CN103554515B - A kind ofly highly heat-resistingly, high press down fire retardant of cigarette and preparation method thereof - Google Patents
A kind ofly highly heat-resistingly, high press down fire retardant of cigarette and preparation method thereof Download PDFInfo
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- CN103554515B CN103554515B CN201310482958.4A CN201310482958A CN103554515B CN 103554515 B CN103554515 B CN 103554515B CN 201310482958 A CN201310482958 A CN 201310482958A CN 103554515 B CN103554515 B CN 103554515B
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 235000019504 cigarettes Nutrition 0.000 title claims abstract description 17
- -1 organo montmorillonite Chemical compound 0.000 claims abstract description 31
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 24
- 230000004048 modification Effects 0.000 claims abstract description 23
- 238000012986 modification Methods 0.000 claims abstract description 23
- 229920000962 poly(amidoamine) Polymers 0.000 claims abstract description 20
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 20
- LOZAIRWAADCOHQ-UHFFFAOYSA-N triphosphazene Chemical compound PNP=NP LOZAIRWAADCOHQ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 51
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 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
- 239000012065 filter cake Substances 0.000 claims description 5
- 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
- 239000000126 substance Substances 0.000 abstract description 11
- 239000000843 powder Substances 0.000 abstract description 10
- 230000004580 weight loss Effects 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000002687 intercalation Effects 0.000 abstract description 4
- 238000009830 intercalation Methods 0.000 abstract description 4
- 230000004927 fusion Effects 0.000 abstract description 3
- 238000010094 polymer processing Methods 0.000 abstract description 3
- 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 description 10
- 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
- 238000005516 engineering process Methods 0.000 description 5
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 238000011160 research 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
- 229920000642 polymer Polymers 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
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect 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
- 238000003786 synthesis reaction 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
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 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
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000004760 silicates Polymers 0.000 description 1
- 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 and a kind ofly highly heat-resistingly, high press down fire retardant of cigarette and preparation method thereof, described fire retardant first carries out organic modification by quaternary ammonium salt to inorganic polynite, and the organo montmorillonite then obtained by modification is carried out terminal groups modification process to Amino End Group polyamidoamine Triphosphazene dendritic macromole and obtains.Fire retardant of the present invention 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 DEG C, illustrates to have excellent thermotolerance; And the interlamellar spacing of organo montmorillonite reaches 2.83 ~ 5.42nm, illustrate with polymkeric substance have good consistency, can directly applying in polymer processing, without the need to carrying out loaded down with trivial details solution or fusion intercalation process again, there is the advantages such as preparation and use cost is low, easy handling.
Description
Technical field
The present invention relates to a kind of fire retardant and preparation method thereof, specifically, relate to a kind ofly highly heat-resistingly, high press down fire retardant of 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, can produce a large amount of toxic gas when burning, and has now been limited to use.
Halogen-free flame retardants because of its there is safety, press down cigarette, the advantage such as nontoxic, inexpensive has attracted the sight of numerous investigator.The research of halogen-free flame retardants mainly contains three directions: 1) inorganic combustion inhibitor, mainly comprise the metal hydroxides such as magnesium hydroxide, aluminium hydroxide, due to magnesium hydroxide, aluminium hydroxide there is 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, thus 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, heat insulation, oxygen barrier can be played, press down cigarette effect, but halogen-free expansion fire retardant building-up process relative complex, and preparation process can bring 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 while improving Flame Retardancy energy, also toxic gas can not be produced in combustion processes, 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 bad, so investigator does organically-modified to layered silicate, one of them method is that the dendroid fire retardant intercalation of Nitrogen-and Phosphorus-containing system is entered phyllosilicate nano fire retardant, obtain a kind of mixed type fire retardant, by the consistency of each component in the dendriform type fire retardant increase system of Nitrogen-and Phosphorus-containing system.
Although the nanostructure that the branch-shape polymer of phosphorus-nitrogen containing has and good consistency and the flame retardant resistance excellent properties such as by force, has the advantages such as nontoxic, fire-retardant and heat-resisting, can obtain application in the material such as plastics, rubber.But it is worth noting that macromolecular material can produce a large amount of toxic gas and smog in combustion.Therefore, also should consider in the research of flame-retarded technology to press down the problem such as cigarette, attenuation, and how improve consistency poor between layered silicate and polymkeric substance, heat resisting temperature not high-technology bottleneck, by very crucial to the widespread use of layered silicate based flame retardant.
Summary of the invention
For the problems referred to above that prior art exists, the object of this invention is to provide and a kind ofly highly heat-resistingly, high press down fire retardant of 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, the high fire retardant pressing down cigarette, be first carry out organic modification by quaternary ammonium salt to inorganic polynite, the organo montmorillonite then obtained by modification is carried out terminal groups modification process to Amino End Group polyamidoamine Triphosphazene dendritic macromole 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 pressing down the fire retardant of cigarette of height of the present invention, comprises the steps:
A) inorganic polynite is added in deionized water, be mixed with suspension;
B) at 60 ~ 80 DEG C, added by quaternary ammonium salt in the suspension that step a) prepares, insulation reaction 5 ~ 7 hours, filter, exist with deionized water wash filter cake to without Cl-, drying, obtains the organo montmorillonite of modification;
C) at N
2under protection, at 50 ~ 60 DEG C; by step b) organo montmorillonite that obtains adds in the methanol aqueous solution of Amino End Group polyamidoamine Triphosphazene dendritic macromole; isothermal reaction 7 ~ 9 hours, filters, and the solid of collection is heat-resisting, the high fire retardant pressing down cigarette of described height.
As a kind of preferred version, the massfraction inorganic polynite shared by of step a) 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 Amino End Group polyamidoamine Triphosphazene dendritic macromole be that G1 generation is to any one in G3 generation.
As a kind of preferred version, step c) described in Amino End Group polyamidoamine Triphosphazene dendritic macromole methanol aqueous solution in, volume fraction shared by methyl alcohol is 40 ~ 70%, and the massfraction shared by Amino End Group polyamidoamine Triphosphazene dendritic macromole is 15 ~ 25%.
As a kind of preferred version, step c) in organo montmorillonite and the mol ratio of Amino End Group polyamidoamine Triphosphazene dendritic macromole be 4:1 ~ 8:1.
Amino End Group polyamidoamine Triphosphazene dendritic macromole described in the present invention is known polymer, its preparation method and structure and performance can refer to document: Guan Lijuan, the synthesis of multifunction multi-level tripolyphosphazene core dendritic macromole, Structure and Properties research (38 ~ 42), Beijing University of Chemical Technology's Master's thesis.
Due to the dendritic polymer of polyphosphonitrile, that a class is alternately arranged as the line style of main chain or the polymkeric substance of ring-type with nitrogen phosphorus double bond, its character is between mineral compound, between organic compound and macromolecular compound, there is the title of " inorganic rubber ", it has high heat stability, smoke-suppressing, chemical stability and radiation resistance, has a wide range of applications in the industry such as industry, agricultural, medicine, space flight, energy-saving and environmental protection.
The present invention carries out organic modification by adopting quaternary ammonium salt to inorganic polynite, and the polyphosphonitrile dendritic polymer of organo montmorillonite to different algebraically then obtained by modification carries out terminal groups modification process, obtains high heat-resisting, the high fire retardant pressing 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 DEG C, illustrates to have excellent thermotolerance; And the interlamellar spacing of organo montmorillonite reaches 2.83 ~ 5.42nm, illustrate with polymkeric substance have good consistency, can directly applying in polymer processing, without the need to carrying out loaded down with trivial details solution or fusion intercalation process again, 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.
" nano composite polymer/laminated silicate material theory and practice " (QiZongNeng is adopted in embodiment, Shang Wenyu writes, Chemical Industry Press, 2002) the thermal weight loss core temperature of the method test polynite reported, adopts the interlamellar spacing of small-angle diffraction method test organo montmorillonite; Transmission electron microscope method is adopted to observe the size of fire retardant powder.
MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride used in embodiment is provided by Shanghai Bang Cheng Chemical Co., Ltd..
Inorganic polynite used in embodiment is provided by Zhejiang Feng Hong clay company limited.
The Amino End Group polyamidoamine Triphosphazene dendritic macromole used in embodiment participates in document " Guan Lijuan; the synthesis of multifunction multi-level tripolyphosphazene core dendritic macromole, Structure and Properties research (38 ~ 42), Beijing University of Chemical Technology's Master's thesis " preparation and obtains:
One, glycine ethyl ester hydrochloride and triethylamine are added in dry benzene, filter after backflow 6h, obtain glycine ethyl ester benzole soln, under cryosel bath condition, above-mentioned solution is slowly added dropwise in the benzole soln containing hexachlorocyclotriphosphazene and triethylamine, after room temperature reaction 35h, be warming up to 50 DEG C and continue reaction 6h, after reaction terminates, reactant after filtration, underpressure distillation concentrated after, pour boiling range into be precipitation in the sherwood oil of 30 ~ 60 DEG C, to filter, after dry, purifying obtains the dendritic macromole Amino End Group polyamidoamine Triphosphazene of G0.5, is 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, after stirring deoxidation 2h, the dry absolute methanol solution being dissolved with G0.5 is slowly added dropwise in above-mentioned quadrol methanol solution in-10 ~-5 DEG C, 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, after the anhydrous methanol being dissolved with G1.0 is stirred deoxidation 2h, refining methyl acrylate is slowly added dropwise to, drip several sodium methylates again, 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 being dissolved with G1.5 is slowly added dropwise in quadrol, after room temperature reaction 72h, removes excessive quadrol, after dry purifying, obtain G2.0;
Five, the operation of repeating step three and step 4 can obtain G3.0.
Embodiment 1
Inorganic for 20g polynite is added in deionized water, is mixed with the suspension that massfraction is 5%; Gained suspension is placed in the water bath with thermostatic control of 60 DEG C, 30g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride is added in suspension, finishes, insulation reaction 5h under violent stirring, filter, with deionized water wash filter cake extremely without Cl
-exist, 80 DEG C of oven dry, obtain the organo montmorillonite of modification.
G-1 that 2.5g massfraction is 20% methanol aqueous solution (volume fraction shared by methyl alcohol is 40%) for Amino End Group polyamidoamine Triphosphazene dendritic macromole is added, at N in flask
2under protection, at 50 DEG C, slowly add the organo montmorillonite 10g that modification obtains, finish, insulation reaction 7h under violent stirring, filter, dry pale powder solid, be heat-resisting, the high fire retardant pressing down cigarette of described height.
Test data about the interlamellar spacing of the median size of obtained flame-retardant agent powder, thermal weight loss core temperature and organo montmorillonite is shown in Table 1.
Embodiment 2
Inorganic for 20g polynite is added in deionized water, is mixed with the suspension that massfraction is 10%; Gained suspension is placed in the water bath with thermostatic control of 70 DEG C, 35g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride is added in suspension, finishes, insulation reaction 6h under violent stirring, filters, with deionized water wash filter cake to existing without Cl-, 80 DEG C of oven dry, obtain the organo montmorillonite of modification.
G-2 that 2.5g massfraction is 20% methanol aqueous solution (volume fraction shared by methyl alcohol is 55%) for Amino End Group polyamidoamine Triphosphazene dendritic macromole is added, at N in flask
2under protection, at 55 DEG C, slowly add the organo montmorillonite 15g that modification obtains, finish, insulation reaction 8h under violent stirring, filter, dry pale powder solid, be heat-resisting, the high fire retardant pressing down cigarette of described height.
Test data about the interlamellar spacing of the median size of obtained flame-retardant agent powder, thermal weight loss core temperature and organo montmorillonite is shown in Table 1.
Embodiment 3
Inorganic for 20g polynite is added in deionized water, is mixed with the suspension that massfraction is 15%; Gained suspension is placed in the water bath with thermostatic control of 80 DEG C, 40g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride is added in suspension, finishes, insulation reaction 7h under violent stirring, filters, with deionized water wash filter cake to existing without Cl-, 80 DEG C of oven dry, obtain the organo montmorillonite of modification.
G-3 that 2.5g massfraction is 20% methanol aqueous solution (volume fraction shared by methyl alcohol is 70%) for Amino End Group polyamidoamine Triphosphazene dendritic macromole is added, at N in flask
2under protection, at 60 DEG C, slowly add the organo montmorillonite 20g that modification obtains, finish, insulation reaction 9h under violent stirring, filter, dry pale powder solid, be heat-resisting, the high fire retardant pressing down cigarette of described height.
Test data about the interlamellar spacing of the median size of obtained flame-retardant agent powder, thermal weight loss core temperature and organo montmorillonite 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 (DEG C) | 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 carries out organic modification by adopting quaternary ammonium salt to inorganic polynite, then the polyphosphonitrile dendritic polymer of organo montmorillonite to different algebraically obtained by modification carries out terminal groups modification process, obtains high heat-resisting, the high fire retardant pressing 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 DEG C, illustrates to have excellent thermotolerance; And the interlamellar spacing of organo montmorillonite reaches 2.83 ~ 5.42nm, illustrate with polymkeric substance have good consistency, can directly applying in polymer processing, without the need to carrying out loaded down with trivial details solution or fusion intercalation process again, 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 (9)
1. one kind high heat-resisting, the high fire retardant pressing down cigarette, it is characterized in that: described fire retardant first carries out organic modification by quaternary ammonium salt to inorganic polynite, the organo montmorillonite then obtained by modification is carried out terminal groups modification process to Amino End Group polyamidoamine Triphosphazene dendritic macromole and obtains; The algebraically of described Amino End Group polyamidoamine Triphosphazene dendritic macromole is that G1 generation is to any one in G3 generation.
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 DEG C, quaternary ammonium salt is added in the suspension that step a) prepares, insulation reaction 5 ~ 7 hours, filter, with deionized water wash filter cake to without Cl
-exist, dry, obtain the organo montmorillonite of modification;
C) at N
2under protection, at 50 ~ 60 DEG C, by step b) organo montmorillonite that obtains adds in the methanol aqueous solution of Amino End Group polyamidoamine Triphosphazene dendritic macromole, isothermal reaction 7 ~ 9 hours, and filter, the solid of collection is described fire retardant; The algebraically of described Amino End Group polyamidoamine Triphosphazene dendritic macromole is that G1 generation is to any one in G3 generation.
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: the massfraction inorganic polynite shared by of step a) in described suspension is 5 ~ 15%.
8. preparation method as claimed in claim 4, is characterized in that: step b) in quaternary ammonium salt and the mass ratio of inorganic polynite be 1:1.5 ~ 1:2; Step c) in organo montmorillonite and the mol ratio of Amino End Group polyamidoamine Triphosphazene dendritic macromole be 4:1 ~ 8:1.
9. preparation method as claimed in claim 4, it is characterized in that: step c) described in Amino End Group polyamidoamine Triphosphazene dendritic macromole methanol aqueous solution in, volume fraction shared by methyl alcohol is 40 ~ 70%, and the massfraction shared by Amino End Group polyamidoamine Triphosphazene dendritic macromole is 15 ~ 25%.
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|---|---|---|---|
| CN201310482958.4A CN103554515B (en) | 2013-10-15 | 2013-10-15 | A kind ofly highly heat-resistingly, high press down fire retardant of cigarette and preparation method thereof |
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