CN102675895A - Flame-retardant composite material with DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) modified nano mesoporous molecular sieve - Google Patents
Flame-retardant composite material with DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) modified nano mesoporous molecular sieve Download PDFInfo
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Abstract
The invention discloses a flame-retardant composite material with DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) modified nano mesoporous molecular sieve, belongs to the fields of nano mesoporous molecular sieve flame-retardant synergists and halogen-free flame-retardant composite materials, and particularly relates to the preparation method of the DOPO modified nano mesoporous molecular sieve and the flame-retardant composite material with the DOPO modified nano mesoporous molecular sieve. The DOPO is of a hexahydric phosphorus-heterocyclic-ring structure, and is a novel flame retardant intermediate. The nano mesoporous molecular sieve is the flame-retardant synergist. The invention discloses the method for preparing the DOPO modified nano mesoporous molecular sieve and the flame-retardant composite material with the DOPO modified nano mesoporous molecular sieve. Since the compound flame-retardant synergist plays a role in phosphorus/silicon synergistic flame retardance, the obtained product has good expandable carbon forming property, the flame-retardant efficiency of the material is obviously increased, the remaining amount of the residual carbon and the compact degree of a carbon layer are increased, and further the flame redardancy of the composite material is improved to a greater degree.
Description
Technical field
The present invention relates to a kind of flame-proof composite material, particularly relate to a kind of flame-proof composite material of DOPO modified Nano mesopore molecular sieve.
Background technology
1. macromolecular material has brought hidden danger when being widely used, also for the human security of the lives and property; Because the overwhelming majority is can incendiary in them; And the toxic gas volume that produces during burning is big, heat is big; The height of temperature and the black smoke that produces owing to incomplete combustion dense etc., these factors are all given and are fled from a calamity, lifesaving and fire-fighting work have brought various new problems.
2. in the production and application of fire retardant; People when exploring the synthesizing new efficient flame-retarding agent, also to flame retardant effect preferably fire retardant carry out compositely, utilize the interaction between the fire retardant; In the hope of raising flame-retarded efficiency, the synergistic effect of alleged fire retardant usually.Flame-retardant system good flame retardation effect with synergistic effect, flame retardant properties strengthen, not only can be fire-retardant but also can press down cigarette, also have some specific functions; Its applied range, cost is low, can increase economic efficiency, and is to realize one of low non-halogen effective way of halogen of fire retardant.
3. when the compound of most of phosphonium flame retardants and nitrogenous or halogen uses jointly, can increase substantially flame retardant effect.People have made many summaries to the mechanism of action and the application of phosphorus/nitrogen collaboration system and phosphorus/halogen collaboration system.But cooperative flame retardant effect and application to phosphorus/silicon rarely have report.Silicone flame retardant is a kind of novel halogen-free flame retardants, also is that a kind of charcoal becoming presses down fumicants, or a kind of good dispersant, can increase the consistency of storeroom.It is as a family macromolecule fire retardant, has efficient, nontoxic, low cigarette, anti-drippage, characteristics such as pollution-free.Organophosphorous fire retardant has high thermal stability, and the anti-property separated out is good, high-efficiency low-toxicity, characteristics such as non-volatile.Both are combined, can obtain the better composite fire retardant of flame retardant effect.
4. 9; The 10-dihydro-9-oxy is assorted-and 10-phospho hetero phenanthrene-10-oxide compound (DOPO) has hexa-atomic phosphorus heterocycle structure; Have active P-H key, be easy to generation addition reactions such as two keys, can be used for polyester flame-retardant; The chemical modification of macromolecular material such as ethoxyline resin antiflaming and Z 150PH, it is fire-retardant also to be widely used in electronics, circuit card and luminescent material abroad.(J Polym Sci such as Liu ying ying; Part A 2002,40 2329-2339), carry out copolymerization with phenol then with DOPO and terephthaldehyde's aldehyde reaction; Obtain phosphorous epoxy resin, improved the second-order transition temperature and the limiting oxygen index(LOI) of epoxy resin.
5. nano mesoporous molecular screen is a kind of novel nano particle of double nano structure, not only has nano level particle size but also have nano level one dimension straight hole road.Also have specific surface area big simultaneously, hydrothermal stability height and aperture can be in advantages such as 2-10nm adjustable.In recent years; The seminar at contriver place has studied the application of nano mesoporous molecular screen in polymkeric substance at home and abroad; Once studied the nano mesoporous molecular screen MCM-41 that in Vestolen PP 7052, Vilaterm, epoxy resin-base, adds low levels, test result shows that dosing nano mesoporous molecular screen MCM-41 has played increase-volume and toughness reinforcing effect really.It also has very strong polarity, good adsorption ability and catalytic capability simultaneously, is a kind of well behaved fire retarding synergist.Declared once like our research group that directly (application number is: 201110120576.8) as the fire retarding synergist polypropylene flame redardant with nano mesoporous molecular screen; Obviously improved the flame retarding efficiency of polymkeric substance behind the adding nano mesoporous molecular screen; Increased the carbon residue residual content, alleviated polymkeric substance because the adding of a large amount of fire retardants causes the problem of mechanical properties decrease.And for example application number is: disclose nano mesoporous molecular screen synergistic expandable flame retardant rubber and preparation method thereof among the CN 201110120587.6.This material is to be obtained by the direct blend of nano mesoporous molecular screen, polyphosphoric acid amine, tetramethylolmethane and trimeric cyanamide etc. and resin, and its flame retardant effect is good, smoke-producing amount is little but the raising of further flame retardant properties is restricted.
Summary of the invention
The object of the present invention is to provide a kind of flame-proof composite material of DOPO modified Nano mesopore molecular sieve; The present invention at first provides a kind of usefulness 9, and the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound (DOPO) modified Nano mesopore molecular sieve, for flame retardant area provides a kind of novel fire retarding synergist; This fire retarding synergist; Through composite silicon, two kinds of elements of phosphorus of containing simultaneously, flame retardant effect is good, with above-mentioned DOPO modified Nano mesopore molecular sieve preparation flame-proof composite material.
The objective of the invention is to realize through following technical scheme:
A kind of flame-proof composite material of DOPO modified Nano mesopore molecular sieve, this flame-proof composite material are to make by the blend of following mass percent prescription: polymeric substrate 66 ~ 69.5%; Expansion type flame retardant 30% ~ 26%; DOPO modified Nano mesopore molecular sieve 0.5 ~ 4%; Wherein, expansion type flame retardant is to be formed by the proportioning of 1:0.63:0.33 is composite by ammonium polyphosphate, tetramethylolmethane and trimeric cyanamide.
The flame-proof composite material of described a kind of DOPO modified Nano mesopore molecular sieve, its said nano mesoporous molecular screen is for no duct and pore passage structure is arranged:
(1) no duct structure is: through the nano mesoporous molecular screen of high-temperature calcination, soft material, i.e. template are not being filled in inside, duct;
(2) there is pore passage structure to be: through the nano mesoporous molecular screen of high-temperature calcination, no template in the duct; It is the novel nano particle of double nano structure, has the uniform pore passage structure in aperture, and the aperture is 2～10 nm.
The flame-proof composite material of described a kind of DOPO modified Nano mesopore molecular sieve, the synthesizing of its said DOPO modified Nano mesopore molecular sieve:
(1) through adding silane coupling agent; Make two kinds of materials " coupling " that nature difference is very big; The preparation raw material comprises 9, the 10-dihydro-9-oxy is assorted-and 10-phospho hetero phenanthrene-10-oxide compound (DOPO), γ-glycidyl ether oxygen propyl trimethoxy silicane KH-560, nano mesoporous molecular screen; Synthesize two steps and carry out the first step: DOPO and silane coupling agent KH-560 are joined in the reactor drum, add organic solvent, protection of inert gas is stirred and is reacted, and obtains DOPO type silane coupling agent;
(2) nano mesoporous molecular screen and DOPO type silane coupling agent are reacted, also obtain the white powder product, be the nano mesoporous molecular screen of surface-treated with the inert solvent washing and drying through suction filtration.
The flame-proof composite material of described a kind of DOPO modified Nano mesopore molecular sieve, in the synthetic DOPO type silane coupling agent of its said the first step, used solvent is absolute ethyl alcohol and toluene; Reaction times is 6 ~ 10 hours.
The flame-proof composite material of described a kind of DOPO modified Nano mesopore molecular sieve, in its said second step, DOPO type silane coupling agent and nano mesoporous molecular screen mass ratio are 3% ~ 10%; , temperature of reaction is 80 ~ 120 ℃.
Advantage of the present invention and effect are:
(1) silicone flame retardant is a kind of novel halogen-free flame retardants, also is that a kind of charcoal becoming presses down fumicants, or a kind of good dispersant, can increase the consistency of storeroom.Organophosphorous fire retardant has high thermal stability, and the anti-property separated out is good, high-efficiency low-toxicity, characteristics such as non-volatile.Both are combined, improve flame retarding efficiency, performance satisfies the environment-friendly modified nano mesoporous molecular screen fire retarding synergist flame-proof composite material of application requiring.
(2) silicon-phosphorus synergist adds simultaneously, is reaching under the fire-retardant rank of vertical combustion, can reduce the consumption of expansion type flame retardant.
(3) synthetic silicon phosphorus fire retardant of the present invention can effectively promote into the charcoal process in the application of flame-retardant polymer, improves flame retardant properties and does not have molten drop, and the amount of being fuming is little, and is little to people around and environmental influence.
(4) preparation method of this based flame retardant is simple, and processing condition are gentle, are applicable to mass production.
Description of drawings
Fig. 1 is unmodified nano mesoporous molecular screen MCM-41 and DOPO modified Nano mesopore molecular sieve examination of infrared spectrum figure as a result;
Fig. 2 is a DOPO type silane coupling agent building-up process reaction formula;
Fig. 3 is the reaction formula of the nano mesoporous molecular screen reaction process of surface-treated.
Embodiment
Below in conjunction with embodiment the present invention is elaborated.
In order to investigate the DOPO modified Nano mesopore molecular sieve of preparation, the present invention has carried out examination of infrared spectrum with the nano mesoporous molecular screen of unmodified nano mesoporous molecular screen MCM-41 and DOPO modification, and its result sees Fig. 1.The ir spectra of the nano mesoporous molecular screen MCM-41 that a following curve is a non-modified among the figure, above the ir spectra that curve is the nano mesoporous molecular screen of DOPO modification.Can find out relatively that from both ir spectras the MCM-41 after the DOPO modification is at 1500-400cm
-1The skeletal vibration peak that also keeps it, 1640cm
-1It is the flexural vibration peak of hydroxyl.At 2463cm
-1The place is the vibration peak of the P-H of DOPO, 1477cm
-1The place is the vibration peak of P-C, 1238cm
-1Locate the absorption peak that existing Si-O-Si antisymmetric stretching vibration absorption peak has the P=O key stretching vibration among the DOPO to cause again, peak, 953cm are strengthened for the two in the peak here
-1The place is the stretching vibration peak of P-O-C.Therefore, can confirm that DOPO can carry out reaction modifying to nano mesoporous molecular screen.
The flame retardant properties of the flame-proof composite material of following examples and relative proportion is tested by standard ISO 4589-1984.
Embodiment 1:
(1) takes by weighing 21.6gDOPO and 100ml absolute ethyl alcohol and join and take back stream, stir, in the there-necked flask of nitrogen protection, add the 23.6gKH-560 silane coupling agent then, slowly be warmed up to 75 ℃, reacted 6 hours, obtain DOPO type silane coupling agent.
(2) take by weighing 10g mesopore molecular sieve MCM-41 and join in the 100ml there-necked flask, add the 50ml deionized water again, be made into the slurry of certain solubility, be fixed in the magnetic stirring apparatus, be heated to 80 ℃ while stirring; Add DOPO type silane coupling agent (volume ratio 1:1) again through the absolute ethyl alcohol dilution; The quality of DOPO type silane coupling agent is 3% of a mesopore molecular sieve quality; Continue to stir after 10 hours, powered-down, cooling, suction filtration are with absolute ethanol washing, suction filtration again; Be put in drying in 100 ℃ of baking ovens, obtain the mesopore molecular sieve MCM-41 of surface-treated.
Nano mesoporous molecular screen 1g with the DOPO modification of embodiment 1 preparation; Expansion type flame retardant 30g (expansion type flame retardant is to be formed by the proportioning of 1:0.63:0.33 is composite by ammonium polyphosphate, tetramethylolmethane and trimeric cyanamide); Vestolen PP 7052 69g puts into the blend of torque blender; Blending temperature is 180 ℃, and the blend time is 8 minutes, obtains Vestolen PP 7052/expansion type flame retardant/DOPO-MCM-41 blend.
Comparative Examples 1:
Directly use Vestolen PP 7052.
Comparative Examples 2:
Take by weighing expansion type flame retardant 30g (expansion type flame retardant is to be formed by the proportioning of 1:0.63:0.33 is composite by ammonium polyphosphate, tetramethylolmethane and trimeric cyanamide); Vestolen PP 7052 70g puts into the blend of torque blender; Blending temperature is 180 ℃; The blend time is 8 minutes, obtains Vestolen PP 7052/expansion type flame retardant blend.
Comparative Examples 3:
Take by weighing expansion type flame retardant 30g (expansion type flame retardant is to be formed by the proportioning of 1:0.63:0.33 is composite by ammonium polyphosphate, tetramethylolmethane and trimeric cyanamide); Vestolen PP 7052 69g; Nano mesoporous molecular screen MCM-41 1g puts into the blend of torque blender, and blending temperature is 180 ℃; The blend time is 8 minutes, obtains Vestolen PP 7052/expansion type flame retardant/nano mesoporous molecular screen blend.
The flame retardant properties of Comparative Examples 1 ~ 3 and embodiment 1 is as shown in table 1.
From the Comparative Examples 1 ~ 3 of table 1, find out: under the identical situation of expanding fire retardant consumption (Comparative Examples 3 embodiment 1), the collaborative expandable flame retardant effect of DOPO modified Nano mesopore molecular sieve obviously is better than the collaborative expandable flame retardant effect of independent interpolation nano mesoporous molecular screen.
The flame retardant properties of table 1 Comparative Examples 1 ~ 4 and embodiment 1 ~ 2:
| ? | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 | Embodiment 1 |
| PP | 100 | 70 | 69 | 69 |
| IFR consumption (part) | 0 | 30 | 30 | 30 |
| Nano mesoporous molecular screen MCM-41 consumption (part) | 0 | 0 | 1 | 0 |
| DOPO-MCM-4 consumption (part) | 0 | 0 | 0 | 1 |
| The vertical combustion rank | No rank | V-1 | V-1 | V-0 |
| Oxygen index/% | 17.4 | 24.4 | 28.1 | 32.6 |
Claims (5)
1. the flame-proof composite material of a DOPO modified Nano mesopore molecular sieve is characterized in that, this flame-proof composite material is to make by the blend of following mass percent prescription: polymeric substrate 66 ~ 69.5%; Expansion type flame retardant 30% ~ 26%; DOPO modified Nano mesopore molecular sieve 0.5 ~ 4%; Wherein, expansion type flame retardant is to be formed by the proportioning of 1:0.63:0.33 is composite by ammonium polyphosphate, tetramethylolmethane and trimeric cyanamide.
2. the flame-proof composite material of a kind of DOPO modified Nano mesopore molecular sieve according to claim 1 is characterized in that, said nano mesoporous molecular screen is for no duct and pore passage structure is arranged:
(1) no duct structure is: through the nano mesoporous molecular screen of high-temperature calcination, soft material, i.e. template are not being filled in inside, duct;
(2) there is pore passage structure to be: through the nano mesoporous molecular screen of high-temperature calcination, no template in the duct; It is the novel nano particle of double nano structure, has the uniform pore passage structure in aperture, and the aperture is 2～10 nm.
3. the flame-proof composite material of a kind of DOPO modified Nano mesopore molecular sieve according to claim 1 is characterized in that, the synthesizing of said DOPO modified Nano mesopore molecular sieve:
(1) through adding silane coupling agent; Make two kinds of materials " coupling " that nature difference is very big; The preparation raw material comprises 9, the 10-dihydro-9-oxy is assorted-and 10-phospho hetero phenanthrene-10-oxide compound (DOPO), γ-glycidyl ether oxygen propyl trimethoxy silicane KH-560, nano mesoporous molecular screen; Synthesize two steps and carry out the first step: DOPO and silane coupling agent KH-560 are joined in the reactor drum, add organic solvent, protection of inert gas is stirred and is reacted, and obtains DOPO type silane coupling agent;
(2) nano mesoporous molecular screen and DOPO type silane coupling agent are reacted, also obtain the white powder product, be the nano mesoporous molecular screen of surface-treated with the inert solvent washing and drying through suction filtration.
4. the flame-proof composite material of a kind of DOPO modified Nano mesopore molecular sieve according to claim 3 is characterized in that, in the synthetic DOPO type silane coupling agent of the said the first step, used solvent is absolute ethyl alcohol and toluene; Reaction times is 6 ~ 10 hours.
5. the flame-proof composite material of a kind of DOPO modified Nano mesopore molecular sieve according to claim 3 is characterized in that, in said second step, DOPO type silane coupling agent and nano mesoporous molecular screen mass ratio are 3% ~ 10%; , temperature of reaction is 80 ~ 120 ℃.
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| CN108864475A (en) * | 2018-07-24 | 2018-11-23 | 山东大学 | A kind of silicon-phospha flame retarded rigid foam of polymers and preparation method thereof |
| CN112778716A (en) * | 2020-12-31 | 2021-05-11 | 河南省科学院同位素研究所有限责任公司 | Halogen-free flame-retardant reinforced PET material with high heat deformation temperature and preparation method thereof |
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Application publication date: 20120919 |