CN101665513A - Flame-retardant polystyrene/layered inorganic nanocomposite and preparation method thereof - Google Patents
Flame-retardant polystyrene/layered inorganic nanocomposite and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a flame-retardant polystyrene/layered inorganic nanocomposite and a preparation method thereof, which is characterized in that phenyl dichlorophosphate is taken as a reactionmatrix for being reacted with polyol or polyphenol which is partially acrylated or partially methacrylated, and then the reaction with a nitrogen-containing compound with a reactive amino group is carried out, thereby obtaining the flame-retardant comonomer which simultaneously has an active double bond and a phosphorus-nitrogen flame-retardant element; the phosphorus-nitrogen monomer and styreneare used for preparing the flame-retardant polystyrene/layered inorganic nanocomposite through the free radical in-situ intercalation polymerization method in the presence of a layered inorganic; a phosphorus-nitrogen-containing flame retardant which is connected with a polymer molecular chain by the chemical bond way has better compatibility with a resin substrate and is more environment-friendly, and the flame retardant has no migration and no loss; the layered inorganic can further improve the thermal stability and the flame-retardant performance of a polymer substrate; and the flame-retardant polystyrene/layered inorganic nanocomposite can be directly prepared into a flame-retardant polystyrene material and can also be prepared into a flame-retardant masterbatch to be added in other plastics.
Description
Technical field
The invention belongs to flame-retardant polymer/laminated inorganic matter mixture technical field, be specifically related to phosphorous nitrogen fire retardant polystyrene/layered inorganic nanocomposite and preparation method thereof.
Background technology
Polystyrene (PS) is as one of five big general-purpose plastics, have have excellent moldability, matter is hard, transparent, electrical insulating property, agent of low hygroscopicity, easy dyeing and advantage such as cheap, has been widely used in industries such as electronics, automobile, building, toy, packing.But polystyrene easily when burning and burning drippage serious, these drawbacks limit its promote the use of in the demanding occasion of fire-protection rating.Usually adopt at present and add halogenated flame retardant or add the inflammableness problem that phosphorated organic or inorganic compound solves polystyrene.But these ordinary methods have a lot of shortcomings, such as fire retardant consumption big (generally must reach 20-50wt%) usually, this can cause the polymer materials mechanical property to descend, and As time goes on can reduce even lose flame retardant effect because of migration, the loss of fire retardant.
A kind of flame-proof polystyrene composition of Chinese patent publication number CN1966567A report, by weight with 100 parts of polystyrene resins, 8～25 parts of bromine-containing compounds and 2～6 parts of antimonous oxide melt blendings, obtained flame-retardant polystyrene product has good flame retardancy, fire-retardant rank can reach FV-0 level (GB/T4609-93), oxygen index can reach 28, can be used for multiple severe environment.A kind of expandable polystyrene foam compositions of Chinese patent publication number CN101087818A report with flame retardant resistance, its flame-retardant composition is a kind of bromated ring compound, this fire retardant has flame retardant resistance preferably, avoided other bromine-containing compounds can not be in vinylbenzene consoluet drawback, can in styrene monomer, fully dissolve, therefore when producing polystyrene foam, can guarantee even, the stable performance of the foam that generates.Though above-mentioned two kinds of method effects by the flame retardant resistance of interpolation bromine-containing compound raising polystyrene are better, but because of bromine-containing compound can generate deleterious corrosive gases when the polymer combustion, environment is polluted, harm humans health, do not meet environmental requirement, and problems such as fire retardant surface transport, loss take place in small molecules fire retardant easily in the use of material matrix.
A kind of Halogenless fire retarded polymer foam materials of Chinese patent publication number CN101014650A report, in the polystyrene melting process, can be incorporated into fire retardant and organic blowing agent in the matrix polymer together, used foam material is mainly polystyrene foamed or polystyrene foam sheet or particle, and used halogen-free flame retardants is a kind of phosphorated ring compound.International monopoly WO2009037236 (A1) has reported a kind of fire retardant polystyrene or modified polystyrene, its matrix is at least a kind of of polystyrene and high-impact polystyrene, perhaps both mixtures, its fire retardant consists of expanded graphite, P contained compound and fluoropolymer; Mechanical property, the flame retardant properties of its final product all are improved largely than polymeric matrix, can satisfy needs of production preferably.Though above-mentioned two routine fire retardant polystyrenes have adopted the present relatively halogen-free flameproof method of environmental protection, by adding phosphorus flame retardant, a large amount of uses of bromine-containing compound have been avoided, but because its most of fire retardant that adopts is still for small molecules, this class flame retardant products still exist in use can run off because of fire retardant, shortcoming that the migration product performance worsen.
Chinese patent publication number CN101033266A has reported the preparation method of a kind of polymkeric substance/organic montmorillonite nano composite flame-proof master batch, adopt emulsion polymerization to make the acrylic ester monomer or the styrene monomer generation polymerization that enter into the organo montmorillonite interlayer obtain polymkeric substance/organic montmorillonite nano mixture fire-retardant master granule, with gained master batch and acrylonitrile-butadiene-styrene (ABS) (ABS) and high-impact polystyrene melt blendings such as (HIPS), can prepare flame retardant plastics again with good flame-retardance energy and mechanical property.International Patent Publication No. WO 2009023425A1 has reported a kind of method for preparing polyolefine, polystyrene clay nano mixture, its polymerization process was divided into for two steps: the first step is to utilize the initiator with initiated polymerization function to make interlayer monomer generation polymerization, and second step was to utilize the polymerization of oil-soluble initiator trigger monomer.This method can make height layer from polymer nanocomposite, and the mechanical property of product is compared with polymeric matrix and is improved largely.This method can be used for mass polymerization and suspension polymerization.From above-mentioned patent as can be seen, though the method for introducing lamella inorganic structures such as clay in polymkeric substance can significantly improve flame retardant properties, the mechanical property of polymkeric substance, flame-retardant composition is single, flame retarding efficiency is not high but prior art still exists, and is difficult to satisfy the shortcoming of fire-retardant demanding occasion.
Summary of the invention
The objective of the invention is to propose a kind of fire retardant polystyrene/layered inorganic nanocomposite and preparation method thereof, utilize homemade phosphorous nitrogen comonomer and styrene monomer and the in-situ inserted polymerization of laminated inorganic matter, utilize phosphorus in the polymkeric substance, nitrogen element cooperative flame retardant principle and polymer nanocomposites disperse phase height to become more meticulous and nanometer size effect improves the flame retardant properties and the thermostability of polystyrene, thereby prevent migration, the loss of phosphonium flame retardant, improve its flame retarding efficiency.
The preparation method of the used phosphorous nitrogen comonomer of homemade polymerizable among the present invention, it is characterized in that with the phosphorus dichloride acid phenenyl ester be response matrix, the polyvalent alcohol or the polyphenol that add part propylene acidifying or part methyl acrylated by the reaction mol ratio, add attached sour agent triethylamine or pyridine ,-5～5 ℃ of ice baths are stirred to and no longer include the hydrogenchloride generation in solvent; Add the nitrogenous compound that has a reactive amino group according to the reaction mol ratio then, under-5～5 ℃ of condition of ice bath, stirred 8～12 hours, remove attached sour agent salt and solvent, resulting light yellow transparent liquid is polymerisable phosphorus-nitrogen-containing halogen-free comonomer.
The polyvalent alcohol or the polyphenol of described part propylene acidifying or part methyl acrylated, its chemical structural formula can be expressed as HOR
1[O (C=O) CR
2=CH
2]
m, R in the formula
1For containing the alkyl or aryl of 1-12 carbon, R
2Be CH
3Or H, m is 1,2 or 3; The polyvalent alcohol of this part propylene acidifying or part methyl acrylated or polyphenol comprise methacrylic acid-beta-hydroxy ethyl ester, senecioate-hydroxyl ethyl ester, 2-hydroxyl dimethyl allene acid glyceride, 2-hydroxyl glycerol diacrylate, 1-methylol-3,5-dimethyl allene acid phenenyl ester or 1-methylol-3,5-diacrylate phenyl ester.
Described solvent is selected from tetrahydrofuran (THF), methylene dichloride, chloroform, ether or dioxane.
The described nitrogenate that has a reactive amino group is selected from alkylamine, comprises diethylamine, dimethylamine, dipropyl amine, ethylenimine, Pyrrolidine, piperidines, pyridine, ethamine, propylamine, Isopropylamine, n-Butyl Amine 99, sec-butylamine or TERTIARY BUTYL AMINE.
Phosphorus-nitrogen-containing halogen-free comonomer among the present invention of employing method for preparing, for having the monomer molecule of activity double key and phosphorus nitrogen ignition-proof element simultaneously, its chemical structural formula can be expressed as:
In the formula, R is the functional group of part propylene acidifying or part methyl acrylated; R ' is for having the nitrogen-containing functional group of a tertiary amine or secondary amine.
The preparation method of fire retardant polystyrene/layered inorganic nanocomposite of the present invention, it is characterized in that utilizing above-mentioned homemade phosphorous nitrogen fire-resistant copolyesters monomer, select one of free radical mass polymerization, suspension polymerization or three kinds of modes of emulsion polymerization for use, under initiator causes, pass through in-situ inserted free-radical polymerized, phosphor nitrogen combustion inhibitor is fixed in the polystyrene molecular chain in the chemical bond mode, and interact with laminated inorganic matter, obtain containing the fire retardant polystyrene of laminated inorganic matter;
Described free radical mass polymerization is: will be stirred to evenly by the laminated inorganic matter of monomer total mass 0.05-40%, the phosphorous-containing monomers of 5-50% and the vinylbenzene of 50-90%, and form the dispersion liquid of stable phosphorous-containing monomers, vinylbenzene and laminated inorganic matter; After being heated to 50-100 ℃ kick off temperature, add the oil soluble radical initiator with respect to the 0.02-3% of monomer total mass, polyreaction begins; By the time monomer conversion is 35% when following, with viscous mixture 60-200 ℃ of polymerization, until reacting completely;
Described free radical suspensioning polymerization method is: will by monomer total mass 1-3 doubly deionized water and after the dispersion agent of 0.05-3% stirs, add and press the phosphorous-containing monomers of monomer total mass 5-50%, the vinylbenzene of 50-90%, oil-soluble initiator and the 0.05-40% laminated inorganic matter of 0.02-3%; Stir polymerization at 60-200 ℃ after stirring into homogeneous phase solution, after question response is complete, obtains particulate solid after filtering, clean, drying and be fire retardant polystyrene/layered inorganic nanocomposite;
Described free-radical emulsion polymerization method is: after will stirring by the water-soluble radical initiator of the emulsifying agent of doubly deionized water of monomer total mass 0.5-3,0.1-3% and 0.02-3%, add the vinylbenzene and the phosphorous-containing monomers that are dispersed with laminated inorganic matter, wherein the quality of laminated inorganic matter accounts for 0.05-40%, and the mass concentration of phosphorous-containing monomers is 5-50%; Stir polymerization at 5-100 ℃, after question response finished, breakdown of emulsion was isolated the pressed powder product.
Used laminated inorganic matter is selected from a kind of or its mixture in organo-clay, organically-modified double-hydroxide, organically-modified zirconium phosphate or the organically-modified titanium phosphate; Its medium clay soil is optional from montmorillonite, hectorite, saponite, vermiculite, beidellite, hectorite, silica, halloysite, talcum powder, fibrous morphology crystals or illite mineral, or the mixture of above-mentioned substance; The properties-correcting agent of organo-clay or organically-modified zirconium phosphate or organically-modified titanium phosphate can be selected from secondary amine, tertiary amine, level Four halogeno-amine or alkylphosphines compounds, comprises palmityl trimethyl ammonium chloride, octadecyl trimethylammonium bromide, Dodecyl trimethyl ammonium chloride, dodecyl benzyl dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, cetyl trimethylammonium bromide, octadecyl trimethylammonium bromide, dodecyl dimethyl benzyl ammonium bromide, Trimethyllaurylammonium bromide or two octadecyl dimethyl brometo de amonio; The structural formula of described double-hydroxide can be expressed as [M
2+ 1-xM
3+ x(OH)
2] A
N- X/nMH
2O, wherein M
2+Be divalent metal, comprise Ca
2+, Mg
2+, Ni
2+, Co
2+, Zn
2+, Mn
2+Or Cu
2+M
3+Be trivalent metal cation, comprise Al
3+, Cr
3+, Co
3+, Ni
3+, Mn
3+, Fe
3+Or V
3+A is the interlayer inorganic anion, comprises Cl
-, NO
3 -, SO
4 2-Or CO
3 2-, can be the Organoalkyl carboxylate anion also, comprise [CH
3(CH
2)
nCOO
-, n=8,10,12,14,16,20, or the alkylsulphonic acid negatively charged ion, comprise sodium laurylsulfonate or pentadecyl sodium sulfonate; Organically-modified double-hydroxide is a kind of, two or more the mixture in the above-mentioned double-hydroxide;
Described oil soluble radical initiator can be disclosed any oil soluble radical initiator, generally be selected from: (1) peroxide initiator comprises dibenzoyl peroxide, peroxidation two acyls, dilauroyl peroxide, peroxyesters, peroxy dicarbonates, isopropyl benzene hydroperoxide, dicumyl peroxide or di-tert-butyl peroxide; (2) azo-initiator comprises Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) or azo-bis-iso-dimethyl; (3) oil soluble oxidation-reduction trigger system, oxygenant wherein are selected from hydroperoxide, benzoyl peroxide, dialkyl or peroxidation diacyl compound; Reductive agent wherein is selected from tertiary amine, naphthenate, mercaptan or organometallic compound.
Described water-soluble radical initiator can be disclosed any water-soluble radical initiator, generally is selected from: (1) inorganic peroxy class initiator comprises Potassium Persulphate, ammonium persulphate, hydroperoxide and hydrogen peroxide; (2) azo-initiator, comprise 2,2 '-azo diisobutyl amidine dihydrochloride (AIBA, V-50), 2,2 '-azo [2-(2-tetrahydroglyoxaline-2-yl) propane] dihydrochloride (be called for short AIBA, VA-044), 4,4 '-azo two (4-cyanopentanoic acid) (is called for short ACVA, V-501) and azo di-isopropyl tetrahydroglyoxaline (be called for short AIP, VA-061); (3) water soluble oxidized-reduction system, wherein oxygenant is selected from hydrogen peroxide, persulphate or hydroperoxide, and reductive agent is selected from Fe
2+, Cu
+, S-WAT, sodium bisulfite, Sulfothiorine, alcohol, amine, oxalic acid or glucose; Described water soluble oxidized-reduction initiator system is chosen as the combination of any oxygenant and any reductive agent.
Described dispersion agent is the mixture of disclosed any dispersion agent or several dispersion agents, comprise (1) water soluble organic polymer dispersion agent, be selected from: polyvinyl alcohol, polyacrylic acid, poly-methyl acrylate class, maleic anhydride-styrene copolymers, methylcellulose gum, hydroxypropylcellulose, gelatin or sodiun alginate; (2) water-fast inorganic powder is selected from: magnesiumcarbonate, lime carbonate, calcium phosphate or talcum powder.
Described emulsifying agent is the mixture of disclosed any emulsifying agent or several emulsifying agents; Comprise sodium soap R
3COONa (R
3=C
11～17), alkyl sodium sulfonate R
4SO
3Na (R
4=C
11～17), sodium alkylarysulfonate, rosined soap, ammonium salt, amino acid, ethylene oxide polymer or R
5-(OC
2H
4)
n-OH, R
5CO-(OC
2H
4)
n-OH, R
5-C
6H
4(OC
2H
4)
n-OH, wherein R
5=C
10～16
The present invention is by the fire retardant polystyrene/layered inorganic compound nano-complex of method for preparing, it is characterized in that containing vinylbenzene-phosphorus nitrogen monomer copolymer and the laminated inorganic matter that is scattered in wherein, described multipolymer is made of by the covalent linkage link styrene monomer and phosphorous nitrogen monomer; And contain in this mixture and be the laminated inorganic matter of 0.05-40% by weight.
The present invention is the polyvalent alcohol or polyphenol reaction acquisition half affixture of response matrix and part propylene acidifying or part methyl acrylated owing to having taked with the phosphorus dichloride acid phenenyl ester, with the nitrogenous compound reaction that has a reactive amino group, the phosphorous nitride of resultant light yellow transparent liquid is for having the fire-retardant monomer of polymerizable of activity double key and phosphorus nitrogen ignition-proof element simultaneously again; In the presence of layered inorganic compound, it is incorporated in the polystyrene by free-radical polymerized method as reactive flame retardant, prepared fire retardant polystyrene/layered inorganic nanocomposite has high flame retardant efficient.Compare with existing additive flame retardant, the phosphorus-nitrogen-containing halogen-free flame retardant of the present invention's preparation is owing to being connected in the polymer molecular chain, and is better with the consistency of resin matrix, do not move, do not run off; The fire retardant that employing the inventive method prepares can form the charcoal layer that expands preferably owing to utilized phosphorus nitrogen element cooperative flame retardant principle in the molecule, and base material is had better flameproof protection effect and the not halogen-containing environment friendly flame retardant that belongs to; In addition, added laminated inorganic matter and made polymer nanocomposites, thereby made polymeric matrix have better flame retardant resistance and thermostability.Described available three kinds of production technique are maturation and desired raw material wide material sources very, are easy to suitability for industrialized production; Can directly be prepared into polystyrene material, also can be made into fire-retardant master granule and add in the polymer materialss such as polystyrene, ABS, SAN, have wide prospect in industrial application with anti-flaming function.
Embodiment
Embodiment 1:
In the 250ml three-necked bottle of mechanical stirring and constant pressure funnel is housed, add 21.1g (0.1mol) phosphorus dichloride acid phenenyl ester and 80ml tetrahydrofuran (THF), stir at-5～5 ℃ of ice baths, after 20 minutes, add 21.2g (0.21mol) triethylamine, again under continue stirring in 2 hours the slow mixing solutions of dropwise addition of acrylic acid hydroxyl ethyl ester 11.6g (0.1mol) and 20ml tetrahydrofuran (THF), continue reaction 4 hours.Then diethylamine 7.32g (0.1mol) is dissolved in the 80ml tetrahydrofuran (THF), slowly splashes in the above-mentioned reaction system under under-5～5 ℃ of condition of ice bath, continuing to stir, reacted 8 hours.Decompress filter is removed triethylamine salt, and underpressure distillation removes and desolvates, and the light yellow transparent liquid that obtains is product of the present invention.Productive rate is 80%.
Products therefrom is through nmr analysis, the peak position of chemical shift at 7.1～7.3ppm place is the phenyl ring peak position, three identical peaks of integral area that chemical shift occurs at 5.8ppm, 6.1ppm, 6.4ppm place are respectively three hydrogen peak positions on two keys of Hydroxyethyl acrylate, and chemical shift is respectively (O-CH on the Hydroxyethyl acrylate at two peaks at 4.2ppm, 4.4ppm place
2-CH
2-) two methylene radical on the peak position of hydrogen, and the peak that appears on the 3.1ppm is-N (CH
2)
2The peak position of last four hydrogen, the peak that appears on the 1.06ppm is the peak position of six hydrogen on the methyl.
Explanation thus, the fire-retardant monomer of the phosphorous nitrogen of polymerizable of the present invention that adopts method for preparing to obtain is for having the monomer molecule of activity double key and phosphorus nitrogen ignition-proof element simultaneously.
But the fire-retardant monomer of the phosphorus-nitrogen-containing halogen-free of getting above-mentioned preparation 0.5 gram (account for monomer total mass 10%), vinylbenzene 4.5 grams, after (0.05g account for monomer total mass 5%) cetyl trimethylammonium bromide montmorillonite modified (OMMT) stirs at normal temperatures, add and cause required 0.05g Diisopropyl azodicarboxylate, be warming up to 90 ℃, the question response transformation efficiency stops to heat up when 20% left and right sides, and mixture transferred in another reactor, respectively in 60 ℃ and 80 ℃ reaction 20 hours down.Stopped reaction obtains fire retardant polystyrene/organic montmorillonite nano mixture.Product is peeled off each other through X-ray diffraction (XRD) and transmission electron microscope (TEM) demonstration intercalation clay lamella, fully separately in polymer matrices, is exfoliated matrix material.By thermogravimetric analysis (TGA) test, the temperature T of this nano-complex weightlessness 10% under the air
10%It is 320 ℃; Miniature calorimeter shows that its hot release capacity (heat release capacity) is 493Jg
-1K
-1, it is 35.9KJ/g that total heat discharges (THR).And the T of synthetic polystyrene under the equal conditions
10%Be 302 ℃, hot release capacity is 915Jg
-1K
-1, THR is 39.0KJ/g.Fire retardant polystyrene/organo montmorillonite that this explanation the inventive method preparation is obtained has better thermostability and low incendivity than pure polystyrene.
Embodiment 2:
In the 250ml three-necked bottle of mechanical stirring and constant pressure funnel is housed, add 21.1g (0.1mol) phosphorus dichloride acid phenenyl ester and 80ml methylene dichloride, ice bath stirs, after 10 minutes, add 21.2g (0.21mol) triethylamine, again under continue stirring in 2 hours the slow mixing solutions of dropwise addition of acrylic acid hydroxyl ethyl ester 11.6g (0.1mol) and 20ml methylene dichloride, continue reaction 4 hours.Then diethylamine 7.32g (0.1mol) is dissolved in the 60ml methylene dichloride, under continuing stirring, slowly splashes in the above-mentioned reaction system, reacted 8 hours.Decompress filter is removed triethylamine salt, and underpressure distillation removes and desolvates, and the light yellow transparent liquid that obtains is product of the present invention.Productive rate is 85%.
Products therefrom is through nmr analysis, the peak position of chemical shift at 7.13～7.38ppm place is the phenyl ring peak position, three identical peaks of integral area that chemical shift occurs at 5.8ppm, 6.1ppm, 6.4ppm place are respectively three hydrogen peak positions on two keys of Hydroxyethyl acrylate, and chemical shift is respectively (O-CH on the Hydroxyethyl acrylate at two peaks at 4.28ppm, 4.38ppm place
2-CH
2-) two methylene radical on the peak position of hydrogen, and the peak that appears on the 3.15ppm is-N (CH
2)
2The peak position of last four hydrogen, the peak that appears on the 1.06ppm is the peak position of six hydrogen on the methyl.
The magnalium double-hydroxide of getting the phosphorous nitrogen monomer of polymerizable, vinylbenzene, the sodium laurylsulfonate modification of above-mentioned preparation prepares in embodiment 1 under the condition that nano-complex sets and carries out Raolical polymerizable.Wherein phosphorous nitrogen monomer, vinylbenzene mass ratio are 9: 1, and magnalium double-hydroxide quality is 3% of a monomer total mass.Final obtained flame-retardant polystyrene/modification magnalium double hydroxide nano mixture shows that through XRD and TEM the obtained nano-complex of the inventive method is exfoliated.TGA analyzes under air conditions, and the temperature of its weightlessness 10%, 50% is respectively 302 ℃, 371 ℃, and the equal conditions temperature of the polystyrene weightlessness 10%, 50% of preparation down is respectively 302 ℃, 353 ℃; Miniature calorimeter test shows that the heat release capacity of this nano-complex is 577Jg
-1K
-1, total heat burst size THR is 36.0KJ/g, and the heat release capacity of polystyrene is 915Jg
-1K
-1, THR is 39.0KJ/g.
Embodiment 3:
In the 250ml three-necked bottle of mechanical stirring and constant pressure funnel is housed, add 21.1g (0.1mol) phosphorus dichloride acid phenenyl ester and 80ml tetrahydrofuran (THF), ice bath stirs, after 10 minutes, add 21.2g (0.21mol) triethylamine, again under continue stirring in 2 hours the slow mixing solutions of dropwise addition of acrylic acid hydroxyl ethyl ester 11.6g (0.1mol) and 20ml tetrahydrofuran (THF), continue reaction 4 hours.Then diethylamine is dissolved in the 80ml tetrahydrofuran (THF), under continuing stirring, slowly splashes in the above-mentioned reaction system, reacted 8 hours.Decompress filter is removed triethylamine salt, and underpressure distillation removes and desolvates, and the yellow transparent liquid that obtains is product of the present invention.Productive rate is 80%.
Products therefrom is through nmr analysis, the peak position of chemical shift at 7.1～7.3ppm place is the phenyl ring peak position, three identical peaks of integral area that chemical shift occurs at 5.8ppm, 6.1ppm, 6.4ppm place are respectively three hydrogen peak positions on two keys of Hydroxyethyl acrylate, and chemical shift is respectively (O-CH on the Hydroxyethyl acrylate at two peaks at 4.2ppm, 4.4ppm place
2-CH
2-) two methylene radical on the peak position of hydrogen, and the peak that appears on the 3.1ppm is-N (CH
2)
2The peak position of last four hydrogen, the peak that appears on the 1.06ppm is the peak position of six hydrogen on the methyl.
Get the phosphorous nitrogen monomer of polymerizable, the vinylbenzene of above-mentioned preparation, the alpha zirconium phosphate of cetyl trimethylammonium bromide modification is put into a reactor, stir.And adding initiator dibenzoyl peroxide.Wherein, phosphorus nitrogen comonomer and vinylbenzene mass ratio are 9: 1, and organically-modified alpha zirconium phosphate add-on is 5% of an amount of monomer, and the initiator addition is 1% of a monomer mass.Stirring is warming up to 90 ℃ and begins reaction, when monomer conversion during in 20% left and right sides, reaction mixture is transferred in another reactor, under 70 ℃ and 80 ℃, reacted respectively 20 hours, final resultant fire retardant polystyrene/alpha zirconium phosphate nano-complex shows through XRD and TEM test, the lamella alpha zirconium phosphate is dispersed in the polymeric matrix fully, is exfoliated structure.Thermogravimetric analysis shows that its temperature of weightless 10% and 50% is respectively 314 ℃ and 381 ℃; Miniature calorimeter shows that its hot release capacity is 596Jg
-1K
-1, it is 35.9KJ/g that total heat discharges THR.And the temperature of prepared polystyrene weightless 10% and 50% is respectively 305 ℃ and 360 ℃ under the equal conditions; The heat release capacity that miniature calorimeter shows is 922Jg
-1K
-1, it is 39.2KJ/g that total heat discharges THR.
Embodiment 4:
In the 250ml three-necked bottle of mechanical stirring and constant pressure funnel is housed, add 21.1g (0.1mol) phosphorus dichloride acid phenenyl ester and 80ml methylene dichloride, ice bath stirs, after 10 minutes, add 21.2g (0.21mol) triethylamine, again under continue stirring in 2 hours the slow mixing solutions of dropwise addition of acrylic acid hydroxyl ethyl ester 11.6g (0.1mol) and 20ml methylene dichloride, continue reaction 4 hours.Then diethylamine 7.32g (0.1mol) is dissolved in the 60ml methylene dichloride, under continuing stirring, slowly splashes in the above-mentioned reaction system, reacted 8 hours.Decompress filter is removed triethylamine salt, and underpressure distillation removes and desolvates, and the light yellow transparent liquid that obtains is product of the present invention.Productive rate is 85%.
Products therefrom is through nmr analysis, the peak position of chemical shift at 7.13～7.38ppm place is the phenyl ring peak position, three identical peaks of integral area that chemical shift occurs at 5.8ppm, 6.1ppm, 6.4ppm place are respectively three hydrogen peak positions on two keys of Hydroxyethyl acrylate, and chemical shift is respectively (O-CH on the Hydroxyethyl acrylate at two peaks at 4.28ppm, 4.38ppm place
2-CH
2-) two methylene radical on the peak position of hydrogen, and the peak that appears on the 3.15ppm is-N (CH
2)
2The peak position of last four hydrogen, the peak that appears on the 1.06ppm is the peak position of six hydrogen on the methyl.
The fire-retardant monomer of the above-mentioned phosphorous nitrogen of 2g, 18g vinylbenzene, 0.2g dibenzoyl peroxide are joined in the 250ml there-necked flask, stir, then in reactor, add 100ml deionized water, 0.1g polyvinyl alcohol, 1.0g organo montmorillonite, after stirring, react 2h and 20h at 95 ℃ and 80 ℃ respectively.After question response finishes, filter, with a certain amount of deionized water and methyl alcohol priority washing leaching cake.With filter cake vacuum-drying, obtain fire retardant polystyrene/organic montmorillonite nano mixture at last.Products therefrom is shown as exfoliated structure through XRD and TEM, and weightless 10% and 50% temperature is respectively 325 ℃ and 386 ℃, and miniature calorimeter shows that its hot release capacity is 498Jg
-1K
-1, it is 35.6KJ/g that total heat discharges THR.And the temperature of the polystyrene that equal conditions prepares down weightless 10% and 50% is respectively 305 ℃ and 356 ℃, and miniature calorimeter shows that its hot release capacity is 942Jg
-1K
-1, it is 39.6KJ/g that total heat discharges THR.
Embodiment 5:
In the 250ml three-necked bottle of mechanical stirring and constant pressure funnel is housed, add 21.1g (0.1mol) phosphorus dichloride acid phenenyl ester and 80ml tetrahydrofuran (THF), ice bath stirs, after 10 minutes, add 21.2g (0.21mol) triethylamine, again under continue stirring in 2 hours the slow mixing solutions of dropwise addition of acrylic acid hydroxyl ethyl ester 11.6g (0.1mol) and 20ml tetrahydrofuran (THF), continue reaction 4 hours.Then diethylamine is dissolved in the 80ml tetrahydrofuran (THF), under continuing stirring, slowly splashes in the above-mentioned reaction system, reacted 8 hours.Decompress filter is removed triethylamine salt, and underpressure distillation removes and desolvates, and the yellow transparent liquid that obtains is product of the present invention.Productive rate is 80%.
Products therefrom is through nmr analysis, the peak position of chemical shift at 7.1～7.3ppm place is the phenyl ring peak position, three identical peaks of integral area that chemical shift occurs at 5.8ppm, 6.1ppm, 6.4ppm place are respectively three hydrogen peak positions on two keys of Hydroxyethyl acrylate, and chemical shift is respectively (O-CH on the Hydroxyethyl acrylate at two peaks at 4.2ppm, 4.4ppm place
2-CH
2-) two methylene radical on the peak position of hydrogen, and the peak that appears on the 3.1ppm is-N (CH
2)
2The peak position of last four hydrogen, the peak that appears on the 1.06ppm is the peak position of six hydrogen on the methyl.
In a 250ml there-necked flask, add 0.12g sodium laurylsulfonate, 80ml deionized water, be warming up to 50 ℃ and open stirring, will the fire-retardant monomer of the above-mentioned phosphorous nitrogen of 2g, 18g vinylbenzene, 0.6g cetyl trimethylammonium bromide montmorillonite modified joins in the there-necked flask after mixing.After stirring, the 10ml deionized water that is dissolved with the 0.1g Potassium Persulphate is added drop-wise in the reaction mixture reaction 10h.After reaction finished, with Tai-Ace S 150 and salt naphtenic acid, filtration then, methyl alcohol, deionized water wash, drying obtained fire retardant polystyrene/organic montmorillonite nano mixture.Product is shown as exfoliated structure through XRD and TEM, and the TGA test result shows: weightless 10% and 50% temperature is respectively 330 ℃ and 390 ℃, and miniature calorimeter shows that its hot release capacity is 502Jg
-1K
-1, it is 36.2KJ/g that total heat discharges THR.And the temperature of the polystyrene that equal conditions prepares down weightless 10% and 50% is respectively 315 ℃ and 365 ℃, and miniature calorimeter shows that its hot release capacity is 945Jg
-1K
-1, it is 39.2KJ/g that total heat discharges THR.
Claims (9)
1, the preparation method of the phosphorous nitrogen comonomer of a kind of polymerizable, it is characterized in that with the phosphorus dichloride acid phenenyl ester be response matrix, the polyvalent alcohol or the polyphenol that add part propylene acidifying or part methyl acrylated by the reaction mol ratio, add attached sour agent triethylamine or pyridine ,-5～5 ℃ of ice baths are stirred to and no longer include the hydrogenchloride generation in solvent; Add the nitrogenous compound that has a reactive amino group according to the reaction mol ratio then, under-5～5 ℃ of condition of ice bath, stirred 8～12 hours, remove attached sour agent salt and solvent, resulting light yellow transparent liquid is polymerisable phosphorus-nitrogen-containing halogen-free comonomer.
2, the preparation method of the phosphorous nitrogen comonomer of polymerizable according to claim 1 is characterised in that the polyvalent alcohol or the polyphenol of described part propylene acidifying or part methyl acrylated, and its chemical structural formula is HOR
1[O (C=O) CR
2=CH
2]
m, R in the formula
1For containing the alkyl or aryl of 1-12 carbon, R
2Be CH
3Or H, m is 1,2 or 3; The polyvalent alcohol of this part propylene acidifying or part methyl acrylated or polyphenol comprise methacrylic acid-beta-hydroxy ethyl ester, senecioate-hydroxyl ethyl ester, 2-hydroxyl dimethyl allene acid glyceride, 2-hydroxyl glycerol diacrylate, 1-methylol-3,5-dimethyl allene acid phenenyl ester or 1-methylol-3,5-diacrylate phenyl ester.
3, the preparation method of the phosphorous nitrogen comonomer of polymerizable according to claim 1 is characterised in that described solvent is selected from tetrahydrofuran (THF), methylene dichloride, chloroform, ether or dioxane.
4, the preparation method of the phosphorous nitrogen comonomer of polymerizable according to claim 1, be characterised in that the described nitrogenate that has a reactive amino group is selected from alkylamine, comprises diethylamine, dimethylamine, dipropyl amine, ethylenimine, Pyrrolidine, piperidines, pyridine, ethamine, propylamine, Isopropylamine, n-Butyl Amine 99, sec-butylamine or TERTIARY BUTYL AMINE.
5, the phosphorus-nitrogen-containing halogen-free comonomer of the described method of claim 1 preparation is characterized in that having simultaneously the monomer molecule of activity double key and phosphorus nitrogen ignition-proof element, and its chemical structural formula is:
In the formula, R is the functional group of part propylene acidifying or part methyl acrylated; R ' is for having the nitrogen-containing functional group of a tertiary amine or secondary amine.
6, a kind of preparation method of fire retardant polystyrene/layered inorganic nanocomposite, it is characterized in that: be response matrix with the phosphorus dichloride acid phenenyl ester earlier, the polyvalent alcohol or the polyphenol that add part propylene acidifying or part methyl acrylated by the reaction mol ratio, add attached sour agent triethylamine or pyridine ,-5～5 ℃ of ice baths are stirred to and no longer include the hydrogenchloride generation in solvent; Add the nitrogenous compound that has a reactive amino group according to the reaction mol ratio then, under-5～5 ℃ of condition of ice bath, stirred 8～12 hours, remove attached sour agent salt and solvent, resulting light yellow transparent liquid is polymerisable phosphorus-nitrogen-containing halogen-free comonomer;
Utilize the phosphorous nitrogen fire-resistant copolyesters monomer of above-mentioned preparation again, select one of free radical mass polymerization, suspension polymerization or three kinds of modes of emulsion polymerization for use, under initiator causes, pass through in-situ inserted free-radical polymerized, phosphor nitrogen combustion inhibitor is fixed in the polystyrene molecular chain in the chemical bond mode, and interact with laminated inorganic matter, obtain containing the fire retardant polystyrene of laminated inorganic matter;
Described free radical mass polymerization is: will be stirred to evenly by the laminated inorganic matter of monomer total mass 0.05-40%, the phosphorous-containing monomers of 5-50% and the vinylbenzene of 50-90%, and form the dispersion liquid of stable phosphorous-containing monomers, vinylbenzene and laminated inorganic matter; After being heated to 50-100 ℃ kick off temperature, add the oil soluble radical initiator with respect to the 0.02-3% of monomer total mass, polyreaction begins; By the time monomer conversion is 35% when following, with viscous mixture 60-200 ℃ of polymerization, until reacting completely;
Described free radical suspensioning polymerization method is: will by monomer total mass 1-3 doubly deionized water and after the dispersion agent of 0.05-3% stirs, add and press the phosphorous-containing monomers of monomer total mass 5-50%, the vinylbenzene of 50-90%, oil-soluble initiator and the 0.05-40% laminated inorganic matter of 0.02-3%; Stir polymerization at 60-200 ℃ after stirring into homogeneous phase solution, after question response is complete, obtains particulate solid after filtering, clean, drying and be fire retardant polystyrene/layered inorganic nanocomposite;
Described free-radical emulsion polymerization method is: after will stirring by the water-soluble radical initiator of the emulsifying agent of doubly deionized water of monomer total mass 0.5-3,0.1-3% and 0.02-3%, add the vinylbenzene and the phosphorous-containing monomers that are dispersed with laminated inorganic matter, wherein the quality of laminated inorganic matter accounts for 0.05-40%, and the mass concentration of phosphorous-containing monomers is 5-50%; Stir polymerization at 5-100 ℃, after question response finished, breakdown of emulsion was isolated the pressed powder product;
Used laminated inorganic matter is selected from a kind of or its mixture in organo-clay, organically-modified double-hydroxide, organically-modified zirconium phosphate or the organically-modified titanium phosphate; Its medium clay soil is selected from montmorillonite, hectorite, saponite, vermiculite, beidellite, hectorite, silica, halloysite, talcum powder, fibrous morphology crystals or illite mineral, or the mixture of above-mentioned substance; The properties-correcting agent of organo-clay or organically-modified zirconium phosphate or organically-modified titanium phosphate is selected from secondary amine, tertiary amine, level Four halogeno-amine or alkylphosphines compounds, comprises palmityl trimethyl ammonium chloride, octadecyl trimethylammonium bromide, Dodecyl trimethyl ammonium chloride, dodecyl benzyl dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, cetyl trimethylammonium bromide, octadecyl trimethylammonium bromide, dodecyl dimethyl benzyl ammonium bromide, Trimethyllaurylammonium bromide or two octadecyl dimethyl brometo de amonio; The structural formula of described double-hydroxide is [M
2+ 1-xM
3+ x(OH)
2] A
N- X/nMH
2O, wherein M
2+Be divalent metal, comprise Ca
2+, Mg
2+, Ni
2+, Co
2+, Zn
2+, Mn
2+Or Cu
2+M
3+Be trivalent metal cation, comprise Al
3+, Cr
3+, Co
3+, Ni
3+, Mn
3+, Fe
3+Or V
3+A is the interlayer inorganic anion, comprises Cl
-, NO
3 -, SO
4 2-Or CO
3 2-, or the Organoalkyl carboxylate anion, comprise [CH
3(CH
2)
nCOO
-, n=8,10,12,14,16,20, or the alkylsulphonic acid negatively charged ion, comprise sodium laurylsulfonate or pentadecyl sodium sulfonate; Organically-modified double-hydroxide is a kind of, two kinds or the two or more mixture in the above-mentioned double-hydroxide;
Described oil soluble radical initiator is selected from: (1) peroxide initiator comprises dibenzoyl peroxide, peroxidation two acyls, dilauroyl peroxide, peroxyesters, peroxy dicarbonates, isopropyl benzene hydroperoxide, dicumyl peroxide or di-tert-butyl peroxide; (2) azo-initiator comprises Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) or azo-bis-iso-dimethyl; (3) oil soluble oxidation-reduction trigger system, oxygenant wherein are selected from hydroperoxide, benzoyl peroxide, dialkyl or peroxidation diacyl compound; Reductive agent wherein is selected from tertiary amine, naphthenate, mercaptan or organometallic compound;
Described water-soluble radical initiator is selected from: (1) inorganic peroxy class initiator comprises Potassium Persulphate, ammonium persulphate, hydroperoxide or hydrogen peroxide; (2) azo-initiator, comprise 2,2 '-azo diisobutyl amidine dihydrochloride, 2,2 '-azo [2-(2-tetrahydroglyoxaline-2-yl) propane] dihydrochloride, 4,4 '-azo two (4-cyanopentanoic acid) or azo di-isopropyl tetrahydroglyoxalines; (3) water soluble oxidized-reduction system, wherein oxygenant is selected from hydrogen peroxide, persulphate or hydroperoxide, and reductive agent is selected from Fe
2+, Cu
+, S-WAT, sodium bisulfite, Sulfothiorine, alcohol, amine, oxalic acid or glucose; Described water soluble oxidized-reduction initiator system is the combination of any oxygenant and any reductive agent.
7, as the preparation method of fire retardant polystyrene/layered inorganic nanocomposite as described in the claim 6, be characterised in that described dispersion agent is the mixture of following any dispersion agent or several dispersion agents, comprise (1) water soluble organic polymer dispersion agent, be selected from: polyvinyl alcohol, polyacrylic acid, poly-methyl acrylate class, maleic anhydride-styrene copolymers, methylcellulose gum, hydroxypropylcellulose, gelatin or sodiun alginate; (2) water-fast inorganic powder is selected from: magnesiumcarbonate, lime carbonate, calcium phosphate or talcum powder.
8, as the preparation method of fire retardant polystyrene/layered inorganic nanocomposite as described in the claim 6, be characterised in that described emulsifying agent is the mixture of following any emulsifying agent or several emulsifying agents; Comprise sodium soap R
3COONa (R
3=C
11～17), alkyl sodium sulfonate R
4SO
3Na (R
4=C
11～17), sodium alkylarysulfonate, rosined soap, ammonium salt, amino acid, ethylene oxide polymer or R
5-(OC
2H
4)
n-OH, R
5CO-(OC
2H
4)
n-OH, R
5-C
6H
4(OC
2H
4)
n-OH, wherein R
5=C
10～16
9, the fire retardant polystyrene/layered inorganic nanocomposite of the described method preparation of claim 6, it is characterized in that containing vinylbenzene-phosphorus nitrogen monomer copolymer and the laminated inorganic matter that is scattered in wherein, described multipolymer is made of by the covalent linkage link styrene monomer and phosphorous nitrogen monomer; And contain in this mixture and be the laminated inorganic matter of 0.05-40% by weight.
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