generates the organic-silicon-modified fire-retardant char-forming agent of polymerization of phosphorated.
Commonly used whipping agent and char-forming agent both can be separately and POCl3, METHYL TRICHLORO SILANE generation polycondensation among the above-mentioned IFR; Also can with whipping agent and char-forming agent in the composite mixing of required ratio after again with POCl3 and METHYL TRICHLORO SILANE generation polycondensation, generate the organic-silicon-modified halogen-free expansible polymerization fire retardant of phosphorated.
METHYL TRICHLORO SILANE has three Si-Cl keys, and POCl3 has three P-Cl keys, contains 2-3-NH on trimeric cyanamide and the verivate thereof
2, and contain a plurality of-OH on the char-forming agents such as tetramethylolmethane and verivate thereof.As POCl3 and METHYL TRICHLORO SILANE and these-NH
2When polycondensation takes place in ,-OH, because the presence bit inhibition effect, so be difficult at the intermolecular corresponding one by one simplification compound that generates clear and definite structure, and be more prone to become cross-linked polymer in each intermolecular polycondensation that is cross-linked with each other.Gone up the organosilicon gene because of joining on this base polymer, increased the consistency with the macromolecule matrix material greatly, therefore can be widely used in the various macromolecular materials as additive flame retardant.
The present invention compared with prior art has following significant advantage:
1, on the whipping agent of IFR, char-forming agent, introduces phosphoric, can better bring into play the cooperative flame retardant effect.
2, adopt cheap METHYL TRICHLORO SILANE as organosilicon modifier,, introduced element silicon on the char-forming agent, also can improve the cooperative flame retardant effect at the whipping agent of IFR.
3, because of on this based flame retardant, having introduced the organosilicon gene; Make that hydrophilic whipping agent, char-forming agent have had good hydrophobic performance originally; Strengthen the consistency with polymer base material, can obviously improve the mechanical mechanics property and the processing characteristics of this type fire retardant material.
This based flame retardant preparation method of the present invention is following:
Both the composite mixture that takes by weighing in a certain amount of halogen-free expansion fire retardant (IFR) used usually whipping agent or char-forming agent or mix is added in the reaction vessel.According to contained-NH
2, group such as OH mole number, add the POCl3 of 0.1-0.3 times of mole number, if be necessary, add proper amount of diluting, stir and make it evenly moistening.The heating control reaction temperature is at 60-95 ℃, and stirring reaction 2-6 hour, detection was not emitted stopped reaction to there being HCl, is cooled to room temperature.Add diluted METHYL TRICHLORO SILANE again, the add-on mole number is-NH
2The 0.05-0.25 of ,-OH mole number doubly.It is evenly moistening that stirring makes it.Controlled temperature 40-95 ℃, reacted 2-8 hour, detect and do not emit stopped reaction to there being HCl.The HCl gas that reaction is emitted absorbs with alkali lye.Heating evaporation removes and desolvates, and the diluting solvent of recovery can be recycled.Add an amount of zero(ppm) water, be heated with stirring to 50-60 ℃ of half a hour, cooling, filter, washing do not have cl ions to filtrating, oven dry is sent out can obtain the described fire retardant of Ben Fa alliance.
The whipping agent that the present invention adopted is at least a in trimeric cyanamide (MEL), melamine cyanurate (MCA), melamine phosphate (MP), the melamine polyphosphate (MPOP).
The char-forming agent that the present invention adopted is at least a in tetramethylolmethane, NSC 65881, tripentaerythritol, the trihydroxyethyl isocyanuric salt.
The diluting solvent that the present invention adopted is a kind of in methylene dichloride, trichloroethane, hexanaphthene, acetone, the benzene.
Embodiment
Below through specific embodiment the present invention is done further description, but can not be interpreted as that the present invention only limits to following embodiment.Make some non-intrinsically safes according to content according to the invention and improve and adjustment, still belong to protection scope of the present invention.
Embodiment 1
Take by weighing 63g (0.5mol) trimeric cyanamide (MEL) and be added in the there-necked flask that whisking appliance, prolong are housed, the prolong upper end connects gas absorbing device, and there-necked flask places temperature automatically controlled water-bath.Add 52g (0.34mol) POCl3, stir and make it even moistening heating, 60 ℃ of stirring reaction 1.5h of temperature control are warming up to 90 ℃ of reaction 4h, have not had with the PH detection paper to stop heating after HCl gas is emitted, and the HCl gas of emitting in the reaction process absorbs with alkali lye.Be chilled to 40 ℃; , add 26g (0.17mol) METHYL TRICHLORO SILANE that has diluted with the 26g methylene dichloride, stir and make it evenly moistening, heating, at 45 ℃ of stirring reaction 1h, 60 ℃ of stirring reaction 2h, 90 ℃ of stirring reaction 2h, detection has not had HCl gas and has emitted.Evaporation removes methylene dichloride, and the methylene dichloride of recovery can be recycled.Add 200ml zero(ppm) water after removing solvent, control 60 ℃ and stir 0.5h.Cooling, filtration, being washed with distilled water to does not have cl ions, oven dry in the filtrating, obtain white hydrophobic powder 78.6g, yield 92.5%, the hydrophobicity of product is fine, puts into one week of water and does not still sink.
The theoretical P content 12.3% of this product, actual measurement 11.3%
Embodiment 2
Take by weighing 63.5g (0.25mol) melamine cyanurate (MCA) and put into reaction system like embodiment 1; Add 17g (0.111mol) POCl3 (with the dilution of 40g trichloroethane), stir and make it even moistening heating, 60 ℃ of stirring reaction 1.5h of temperature control; Being warming up to detect behind 90 ℃ of reaction 2.5h has not had HCl and has emitted; Be chilled to 40 ℃, add 8.5g (0.056mol) METHYL TRICHLORO SILANE, stir and make it evenly moistening through the dilution of 20g trichloroethane.Heating, 45 ℃ of stirring reaction 1h of temperature control, 60 ℃ of 2h, 90 ℃ of 4h, detection has not had HCl and has emitted stopped reaction, removes thinner, and the subsequent purification measure is with embodiment 1.Obtain white hydrophobic powder 67g after the drying, yield 94.7%, the product hydrophobicity is fine, puts into water and does not still sink after one week.The theoretical P content 4.8% of this product, 300 ℃ of calcination 30min of retort furnace are put in actual measurement 4.4%, and weightless 1.6%.
Embodiment 3
Take by weighing 56g (0.25mol) melamine phosphate (MP) and put into reaction system, add 15.3g (0.1mol) POCl3 (having used the 25g acetone diluted), stir and make it evenly moistening like embodiment 1; Heating, 60 ℃ of stirring reaction 1h of temperature control, being warming up to detect behind 90 ℃ of reaction 3h has not had HCl and has emitted; Be chilled to 40 ℃, add, stir and make it evenly moistening through the 10g of 20g acetone diluted (0.067mol) METHYL TRICHLORO SILANE; Heating, 45 ℃ of stirring reaction 1h of temperature control, 60 ℃ of 2h; 90 ℃ of 3h, detection has not had HCl and has emitted.Follow-up obtains white hydrophobic powder 59g as embodiment 1 after the drying, yield 92.9%, and hydrophobic performance is the same, at 300 ℃ of calcination 300min weightless 4.8%.
Embodiment 4
Take by weighing 52g (0.25/n mol) melamine polyphosphate (MPOP) and put into reaction system like embodiment 1; Add 12g (0.078mol) POCl3 (with the dilution of 28g hexanaphthene); It is evenly moistening that stirring makes it; Heating, 60 ℃ of stirring reaction 1h of temperature control, being warming up to detect behind 90 ℃ of reaction 3h has not had HCl and has emitted.Be chilled to 40 ℃, add 13g (0.09mol) METHYL TRICHLORO SILANE, stir and make it evenly moistening through the dilution of 27g hexanaphthene, heating, 45 ℃ of stirring reaction 1h of temperature control, 60 ℃ of 2h, 90 ℃ of 3h, detection has not had HCl and has emitted.The subsequent disposal measure is with embodiment 1.Drying obtains white hydrophobic powder 54.5g, yield 93.2%, and hydrophobic performance is the same, at 300 ℃ of calcination 30min weightless 4.4%.
Embodiment 5
Take by weighing levigated 51g (0.375mol) tetramethylolmethane and add in the reaction system like embodiment 1, add 60g (0.392mol) POCl3, stir; Heating, 60 ℃ of stirring reaction 1h of temperature control are warming up to 90 ℃ of reaction 6h and detect and not had HCl and emit; Be chilled to 40 ℃ and add 18g (0.121mol) METHYL TRICHLORO SILANE (with the dilution of 22g benzene) heating, 45 ℃ of stirring reaction 1h of temperature control, 60 ℃ of 2h; 90 ℃ of 4h, detecting has not had HCl and has emitted, and the subsequent disposal measure is with embodiment 1; Obtain white crystals sprills 65g after the drying, yield 87.1%.Hydrophobic performance is the same, at 260 ℃ of calcination 30min weightless 5.1%.
Embodiment 6
Take by weighing NSC 65881 51g (0.2mol) and put into reaction system, add 46g (0.30mol) POCl3, stir like embodiment 1, heating, 60 ℃ of stirring reaction 1h of temperature control are warming up to 90 ℃ of reaction 5h and detect and do not had HCl and emit.Be chilled to 40 ℃, add 15g (0.1mol) METHYL TRICHLORO SILANE (with the dilution of 25g benzene), stir and make it evenly moistening, heating, 45 ℃ of stirring reaction 1h of temperature control, 60 ℃ of 2h, 90 ℃ of 4h, detection has not had HCl and has emitted.The subsequent disposal measure is with embodiment 1.Dry white hydrophobic powder 62g, yield 89.3%, hydrophobic performance is the same.
Embodiment 7
Take by weighing 28.5g (0.227mol) trimeric cyanamide and 28.5 (0.21mol) tetramethylolmethane, put into the high speed disintegrator pulverizing and mix, change over to again in the reaction system like embodiment 1; Add 43g (0.281mol) POCl3; It is evenly moistening that stirring makes it, heating, 60 ℃ of stirring reaction 1h of temperature control; 90 ℃ of 6h, detection has not had HCl and has emitted.Be chilled to 40 ℃, add 34g (0.227mol) METHYL TRICHLORO SILANE of having crossed with acetone diluted, stir and make it evenly moistening, heating, 45 ℃ of 1h of temperature control, 60 ℃ of 2h, 90 ℃ of 2h, detection has not had HCl and has emitted.The subsequent disposal measure is with embodiment 1, dry white hydrophobic powder 73.1g, yield 93.3%.Hydrophobic performance is the same, at 260 ℃ of scorching hot 30min weightless 1.8%.
Embodiment 8
Taking by weighing 63g (0.25mol) melamine cyanurate (MCA) and 64g (0.25mol) NSC 65881 mixes in high speed disintegrator in the reaction system of back immigration like embodiment 1; Add 76.5g (0.5mol) POCl3 (diluting with methylene dichloride); It is evenly moistening that stirring makes it, heating, 60 ℃ of stirring reaction 1h of temperature control; 90 ℃ of 3h, detection has not had HCl and has emitted.Be chilled to 40 ℃, add 25g (0.167mol) METHYL TRICHLORO SILANE (diluting with methylene dichloride earlier), stir and make it evenly moistening.Heating, 45 ℃ of 1h of temperature control, 60 ℃ of 2h, 90 ℃ of 3h, detecting has not had HCl and has emitted, the subsequent disposal measure is with embodiment 1, after the drying product 147.2g, yield 95%, hydrophobic performance is the same, at 260 ℃ of calcination 30min, weightless 1.6%.
Embodiment 9
Taking by weighing 51g (0.2mol) melamine cyanurate (MCA) and 53.2g (0.2mol) trihydroxyethyl isocyanuric salt mixes in high speed disintegrator in the reaction system of back immigration with enforcement 1; Add 31g (0.203mol) POCl3 of having used acetone diluted, stir and make it evenly moistening.Heating, 60 ℃ of stirring reaction 1h of temperature control, 90 ℃ of 2h, detection has not had HCl and has emitted.Be chilled to 40 ℃, add 21g (0.14mol) METHYL TRICHLORO SILANE of having used acetone diluted, stir and make it evenly moistening.Heating, 45 ℃ of stirring reaction 1h of temperature control, 60 ℃ of 2h, 90 ℃ of 2h, detection has not had HCl and has emitted.The subsequent disposal measure is with embodiment 1.The dry product 108.6g that gets, yield 90.7%, hydrophobic performance is the same, at 260 ℃ of calcination 30min weightless 2.8%.
The application implementation example
To be re-dubbed halogen-free expansion fire retardant (IFR) by fire retardant and the ammonium polyphosphate (APP) that the foregoing description condition makes; The mass ratio of whipping agent and char-forming agent is 1: 1 basically when composite; Add APP more on demand, making the IFR P content that is re-dubbed is 18.00-18.5%.Similarity condition is used the ammonium polyphosphate (APP) without any processing to add trimeric cyanamide (MEL) to add to become tetrol (PER) and ammonium polyphosphate to add melamine cyanurate (MCA) in season to add the composite fire retardant that forms of trihydroxyethyl isocyanuric salt (being called for short the match gram) as reference examples.With Vestolen PP 7052 (PP) and fire retardant, filler, oxidation inhibitor, lubricant by the proportioning in the following table in high-speed mixer behind the thorough mixing; Join extruding pelletization in the twin screw extruder again; Pellet is at 90-95 ℃ of dry 2h; Using the injection moulding machine injection moulding is various standard strips, and by relevant criterion its flame retardant properties of test and mechanical property, its result sees table 2:
The proportioning (WT%) of table 1 preparation polypropylene flame redardant sample
Table 2 each routine flame retardant properties and mechanical property
Can find out that from last table the fire retardant of embodiment of the invention gained is being used for Vestolen PP 7052, flame retardant properties and mechanical property all are superior to undressed same based flame retardant.
Claims (7)
1. one type of organic-silicon-modified phosphor-containing halogen-free expansion type flame retardant is characterized in that, whipping agent, the char-forming agent polycondensation adopted by POCl3 and METHYL TRICHLORO SILANE and common halogen-free expansion type flame-proof type form.
2. fire retardant according to claim 1 is characterized in that, the whipping agent of employing is at least a in trimeric cyanamide (MEL) and verivate melamine cyanurate (MCA) thereof, melamine phosphate (MP), the melamine polyphosphate (MPOP).
3. fire retardant according to claim 1 is characterized in that, the char-forming agent of employing is at least a in tetramethylolmethane, NSC 65881, tripentaerythritol, the trihydroxyethyl isocyanuric salt.
4. fire retardant according to claim 1 is characterized in that, in POCl3 and whipping agent, the char-forming agent-and NH
2The mol ratio of ,-OH group total mole number is 0.1-0.3: 1.In METHYL TRICHLORO SILANE and whipping agent, the char-forming agent-NH
2The mol ratio of ,-OH group total mole number is 0.05-0.25: 1
5. the preparation method of the described fire retardant of claim 1; Comprise: the above-mentioned whipping agent that will select for use, char-forming agent or both composite mixtures are added in the reaction system, add POCl3 again, if be necessary; Can add an amount of thinner, stir and make it evenly moistening.Reacted 2-8 hour down at 50-100 ℃.Add METHYL TRICHLORO SILANE after the cooling again, also can add an amount of thinner in case of necessity, stir and make it evenly moistening,, reaction product is carried out purifying, drying 40-100 ℃ of reaction 2-8 hour.
6. preparation method according to claim 5 is characterized in that, described thinner can be a kind of in methylene dichloride, trichloroethane, hexanaphthene, acetone and the benzene.
7. preparation method according to claim 5, its purification process is: distillation eliminates diluting solvent, adds zero(ppm) water, and heated and stirred is filtered, and washing does not have cl ions in filtrating.
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| CN107722334A (en) * | 2017-08-21 | 2018-02-23 | 宁波中金石化有限公司 | A kind of preparation method of fire-retardant pentane foaming agent |
| CN107987517A (en) * | 2017-12-04 | 2018-05-04 | 上海至正道化高分子材料股份有限公司 | A kind of charging pile cable hydrolysis high-performance refractory environment-friendly polyurethane protective cover material and preparation method and cable |
| CN109468058A (en) * | 2018-09-30 | 2019-03-15 | 浙江凌志新材料有限公司 | A kind of weather-proof cracking resistance organosilicon fireproof coating of ultrathin type |
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| CN109468058A (en) * | 2018-09-30 | 2019-03-15 | 浙江凌志新材料有限公司 | A kind of weather-proof cracking resistance organosilicon fireproof coating of ultrathin type |
| CN109468058B (en) * | 2018-09-30 | 2020-12-29 | 浙江凌志新材料有限公司 | Ultrathin weather-resistant anti-cracking organic silicon fireproof coating |
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