CN104045821B - Phosphoric flame-proof copolyester ionomer/nano composite material and preparation method thereof - Google Patents
Phosphoric flame-proof copolyester ionomer/nano composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of phosphoric flame-proof copolyester ionomer/nano composite material and preparation method thereof, this phosphoric flame-proof copolyester ionomer/nano composite material is by terephthalic acid or dimethyl terephthalate (DMT), ethylene glycol, phosphorous ion monomer [i] or phosphorous ion monomer [ii], inorganic nano-particle is or/and organically-modified inorganic nano-particle forms through in-situ polymerization, in this matrix material, phosphorous ionic group structural unit number is the 2-5% of the structural unit number of terephthalic acid or dimethyl terephthalate (DMT), inorganic nano-particle is or/and organically-modified inorganic nano-particle accounts for the 0.5-10% of this matrix material total mass.This phosphoric flame-proof copolyester ionomer/nano composite material has excellent flame retardant properties, anti-dropping performance and crystal property simultaneously, and intrinsic viscosity can reach 0.6-1.0dL/g, thus can directly use as the raw material preparing fiber, engineering plastics and film etc.
Description
Technical field
The invention belongs to anti-flaming nano composite material and preparing technical field thereof, be specifically related to a kind of phosphoric flame-proof copolyester ionomer/nano composite material and preparation method thereof.
Background technology
Polyester (refers in particular to polyethylene terephthalate, PET) as one of most important hemicrystalline synthesized polymer material, wrapping material, synthon, film and engineering plastics are widely used as because it has the advantages such as high strength, thermotolerance, dimensional stability and chemical resistance.Polyester is since last century, the fifties realized commercialization first, and its application development is swift and violent, all can see its figure in a lot of field such as clothes, furnishing fabric, food, electronic apparatus, health care, automobile, building.At present, trevira is one with fastest developing speed in various synthon, output is high, the most most widely used.But polyester belongs to inflammable material, its oxygen index only has 22.0, and make it in the field that has certain requirements to fire prevention, the application as aspects such as textiles, fire retardant protective clothing, electron devices in hotel furnishing fabric, the vehicles is greatly limited.
In order to reduce the potential fire hazard of polyester in application process, usually mainly adopting and ignition-proof element being introduced polyester molecule chain, adding fire retardant and carry out physical blending and in the method that fabric face carries out applying Final finishing, flame-retarded modification is carried out to polyester.Although halogen containing flame-retardant wherein used has more excellent flame retardant effect, but it can discharge corrodibility toxic gas when burning, as hydrogen halide, dioxin etc., easily make people suck rear death by suffocation, European Union has promulgated the use of relevant it is forbidden by decree to halogen-containing flame retardant already.Being introduced in polyester by the mode of copolymerization by phosphor-containing flame-proof monomer is one of the most effective fire-retardant mode (Wang Yuzhong work, the flame-retarded design of trevira, Sichuan Science Press, 1994), which can be avoided fire retardant and polyester matrix poor compatibility, be moved frosting and the problem that declines such as the processing caused and flame retardant properties.The people such as Asrar and Chang (Asrar, J.; Berger, P.A.; Hurlbut, J.JournalofPolymerScience:PartA:PolymerChemistry, 1999,37,3119-3128.Chang, S.-J.; Chang, F.-C.JournalofAppliedPolymerScience, 1999,72,109-122.) report traditional main chain and side base phosphorous copolyester respectively, what it was introduced is phosphorous reactive flame retardant.Although above-mentioned phosphorous reactive flame retardant can play good fire retardation, but as can be seen from the summary and test result of author, because fire-retardant group that space is larger destroys the regularity of molecular chain, thus reduce the crystallizing power of polyester, and then greatly affect its workability.Meanwhile, from the people such as Sato (Sato, M.; Endo, S.; Araki, Y.; Matsuoka, G.; Gyobu, S.; Takeuchi, H.JournalofAppliedPolymerScience, 2000,78, result of study 1134-1138.) is seen, the short molten drop fire retardant mechanism of traditional phosphor-containing flame-retardant copolyester has increased the weight of melting drip phenomenon when burning further, easily causes secondary to endanger.
At present, production of polyester enterprise of China is numerous, and become the first in the world macrocyclic polyester producing country, production capacity relative surplus, particularly bulk product is many, and the differentiated product of high additive value is few, compared with same kind of products at abroad, does not have competitive edge; Simultaneously due to appreciation of the RMB, polyester outlet obstructions, market competition is aggravated further.Therefore research and develop the polyester product innovation of high comprehensive performance, the competitive power strengthening product is one of approach changing China's polyester industry present situation.
Summary of the invention
The object of the invention is for prior art Problems existing, a kind of phosphoric flame-proof copolyester ionomer/nano composite material is provided, this matrix material has good flame retardant properties, anti-dropping performance and crystal property, can overcome the problem of existing independent employing phosphorous reactive flame retardant resulting materials over-all properties difference.
Two of object of the present invention is to provide the preparation method of above-mentioned phosphoric flame-proof copolyester ionomer/nano composite material.
In research searching process, the present inventor finds that the crystal property reduction of the fire retardant of phosphorous ion monomer is because the addition of phosphonium ion monomer too much causes, if and reduce the addition of phosphonium ion monomer, its flame retardant properties and anti-molten performance can be affected again, therefore need to find one and namely have contribution to flame retardant properties, the synergist of phosphonium flame retardant crystal property can be improved again.
Phosphoric flame-proof copolyester ionomer/nano composite material provided by the invention is or/and organically-modified inorganic nano-particle forms through in-situ polymerization by terephthalic acid or dimethyl terephthalate (DMT), ethylene glycol, phosphorous ion monomer [i] or phosphorous ion monomer [ii], inorganic nano-particle, in this matrix material, phosphorous ionic group structural unit number is the 2-5% of the structural unit number of terephthalic acid or dimethyl terephthalate (DMT), and inorganic nano-particle is or/and organically-modified inorganic nano-particle accounts for the 0.5-10% of this matrix material total mass; The general structure of above-mentioned phosphorous ion monomer [i] is as follows:
In formula, R
1, R
2, R
3, R
4for carboxyl or ester group, can be identical or not identical; X, Y are O or S atom, can be identical or not identical; M
1for any one in alkali metal atom.
The general structure of above-mentioned phosphorous ion monomer [ii] is as follows:
In formula, R
5, R
6, R
7, R
8for hydroxyl, ester group or 2-hydroxy ethoxy, can be identical or not identical; W, Z are O or S atom, can be identical or not identical; M
2for any one in alkali metal atom; Phosphorous ionic group structural unit is from any one in general structure A, B, C, D, E, F.
The M of phosphorous ion monomer [i] and [ii] in above-mentioned phosphoric flame-proof copolyester ionomer/nano composite material
1and M
2preferred Na or K atom.
Inorganic nano-particle described in above-mentioned phosphoric flame-proof copolyester ionomer/nano composite material is at least one in nano barium sulfate, nano silicon, nano titanium oxide and nano zine oxide; Described organically-modified inorganic nano-particle is at least one in organic modified sheet silicate, organically-modified layered double-hydroxide, organically-modified bedded zirconium phosphate and organically-modified carbon nanotube.
In above-mentioned phosphoric flame-proof copolyester ionomer/nano composite material, preferred phosphorous ionic group structural unit number is the 3-4% of the structural unit number of terephthalic acid representative.
Preferred inorganic nano-particle in above-mentioned phosphoric flame-proof copolyester ionomer/nano composite material is or/and organically-modified inorganic nano-particle is the 0.5-5% of phosphoric flame-proof copolyester ionomer/nano composite material total mass; Be more preferably phosphoric flame-proof copolyester ionomer/nano composite material total mass 1-5%.
The intrinsic viscosity of above-mentioned phosphoric flame-proof copolyester ionomer/nano composite material is 0.6-1.0dL/g, meets its application requiring as trevira.
The preparation method of above-mentioned phosphoric flame-proof copolyester ionomer/nano composite material provided by the invention, the method is by terephthalic acid or dimethyl terephthalate (DMT), ethylene glycol and catalyzer proportioning routinely, after adopting direct esterification or ester-interchange method to carry out esterification, be prepared from through polycondensation, it is characterized in that before esterification or before esterification aftercondensated, add in reaction system and count phosphorous ion monomer [i] or the phosphorous ion monomer [ii] of 2-5% by the molecular fraction of terephthalic acid or dimethyl terephthalate (DMT) and account for the inorganic nano-particle of matrix material total mass 0.5-10% or/and organically-modified inorganic nano-particle, carry out in-situ polymerization.
In above preparation method, before esterification or before esterification aftercondensated, the organic solution preferably adding phosphorous ion monomer [i] or phosphorous ion monomer [ii] in reaction system and the inorganic nano-particle that is scattered in organic solvent are or/and organically-modified inorganic nano-particle.
The organic solution of phosphorous particle monomer body [i] or phosphorous ion monomer [ii] refers to and phosphorous particle monomer [i] or phosphorous ion monomer [ii] is dissolved in the organic solution formed in organic solvent completely.The object of the organic solution of phosphorous ion monomer [i] or phosphorous ion monomer [ii] is adopted to be to make phosphorous ion monomer [i] or phosphorous ion monomer [ii] more can be compatible with polyester, and be easy to phosphorous ion monomer and terephthalic acid or dimethyl terephthalate (DMT) and react, phosphorous ion monomer is connected on the molecular chain main chain of terephthalic acid or dimethyl terephthalate (DMT) with chemical bond-linking.Adopt the inorganic nano-particle be scattered in organic solvent or/and the object of organically-modified inorganic nano-particle is to make inorganic nanoparticles first be dispersed in the organic solvent with polyester with fine consistency, again the above-mentioned organic solvent containing organic/inorganic nano ion is joined in reaction system, and then make inorganic nano-particle well disperse in the polyester.In order to avoid in the organic solution adding phosphorous ion monomer [i] or phosphorous ion monomer [ii] in reaction system and the inorganic nano-particle that is scattered in organic solvent or/and melt solidifying in organically-modified inorganic nano-particle subprocess; preferably under nitrogen protection in more than 220 DEG C, by the organic solution of phosphorous ion monomer [i] or phosphorous ion monomer [ii] and the inorganic nano-particle that is scattered in organic solvent or/and organically-modified inorganic nano-particle is added drop-wise in reaction system.In order to avoid making melt solidifying because drop rate is too fast further, can by the organic solution of phosphorous ion monomer [i] or phosphorous ion monomer [ii] and the inorganic nano-particle be scattered in organic solvent or/and organically-modified inorganic nano-particle be slowly added drop-wise in reaction system, preferred drop rate is 2 ~ 3 drops/sec.
The general structure of the phosphorous ion monomer [i] that above preparation method is used is as follows:
In formula, R
1, R
2, R
3, R
4for carboxyl or ester group, can be identical or not identical; X, Y are O or S atom, can be identical or not identical; M
1for any one in alkali metal atom.
The general structure of the phosphorous ion monomer [ii] that above preparation method is used is as follows:
In formula, R
5, R
6, R
7, R
8, be hydroxyl, ester group or 2-hydroxy ethoxy, can be identical or not identical; W, Z are O or S atom, can be identical or not identical; M
2for any one in alkali metal atom.
M in the phosphorous ion monomer [i] that above preparation method is used and [ii]
1and M
2preferred Na or K atom.
Above preparation method inorganic nano-particle used is at least one in nano barium sulfate, nano silicon, nano titanium oxide and nano zine oxide; Organically-modified inorganic nano-particle used is at least one in organic modified sheet silicate, organically-modified layered double-hydroxide, organically-modified bedded zirconium phosphate and organically-modified carbon nanotube.
In the phosphorous ion monomer [i] that above preparation method is used and [ii], R
1, R
2, R
3, R
4the ester group group represented is preferably the methyl esters group after monohydroxy-alcohol esterification or ethyl ester group, or is any one in glycol ester group, propylene glycol ester group, butanediol ester group, glycol ether ester group, DOPCP group, glycerine ester group or the tetramethylolmethane ester group after polyhydric alcohol; R
5, R
6, R
7, R
8the ester group group represented is preferably any one in the acetate group after anhydride esterifying, propionic ester group, phthalate group or terephthalate groups.
The phosphorous ion monomer [i] that above preparation method is used and phosphorous ion monomer [ii] amount preferably press the 3-4% of terephthalic acid or dimethyl terephthalate (DMT) mole percent.
The inorganic nano-particle that above preparation method is used is or/and organically-modified inorganic nano-particle amount is preferably phosphoric flame-proof copolyester ionomer/nano composite material total mass 0.5-5%; Be more preferably phosphoric flame-proof copolyester ionomer/nano composite material total mass 1-5%.
Processing step and the condition of conventional direct esterification of the present invention or ester-interchange method are specific as follows:
Direct esterification: terephthalic acid, ethylene glycol and catalyzer join in reaction vessel by ratio routinely; be forced into 0.1Mpa under nitrogen protection; then 220 ~ 260 DEG C are warming up to; after controlling reaction vessel internal pressure 0.3 ~ 0.4Mpa esterification to anhydrous generation; vacuumize the excessive ethylene glycol of removal in 240 ~ 260 DEG C and obtain prepolymer; then in 260 ~ 280 DEG C of high vacuum (pressure≤150Pa in reaction vessel; preferred 20-150Pa) under polycondensation 0.5 ~ 3h, cooling obtain phosphoric flame-proof copolyester ionomer/nano composite material.Wherein, phosphorous ion monomer [i] or phosphorous ion monomer [ii], inorganic nano-particle are or/and organically-modified inorganic nano-particle can be selected to add reaction system before esterification or before esterification aftercondensated.
Ester-interchange method: dimethyl terephthalate (DMT), ethylene glycol and catalyzer join in reaction vessel by ratio routinely, normal pressure is warming up to 180 ~ 240 DEG C of transesterifys extremely without after methyl alcohol generation, vacuumize the excessive ethylene glycol of removal in 240 ~ 260 DEG C and obtain prepolymer, then in 260 ~ 280 DEG C of high vacuum (pressure≤150Pa in reaction vessel, preferred 20-150Pa) under polycondensation 0.5 ~ 3h, cooling obtain phosphoric flame-proof copolyester ionomer/nano composite material.Wherein, phosphorous ion monomer [i] or phosphorous ion monomer [ii], inorganic nano-particle are or/and organically-modified inorganic nano-particle can be selected to add reaction system before transesterify or before transesterify aftercondensated.
Catalyzer selected by above preparation method is at least one in zinc acetate, manganese acetate, Cobaltous diacetate, antimonous oxide, antimony glycol, titanic acid ester and organotin.
Compared with prior art, tool has the following advantages in the present invention:
1, because inorganic nano-particle contained in phosphoric flame-proof copolyester ionomer/nano composite material provided by the invention is or/and organically-modified inorganic nano-particle can play the effect of nucleator, thus make phosphoric flame-proof copolyester ionomer molecule namely crystallizable at relatively high temperatures, and then make the crystal property of matrix material be able to obvious improvement.
2, because inorganic nano-particle contained in phosphoric flame-proof copolyester ionomer/nano composite material provided by the invention is or/and organically-modified inorganic nano-particle can be dispersed in phosphoric flame-proof copolyester ionomer, when matrix material is in the higher environment of temperature, can trap heat, the intervention of oxygen and the small molecules release avoiding composite inner base material (phosphoric flame-proof copolyester ionomer) decomposes to generate, thus reasonable fire retardation can be played, even if make when phosphorous ion monomer addition declines, the flame retardant properties of matrix material also can not be subject to too large impact.
3, because phosphorous ionic group in phosphoric flame-proof copolyester ionomer/nano composite material provided by the invention is bifunctional, both can be easy to introduce in the middle of polyester molecule chain, there is not end-blocking effect, its " ionic group aggressiveness " can produce stable crosslinked action again, the reactive force between molecular chain can be strengthened, thus melt viscosity can be increased on the one hand, the heterocycle of nonionic structure part of phosphorous ionic group itself is consistent with the one-tenth charcoal anti-dropping effect of ionic structure part on the other hand, jointly can promote into charcoal; Moreover inorganic nano-particle can hinder the motion of polymer molecular chain, and then play viscosifying action, based on the reason of this three aspect, this phosphoric flame-proof copolyester ionomer/nano composite material has excellent anti-dropping performance.
4, because phosphorous ion monomer in phosphoric flame-proof copolyester ionomer/nano composite material provided by the invention is connected on the molecular chain main chain of terephthalic acid or dimethyl terephthalate (DMT) with chemical bond-linking, thus commixed type fire retardant problem can be avoided completely, the problem includes: materials compatibility problem.
5, because inorganic nano-particle in phosphoric flame-proof copolyester ionomer/nano composite material provided by the invention adds in In-situ reaction mode, thus without the need to again blended, simplify the preparation section of material, and whole preparation method is simple, maturation, is easy to suitability for industrialized production.
6, because the intrinsic viscosity of phosphoric flame-proof copolyester ionomer/nano composite material provided by the present invention can reach 0.6-1.0dL/g, thus can directly use as the raw material preparing fiber, engineering plastics and film etc.
Accompanying drawing explanation
The 31P nuclear magnetic spectrogram of the phosphoric flame-proof copolyester ionomer/nano composite material of Fig. 1 prepared by the embodiment of the present invention 7 after purifying.
The one-tenth charcoal design sketch of the pure polyester of Fig. 2 prepared by comparative example 1.
Fig. 3 is the one-tenth charcoal design sketch of the flame-proof copolyester of phenanthrene-succinic acid (DDP) of mixing containing the assorted-10-phosphinylidyne of conventional flame retardant 9,10-dihydro-9-oxy.
The one-tenth charcoal design sketch of phosphoric flame-proof copolyester ionomer/nano composite material that Fig. 4 obtains for the embodiment of the present invention 4.
Fig. 5 be the phosphoric flame-proof copolyester ionomer (b) prepared of pure polyester (a), comparative example 2 prepared by comparative example 1 and the embodiment of the present invention 7 prepare the DSC of phosphoric flame-proof copolyester ionomer/nano composite material (c) scan temperature lowering curve figure.
Embodiment
Provide embodiment below so that the invention will be further described.What be necessary to herein means out is that following examples can not be interpreted as limiting the scope of the invention; if the person skilled in the art in this field makes some nonessential improvement and adjustment according to the invention described above content to the present invention, still belong to scope.
What deserves to be explained is: 1) intrinsic viscosity of following examples gained phosphoric flame-proof copolyester ionomer/nano composite material is with phenol/1,1,2,2-tetrachloroethane (1:1, v:v) be solvent, be mixed with the solution that concentration is 0.5g/dL, record at 25 DEG C with dark type viscometer.2) limiting oxygen index(LOI) test adopts HC-2C oxygen index instrument to test according to ASTMD2863-97 testing standard, batten size: 120 × 6.5 × 3.2mm
3.3) fusing point of material and Tc adopt DSC (TAQ200) to record, and test temperature rate is 10 DEG C/min, nitrogen flow rate 50ml/min.4) decomposition temperature adopts TGA (NETZSCH209F1) to record, and test temperature rise rate is 10 DEG C/min, nitrogen flow rate 50ml/min.5) polynite of the octadecyl trimethyl ammonium chloride modification that following examples are used, nano silicon, nano titanium oxide and nano zine oxide are commercial.
The phosphorous ion monomer 2 that following examples are used, luxuriant and rich with fragrance oxa-potassium hypophosphite (DHPPO-K) of 8-(2-hydroxyl-oxethyl) carbonyl, concrete is prepared as follows: by 89.1g p-Xylol base ether, 160ml phosphorus trichloride and 65g aluminum chloride add in 250ml there-necked flask and stir, in 75 DEG C of reaction 24h, then pour in cold water, be dispersed in 400ml strong base solution after separating out white precipitate filtering and washing, lower 30% hydrogen peroxide dripping 200ml is stirred in 80 DEG C, reaction 12h, use hcl acidifying suction filtration afterwards, the white powder redispersion obtained is in strong base solution, with 200g potassium permanganate in 90 DEG C of oxidizing reaction 8h, rear suction filtration, the light green clear filtrate hcl acidifying obtained, separate out white powder 2, luxuriant and rich with fragrance oxa-Hypophosporous Acid, 50 (DCPPO-OH) of 8-dicarboxyl, wash twice post-drying with water, the DCPPO-OH of 50g is added in 700ml methyl alcohol, add the 13ml vitriol oil again, backflow 24h, obtain 2, luxuriant and rich with fragrance oxa-Hypophosporous Acid, 50 (DMPPO-OH) of 8-(methoxyl group) carbonyl, 52.2gDMPPO-OH and 150ml ethylene glycol is added in 250mL reaction flask, stir, add in 10.35g Anhydrous potassium carbonate at 50 DEG C and salify, high vacuum (<70Pa) transesterify 8h obtains phosphorous ion monomer 2, the ethylene glycol solution of luxuriant and rich with fragrance oxa-potassium hypophosphite (DHPPO-K) of 8-(2-hydroxyl-oxethyl) carbonyl.The structural formula of luxuriant and rich with fragrance oxa-potassium hypophosphite (DHPPO-K) of phosphorous ion monomer 2,8-(2-hydroxyl-oxethyl) carbonyl is above:
(structural formula is luxuriant and rich with fragrance oxa-sodium hypophosphite (DHPPO-Na) of following examples phosphorous ion monomer 2,8-(2-hydroxyl-oxethyl) carbonyl used
), (structural formula is the luxuriant and rich with fragrance oxa-potassium hypophosphite of phosphorous ion monomer 2,8-acetyl oxo
), (structural formula is the luxuriant and rich with fragrance oxa-sodium hypophosphite of phosphorous ion monomer 2,8-acetyl oxo
) preparation method and above phosphorous ion monomer 2, luxuriant and rich with fragrance oxa-potassium hypophosphite (DHPPO-K) of 8-(2-hydroxyl-oxethyl) carbonyl is substantially identical, just adopt during preparation raw material and phase application quantity slightly different, but be all that those skilled in the art can regulate.
The preparation method of following examples layered dihydroxyl compound used (LDH) is as follows: in the reaction flask of 500ml, add 250ml deionized water, 38.40gMg (NO
3)
26H
2o and 28.13gAl (NO
3)
39H
2o; drip the deionized water solution containing 43.2g sodium lauryl sulphate under nitrogen protection, drip the NaOH solution of 0.08g/ml, control ph remains on about 10; the precipitation separated out is suction filtration after static-aging 24h under nitrogen atmosphere, repeatedly dries with deionized water wash.
The preparation method of following examples organically-modified zirconium phosphate used is as follows: in 250ml there-necked flask, add 150ml deionized water and 10g zirconium oxychloride, mechanical stirring is dissolved completely to zirconium oxychloride, the 25ml phosphate aqueous solution of slow dropping 8mol/L, simultaneously ultrasonic, control temperature 45 DEG C, reaction 8h, centrifugation goes out after zirconium phosphate deionized water is washed till neutrality to add in 150ml deionized water again, stir the lower aqueous solution slowly dripping zirconium phosphate 2.5 times moles metering methylamine, in 40 DEG C of reaction 8h, centrifugation, namely deionized water wash obtains the zirconium phosphate of methylamine modification for 4 times, the zirconium phosphate of above methylamine modification is scattered in the deionized water of 150ml, the aqueous solution that 100ml contains 21.58g octadecyl trimethyl ammonium chloride is slowly dripped under 50 DEG C of mechanical stirring, reaction 8h, through centrifugal, suction filtration isolates precipitation, and with in deionized water repetitive scrubbing to filtrate without chlorion.
The preparation method of following examples organically-modified multi-walled carbon nano-tubes used (MWNT) is as follows: in the reaction flask of 250ml, add 0.5g multi-walled carbon nano-tubes and 66.7ml the vitriol oil and concentrated nitric acid mixed solution (v/v3/1), in 50 ~ 60 DEG C of stirring reaction 10h, period ultrasonic disperse, pour in large water gaging after reaction terminates, filtration washing is to neutral, the thionyl chloride that 250ml reaction flask adds 40ml is placed in again after oven dry, in 65 DEG C of reaction 24h under nitrogen protection, add a small amount of tetrahydrofuran (THF) after cooling to filter, 4 times are washed again with tetrahydrofuran (THF), dry in 60 DEG C.
Following examples nano barium sulfate used is prepared as follows: 50.47g barium hydroxide octahydrate is dissolved in the 425ml ethylene glycol of about 70 DEG C, suction filtration while hot, removing impurity, filtrate drips the sulfuric acid of 1.5mol/L under strong stirring, regulate pH to neutral, the suspension obtained is heated to 190 DEG C and dewaters.
The method more than preparing the ethylene glycol solution of phosphorous ion monomer, inorganic nano-particle and organically-modified inorganic nano-particle is this area common method; other ordinary method of this area can be adopted to prepare other organic solutions of phosphorous ion monomer, inorganic nano-particle and organically-modified inorganic nano-particle, and above-mentioned preparation method does not form any restriction to scope yet.The phosphorous ion monomer 2 enumerated although above-mentioned, luxuriant and rich with fragrance oxa-potassium hypophosphite (DHPPO-K) of 8-(2-hydroxyl-oxethyl) carbonyl, phosphorous ion monomer 2, the structural formula of luxuriant and rich with fragrance oxa-sodium hypophosphite (DHPPO-Na) of 8-(2-hydroxyl-oxethyl) carbonyl all belongs to the general structure (A) in phosphorous ion monomer [i], phosphorous ion monomer 2, the structural formula of the luxuriant and rich with fragrance oxa-potassium hypophosphite of 8-acetyl oxo, the luxuriant and rich with fragrance oxa-sodium hypophosphite of phosphorous ion monomer 2,8-acetyl oxo all belongs to the general structure (E) in phosphorous ion monomer [ii].But because the general structure in its structural formula and phosphorous ion monomer [i], phosphorous ion monomer [ii] is close.According to the method for luxuriant and rich with fragrance oxa-potassium hypophosphite (DHPPO-K) of above-mentioned preparation phosphorous ion monomer 2,8-(2-hydroxyl-oxethyl) carbonyl, be easy to the phosphorous ion monomer obtaining similar structures general formula.
Embodiment 1
First by 830g terephthalic acid, 434mL ethylene glycol and 0.46g tetrabutyl titanate join in reactor, be forced into 0.1MPa, stirred under nitrogen atmosphere is warming up to 240 DEG C and starts esterification, control pressure 0.3MPa, be warming up to 260 DEG C after about 1h and continue esterification to anhydrous generation, Pressure Drop is to normal pressure, vacuumize after about 0.5h extracts excessive ethylene glycol out in 260 DEG C and stop vacuumizing, nitrogen is passed in system, drip containing the phosphorous ion monomer 2 of 44.6g with the speed of 2 ~ 3 drops/sec in reactor after getting back to normal pressure, the ethylene glycol solution of luxuriant and rich with fragrance oxa-potassium hypophosphite (DHPPO-K) of 8-(2-hydroxyl-oxethyl) carbonyl and 20.38g are scattered in the polynite of the octadecyl trimethyl ammonium chloride modification in 150ml ethylene glycol in advance, and to control in dropping process system temperature more than 220 DEG C, add rear stopping and leading to nitrogen, again vacuumize, system is in 260 DEG C of rough vacuum precondensation 0.5h (being evacuated to about 150Pa through about 0.5h with lower pumping speed), then polycondensation 2h under 280 DEG C of high vacuum (in reaction chamber pressure≤150Pa), discharging.
Embodiment 2
First by 830g terephthalic acid, 434mL ethylene glycol and 0.46g tetrabutyl titanate join in reactor, esterification (difference is control pressure 0.4MPa) is carried out by the method for embodiment 1, after esterification terminates, Pressure Drop is to normal pressure, vacuumize after about 0.5h extracts excessive ethylene glycol out in 260 DEG C and stop vacuumizing, nitrogen is passed in system, drip containing the phosphorous ion monomer 2 of 66.9g with the speed of 2 ~ 3 drops/sec in reactor after getting back to normal pressure, the ethylene glycol solution of the luxuriant and rich with fragrance oxa-potassium hypophosphite of 8-(2-hydroxyl-oxethyl) carbonyl and 5.11g are scattered in the polynite of the octadecyl trimethyl ammonium chloride modification in 50ml ethylene glycol in advance, and to control in dropping process system temperature more than 220 DEG C, method again by embodiment 1 after adding carries out polycondensation.
Embodiment 3
First by 830g terephthalic acid, 434mL ethylene glycol, 0.46g tetrabutyl titanate and containing the phosphorous ion monomer 2 of 66.9g, the ethylene glycol solution of the luxuriant and rich with fragrance oxa-potassium hypophosphite of 8-(2-hydroxyl-oxethyl) carbonyl joins in reactor, esterification is carried out by the method for embodiment 1, after esterification terminates, Pressure Drop is to normal pressure, vacuumize after about 0.5h extracts excessive ethylene glycol out in 260 DEG C and stop vacuumizing, nitrogen is passed in system, in reactor, drip with the speed of 2 ~ 3 drops/sec the polynite that 10.28g is scattered in the octadecyl trimethyl ammonium chloride modification in 120ml ethylene glycol in advance after getting back to normal pressure, and to control in dropping process system temperature more than 220 DEG C, method again by embodiment 1 after adding is carried out polycondensation and is got final product (difference is that the high vacuum polycondensation time is 0.5 hour).
Embodiment 4
First by 830g terephthalic acid, 434mL ethylene glycol and 0.46g tetrabutyl titanate join in reactor, esterification is carried out by the method for embodiment 1, after esterification terminates, Pressure Drop is to normal pressure, vacuumize after about 0.5h extracts excessive ethylene glycol out in 260 DEG C and stop vacuumizing, nitrogen is passed in system, drip containing the phosphorous ion monomer 2 of 66.9g with the speed of 2 ~ 3 drops/sec in reactor after getting back to normal pressure, the ethylene glycol solution of the luxuriant and rich with fragrance oxa-potassium hypophosphite of 8-(2-hydroxyl-oxethyl) carbonyl and 20.77g are scattered in the polynite of the octadecyl trimethyl ammonium chloride modification in 240ml ethylene glycol in advance, and to control in dropping process system temperature more than 220 DEG C, method again by embodiment 1 after adding carries out polycondensation.
Embodiment 5
First by 830g terephthalic acid, 434mL ethylene glycol and 0.46g tetrabutyl titanate join in reactor, (difference is to carry out esterification by the method for embodiment 1, early stage, esterification temperature was 220 DEG C, later stage esterification temperature asks 240 DEG C), after esterification terminates, Pressure Drop is to normal pressure, vacuumize after about 0.5h extracts excessive ethylene glycol out in 240 DEG C and stop vacuumizing, nitrogen is passed in system, drip containing the phosphorous ion monomer 2 of 64.5g with the speed of 2 ~ 3 drops/sec in reactor after getting back to normal pressure, the ethylene glycol solution of the luxuriant and rich with fragrance oxa-sodium hypophosphite of 8-(2-hydroxyl-oxethyl) carbonyl and 20.72g are scattered in the polynite of the octadecyl trimethyl ammonium chloride modification in 240ml ethylene glycol in advance, and to control in dropping process system temperature more than 220 DEG C, method again by embodiment 1 after adding is carried out polycondensation and is got final product (difference is that the high vacuum polycondensation time is 1.5h).
Embodiment 6
First by 970g dimethyl terephthalate (DMT), 620mL ethylene glycol and 0.24g zinc acetate join in reactor, under nitrogen protection normal pressure, 180 DEG C of esterifications 3 hours, after esterification terminates, vacuumize after about 0.5h extracts excessive ethylene glycol out in 240 DEG C and stop vacuumizing, nitrogen is passed in system, drip containing the phosphorous ion monomer 2 of 66.9g with the speed of 2 ~ 3 drops/sec in reactor after getting back to normal pressure, the ethylene glycol solution of the luxuriant and rich with fragrance oxa-potassium hypophosphite of 8-(2-hydroxyl-oxethyl) carbonyl and 20.77g are scattered in the polynite of the octadecyl trimethyl ammonium chloride modification in 240ml ethylene glycol in advance, and add 0.46g antimonous oxide, and to control in dropping process system temperature more than 220 DEG C, add rear stopping and leading to nitrogen, start to vacuumize, system is at 260 DEG C of rough vacuum precondensation 0.5h, then high vacuum stage of Fig (≤150Pa) is entered, at 260 DEG C of polycondensation 3h, discharging.
Embodiment 7
First by 830g terephthalic acid, 434mL ethylene glycol and 0.46g tetrabutyl titanate join in reactor, esterification (difference is that esterification in early stage and later stage esterification temperature are 260 DEG C) is carried out by the method for embodiment 1, after esterification terminates, Pressure Drop is to normal pressure, vacuumize after about 0.5h extracts excessive ethylene glycol out in 260 DEG C and stop vacuumizing, nitrogen is passed in system, drip containing the phosphorous ion monomer 2 of 111.5g with the speed of 2 ~ 3 drops/sec in reactor after getting back to normal pressure, the ethylene glycol solution of the luxuriant and rich with fragrance oxa-potassium hypophosphite of 8-(2-hydroxyl-oxethyl) carbonyl and 21.55g are scattered in the polynite of the octadecyl trimethyl ammonium chloride modification in 240ml ethylene glycol in advance, and to control in dropping process system temperature more than 220 DEG C, method again by embodiment 1 after adding carries out polycondensation can (difference be that high vacuum condensation temperature is 260 DEG C, the polycondensation time is 3h).
Embodiment 8
First by 830g terephthalic acid, 434mL ethylene glycol and 0.46g tetrabutyl titanate join in reactor, esterification is carried out by the method for embodiment 1, after esterification terminates, Pressure Drop is to normal pressure, vacuumize after about 0.5h extracts excessive ethylene glycol out in 260 DEG C and stop vacuumizing, nitrogen is passed in system, drip containing the phosphorous ion monomer 2 of 66.9g with the speed of 2 ~ 3 drops/sec in reactor after getting back to normal pressure, the ethylene glycol solution of the luxuriant and rich with fragrance oxa-potassium hypophosphite of 8-(2-hydroxyl-oxethyl) carbonyl and 20.77g are scattered in the layered dihydroxyl compound (LDH) in 240ml ethylene glycol in advance, and to control in dropping process system temperature more than 220 DEG C, method again by embodiment 1 after adding carries out polycondensation.
Embodiment 9
First by 830g terephthalic acid, 434mL ethylene glycol, 0.46g tetrabutyl titanate and the organically-modified zirconium phosphate of 20.77g be scattered in ethylene glycol join in reactor, esterification is carried out by the method for embodiment 1, after esterification terminates, Pressure Drop is to normal pressure, vacuumize after about 0.5h extracts excessive ethylene glycol out in 260 DEG C and stop vacuumizing, nitrogen is passed in system, drip containing the phosphorous ion monomer 2 of 66.9g with the speed of 2 ~ 3 drops/sec in reactor after getting back to normal pressure, the ethylene glycol solution of the luxuriant and rich with fragrance oxa-potassium hypophosphite of 8-(2-hydroxyl-oxethyl) carbonyl, and to control in dropping process system temperature more than 220 DEG C, method again by embodiment 1 after adding carries out polycondensation.
Embodiment 10
First by 830g terephthalic acid, 434mL ethylene glycol and 0.46g tetrabutyl titanate join in reactor, esterification is carried out by the method for embodiment 1, after esterification terminates, Pressure Drop is to normal pressure, vacuumize after about 0.5h extracts excessive ethylene glycol out in 260 DEG C and stop vacuumizing, nitrogen is passed in system, drip containing the phosphorous ion monomer 2 of 66.9g with the speed of 2 ~ 3 drops/sec in reactor after getting back to normal pressure, the ethylene glycol solution of the luxuriant and rich with fragrance oxa-potassium hypophosphite of 8-(2-hydroxyl-oxethyl) carbonyl and the 53.56g nano barium sulfate be scattered in ethylene glycol, and to control in dropping process system temperature more than 220 DEG C, method again by embodiment 1 after adding carries out polycondensation.
Embodiment 11
First by 830g terephthalic acid, 434mL ethylene glycol and 0.46g tetrabutyl titanate join in reactor, esterification is carried out by the method for embodiment 1, after esterification terminates, Pressure Drop is to normal pressure, vacuumize after about 0.5h extracts excessive ethylene glycol out in 260 DEG C and stop vacuumizing, nitrogen is passed in system, drip containing the phosphorous ion monomer 2 of 66.9g with the speed of 2 ~ 3 drops/sec in reactor after getting back to normal pressure, the ethylene glycol solution of the luxuriant and rich with fragrance oxa-potassium hypophosphite of 8-(2-hydroxyl-oxethyl) carbonyl and the 113.07g nano barium sulfate be scattered in ethylene glycol, and to control in dropping process system temperature more than 220 DEG C, method again by embodiment 1 after adding carries out polycondensation.
Embodiment 12
First by 830g terephthalic acid, 434mL ethylene glycol and 0.46g tetrabutyl titanate join in reactor, esterification is carried out by the method for embodiment 1, after esterification terminates, Pressure Drop is to normal pressure, vacuumize after about 0.5h extracts excessive ethylene glycol out in 260 DEG C and stop vacuumizing, nitrogen is passed in system, drip containing the phosphorous ion monomer 2 of 89.2g with the speed of 2 ~ 3 drops/sec in reactor after getting back to normal pressure, the ethylene glycol solution of the luxuriant and rich with fragrance oxa-potassium hypophosphite of 8-(2-hydroxyl-oxethyl) carbonyl and 21.16g are scattered in the nano silicon in 150ml ethylene glycol, and to control in dropping process system temperature more than 220 DEG C, method again by embodiment 1 after adding carries out polycondensation.
Embodiment 13
First by 830g terephthalic acid, 434mL ethylene glycol and 10.47g nano titanium oxide join in reactor, esterification is carried out by the method for embodiment 1, after esterification terminates, Pressure Drop is to normal pressure, vacuumize after about 0.5h extracts excessive ethylene glycol out in 260 DEG C and stop vacuumizing, nitrogen is passed in system, drip containing the phosphorous ion monomer 2 of 89.2g with the speed of 2 ~ 3 drops/sec in reactor after getting back to normal pressure, the ethylene glycol solution of the luxuriant and rich with fragrance oxa-potassium hypophosphite of 8-(2-hydroxyl-oxethyl) carbonyl, and to control in dropping process system temperature more than 220 DEG C, after adding, polycondensation is carried out again by the method for embodiment 1.
Nano titanium oxide in this embodiment is not only as catalysts but also as nano particle additive.
Embodiment 14
First by 830g terephthalic acid, 434mL ethylene glycol, the ethylene glycol solution of 0.46g tetrabutyl titanate and 21.16g modified multiwalled carbon nanotube joins in reactor, esterification is carried out by the method for embodiment 1, after esterification terminates, Pressure Drop is to normal pressure, vacuumize after about 0.5h extracts excessive ethylene glycol out in 260 DEG C and stop vacuumizing, nitrogen is passed in system, drip containing the phosphorous ion monomer 2 of 89.2g with the speed of 2 ~ 3 drops/sec in reactor after getting back to normal pressure, the ethylene glycol solution of the luxuriant and rich with fragrance oxa-potassium hypophosphite of 8-(2-hydroxyl-oxethyl) carbonyl, and to control in dropping process system temperature more than 220 DEG C, method again by embodiment 1 after adding carries out polycondensation.
Embodiment 15
First by 830g terephthalic acid, 434mL ethylene glycol and 0.46g tetrabutyl titanate join in reactor, esterification is carried out by the method for embodiment 1, after esterification terminates, Pressure Drop is to normal pressure, vacuumize after about 0.5h extracts excessive ethylene glycol out in 260 DEG C and stop vacuumizing, nitrogen is passed in system, drip containing the phosphorous ion monomer 2 of 66.9g with the speed of 2 ~ 3 drops/sec in reactor after getting back to normal pressure, the ethylene glycol solution of the luxuriant and rich with fragrance oxa-potassium hypophosphite of 8-(2-hydroxyl-oxethyl) carbonyl and 113.07g are scattered in the nano zine oxide in ethylene glycol, and to control in dropping process system temperature more than 220 DEG C, method again by embodiment 1 after adding carries out polycondensation.
Embodiment 16
First by 830g terephthalic acid, 434mL ethylene glycol and 0.46g tetrabutyl titanate join in reactor, esterification is carried out by the method for embodiment 1, after esterification terminates, Pressure Drop is to normal pressure, vacuumize after about 0.5h extracts excessive ethylene glycol out in 260 DEG C and stop vacuumizing, nitrogen is passed in system, drip containing the phosphorous ion monomer 2 of 36.2g with the speed of 2 ~ 3 drops/sec in reactor after getting back to normal pressure, the ethylene glycol solution of the luxuriant and rich with fragrance oxa-potassium hypophosphite of 8-acetyl oxo and 20.47g are scattered in the polynite of the octadecyl trimethyl ammonium chloride modification in 150ml ethylene glycol in advance, and to control in dropping process system temperature more than 220 DEG C, method again by embodiment 1 after adding carries out polycondensation.
Embodiment 17
First by 970g dimethyl terephthalate (DMT), 434mL ethylene glycol and 0.24g zinc acetate join in reactor, esterification is carried out by the method for embodiment 6, after esterification terminates, vacuumize after about 0.5h extracts excessive ethylene glycol out in 260 DEG C and stop vacuumizing, nitrogen is passed in system, drip containing the phosphorous ion monomer 2 of 86.5g with the speed of 2 ~ 3 drops/sec in reactor after getting back to normal pressure, the ethylene glycol solution of the luxuriant and rich with fragrance oxa-sodium hypophosphite of 8-acetyl oxo and the 53.47g nano barium sulfate be scattered in ethylene glycol, and add 0.46g antimonous oxide, and to control in dropping process system temperature more than 220 DEG C, method again by embodiment 6 after adding carries out polycondensation can (difference be that rough vacuum polycondensation and high vacuum condensation temperature are 280 DEG C, the low high vacuum polycondensation time is 0.5h).
Embodiment 18
First by 830g terephthalic acid, 434mL ethylene glycol and 0.46g tetrabutyl titanate join in reactor, esterification is carried out by the method for embodiment 1, after esterification terminates, Pressure Drop is to normal pressure, vacuumize after about 0.5h extracts excessive ethylene glycol out in 260 DEG C and stop vacuumizing, nitrogen is passed in system, drip containing the phosphorous ion monomer 2 of 54.3g with the speed of 2 ~ 3 drops/sec in reactor after getting back to normal pressure, the ethylene glycol solution of the luxuriant and rich with fragrance oxa-potassium hypophosphite of 8-acetyl oxo and 20.33g are scattered in the layered dihydroxyl compound (LDH) in 240ml ethylene glycol in advance, and to control in dropping process system temperature more than 220 DEG C, method again by embodiment 1 after adding carries out polycondensation.
Embodiment 19
First by 830g terephthalic acid, 434mL ethylene glycol, 0.46g tetrabutyl titanate and the organically-modified zirconium phosphate of 20.33g be scattered in ethylene glycol join in reactor, esterification is carried out by the method for embodiment 1, after esterification terminates, Pressure Drop is to normal pressure, vacuumize after about 0.5h extracts excessive ethylene glycol out in 260 DEG C and stop vacuumizing, nitrogen is passed in system, drip containing the phosphorous ion monomer 2 of 54.3g with the speed of 2 ~ 3 drops/sec in reactor after getting back to normal pressure, the ethylene glycol solution of the luxuriant and rich with fragrance oxa-potassium hypophosphite of 8-acetyl oxo, and to control in dropping process system temperature more than 220 DEG C, method again by embodiment 1 after adding carries out polycondensation.
Embodiment 20
First by 830g terephthalic acid, 434mL ethylene glycol and 10.57g nano titanium oxide join in reactor, esterification is carried out by the method for embodiment 1, after esterification terminates, Pressure Drop is to normal pressure, vacuumize after about 0.5h extracts excessive ethylene glycol out in 260 DEG C and stop vacuumizing, nitrogen is passed in system, drip containing the phosphorous ion monomer 2 of 72.4g with the speed of 2 ~ 3 drops/sec in reactor after getting back to normal pressure, the ethylene glycol solution of the luxuriant and rich with fragrance oxa-potassium hypophosphite of 8-acetyl oxo, and to control in dropping process system temperature more than 220 DEG C, after adding, polycondensation is carried out again by the method for embodiment 1.
Nano titanium oxide in this embodiment is not only as catalysts but also as nano particle additive.
Embodiment 21
First by 830g terephthalic acid, 434mL ethylene glycol, the ethylene glycol solution of 0.46g tetrabutyl titanate and 20.33g modified multiwalled carbon nanotube joins in reactor, esterification is carried out by the method for embodiment 1, after esterification terminates, Pressure Drop is to normal pressure, vacuumize after about 0.5h extracts excessive ethylene glycol out in 260 DEG C and stop vacuumizing, nitrogen is passed in system, drip containing the phosphorous ion monomer 2 of 54.3g with the speed of 2 ~ 3 drops/sec in reactor after getting back to normal pressure, the ethylene glycol solution of the luxuriant and rich with fragrance oxa-potassium hypophosphite of 8-acetyl oxo, and to control in dropping process system temperature more than 220 DEG C, method again by embodiment 1 after adding carries out polycondensation.
Embodiment 22
First by 830g terephthalic acid, 434mL ethylene glycol and 0.46g tetrabutyl titanate join in reactor, esterification is carried out by the method for embodiment 1, after esterification terminates, Pressure Drop is to normal pressure, vacuumize after about 0.5h extracts excessive ethylene glycol out in 260 DEG C and stop vacuumizing, nitrogen is passed in system, drip containing the phosphorous ion monomer 2 of 66.9g with the speed of 2 ~ 3 drops/sec in reactor after getting back to normal pressure, the ethylene glycol solution of the luxuriant and rich with fragrance oxa-potassium hypophosphite of 8-(2-hydroxyl-oxethyl) carbonyl, be scattered in the 10.385g nano barium sulfate in ethylene glycol and the polynite being scattered in the 10.385g octadecyl trimethyl ammonium chloride modification in ethylene glycol, and to control in dropping process system temperature more than 220 DEG C, method again by embodiment 1 after adding carries out polycondensation.
Comparative example 1 (formula with reference to embodiment 7)
First 830g terephthalic acid, 434mL ethylene glycol and 0.46g tetrabutyl titanate are joined in reactor, esterification is carried out by the method for embodiment 1, after esterification terminates, Pressure Drop is to normal pressure, vacuumize after about 0.5h extracts excessive ethylene glycol out in 260 DEG C and stop vacuumizing, then carry out polycondensation by the method for embodiment 1 and can obtain pure polyester.
Comparative example 2 (formula with reference to embodiment 7)
First by 830g terephthalic acid, 434mL ethylene glycol and 0.46g tetrabutyl titanate join in reactor, esterification is carried out by the method for embodiment 1, after esterification terminates, Pressure Drop is to normal pressure, vacuumize after about 0.5h extracts excessive ethylene glycol out in 260 DEG C and stop vacuumizing, nitrogen is passed in system, drip containing the phosphorous ion monomer 2 of 111.5g with the speed of 2 ~ 3 drops/sec in reactor after getting back to normal pressure, the ethylene glycol solution of the luxuriant and rich with fragrance oxa-potassium hypophosphite of 8-(2-hydroxyl-oxethyl) carbonyl, and to control in dropping process system temperature more than 220 DEG C, method again by embodiment 1 after adding carries out polycondensation can obtain phosphoric flame-proof copolyester ionomer.
The polynite of the octadecyl trimethyl ammonium chloride modification that above embodiment adopts is a class of organic modified silicate, because other organic modified silicate is similar to the polynite effect here of octadecyl trimethyl ammonium chloride modification, therefore not exhaustive, but this is not construed as limiting the invention.Equally, organically-modified multi-walled carbon nano-tubes is a class of organically-modified carbon nanotube, because other organically-modified carbon nanotube (as organically-modified Single Walled Carbon Nanotube) is similar to the effect here of organically-modified multi-walled carbon nano-tubes, therefore not exhaustive here.
Except the catalyzer such as zinc acetate, antimonous oxide, tetrabutyl titanate that above embodiment provides, other catalyzer conventional in this area is as violent in acetic acid, Cobaltous diacetate, antimony glycol, other catalyzer such as titanate ester and organotin, its consumption also can be different according to used catalyzer, carry out accommodation.Because above-mentioned catalyst action is similar, the present invention is not exhaustive at this.
Whether be connected on the molecular chain main chain of terephthalic acid or dimethyl terephthalate (DMT) to investigate phosphorous ion monomer in phosphoric flame-proof copolyester ionomer/nano composite material, the phosphoric flame-proof copolyester ionomer/nano composite material prepared by embodiment 7 is used by the present invention after purifying
31p nuclear-magnetism carbon spectrum characterizes, and as shown in Figure 1, as can be seen from the figure, phosphorous ionic group is successfully incorporated in polyester molecule chain, can avoid commixed type fire retardant problem completely, the problem includes: materials compatibility problem; And inorganic nano-particle does not have much impact to ionomeric polymerization.
In order to investigate the anti-dropping performance of phosphoric flame-proof copolyester ionomer/nano composite material provided by the present invention, the present inventor gives pure polyester prepared by comparative example 1, containing conventional flame retardant 9, phosphoric flame-proof copolyester ionomer/nano composite material that the flame-proof copolyester that the assorted-10-phosphinylidyne of 10-dihydro-9-oxy mixes phenanthrene-succinic acid (DDP) is prepared with embodiment 4 become charcoal design sketch (as shown in Figures 2 to 4), the substrate polyester of three kinds of materials is all identical, as can be seen from the figure, containing conventional flame retardant 9, the mix flame-proof copolyester of phenanthrene-succinic acid (DDP) of the assorted-10-phosphinylidyne of 10-dihydro-9-oxy further promotes molten drop phenomenon, even and if phosphoric flame-proof copolyester ionomer/nano composite material provided by the present invention is when phosphorus content is lower, still can have good anti-dropping effect.
In order to investigate the crystal property of phosphoric flame-proof copolyester ionomer/nano composite material provided by the present invention, the present inventor give comparative example 1 prepare pure polyester, comparative example 2 prepare phosphoric flame-proof copolyester ionomer and embodiment 7 prepare phosphoric flame-proof copolyester ionomer/nano composite material DSC scan temperature lowering curve, as shown in Figure 5.As can be seen from the figure the peak crystallization of pure polyester is less, and crystallinity is general, and phosphoric flame-proof copolyester ionomer does not observe obvious peak crystallization substantially, illustrates that crystal property is very poor; And phosphoric flame-proof copolyester ionomer/nano composite material provided by the invention can at a higher temperature just can crystallization, and peak crystallization is very strong, show that phosphoric flame-proof copolyester ionomer/nano composite material provided by the invention has excellent crystal property.
Following table gives the parameter such as flame retardant properties (oxygen index), anti-dropping performance, crystal property characterizing embodiment 1 to embodiment 22 and comparative example 1,2.
As can be seen from above-mentioned data, pure polyester prepared by comparative example 1, although Tc is higher, its oxygen index only has 22.0vol.%, the one-tenth charcoal design sketch of the polyester provided in composition graphs 2 again, can find out the anti-dropping performance of pure polyester and flame retardant properties bad.Although the oxygen index of the phosphoric flame-proof copolyester ionomer prepared by comparative example 2 obtains large increase (oxygen index is 29.0vol.%), its Tc does not measure under identical condition, illustrates that its crystal property is very poor.Phosphoric flame-proof copolyester ionomer/nano composite material provided by the invention oxygen index when phosphonium flame retardant addition is lower just can reach more than 27.0vol.%; Tc is generally higher, and this point can be confirmed from Fig. 5.
In summary it can be seen, phosphoric flame-proof copolyester ionomer/nano composite material provided by the invention has excellent flame retardant properties, anti-dropping performance and crystal property simultaneously, crystal property is particularly remarkable, its intrinsic viscosity also can reach 0.6-1.0dL/g simultaneously, be a kind of matrix material with development prospect, the fields such as fiber, engineering plastics and film can be widely used in.
Claims (10)
1. phosphoric flame-proof copolyester ionomer/nano composite material, it is characterized in that this matrix material is by terephthalic acid or dimethyl terephthalate (DMT), ethylene glycol, phosphorous ion monomer [i] or phosphorous ion monomer [ii], inorganic nano-particle is or/and organically-modified inorganic nano-particle forms through in-situ polymerization, in this matrix material, phosphorous ionic group structural unit number is the 2-5% of the structural unit number of terephthalic acid or dimethyl terephthalate (DMT), inorganic nano-particle and/or organically-modified inorganic nano-particle account for the 0.5-10% of this matrix material total mass,
The general structure of above-mentioned phosphorous ion monomer [i] is as follows:
In formula, R
1, R
2, R
3, R
4for carboxyl or ester group, can be identical or not identical; X, Y are O or S atom, can be identical or not identical; M
1for any one in alkali metal atom;
The general structure of above-mentioned phosphorous ion monomer [ii] is as follows:
In formula, R
5, R
6, R
7, R
8for hydroxyl, ester group or 2-hydroxy ethoxy, can be identical or not identical; W, Z are O or S atom, can be identical or not identical; M
2for any one in alkali metal atom; Phosphorous ionic group structural unit from any one in general structure A, B, C, D, E, F,
Wherein said inorganic nano-particle is at least one in nano barium sulfate, nano silicon, nano titanium oxide and nano zine oxide; Described organically-modified inorganic nano-particle is at least one in organic modified sheet silicate, organically-modified layered double-hydroxide, organically-modified bedded zirconium phosphate and organically-modified carbon nanotube.
2. phosphoric flame-proof copolyester ionomer/nano composite material according to claim 1, is characterized in that the M in phosphorous ion monomer described in this matrix material [i] and [ii]
1and M
2for Na or K atom.
3. phosphoric flame-proof copolyester ionomer/nano composite material according to claim 1 and 2, is characterized in that phosphorous ionic group structural unit number described in this matrix material is the 3-4% of the structural unit number of terephthalic acid or dimethyl terephthalate (DMT) representative.
4. phosphoric flame-proof copolyester ionomer/nano composite material according to claim 1 and 2, is characterized in that inorganic nano-particle described in this matrix material or/and organically-modified inorganic nano-particle is the 0.5-5% of phosphoric flame-proof copolyester ionomer/nano composite material total mass.
5. phosphoric flame-proof copolyester ionomer/nano composite material according to claim 3, is characterized in that inorganic nano-particle described in this matrix material or/and organically-modified inorganic nano-particle is the 0.5-5% of phosphoric flame-proof copolyester ionomer/nano composite material total mass.
6. the preparation method of phosphoric flame-proof copolyester ionomer/nano composite material according to claim 1, the method is by terephthalic acid or dimethyl terephthalate (DMT), ethylene glycol and catalyzer proportioning routinely, after adopting direct esterification or ester-interchange method to carry out esterification, be prepared from through polycondensation, it is characterized in that before esterification or before esterification aftercondensated, add in reaction system and count phosphorous ion monomer [i] or the phosphorous ion monomer [ii] of 2-5% by the molecular fraction of terephthalic acid or dimethyl terephthalate (DMT) and account for the inorganic nano-particle of matrix material total mass 0.5-10% or/and organically-modified inorganic nano-particle carries out in-situ polymerization,
The general structure of phosphorous ion monomer [i] wherein used is as follows:
In formula, R
1, R
2, R
3, R
4for carboxyl or ester group, can be identical or not identical; X, Y are O or S atom, can be identical or not identical; M
1for any one in alkali metal atom;
The general structure of phosphorous ion monomer [ii] used is as follows:
In formula, R
5, R
6, R
7, R
8,for hydroxyl, ester group or 2-hydroxy ethoxy, can be identical or not identical; W, Z are O or S atom, can be identical or not identical; M
2for any one in alkali metal atom,
Inorganic nano-particle wherein used is at least one in nano barium sulfate, nano silicon, nano titanium oxide and nano zine oxide; Organically-modified inorganic nano-particle used is at least one in organic modified sheet silicate, organically-modified layered double-hydroxide, organically-modified bedded zirconium phosphate and organically-modified carbon nanotube.
7. the preparation method of phosphoric flame-proof copolyester ionomer/nano composite material according to claim 6, is characterized in that the M in phosphorous ion monomer [i] used in the method and [ii]
1and M
2for Na or K atom.
8. the preparation method of the phosphoric flame-proof copolyester ionomer/nano composite material according to claim 6 or 7, the amount of phosphorous ion monomer [i] used in the method and phosphorous ion monomer [ii] that it is characterized in that is the 3-4% by terephthalic acid or dimethyl terephthalate (DMT) mole percent.
9. the preparation method of the phosphoric flame-proof copolyester ionomer/nano composite material according to claim 6 or 7, is characterized in that inorganic nano-particle used in the method is the 0.5-5% of phosphoric flame-proof copolyester ionomer/nano composite material total mass.
10. the preparation method of phosphoric flame-proof copolyester ionomer/nano composite material according to claim 8, is characterized in that inorganic nano-particle used in the method is the 0.5-5% of phosphoric flame-proof copolyester ionomer/nano composite material total mass.
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| CN105866168B (en) * | 2016-03-25 | 2018-06-29 | 北京环境特性研究所 | A kind of discrimination method and device of coating lower substrate material |
| CN110511368B (en) * | 2019-08-09 | 2021-07-27 | 浙江恒澜科技有限公司 | Vinyl nano-silicon sphere compounded high-temperature self-crosslinking flame-retardant anti-dripping copolyester and preparation method thereof |
| WO2021254391A1 (en) * | 2020-06-19 | 2021-12-23 | 四川大学 | High-temperature self-crosslinking-based flame-retardant droplet-resistant copolyester, and preparation method therefor and application thereof |
| CN113584718A (en) * | 2021-06-15 | 2021-11-02 | 苏州市雪漾纺织品有限公司 | Preparation method of environment-friendly non-woven fabric with flame retardant function |
| CN115772303B (en) * | 2021-09-08 | 2024-04-09 | 中国石油化工股份有限公司 | High-fluidity flame-retardant polyvinyl chloride injection molding composition and preparation method thereof |
| CN114634688B (en) * | 2022-04-26 | 2023-09-01 | 华润化学材料科技股份有限公司 | Flame-retardant polyester with good toughness and preparation method thereof |
| CN116120371B (en) * | 2023-02-13 | 2023-12-08 | 杭州师范大学 | Ionic polymer monomer with nitrogen-phosphorus-silicon ternary composite functional group and application thereof in flame retardance of polyester |
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| CN1176995C (en) * | 2002-08-12 | 2004-11-24 | 四川大学 | Phosphorus-contained flame-retarding nano-class ethanediol polyterephthalate/laminated silicate composition and its preparing process and application |
| CN100355831C (en) * | 2005-10-28 | 2007-12-19 | 四川大学 | Phosphorus containing fire retardant copolyester/barium sulphate nano-composite material and its preparation method |
| CN101020744B (en) * | 2007-03-19 | 2010-04-14 | 四川大学 | Nanometer composite polyester material and its double in-situ preparation process |
| CN102924702B (en) * | 2012-11-06 | 2014-04-16 | 四川大学 | Phosphorus heterocycle inflaming retarding copolyester ionomer and preparation method thereof |
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