CN103554515A - High-heat-resistant high-smoke-inhibition flame retardant and preparation method thereof - Google Patents
High-heat-resistant high-smoke-inhibition flame retardant and preparation method thereof Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title abstract description 17
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 23
- 230000004048 modification Effects 0.000 claims abstract description 22
- 238000012986 modification Methods 0.000 claims abstract description 22
- LOZAIRWAADCOHQ-UHFFFAOYSA-N triphosphazene Chemical compound PNP=NP LOZAIRWAADCOHQ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 51
- -1 organo montmorillonite Chemical compound 0.000 claims description 29
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 235000019504 cigarettes Nutrition 0.000 claims description 15
- 239000000725 suspension Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- YXYZMHGSOKYZAF-UHFFFAOYSA-M [Cl-].C(C(=C)C)(=O)OCC[N+](C(C)(C)C)(C)C Chemical group [Cl-].C(C(=C)C)(=O)OCC[N+](C(C)(C)C)(C)C YXYZMHGSOKYZAF-UHFFFAOYSA-M 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000009413 insulation Methods 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000002386 leaching Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 230000004580 weight loss Effects 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 5
- 229920000642 polymer Polymers 0.000 abstract description 5
- 238000009830 intercalation Methods 0.000 abstract description 4
- 230000002687 intercalation Effects 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 229920002521 macromolecule Polymers 0.000 abstract description 2
- 229910017059 organic montmorillonite Inorganic materials 0.000 abstract 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 230000008520 organization Effects 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 5
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 5
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000000412 dendrimer Substances 0.000 description 3
- 229920000736 dendritic polymer Polymers 0.000 description 3
- 239000012757 flame retardant agent Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000002056 nanofire structure Substances 0.000 description 3
- 229910052615 phyllosilicate Inorganic materials 0.000 description 3
- 239000002341 toxic gas Substances 0.000 description 3
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000010094 polymer processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- TXTWXQXDMWILOF-UHFFFAOYSA-N (2-ethoxy-2-oxoethyl)azanium;chloride Chemical compound [Cl-].CCOC(=O)C[NH3+] TXTWXQXDMWILOF-UHFFFAOYSA-N 0.000 description 1
- GFLHLQNGVGTEND-UHFFFAOYSA-N C1=CC=CC=C1.C(C)OC(CN)=O Chemical compound C1=CC=CC=C1.C(C)OC(CN)=O GFLHLQNGVGTEND-UHFFFAOYSA-N 0.000 description 1
- 241000555268 Dendroides Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
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- 238000009835 boiling Methods 0.000 description 1
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- 239000003814 drug Substances 0.000 description 1
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- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
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- 239000002086 nanomaterial Substances 0.000 description 1
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- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Fireproofing Substances (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a high-heat-resistant high-smoke-inhibition flame retardant and a preparation method thereof. The preparation method comprises the following steps: carrying out organization modification on inorganic montmorillonite by using quaternary ammonium salt, and carrying out terminal group modification on amino-terminated polyamide-amine triphosphazene dendriform macromolecules by using the modified organic montmorillonite. The flame retardant is a powdery solid of which the average particle size is 40-80nm; the thermal weight loss central temperature of the flame retardant can reach 400-600 DEG C, which indicates that the flame retardant has excellent heat resistance; the interlamellar spacing of the organic montmorillonite is up to 2.83-5.42nm, which indicates that the flame retardant has favorable compatibility with polymers and can be directly applied to a polymer working process without any complex solution or molten intercalation treatment. The flame retardant has the advantages of low preparation and use cost and the like, and is easy to operate.
Description
Technical field
The present invention relates to a kind of fire retardant and preparation method thereof, specifically, relate to a kind of high heat-resisting, high fire retardant that presses down cigarette and preparation method thereof, belong to halogen-free flame retardants technical field.
Background technology
At present, in chemical industry flame retardant area, applying more is halogenated flame retardant, although the flame retardant effect of this based flame retardant is fine, when burning, can produce a large amount of toxic gases, has now been limited to use.
Halogen-free flame retardants is because of it has safety, presses down cigarette, the advantage such as nontoxic, inexpensive has attracted numerous investigators sight.The research of halogen-free flame retardants mainly contains three directions: 1) inorganic combustion inhibitor, mainly comprise the metal hydroxidess such as magnesium hydroxide, aluminium hydroxide, because magnesium hydroxide, aluminium hydroxide have weighting agent, fire retardant, the functions such as inhibitor of being fuming, be considered to nuisanceless fire retardant.But the flame retardant resistance that these inorganic combustion inhibitors need higher addition to have obtained, thereby the mechanical property of polymkeric substance is reduced greatly, 2) halogen-free expansion fire retardant of Nitrogen-and Phosphorus-containing system, this based flame retardant is not halogen-containing, when the superpolymer containing this based flame retardant is heated, surface can generate the uniform foam layer of one deck, can play heat insulation, oxygen barrier, press down cigarette effect, but halogen-free expansion fire retardant building-up process relative complex, and preparation process can be brought pollution to environment, 3) phyllosilicate nano fire retardant, this based flame retardant is thought a kind of novel, revolutionary fire retardant material by foreign scholar, phyllosilicate nano fire retardant not only can not damage the mechanical property of material when improving Flame Retardancy energy, in combustion processes, can not produce toxic gas yet, and consumption is little, cost is low, flame-retarded efficiency is high, the amount of being fuming is few, the features such as environmental protection, so investigator attempts using silicate nano composition polymer as fire retardant material, but silicate fire retardant in use exists with macromolecular material (as plastics, rubber etc.) consistency is bad, so it is organically-modified that investigator has done layered silicate, one of them method is that the dendroid fire retardant intercalation of Nitrogen-and Phosphorus-containing system is entered to phyllosilicate nano fire retardant, obtain a kind of mixed type fire retardant, the consistency of each component in the dendriform type fire retardant increase system that is by Nitrogen-and Phosphorus-containing.
Although the nanostructure that the branch-shape polymer of phosphorus-nitrogen containing has and preferably consistency and flame retardant resistance wait by force excellent properties, have the advantages such as nontoxic, fire-retardant and heat-resisting, can obtain and apply in the materials such as plastics, rubber.But it is worth noting that macromolecular material can produce a large amount of toxic gases and smog in combustion processes.Therefore, in the research of flame-retarded technology, also should consider to press down the problems such as cigarette, attenuation, and how improve not high-technology bottleneck of consistency poor between layered silicate and polymkeric substance, heat resisting temperature, by very crucial to the widespread use of layered silicate based flame retardant.
Summary of the invention
The problems referred to above that exist for prior art, the object of this invention is to provide a kind of high heat-resisting, high fire retardant that presses down cigarette and preparation method thereof, to meet the service requirements of fire retardant.
For achieving the above object, the technical solution used in the present invention is as follows:
High heat-resisting, a high fire retardant that presses down cigarette, is first by quaternary ammonium salt, inorganic polynite to be carried out to organic modification, and the organo montmorillonite opposite end amino polyamide-amide type Triphosphazene dendritic macromole then obtaining by modification carries out terminal groups modification processing and obtains.
Described quaternary ammonium salt can be MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, acrylyl oxy-ethyl-trimethyl salmiac or methylacryoyloxyethyl dimethylbutyl brometo de amonio; Be preferably MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride.
Heat-resisting, the high preparation method who presses down the fire retardant of cigarette of height, comprises the steps:
A) inorganic polynite is added in deionized water, be mixed with suspension;
B) at 60～80 ℃, quaternary ammonium salt is added in the suspension that step a) prepares, insulation reaction 5～7 hours, filters, to existing without Cl-, dry with deionized water washing leaching cake, obtains the organo montmorillonite of modification;
C) at N
2under protection, at 50～60 ℃; by step b) organo montmorillonite that obtains adds in the methanol aqueous solution of holding amino polyamide-amide type Triphosphazene dendritic macromole; isothermal reaction 7～9 hours, filters, and the solid of collection is heat-resisting, the high fire retardant that presses down cigarette of described height.
As a kind of preferred version, step a) the shared massfraction of inorganic polynite in described suspension is 5～15%.
As a kind of preferred version, step b) in quaternary ammonium salt and the mass ratio of inorganic polynite be 1:1.5～1.2.
As a kind of preferred version, step c) described in the algebraically of the amino polyamide-amide type of end Triphosphazene dendritic macromole be G1 generation to G3 any one in generation.
As a kind of preferred version, in the methanol aqueous solution of the amino polyamide-amide type of the end step c) Triphosphazene dendritic macromole, the shared volume fraction of methyl alcohol is 40～70%, and holding the shared massfraction of amino polyamide-amide type Triphosphazene dendritic macromole is 15～25%.
As a kind of preferred version, step c) in organo montmorillonite with end amino polyamide-amide type Triphosphazene dendritic macromole mol ratio be 4:1～8:1.
The amino polyamide-amide type of end described in the present invention Triphosphazene dendritic macromole is known polymer, its preparation method and structure and performance can refer to document: Guan Lijuan, synthetic, the structure of the multi-level tripolyphosphazene core of multifunction dendritic macromole and performance study (38～42), Beijing University of Chemical Technology's Master's thesis.
Dendritic polymer due to polyphosphonitrile, that a class be take line style that the two key alternative arrangements of nitrogen phosphorus are main chain or the polymkeric substance of ring-type, its character is between mineral compound, organic compound and macromolecular compound, the title that has " inorganic rubber ", it has high heat stability, smoke-suppressing, chemical stability and radiation resistance, in industries such as industry, agricultural, medicine, space flight, energy-saving and environmental protection, has a wide range of applications.
The present invention is by adopting quaternary ammonium salt to carry out organic modification to inorganic polynite, and the organo montmorillonite then obtaining by modification carries out terminal groups modification processing to the polyphosphonitrile dendritic polymer of different algebraically, has obtained high heat-resisting, the high fire retardant that presses down cigarette; Described fire retardant is pulverulent solids, and the median size of powder is 40～80nm; The thermal weight loss core temperature of this fire retardant can reach 400～600 ℃, illustrates and has good thermotolerance; And the interlamellar spacing of organo montmorillonite reaches 2.83～5.42nm, illustrate with polymkeric substance and have good consistency, can directly apply in polymer processing, without carrying out again loaded down with trivial details solution or fusion intercalation, process, there is the advantages such as preparation and use cost is low, easy handling.
Embodiment
Below in conjunction with embodiment, technical solution of the present invention is described in further detail and completely.
In embodiment, adopt < < nano composite polymer/laminated silicate material theory and practice > > (QiZongNeng, Shang Wenyu writes, Chemical Industry Press, 2002) the thermal weight loss core temperature of the method for report test polynite, adopts small-angle diffraction method to test the interlamellar spacing of organo montmorillonite; Adopt transmission electron microscope method to observe the size of fire retardant powder.
MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride Shi You Shanghai Bang Cheng Chemical Co., Ltd. used in embodiment provides.
In embodiment, inorganic polynite used is to be provided by Zhejiang Feng Hong clay company limited.
The amino polyamide-amide type of the end that uses in embodiment Triphosphazene dendritic macromole is to participate in document " Guan Lijuan; synthetic, the structure and performance study (38～42) of the multi-level tripolyphosphazene core of multifunction dendritic macromole, Beijing University of Chemical Technology's Master's thesis " prepare and obtain:
One, glycine ethyl ester hydrochloride and triethylamine are added in dry benzene, after backflow 6h, filter, obtain glycine ethyl ester benzole soln, under cryosel bath condition, above-mentioned solution is slowly added dropwise in the benzole soln that contains hexachlorocyclotriphosphazene and triethylamine, after room temperature reaction 35h, be warming up to 50 ℃ and continue reaction 6h, after reaction finishes, reactant after filtration, underpressure distillation concentrated after, pour boiling range into and be precipitation in the sherwood oil of 30～60 ℃, filter, dry after purifying obtain the amino polyamide-amide type of the dendritic macromole end Triphosphazene of G0.5, be called for short G0.5;
Two, under lucifuge, protection of inert gas and condition of ice bath, methyl alcohol is slowly added dropwise in quadrol, stir after deoxidation 2h, the dry absolute methanol solution that is dissolved with G0.5 is slowly added dropwise in above-mentioned quadrol methanol solution in-10～-5 ℃, after room temperature reaction 72h, remove excessive quadrol, after dry purifying, obtain G1.0;
Three, under the condition of lucifuge, ice bath and protection of inert gas, the anhydrous methanol that is dissolved with G1.0 is stirred after deoxidation 2h, be slowly added dropwise to refining methyl acrylate, drip again several sodium methylates, after room temperature reaction 72h, except desolventizing and excessive propene acid methyl esters, after dry purifying, obtain G1.5;
Four, under lucifuge, protection of inert gas condition, the dry absolute methanol solution that is dissolved with G1.5 is slowly added dropwise in quadrol, after room temperature reaction 72h, remove excessive quadrol, after dry purifying, obtain G2.0;
Five, the operation of repeating step three and step 4 can obtain G3.0.
Embodiment 1
The inorganic polynite of 20g is added in deionized water, be mixed with massfraction and be 5% suspension; Gained suspension is placed in to the water bath with thermostatic control of 60 ℃, 30g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride is added in suspension, finish, insulation reaction 5h under violent stirring, filters, and uses deionized water washing leaching cake extremely without Cl
-exist, 80 ℃ of oven dry, obtain the organo montmorillonite of modification.
In flask, adding 2.5g massfraction is that 20% G-1 is for the methanol aqueous solution (the shared volume fraction of methyl alcohol is 40%) of the amino polyamide-amide type Triphosphazene dendritic macromole of end, at N
2under protection, the organo montmorillonite 10g that slowly adds modification to obtain at 50 ℃, finishes, and insulation reaction 7h under violent stirring filters, and is dried to obtain pale powder solid, is heat-resisting, the high fire retardant that presses down cigarette of described height.
Test data about the interlamellar spacing of median size, thermal weight loss core temperature and the organo montmorillonite of obtained flame-retardant agent powder is shown in Table 1.
Embodiment 2
The inorganic polynite of 20g is added in deionized water, be mixed with massfraction and be 10% suspension; Gained suspension is placed in to the water bath with thermostatic control of 70 ℃, 35g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride is added in suspension, finish, insulation reaction 6h under violent stirring, filters, and with deionized water washing leaching cake, extremely without Cl-, exists, 80 ℃ of oven dry, obtain the organo montmorillonite of modification.
In flask, adding 2.5g massfraction is that 20% G-2 is for the methanol aqueous solution (the shared volume fraction of methyl alcohol is 55%) of the amino polyamide-amide type Triphosphazene dendritic macromole of end, at N
2under protection, the organo montmorillonite 15g that slowly adds modification to obtain at 55 ℃, finishes, and insulation reaction 8h under violent stirring filters, and is dried to obtain pale powder solid, is heat-resisting, the high fire retardant that presses down cigarette of described height.
Test data about the interlamellar spacing of median size, thermal weight loss core temperature and the organo montmorillonite of obtained flame-retardant agent powder is shown in Table 1.
Embodiment 3
The inorganic polynite of 20g is added in deionized water, be mixed with massfraction and be 15% suspension; Gained suspension is placed in to the water bath with thermostatic control of 80 ℃, 40g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride is added in suspension, finish, insulation reaction 7h under violent stirring, filters, and with deionized water washing leaching cake, extremely without Cl-, exists, 80 ℃ of oven dry, obtain the organo montmorillonite of modification.
In flask, adding 2.5g massfraction is that 20% G-3 is for the methanol aqueous solution (the shared volume fraction of methyl alcohol is 70%) of the amino polyamide-amide type Triphosphazene dendritic macromole of end, at N
2under protection, the organo montmorillonite 20g that slowly adds modification to obtain at 60 ℃, finishes, and insulation reaction 9h under violent stirring filters, and is dried to obtain pale powder solid, is heat-resisting, the high fire retardant that presses down cigarette of described height.
Test data about the interlamellar spacing of median size, thermal weight loss core temperature and the organo montmorillonite of obtained flame-retardant agent powder is shown in Table 1.
The test data of table 1. median size, thermal weight loss core temperature and interlamellar spacing
| Embodiment | Median size (nm) | Thermal weight loss core temperature (℃) | Interlamellar spacing (nm) |
| 1 | 40 | 400～450 | 2.83 |
| 2 | 60 | 500～550 | 3.67 |
| 3 | 80 | 550～600 | 5.42 |
From table 1: the present invention is by adopting quaternary ammonium salt to carry out organic modification to inorganic polynite, then the organo montmorillonite obtaining by modification carries out terminal groups modification processing to the polyphosphonitrile dendritic polymer of different algebraically, has obtained high heat-resisting, the high fire retardant that presses down cigarette; Described fire retardant is pulverulent solids, and the median size of powder is 40～80nm; The thermal weight loss core temperature of this fire retardant can reach 400～600 ℃, illustrates and has good thermotolerance; And the interlamellar spacing of organo montmorillonite reaches 2.83～5.42nm, illustrate with polymkeric substance and have good consistency, can directly apply in polymer processing, without carrying out again loaded down with trivial details solution or fusion intercalation, process, there is the advantages such as preparation and use cost is low, easy handling.
Finally be necessary described herein: above embodiment is only for being described in more detail technical scheme of the present invention; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.
Claims (10)
1. one kind high heat-resisting, high fire retardant that presses down cigarette, it is characterized in that: described fire retardant is first by quaternary ammonium salt, inorganic polynite to be carried out to organic modification, the organo montmorillonite opposite end amino polyamide-amide type Triphosphazene dendritic macromole then obtaining by modification carries out terminal groups modification processing and obtains.
2. fire retardant as claimed in claim 1, is characterized in that: described quaternary ammonium salt is MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, acrylyl oxy-ethyl-trimethyl salmiac or methylacryoyloxyethyl dimethylbutyl brometo de amonio.
3. fire retardant as claimed in claim 2, is characterized in that: described quaternary ammonium salt is MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride.
4. a preparation method for fire retardant described in claim 1, is characterized in that, comprises the steps:
A) inorganic polynite is added in deionized water, be mixed with suspension;
B) at 60～80 ℃, quaternary ammonium salt is added in the suspension that step a) prepares, insulation reaction 5～7 hours, filters, to existing without Cl-, dry with deionized water washing leaching cake, obtains the organo montmorillonite of modification;
C) at N
2under protection, at 50～60 ℃, by step b) organo montmorillonite that obtains adds in the methanol aqueous solution of holding amino polyamide-amide type Triphosphazene dendritic macromole, and isothermal reaction 7～9 hours, filters, and the solid of collection is described fire retardant.
5. preparation method as claimed in claim 4, is characterized in that: described quaternary ammonium salt is MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, acrylyl oxy-ethyl-trimethyl salmiac or methylacryoyloxyethyl dimethylbutyl brometo de amonio.
6. preparation method as claimed in claim 5, is characterized in that: described quaternary ammonium salt is MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride.
7. preparation method as claimed in claim 4, is characterized in that: step a) the shared massfraction of inorganic polynite in described suspension is 5～15%.
8. preparation method as claimed in claim 4, is characterized in that: the quaternary ammonium salt step b) and the mass ratio of inorganic polynite are 1:1.5～1:2; Step c) organo montmorillonite in is 4:1～8:1 with the mol ratio of the amino polyamide-amide type Triphosphazene dendritic macromole of end.
9. the preparation method as described in claim 4 or 8, is characterized in that: the algebraically of the described amino polyamide-amide type of end Triphosphazene dendritic macromole is that G1 is for any one in generation to G3.
10. preparation method as claimed in claim 4, it is characterized in that: in the methanol aqueous solution of the amino polyamide-amide type of the end step c) Triphosphazene dendritic macromole, the shared volume fraction of methyl alcohol is 40～70%, and holding the shared massfraction of amino polyamide-amide type Triphosphazene dendritic macromole is 15～25%.
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| CN105237809A (en) * | 2015-11-03 | 2016-01-13 | 上海工程技术大学 | High-heat-resistant organic montmorillonite fire retardant and preparation method thereof |
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