CN101805444A - Droplet-resistant flame-retardant polyester, nanometer compound material thereof and method for preparing same - Google Patents
Droplet-resistant flame-retardant polyester, nanometer compound material thereof and method for preparing same Download PDFInfo
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- CN101805444A CN101805444A CN 201010124613 CN201010124613A CN101805444A CN 101805444 A CN101805444 A CN 101805444A CN 201010124613 CN201010124613 CN 201010124613 CN 201010124613 A CN201010124613 A CN 201010124613A CN 101805444 A CN101805444 A CN 101805444A
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Abstract
The invention discloses droplet-resistant flame-retardant polyester. The flame-retardant polyester is prepared by random copolymerization of a branched monomer, terephthalic acid or dimethyl terephthalate, ethylene glycol and flame-retardant monomer, wherein the branched monomer is an aliphatic compound or aromatic compound having three or more functional groups; and the flame-retardant monomers adopts any of the following structures. The invention also discloses a method for preparing the droplet-resistant flame-retardant polyester, a nanometer compound material containing the droplet-resistant flame-retardant polyester and a method for preparing the nanometer compound material. Because the droplet-resistant flame-retardant polyester provided by the invention simultaneously contains the branched monomer and the fire retardant having the droplet-resistant effect, the melt viscosity of the droplet-resistant flame-retardant polyester at the high temperature is greatly improved, the sensitivity of the droplet-resistant flame-retardant polyester to temperature is lowered, and the droplet-resistant effect is good; because of the nanometer effect and the blocking effect, the nanometer compound material shows better droplet-resistant effect; and the polyester and the nanometer compound material can be directly used as raw materials for preparing fibers, engineering plastics, films and the like.
Description
Technical field
The invention belongs to flame retardant polyester and nanometer composite polyester material and preparing technical field thereof.Be specifically related to a kind of copolyesters and nano composite material and their preparation method that flame retardant properties and refractory drip performance that have simultaneously.
Background technology
Polyester (specially refers to polyethylene terephthalate here, PET) in the synthon of one of three big synthesized polymer materials, because have advantages such as high-modulus, high strength, snappiness, conformality and thermotolerance, make it just become output maximum in the synthon, the fiber species that purposes is the widest in 1972.But the oxygen index of polyester has only 21.0, belongs to flammable fiber, makes it to be very restricted when occasion that fire prevention is had certain requirements is used.Particularly public place fire-retardant product and assembly combustionproperty require and sign national standard (GB20286-2006) promulgation after, as in aviation, railway, the fire-retardant extensive concern that caused more of the trevira that public places such as hotel have a wide range of applications.
Phosphonium flame retardant is considered to a class to the most effective additive flame retardant of polyester, and general addition just can reach fire-retardant requirement (Wang Yuzhong work, the design of fire-retardantization of trevira, Sichuan science and technology press, 1994) at 3-6% (massfraction).But existing polyester comprises flame retardant polyester and also can produce fusion drippage (abbreviation molten drop) that when burning molten drop not only can make the people scald also can cause secondary combustion, causes the heavy losses of people's life and property.Make the research that fire-retardant refractory drips polyester become an international research topic, now existing a considerable amount of bibliographical informations its achievement in research.But these achievements in research often need to add therein anti-molten drop agent (tetrafluoroethylene and derivative thereof etc.) or add inorganics filled thing (glass fibre, silicon-dioxide etc.).Though the adding of these materials can reach certain refractory and drip effect, also limited the range of application of polyester greatly and particularly can not use as fibrous material.
In addition, be subjected to the transfer of developed country's industrialization, factor affecting such as China's human cost is low, the market requirement is huge, China has become first big country of production of polyester.Two of polyester big main raw material terephthalic acids (TPA) and ethylene glycol (EG) are appreciated by crude oil in recent years influences, price rises steadily, increased the production cost of enterprise, domestic many production of polyester scopes of the enterprise are less relatively simultaneously, production technology is comparatively backward, outlet is obstructed in addition, thereby causes domestic polyester supply to increase suddenly, the market competition aggravation.Particularly the polyester overwhelming majority of China is as fiber usefulness, and mainly is as the normal polyester fiber, and this kind polyester significantly glides enterprise profit because of being in the situation that supply exceed demand, in addition cause many in, the production line stopping production of small-scale enterprise.Thereby research and development functional poly ester fiber product innovation is one of approach that changes this predicament.
Summary of the invention
The objective of the invention is at first provides a kind of droplet-resistant flame-retardant polyester at the present problem that exists of flame retardant polyester, and this polyester not only can directly use as fibrous material, also can be directly as engineering plastics, film materials.
Second purpose of the present invention provides a kind of method for preparing above-mentioned droplet-resistant flame-retardant polyester.
The 3rd purpose of the present invention provides a kind of nano composite material that contains above-mentioned droplet-resistant flame-retardant polyester.This matrix material drips effect owing to nano effect can make polyester obtain better refractory, or makes polyester at the content that obtains to reduce when equal refractory drips effect flame-retardant additive.
Last purpose of the present invention provides the method that a kind of preparation contains the nano composite material of above-mentioned droplet-resistant flame-retardant polyester.
Droplet-resistant flame-retardant polyester provided by the invention is to be made by branched monomer, terephthalic acid or dimethyl terephthalate (DMT), ethylene glycol and fire-retardant monomer random copolymerization, branched monomer is to contain trifunctional and above aliphatics or aromatics thereof, functional group is any in carboxylic acid, acid anhydrides or the hydroxyl, wherein fatty compounds contains 3-8 carbon atom, and fire-retardant monomer is any in the following structure:
Or
R in the formula
1, R
2Be alkyl or phenyl or benzyl, can be identical or inequality; X is H or alkali metal or alkali earth metal; N1 is 1 or 2; Y is hydroxyl or carboxyl; Z is S or O element; R
3Aliphatic group or phenyl or benzyl for C3-C15; N is H or carboxyl or hydroxyl; M is hydroxyl or carboxyl, the mol ratio of terephthalic acid or dimethyl terephthalate (DMT) and ethylene glycol is 1: 1.5, the content of branched monomer is the 0.05-5% of droplet-resistant flame-retardant polyester total mass, fire-retardant monomeric content is the 1-25% of droplet-resistant flame-retardant polyester total mass, and the intrinsic viscosity of this flame retardant polyester is 0.50-1.20dL/g.
The method of the droplet-resistant flame-retardant polyester that preparation provided by the invention is above-mentioned, this method is with terephthalic acid or dimethyl terephthalate (DMT), ethylene glycol and catalyzer proportioning routinely, after adopting direct esterification method or ester-interchange method to carry out esterification, be prepared from through polycondensation, it is characterized in that before esterification or the esterification aftercondensated before, in reaction system, add the branched monomer that accounts for droplet-resistant flame-retardant polyester total mass 0.05-5%, preferred 0.5-4%, with the fire-retardant monomer of 1-25%, preferred 3-15%.
The direct esterification method that aforesaid method adopted or the common process step and the condition of ester-interchange method are as follows:
The direct esterification method: add polyester monocase, catalyzer by proportioning in reactor, pressurization is warmed up to 220～260 ℃ and carried out esterification 2～6 hours; After esterification finishes, under the rough vacuum in 260～280 ℃ of polycondensations 0.5～1.5 hour, then under high vacuum in 275～285 ℃ of polycondensations 1～3 hour, extrude the copolyesters melt with nitrogen, water-cooled, promptly.
Ester-interchange method: add polyester monocase, catalyzer by proportioning in reactor, normal pressure carried out transesterification reaction 3～5 hours in 185～275 ℃; After transesterify finishes, under the rough vacuum in 260～280 ℃ of polycondensations 0.5～1.5 hour, then under high vacuum in 275～285 ℃ of polycondensations 1～3 hour, extrude the copolyesters melt with nitrogen, water-cooled, promptly.
Used branched monomer is to contain trifunctional and above aliphatics or aromatics thereof in the aforesaid method, functional group is any in carboxylic acid, acid anhydrides or the hydroxyl, wherein fatty compounds contains 3-8 carbon atom, and the fire retardant monomer is any in the following structure:
Or
R in the formula
1, R
2Be alkyl or phenyl or benzyl, can be identical or inequality; X is H or alkali metal or alkali earth metal; N1 is 1 or 2; Y is hydroxyl or carboxyl; Z is S or O element; R
3Aliphatic group or phenyl or benzyl for C3-C15; N is H or carboxyl or hydroxyl; M is hydroxyl or carboxyl.
Used catalyzer is an antimony glycol in the aforesaid method, antimonous oxide, earth silicon/titanic oxide mixture, any in titanic acid ester or the titanium ethylene glycolate.
The nano composite material that contains above-mentioned droplet-resistant flame-retardant polyester provided by the invention, this material is made up of above-mentioned flame retardant polyester and inorganic nano-particle or lamellar compound, wherein the quality percentage composition of flame retardant polyester is 80-99.5%, the quality percentage composition of inorganic nano-particle or lamellar compound is 0.5-20%, inorganic nano-particle is any in nano silicon, nano titanium oxide or the nano zine oxide, and lamellar compound is any in layered silicate, layered double-hydroxide or the bedded zirconium phosphate.
The method of the above-mentioned droplet-resistant flame-retardant polyester nano composite material of preparation provided by the invention, this method is with terephthalic acid or dimethyl terephthalate (DMT), ethylene glycol and catalyzer be proportioning routinely, after adopting direct esterification method or ester-interchange method to carry out esterification, be prepared from through polycondensation, it is characterized in that before esterification or the esterification aftercondensated before, in reaction system, add the branched monomer that accounts for droplet-resistant flame-retardant polyester total mass 0.05-5%, preferred 0.5-4%, the fire-retardant monomer of 1-25%, preferred 3-15%, with the glycol suspension solution that accounts for nano composite material total mass 0.5-20% nanoparticle or lamellar compound, to prepare this nano composite material by in-situ polymerization.
The direct esterification method that aforesaid method adopted or the common process step of ester-interchange method and condition and noted earlier basic identical.
Used branched monomer is to contain trifunctional and above aliphatics or aromatics thereof in the aforesaid method, functional group is any in carboxylic acid, acid anhydrides or the hydroxyl, wherein fatty compounds contains 3-8 carbon atom, and used fire retardant monomer is any in the following structure:
R in the formula
1, R
2Be alkyl or phenyl or benzyl, can be identical or inequality; X is H or alkali metal or alkali earth metal; N1 is 1 or 2; Y is hydroxyl or carboxyl; Z is S or O element; R
3Aliphatic group or phenyl or benzyl for C3-C15; N is H or carboxyl or hydroxyl; M is hydroxyl or carboxyl.
Used inorganic nano-particle is any in nano silicon, nano titanium oxide or the nano zine oxide in the aforesaid method, and lamellar compound is any in layered silicate, layered double-hydroxide, the bedded zirconium phosphate.
Used catalyzer is an antimony glycol in the aforesaid method, antimonous oxide, earth silicon/titanic oxide mixture, titanic acid ester, any in the titanium ethylene glycolate.
The present invention has following positively effect:
1, owing to contain branched structure in the structural unit of droplet-resistant flame-retardant polyester provided by the invention, thereby can improve polyester melt viscosity at high temperature, reduce the susceptibility of polyester fondant, drip effect thereby the molten drop that slows down polyester plays certain refractory to temperature.
2, because the fire retardant that droplet-resistant flame-retardant polyester provided by the invention added is to have certain refractory to drip the fire retardant of effect, the fire retardant that particularly has metallic element has the catalysis carbon-forming effect, thereby not only can obtain flame retardant effect preferably, and can delay to obtain on the basis of molten drop better refractory at branched structure and drip effect.
3, because droplet-resistant flame-retardant polyester nano composite material provided by the invention, also utilize the nano effect of nanoparticle and the blocking effect and the nano effect of laminated inorganic matter, thereby can play better droplet-resistant flame-retardant effect possessing on the basis of flame retardant polyester that better refractory drips effect.
4, droplet-resistant flame-retardant polyester provided by the present invention and nano composite material thereof not only can be directly in order to the preparation fibers, and the raw material that also can be used as engineering plastics, film etc. uses.
5, preparation method's maturation provided by the invention does not change the preparation technology of traditional preparation process polyester or flame-proof copolyester substantially, and is simple and convenient, is easy to control and suitability for industrialized production.
Description of drawings
Fig. 1 is the phosphorus nuclear-magnetism figure of droplet-resistant flame-retardant polyester.
Fig. 2 is the contrast photo after the droplet-resistant flame-retardant polyester for preparing respectively of pure polyester and embodiment 9, embodiment 17 and the test of nano composite material oxygen index thereof.
Embodiment
Provide embodiment below so that the invention will be further described.Be necessary to be pointed out that at this 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 protection domain of the present invention.
In addition, intrinsic viscosity [η] that what deserves to be explained is following examples products therefrom all be with phenol/sym.-tetrachloroethane (1: 1, v: be solvent v), be mixed with the solution that concentration is 0.5g/dL, record at 25 ℃ with dark type viscometer; Limiting oxygen index(LOI) all is to be made into 120 * 6.5 * 3.2mm
3The standard oxygen exponential spline, on the HC-2C oxygen index instrument according to ASTM D2863-97 standard test; Vertical combustion then is to be made into 125 * 12.7 * 3.2mm
3The standard batten, adopt CZF-2 type vertical combustion instrument according to the UL-94 standard test.
Embodiment 1
With 835g terephthalic acid, 425ml ethylene glycol, 0.5g branched monomer trimesic acid triglycol ester, the fire-retardant monomer DPA (9 of 30g, 10-dihydro-oxa--10 phosphinylidyne phenanthrene-propionic acid of mixing) and the 0.301g antimonous oxide join in the reactor, elder generation's inflated with nitrogen is got rid of air in the still, be pressurized to 0.1Mpa then, and in 2h, be warming up to 240 ℃, continue to boost to 0.3～0.4MPa, esterification 2h; Keep behind the temperature, pressure 1.5h temperature being risen to 260 ℃ gradually, and keep water speed, after about 0.5h pressure is reduced to normal pressure, esterification finishes.Thereafter at 260～270 ℃ of following rough vacuum polycondensation 0.5h, be warming up to subsequently 275～285 ℃ in high vacuum (water-cooled gets final product for the polycondensation after 2 hours down of pressure＜60Pa), discharging.
The intrinsic viscosity of this flame retardant polyester [η] is 0.70dL/g, and oxygen index is 27.5%, vertical combustion grade V-0.
Embodiment 2
With 769g terephthalic acid, 415ml ethylene glycol, 30g branched monomer trimesic acid triglycol ester, the fire-retardant monomer DPA (9 of 60g, 10-dihydro-oxa--10 phosphinylidyne phenanthrene-propionic acid of mixing) and the 0.348g antimony glycol join in the reactor, after step, the condition that provides by embodiment 1 carried out esterification and polycondensation, discharging, water-cooled gets final product.
The intrinsic viscosity of this flame retardant polyester [η] is 0.86dL/g, and oxygen index is 35.4%, vertical combustion grade V-0.
Embodiment 3
With 589g terephthalic acid, 410ml ethylene glycol, 50g branched monomer trimesic acid triglycol ester, the fire-retardant monomer DPP (9 of 150g, 10-dihydro-oxa--10 phosphinylidyne phenanthrene-Succinic Acid of mixing) and the 0.348g antimony glycol join in the reactor, after step, the condition that provides by embodiment 1 carried out esterification and polycondensation, discharging, water-cooled gets final product.
The intrinsic viscosity of this flame retardant polyester [η] is 1.02dL/g, and oxygen index is 36%, vertical combustion grade V-0.
Embodiment 4
With 810g terephthalic acid, 410ml ethylene glycol, 50g branched monomer pyromellitic anhydride, the fire-retardant monomer DPP (9 of 10g, 10-dihydro-oxa--10 phosphinylidyne phenanthrene-Succinic Acid of mixing) and the 0.348g antimony glycol join in the reactor, after step, the condition that provides by embodiment 1 carried out esterification and polycondensation, discharging, water-cooled gets final product.
The intrinsic viscosity of this flame retardant polyester [η] is 1.20dL/g, and oxygen index is 27.0%, vertical combustion grade V-0.
Embodiment 5
With 469g terephthalic acid, 410ml ethylene glycol, 50g branched monomer trimellitic acid 1,2-anhydride, the fire-retardant monomer DPP (9 of 250g, 10-dihydro-oxa--10 phosphinylidyne phenanthrene-Succinic Acid of mixing) and the 0.348g antimony glycol join in the reactor, after step, the condition that provides by embodiment 1 carried out esterification and polycondensation, discharging, water-cooled gets final product.
The intrinsic viscosity of this flame retardant polyester [η] is 0.98dL/g, and oxygen index is 36.0%, vertical combustion grade V-0.
Embodiment 6
534g terephthalic acid, 410ml ethylene glycol, 20g branched monomer glycerol, the fire-retardant monomer HMPPA-Zn of 200g (hydroxymethyl phenyl phospho acid zinc) and 0.348g antimony glycol are joined in the reactor, after step, the condition that provides by embodiment 1 carried out esterification and polycondensation, discharging, water-cooled gets final product.
The intrinsic viscosity of this flame retardant polyester [η] is 0.94dL/g, and oxygen index is 35.5%, vertical combustion grade V-0.
Embodiment 7
782g terephthalic acid, 425ml ethylene glycol, 30g branched monomer trimesic acid triglycol ester and 0.301g antimonous oxide are joined in the reactor, and step and the condition that provides by embodiment 1 carried out esterification earlier.Esterification finishes the back and slowly feed nitrogen in reactor, to contain the fire-retardant monomer 3-of 50g (2-hydroxyl-oxethyl)-3-oxopropyl (phenyl) sodium hypophosphite ethylene glycol solution simultaneously joins in the reactor, after step that provides by embodiment 1 and condition are carried out polycondensation again, discharging, water-cooled gets final product.
The intrinsic viscosity of this flame retardant polyester [η] is 0.68dL/g, and oxygen index is 27.5%, vertical combustion grade V-0.
Embodiment 8
694g terephthalic acid, 425ml ethylene glycol, 30g branched monomer trimesic acid triglycol ester and 0.301g antimonous oxide are joined in the reactor, carry out esterification by step and condition that embodiment 1 provides.Esterification finishes the back and slowly feed nitrogen in reactor, and will contain the fire-retardant monomer 2-of 100g carboxyethyl methylphosphinate phospho acid sodium ethylene glycol solution simultaneously and join in the reactor, after step that provides by embodiment 1 and condition are carried out polycondensation again, discharging, water-cooled gets final product.
The intrinsic viscosity of this flame retardant polyester [η] is 0.52dL/g, and oxygen index is 28.56%, vertical combustion grade V-0.
Embodiment 9
782g terephthalic acid, 425ml ethylene glycol, 30g branched monomer trimesic acid triglycol ester and 0.348g antimony glycol are joined in the reactor, carry out esterification by step and condition that embodiment 1 provides.Esterification finishes the back and slowly feed nitrogen in reactor, to contain the fire-retardant monomer 3-of 50g (2-hydroxyl-oxethyl)-3-oxopropyl (phenyl) magnesium hypophosphite ethylene glycol solution simultaneously joins in the reactor, after step that provides by embodiment 1 and condition are carried out polycondensation again, discharging, water-cooled gets final product.
The intrinsic viscosity of this flame retardant polyester [η] is 0.50dL/g, and oxygen index is 29.0%, vertical combustion grade V-0.
824g terephthalic acid, 425ml ethylene glycol, 10g branched monomer TriMethylolPropane(TMP) and 0.301g antimonous oxide are joined in the reactor, carry out esterification by step and condition that embodiment 1 provides.Esterification finishes the back and slowly feed nitrogen in reactor, to contain the fire-retardant monomer 3-of 30g (2-hydroxyl-oxethyl)-3-oxopropyl (phenyl) sodium hypophosphite ethylene glycol solution simultaneously joins in the reactor, after step that provides by embodiment 1 and condition are carried out polycondensation again, discharging, water-cooled gets final product.
The intrinsic viscosity of this flame retardant polyester [η] is 0.65dL/g, and oxygen index is 27.5%, vertical combustion grade V-0.
Embodiment 11
702g terephthalic acid, 425ml ethylene glycol, the equal tetramethylolmethane of 5g branched monomer and 0.348g antimony glycol are joined in the reactor, carry out esterification by step and condition that embodiment 1 provides.Esterification finishes the back and slowly feed nitrogen in reactor, to contain the fire-retardant monomer 3-of 130g (2-hydroxyl-oxethyl)-3-oxopropyl (phenyl) sodium hypophosphite ethylene glycol solution simultaneously joins in the reactor, after step that provides by embodiment 1 and condition are carried out polycondensation again, discharging, water-cooled gets final product.
The intrinsic viscosity of this flame retardant polyester [η] is 0.79dL/g, and oxygen index is 28.7%, vertical combustion grade V-0.Implement
Example 12
With 795g terephthalic acid, 410ml ethylene glycol, 29.7g branched monomer trimesic acid triglycol ester, the fire-retardant monomer DPA (9 of 59.4g, 10-dihydro-oxa--10 phosphinylidyne phenanthrene-propionic acid of mixing) and the 0.348g antimony glycol join in the reactor, carry out esterification by step and condition that embodiment 1 provides.Esterification finishes the back and slowly feed nitrogen in reactor, and adds and contain the nano silicon glycol suspension solution of 5g through supersound process 30min, after step that provides by embodiment 1 and condition are carried out polycondensation again, and discharging, water-cooled gets final product.
The intrinsic viscosity of this flame retardant polyester nano composite material [η] is 0.72dL/g, and oxygen index is 36.8%, vertical combustion grade V-0.
Embodiment 13
795g terephthalic acid, 410ml ethylene glycol, 29.7g branched monomer trimesic acid triglycol ester, the fire-retardant monomer HMPPA of 59.4g (hydroxymethyl phenyl phospho acid) and 0.348g antimony glycol are joined in the reactor, carry out esterification by step and condition that embodiment 1 provides.Esterification finishes the back and slowly feed nitrogen in reactor, and adds and contain the nano silicon glycol suspension solution of 10g through supersound process 30min, after step that provides by embodiment 1 and condition are carried out polycondensation again, and discharging, water-cooled gets final product.
The intrinsic viscosity of this flame retardant polyester nano composite material [η] is 0.72dL/g, and oxygen index is 36.8%, vertical combustion grade V-0.
Embodiment 14
650g terephthalic acid, 394ml ethylene glycol, 19g branched monomer pyromellitic anhydride, the fire-retardant monomer CEMP of 114g (2-hydroxyethyl methyl phospho acid) and 0.348g antimony glycol are joined in the reactor, carry out esterification by step and condition that embodiment 1 provides.Esterification finishes the back and slowly feed nitrogen in reactor, and adds and contain the nano silicon glycol suspension solution of 50g through supersound process 30min, after step that provides by embodiment 1 and condition are carried out polycondensation again, and discharging, water-cooled gets final product.
The intrinsic viscosity of this flame retardant polyester nano composite material [η] is 0.72dL/g, and oxygen index is 34.2%, vertical combustion grade V-0.
Embodiment 15
604g terephthalic acid, 352ml ethylene glycol, 34g branched monomer trimellitic anhydride, the fire-retardant monomer CEPP of 76.5g (3-(2-hydroxyl-oxethyl)-3-oxopropyl (phenyl) Hypophosporous Acid, 50) and 0.348g antimony glycol are joined in the reactor, carry out esterification by step and condition that embodiment 1 provides.Esterification finishes the back and slowly feed nitrogen in reactor, and adds and contain the nano titanium oxide glycol suspension solution of 150g through supersound process 30min, after step that provides by embodiment 1 and condition are carried out polycondensation again, and discharging, water-cooled gets final product.
The intrinsic viscosity of this flame retardant polyester nano composite material [η] is 0.70dL/g, and oxygen index is 35.5%, vertical combustion grade V-0.
Embodiment 16
With 680g terephthalic acid, 365ml ethylene glycol, 26.4g TriMethylolPropane(TMP), the fire-retardant monomer DPA (9 of 44g, 10-dihydro-oxa--10 phosphinylidyne phenanthrene-propionic acid of mixing) and the 0.348g antimony glycol join in the reactor, carry out esterification by step and condition that embodiment 1 provides.Esterification finishes the back and slowly feed nitrogen in reactor, and adds and contain the nano zine oxide glycol suspension solution of 120g through supersound process 30min, after step that provides by embodiment 1 and condition are carried out polycondensation again, and discharging, water-cooled gets final product.
The intrinsic viscosity of this flame retardant polyester nano composite material [η] is 0.69dL/g, and oxygen index is 32.0%, vertical combustion grade V-0.
Embodiment 17
With 714g terephthalic acid, 373ml ethylene glycol, 27g branched monomer trimesic acid triglycol ester, fire-retardant monomer 36g DPA (9,10-dihydro-oxa--10 phosphinylidyne phenanthrene-propionic acid of mixing) and the 0.348g antimony glycol join in the reactor, carry out esterification by step and condition that embodiment 1 provides.Esterification finishes the back and slowly feed nitrogen in reactor, and adds and contain the magnalium type layered double-hydroxide glycol suspension solution of 100g through supersound process 30min, after step that provides by embodiment 1 and condition are carried out polycondensation again, and discharging, water-cooled gets final product.
The intrinsic viscosity of this flame retardant polyester nano composite material [η] is 0.53dL/g, and oxygen index is 31.5%, vertical combustion grade V-0.
Embodiment 18
With 808g terephthalic acid, 412ml ethylene glycol, the equal tetramethylolmethane of 6.8g branched monomer, contain 30g and join in the reactor through bedded zirconium phosphate glycol suspension solution and the 0.348g antimony glycol of supersound process 30min, carry out esterification by step and condition that embodiment 1 provides.Esterification finishes the back and slowly feed nitrogen in reactor, simultaneously the fire-retardant monomer 3-of 48.5g (2-hydroxyl-oxethyl)-3-oxopropyl (phenyl) sodium hypophosphite ethylene glycol solution is joined in the reactor, after step that provides by embodiment 1 and condition are carried out polycondensation again, discharging, water-cooled gets final product.
The intrinsic viscosity of this flame retardant polyester nano composite material [η] is 0.67dL/g, and oxygen index is 28.8%, vertical combustion grade V-0.
Embodiment 19
With 767g terephthalic acid, 391ml ethylene glycol, the equal tetramethylolmethane of 6.44g branched monomer, contain 80g and join in the reactor through polynite glycol suspension solution and the 0.348g antimony glycol of supersound process 30min, carry out esterification by step and condition that embodiment 1 provides.Esterification finishes the back and slowly feed nitrogen in reactor, simultaneously the fire-retardant monomer 3-of 46g (2-hydroxyl-oxethyl)-3-oxopropyl (phenyl) sodium hypophosphite ethylene glycol solution is joined in the reactor, after step that provides by embodiment 1 and condition are carried out polycondensation again, discharging, water-cooled gets final product.
The intrinsic viscosity of this flame retardant polyester nano composite material [η] is 0.71dL/g, and oxygen index is 28.6%, vertical combustion grade V-0.
With 667g terephthalic acid, 332ml ethylene glycol, the equal tetramethylolmethane of 5.6g branched monomer, contain 200g and join in the reactor through polynite glycol suspension solution and the 0.348g antimony glycol of supersound process 30min, carry out esterification by step and condition that embodiment 1 provides.Esterification finishes the back and slowly feed nitrogen in reactor, simultaneously the fire-retardant monomer 3-of 40g (2-hydroxyl-oxethyl)-3-oxopropyl (phenyl) sodium hypophosphite ethylene glycol solution is joined in the reactor, after step that provides by embodiment 1 and condition are carried out polycondensation again, discharging, water-cooled gets final product.
The intrinsic viscosity of this flame retardant polyester nano composite material [η] is 0.58dL/g, and oxygen index is 28.5%, vertical combustion grade V-0.
Embodiment 21
With 536g terephthalic acid, 373ml ethylene glycol, 45.5g branched monomer trimesic acid triglycol ester, the fire-retardant monomer DPP (9 of 136.5g, 10-dihydro-oxa--10 phosphinylidyne phenanthrene-Succinic Acid of mixing) and the 0.348g antimony glycol join in the reactor, carry out esterification by step and condition that embodiment 1 provides.Esterification finishes the back and slowly feed nitrogen in reactor, and adds and contain the nano titanium oxide glycol suspension solution of 90g through supersound process 30min, after step that provides by embodiment 1 and condition are carried out polycondensation again, and discharging, water-cooled gets final product.
The intrinsic viscosity of this flame retardant polyester nano composite material [η] is 0.70dL/g, and oxygen index is 34.0%, vertical combustion grade V-0
Embodiment 22
With 766g terephthalic acid, 395ml ethylene glycol, 9.3g branched monomer TriMethylolPropane(TMP), contain 70g and join in the reactor through nano silicon glycol suspension solution and the 0.301g antimonous oxide of supersound process 30min, carry out esterification by step and condition that embodiment 1 provides.Esterification finishes the back and slowly feed nitrogen in reactor, simultaneously the fire-retardant monomer 3-of 27.9g (2-hydroxyl-oxethyl)-3-oxopropyl (phenyl) sodium hypophosphite ethylene glycol solution is joined in the reactor, after step that provides by embodiment 1 and condition are carried out polycondensation again, discharging, water-cooled gets final product.
The intrinsic viscosity of this flame retardant polyester nano composite material [η] is 0.60dL/g, and oxygen index is 30.5%, vertical combustion grade V-0.
Embodiment 23
With 632g terephthalic acid, 382.5ml ethylene glycol, the equal tetramethylolmethane of 4.5g branched monomer, contain 100g and join in the reactor through bedded zirconium phosphate glycol suspension solution and the 0.348g antimony glycol of supersound process 30min, carry out esterification by step and condition that embodiment 1 provides.Esterification finishes the back and slowly feed nitrogen in reactor, simultaneously the fire-retardant monomer 3-of 117g (2-hydroxyl-oxethyl)-3-oxopropyl (phenyl) sodium hypophosphite ethylene glycol solution is joined in the reactor, after step that provides by embodiment 1 and condition are carried out polycondensation again, discharging, water-cooled gets final product.
The intrinsic viscosity of this flame retardant polyester nano composite material [η] is 0.72dL/g, and oxygen index is 32.5%, vertical combustion grade V-0.
In order to verify whether phosphonium flame retardant successfully is aggregated on the polyester molecule chain, the present invention has carried out the test of phosphorus nuclear-magnetism with the flame retardant polyester of preparation, the results are shown in Figure 1.Tangible as we can see from the figure phosphorus peak, promptly phosphoric is successfully introduced on the polyester chain.
In addition, it (is pure polyester from left to right successively that molten drop situation after droplet-resistant flame-retardant polyester that the present invention also prepares pure polyester, embodiment 9 and embodiment 17 respectively and the test of nano composite material oxygen index thereof has been taken photo, the droplet-resistant flame-retardant polyester of embodiment 9 preparations, the droplet-resistant flame-retardant polyester nano composite material of embodiment 17 preparations), see Fig. 2.From the photo of Fig. 2 as can be seen the refractory of the droplet-resistant flame-retardant polyester of the present invention's preparation and nano composite material thereof drip effect and be significantly improved.
Claims (10)
1. droplet-resistant flame-retardant polyester, this flame retardant polyester is to be made by branched monomer, terephthalic acid or dimethyl terephthalate (DMT), ethylene glycol and fire-retardant monomer random copolymerization, branched monomer is to contain trifunctional and above aliphatics or aromatics thereof, functional group is any in carboxylic acid, acid anhydrides or the hydroxyl, wherein fatty compounds contains 3-8 carbon atom, and fire-retardant monomer is any in the following structure:
R in the formula
1, R
2Be alkyl or phenyl or benzyl, can be identical or inequality; X is H or alkali metal or alkali earth metal; N1 is 1 or 2; Y is hydroxyl or carboxyl; Z is S or O element; R
3Aliphatic group or phenyl or benzyl for C3-C15; N is H or carboxyl or hydroxyl; M is hydroxyl or carboxyl, the mol ratio of terephthalic acid or dimethyl terephthalate (DMT) and ethylene glycol is 1: 1.5, the content of branched monomer is the 0.05-5% of droplet-resistant flame-retardant polyester total mass, fire-retardant monomeric content is the 1-25% of droplet-resistant flame-retardant polyester total mass, and the intrinsic viscosity of this flame retardant polyester is 0.50-1.20dL/g.
2. method for preparing the described droplet-resistant flame-retardant polyester of claim 1, this method is with terephthalic acid or dimethyl terephthalate (DMT), ethylene glycol and catalyzer proportioning routinely, after adopting direct esterification method or ester-interchange method to carry out esterification, be prepared from through polycondensation, it is characterized in that before esterification or the esterification aftercondensated before, in reaction system, add and account for the branched monomer of droplet-resistant flame-retardant polyester total mass 0.05-5% and the fire-retardant monomer of 1-25%.
3. the method for preparing droplet-resistant flame-retardant polyester according to claim 2, the branched monomer that adds in this method accounts for the 0.5-4% of droplet-resistant flame-retardant polyester total mass, and it is to contain trifunctional and above aliphatics or aromatics thereof, functional group is any in carboxylic acid, acid anhydrides or the hydroxyl, wherein fatty compounds contains 3-8 carbon atom, the fire retardant monomer that adds accounts for the 3-15% of droplet-resistant flame-retardant polyester total mass, and it is in the following structure any:
R in the formula
1, R
2Be alkyl or phenyl or benzyl, can be identical or inequality; X is H or alkali metal or alkali earth metal; N1 is 1 or 2; Y is hydroxyl or carboxyl; Z is S or O element; R
3Aliphatic group or phenyl or benzyl for C3-C15; N is H or carboxyl or hydroxyl; M is hydroxyl or carboxyl.
4. according to claim 2 or the 3 described methods that prepare droplet-resistant flame-retardant polyester, used catalyzer is an antimony glycol in this method, antimonous oxide, earth silicon/titanic oxide mixture, any in titanic acid ester or the titanium ethylene glycolate.
5. nano composite material that contains the described droplet-resistant flame-retardant polyester of claim 1, this material is made up of the described flame retardant polyester of claim 1 and inorganic nano-particle or lamellar compound, wherein the quality percentage composition of droplet-resistant flame-retardant polyester is 80-99.5%, the quality percentage composition of inorganic nano-particle or lamellar compound is 0.5-20%, inorganic nano-particle is any in nano silicon, nano titanium oxide or the nano zine oxide, and lamellar compound is any in layered silicate, layered double-hydroxide or the bedded zirconium phosphate.
6. method for preparing the described droplet-resistant flame-retardant polyester nano composite material of claim 5, this method is with terephthalic acid or dimethyl terephthalate (DMT), ethylene glycol and catalyzer be proportioning routinely, after adopting direct esterification method or ester-interchange method to carry out esterification, be prepared from through polycondensation, it is characterized in that before esterification or the esterification aftercondensated before, in reaction system, add the branched monomer that accounts for droplet-resistant flame-retardant polyester total mass 0.05-5%, fire-retardant monomer of 1-25% and the glycol suspension solution that accounts for nano composite material total mass 0.5-20% nanoparticle or lamellar compound are to prepare this nano composite material by in-situ polymerization.
7. the method for preparing the droplet-resistant flame-retardant polyester nano composite material according to claim 6, the branched monomer that adds in this method accounts for the 0.5-4% of droplet-resistant flame-retardant polyester total mass, and its used branched monomer is to contain trifunctional and above aliphatics or aromatics thereof, functional group is any in carboxylic acid, acid anhydrides or the hydroxyl, wherein fatty compounds contains 3-8 carbon atom, the fire retardant monomer that adds accounts for the 3-15% of droplet-resistant flame-retardant polyester total mass, and it is in the following structure any:
R in the formula
1, R
2Be alkyl or phenyl or benzyl, can be identical or inequality; X is H or alkali metal or alkali earth metal; N1 is 1 or 2; Y is hydroxyl or carboxyl; Z is S or O element; R
3Aliphatic group or phenyl or benzyl for C3-C15; N is H or carboxyl or hydroxyl; M is hydroxyl or carboxyl.
8. according to claim 6 or the 7 described methods that prepare the droplet-resistant flame-retardant polyester nano composite material, used inorganic nano-particle is any in nano silicon, nano titanium oxide or the nano zine oxide in this method, and lamellar compound is any in layered silicate, layered double-hydroxide, the bedded zirconium phosphate.
9. according to claim 6 or the 7 described methods that prepare the droplet-resistant flame-retardant polyester nano composite material, used catalyzer is an antimony glycol in this method, antimonous oxide, earth silicon/titanic oxide mixture, titanic acid ester, any in the titanium ethylene glycolate.
10. the method for preparing the droplet-resistant flame-retardant polyester nano composite material according to claim 8, used catalyzer is an antimony glycol in this method, antimonous oxide, earth silicon/titanic oxide mixture, titanic acid ester, any in the titanium ethylene glycolate.
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| CN102174718A (en) * | 2011-01-21 | 2011-09-07 | 武汉纺织大学 | Method for preparing anti-dripping polyester fibers |
| CN102731758A (en) * | 2012-03-13 | 2012-10-17 | 蓝海永乐（江苏）新材料有限公司 | Foamable flame-retarding polyester capable of being used for supercritical CO2 and preparation method and application thereof |
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| CN102174718B (en) * | 2011-01-21 | 2013-01-02 | 武汉纺织大学 | Method for preparing anti-dripping polyester fibers |
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| CN103665783A (en) * | 2013-11-22 | 2014-03-26 | 江苏裕兴薄膜科技股份有限公司 | Halogen free flame-retardant polyester film and preparation method thereof |
| CN107325271A (en) * | 2017-07-20 | 2017-11-07 | 汕头大学 | A kind of macromolecular flame retardant polyester and its preparation and application |
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