CN1176995C - Phosphorus-contained flame-retarding nano-class ethanediol polyterephthalate/laminated silicate composition and its preparing process and application - Google Patents
Phosphorus-contained flame-retarding nano-class ethanediol polyterephthalate/laminated silicate composition and its preparing process and applicationInfo
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- CN1176995C CN1176995C CNB021336024A CN02133602A CN1176995C CN 1176995 C CN1176995 C CN 1176995C CN B021336024 A CNB021336024 A CN B021336024A CN 02133602 A CN02133602 A CN 02133602A CN 1176995 C CN1176995 C CN 1176995C
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Abstract
The present invention relates to a fire-retardant polyethylene glycol terephthalate/phyllosilicate nanocomposite material containing phosphorus, which uses dimethyl terephthalate or terephthalic acid, ethylene glycol, layer silicate, a response-type fire retardant containing phosphorus, a layer inserting agent, a dispersion medium and a catalyst as raw materials and is prepared by the ester exchange or the direct esterification processes of layer insertion and polymerization in an original position. The nanocomposite material greatly improves the mechanical performance and the thermal performance. Particularly, the nanocomposite material has the performances of fire retardance and dropping resistance. Thereby, the nanocomposite material is a nanometer fire-retardant polyester material with good comprehensive performance and has the advantages of mature preparation method and easy operation. The nanocomposite material can be used as a raw material for preparing fire-retardant plastic products and fire-retardant fibers.
Description
One, technical field
The invention belongs to phosphor-containing flame-proof polymer/inorganic salt nano composite material and its production and use technical field, be specifically related to a kind of phosphor-containing flame-proof polyethylene terephthalate/laminated nm-silicate composite material and its production and use.
Two, background technology
Polyethylene terephthalate (abbreviation polyester) has advantages such as high-modulus, high strength, snappiness, conformality and thermotolerance because of it, be output maximum in the synthon, kind that purposes is the widest.Because this product belongs to combustiblematerials, make it be subjected to certain restriction in application aspect the special trade working suit such as finishing material that requires fire-retardant aviation, railway and other traffic transport industry, hotel, restaurant, place of public amusement and fire-fighting.
Become increasingly active to the research and the application and development of fire-retardant polyester fibre in countries in the world since the seventies, and various fire-retardant polyester fibre kinds are constantly come out.Being used for the flame-retardant modified fire retardant of trevira mainly is halogen-containing and the phosphorated fire retardant.Halogen-containing, though the fire retardant of particularly chloride, bromine comparatively effectively and be widely used, but when burning, easily discharge pungency and corrosive hydrogen halide are arranged, when especially normal and synergist sb oxide is used, its material combustion also can discharge a large amount of cigarettes, these all can cause certain threat to people's life security, thereby the application of halogen containing flame-retardant is restricted.There are some researches show, for polyester, phosphorus is the most effective ignition-proof element (Wang Yuzhong work, " design of fire-retardantization of trevira ", Sichuan science and technology press, 1994), but existing be that the flame-retardant modified phosphorous copolyester that obtains of matrix all exists insoluble problems such as thermal characteristics or mechanical properties decrease, fusion drippage be serious with the polyethylene terephthalate, therefore researching and developing new high performance flame retardant polyester has become one of focus of paying close attention in this field.
There are clay minerals such as a class layered silicate in nature, if you would take off soil (MMT), its structure lamella is a nanoscale, includes three subgrades, in the middle of 2 silicon-oxy tetrahedron subgrades, be embedded 1 alumina octahedral subgrade, connect with covalent linkage by shared Sauerstoffatom between the subgrade.About 1 nanometer of entire structure sheet bed thickness, about 100 nanometers of length and width, because the part aluminium atom in the alumina octahedral subgrade is replaced by the low price atom, lamella has negative charge, superfluous negative charge is by being free on the Na of interlayer
+, Ca
2+, Mg
2+Deng cation balance, and these cation easilies and organic cation exchange, can make the polynite surface from the hydrophilic oleophylic that becomes like this, reduced surface energy, improved and polymeric matrix and monomeric consistency, effectively the mechanical property of some polymers for general use of raising, thermotolerance etc. become the focus that polymeric material field is studied, and many documents have been made report to the progress in domestic and international this field.
UsukiA in 1987, OkadaA takes the lead in having reported with " two-step approach " preparation nylon 6/ montmorillonite composite material (" polymer collection of thesis " (Japanese), 1995,52 (2): 299), report that the particle diameter of finding polynite in polymerization process is dissociated into 40 nanometers by 50 microns, and be dispersed in the nylon-6 matrix body, the tensile strength of material etc. is significantly improved, and Toyota Motor Corporation successfully is applied in it on trolley part.Chuio K is again at " plastics " (Japanese) recently, 2000, usefulness antimony acetate such as report Tsai and properties-correcting agent SB (cocoamphopropionate) handle also and polyethylene terephthalate (PET) polymerization polynite in 51 (11): 47 " present situation of polymer nanocomposites ", generate the PET/MMT matrix material that approximate layer is fully peeled off, this material is compared with pure PET, flexural strength has improved 70%, and heat-drawn wire has improved nearly 30 ℃.
Domestic have several research units also very active in this field performance, spins institute of section etc. as chemistry institute of the Chinese Academy of Sciences, China.Chemistry institute of Chinese Academy of Sciences QiZongNeng etc. has been introduced a kind of polybutylene terephthalate/laminated nm-silicate composite material and preparation method thereof in Chinese patent CN1187506A, make the heat-drawn wire of the matrix material that is obtained and modulus improve more.
In addition, about the flame retardant resistance of polymer/laminated silicate matrix material, report is arranged all both at home and abroad.Gilman etc. are at SMPE Journal, 1997,33 (4): 40 have reported its result of study, the heat release rate of finding MMT nano composite materials such as PA6, PS (polystyrene) and polycaprolactone has obvious reduction, is very difficult but will reach the flame retardant resistance (for example oxygen index LOI 〉=29) that satisfies practical requirement.Shu Zhongjun etc. are at " polymer circular ", and 2000, (4): the PA6/MMT system that 65 reports are studied has also drawn similar conclusion.
Three, summary of the invention
The objective of the invention is provides a kind of phosphor-containing flame-proof polyethylene terephthalate/laminated nm-silicate composite material at the deficiencies in the prior art, this matrix material not only mechanical property is significantly improved, and flame retardant properties satisfies the practicality requirement, can also slow down the fusion drippage significantly.Another object of the present invention provides the preparation method of this matrix material.Last purpose of the present invention provides the purposes of this matrix material.
Phosphor-containing flame-proof polyethylene terephthalate/laminated nm-silicate composite material provided by the invention, its feed composition and content (weight part) are:
30～100 parts of dimethyl terephthalate (DMT) or terephthalic acids
30～100 parts of ethylene glycol
0.5～30 part of layered silicate
0.3～20 part of response type phosphonium flame retardant
0.01～5.0 part of intercalator
10～800 parts in dispersion medium
0.001～0.05 part of catalyzer.
Response type phosphonium flame retardant or have following formula in the prescription:
Wherein R is C
1～C
15Open chain or cyclic alkyl alkene, aryl olefin or alkylaryl alkene, R ' is alkyl or C
6Above aryl or benzyl, as hydroxybenzene phosphine oxide hexenoic acid (I), hydroxybenzene phosphine oxide vinylformic acid (II), hydroxymethyl phosphine oxide hexenoic acid (III), hydroxymethyl phosphine oxide vinylformic acid (IV), concrete structure is as follows:
Preferred hydroxybenzene phosphine oxide vinylformic acid (II) and hydroxymethyl phosphine oxide vinylformic acid (IV).
The also optional apparatus of response type phosphonium flame retardant has 9 of following structure, and the 10-dihydro-9-oxy is mixed-the assorted phenanthrene-Succinic Acid of 10-phosphinylidyne
Or directly adding can synthesize 9, and the 10-dihydro-9-oxy is assorted-the following structure monomer 9 of the assorted phenanthrene-Succinic Acid of 10-phosphinylidyne, the 10-dihydro-9-oxy is assorted-and assorted phenanthrene of 10-phosphinylidyne and methylene-succinic acid:
Layered silicate in the prescription is polynite or Meccah stone, and its cationic exchange total amount is 50～180meq/100g; Intercalator is Dodecyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride or two ten alkyl-dimethyl ammonium chlorides, intercalator also can be 12～cetylamine, 1,6-hexanediamine, thanomin, diethanolamine or lauric acid amine, a time-like after intercalator adopts, need to add protonating agents such as phosphoric acid, hydrochloric acid, sulfonic acid, sulfuric acid or acetic acid, the add-on of protonating agent is 0.01～2.0 part (weight part); Dispersion medium is at least a in water, the ethylene glycol; Catalyzer is antimony acetate or antimonous oxide.
One of preparation method provided by the invention is the in-situ inserted polymerization of transesterify, refer to that promptly layered silicate is through after the intercalation processing of intercalator, the copolyreaction of after transesterification reaction, carrying out again with polyester monocase together as the 3rd monomer and response type phosphonium flame retardant, reaction laminate silicate is dissociated into nanoparticle and is dispersed in the polyester matrix that has the phosphonium flame retardant group, concrete operations are: after above-mentioned formula constituent is weighed respectively, earlier layered silicate is added the dispersion medium high speed and stir, form stable suspensoid; Again intercalator or intercalator and protonating agent are added and are warming up to 60～80 ℃ and fully stir, after the filtration with 2～3 centrifuge drippings of throw out washing; Add dimethyl terephthalate (DMT) and ethylene glycol, fully mix once more, be warming up to 160～230 ℃ and carried out transesterification reaction 2.5～4 hours; Add the response type phosphonium flame retardant then, catalyst mix is even, 245～275 ℃, below the pressure 60Pa, polymerization can obtain phosphor-containing flame-proof polyethylene terephthalate/laminated nm-silicate composite material in 2～3 hours.
Preparation method's provided by the invention two is in-situ inserted polymerizations of direct esterification, and concrete operations are: after above-mentioned formula constituent is weighed respectively, earlier layered silicate is added the dispersion medium high speed and stir, form stable suspensoid; Again intercalator or intercalator and protonating agent are added and are warming up to 60～80 ℃ and fully stir, after the filtration with 2～3 centrifuge drippings of throw out washing; Add terephthalic acid, ethylene glycol and response type phosphonium flame retardant, fully mix once more, be warming up to 160～230 ℃ and carried out esterification 1.5～3 hours; Add catalyzer then, and be evacuated to below the vacuum tightness 60Pa at 245～275 ℃, polymerization can obtain phosphor-containing flame-proof polyethylene terephthalate/laminated nm-silicate composite material in 2～3 hours.
The purposes of the phosphor-containing flame-proof polyethylene terephthalate/laminated nm-silicate composite material of above-mentioned either party's method preparation is the raw material that is used to make flame retardant plastics goods and fire-retardant fibre.
Four, embodiment
Below by embodiment the present invention is specifically described; it is worthy of note that following examples only are used for that the invention will be further described; can not be interpreted as limiting the scope of the invention; and nonessential improvement and adjustment that the professional in present technique field has done according to above-mentioned content of the present invention should belong to protection scope of the present invention.
Embodiment 1
Be earlier polynite 44 grams of 90meq/100g with the cationic exchange total amount, join 1100 gram dispersion medium water high speeds and stir, form stable suspensoid; Again intercalator octadecyl trimethyl ammonium chloride 16.16 grams are added, be warming up to 70 ℃ and fully stirring, then the lower sediment thing is filtered after washing 2～3 times, fully centrifuge dripping; Join again in the dimethyl terephthalate (DMT) (DMT) and 1367.19 gram ethylene glycol (EG) monomers of 3032.81 grams, fully mix once more, be warming up to 160～230 ℃ and carried out transesterification reaction 2.5～4 hours; Add response type phosphonium flame retardant hydroxybenzene phosphine oxide vinylformic acid 183.33 grams then, The catalytic antimony trioxide 1.375 grams mix, be warming up to 245～275 ℃ and be evacuated to below the 60Pa, polymerization got final product in 2～3 hours, and the performance of the phosphor-containing flame-proof polyethylene terephthalate/laminated nm-silicate composite material of gained is seen attached list.
Embodiment 2
The preparation method of present embodiment is identical with enforcement 1, slightly.Different is: 1. the add-on of layered silicate is 110 grams; 2. layered silicate is Meccah stone of cationic exchange total amount 80meq/100g; 3. catalyzer is an antimony acetate.Present embodiment gained composite property is seen attached list.
Embodiment 3
Be earlier polynite 220 grams of 90meq/100g with the cationic exchange total amount, join 5500 gram dispersion medium water high speeds and stir, form stable suspensoid; Again intercalator octadecyl trimethyl ammonium chloride 80.8 grams are added, be warming up to 75 ℃ and fully stirring, then the lower sediment thing is filtered after washing 2～3 times, fully centrifuge dripping; Join again in the terephthalic acid (PTA) and 1441.50 gram ethylene glycol (EG) and phosphonium flame retardant hydroxybenzene phosphine oxide propylene 180.38 grams of 2958.50 grams, fully mix once more, be warming up to 160～230 ℃ and carried out transesterification reaction 1.5～3 hours; Add then after The catalytic antimony trioxide 1.3742 gram mixes, be warming up to 245～275 ℃ and be evacuated to below the 60Pa, polymerization promptly got phosphor-containing flame-proof polyethylene terephthalate/laminated nm-silicate composite material in 2～3 hours, and its performance is seen attached list.
Embodiment 4～6
The preparation method of these three embodiment is identical with embodiment 3, slightly.The different just add-ons of layered silicate and phosphonium flame retardant wherein see attached list, and the composite property of gained are also seen attached list separately.
Embodiment 7
The preparation method of present embodiment is because of identical with embodiment 3, slightly.Different is that the polynite that present embodiment adds is 110 grams; The response type phosphonium flame retardant that adds is 9, and the 10-dihydro-9-oxy is mixed-the assorted phenanthrene-Succinic Acid of 10-phosphinylidyne, and add-on is 704 grams; The composite property of gained is seen attached list.
Embodiment 8
Be earlier polynite 44 grams of 90meq/100g with the cationic exchange total amount, join 1100 gram dispersion medium water high speeds and stir, form stable suspensoid; Again intercalator thanomin 2.684 grams, protonating agent phosphatase 24 .312 are restrained adding, be warming up to 70 ℃ and fully stirring, then the lower sediment thing is filtered after washing 2～3 times, fully centrifuge dripping; Join again in the dimethyl terephthalate (DMT) and 1367.19 gram ethylene glycol monomers of 3032.81 grams, fully mix once more, be warming up to 160～230 ℃ and carried out transesterification reaction 2.5～4 hours; Add response type phosphonium flame retardant hydroxybenzene phosphine oxide vinylformic acid 183.33 grams then, The catalytic antimony trioxide 1.375 grams mix, be warming up to 245～275 ℃ and be evacuated to below the 60Pa, polymerization got final product in 2～3 hours, and the performance of the phosphor-containing flame-proof polyethylene terephthalate/laminated nm-silicate composite material of gained is seen attached list.
The data of surveying from table, the mechanical property of gained matrix material of the present invention, the comparative example A who more only contains fire retardant as notched Izod impact strength, tensile strength, flexural strength has raising by a relatively large margin, and heat-drawn wire, heat decomposition temperature and fusing point also are significantly improved, especially molten drop speed is big especially than the range of decrease of comparative example A, B, illustrate that this matrix material becomes charcoal good, be difficult for causing spot fire, and oxygen index has all reached the level of practical requirement.
Subordinate list
| Embodiment | Laminar silicic acid salts contg (part) | DMT or PTA and EG monomer content (part) | Phosphor-containing flame-proof agent content (part) | Intrinsic viscosity (dl/g) | Breach resistance to impact shock (J/M) | Tensile strength (MPa) | Extension at break (%) | Flexural strength (MPa) | Heat-drawn wire (℃) | Heat decomposition temperature (℃) | Fusing point (℃) | Molten drop speed (dripping/30 seconds) | Oxygen index |
| 1 | 1 | 100 | 4 | 0.625 | 53.5 | 85.5 | 18.6 | 108 | 78.8 | 415.2 | 246.5 | 4.5 | 31.2 |
| 2 | 2.5 | 100 | 4 | 0.635 | 60.1 | 91.0 | 13.5 | 100 | 87.2 | 417.8 | 244.7 | 3.8 | 30.6 |
| 3 | 5 | 100 | 4 | 0.641 | 56.9 | 100.3 | 10.9 | 95 | 92.5 | 419.1 | 241.3 | 3.2 | 30.0 |
| 4 | 7.5 | 100 | 4 | 0.648 | 41.2 | 112.3 | 9.2 | 76 | 100.3 | 420.0 | 236.2 | 0.5 | 29.4 |
| 5 | 2.5 | 100 | 3 | 0.639 | 60.8 | 91.9 | 15.3 | 102 | 88.1 | 418.1 | 245.1 | 3.6 | 29.2 |
| 6 | 5 | 100 | 5 | 0.637 | 56.5 | 99.7 | 10.1 | 88 | 91.6 | 418.8 | 240.6 | 3.4 | 30.9 |
| 7 | 2.5 | 100 | 16 | 0.580 | 44.3 | 73.5 | 8.8 | 65 | - | 386.2 | 218 | 2.1 | 33.8 |
| 8 | 1 | 100 | 4 | 0.620 | 48.6 | 79.5 | 16.1 | 101 | 76.1 | 414.3 | 244.2 | 4.8 | 30.8 |
| A | 100 | 4 | 0.611 | 42.2 | 50.2 | 20.8 | 65 | 63.9 | 411.6 | 236.5 | 22 | 34.6 | |
| B | 1 | 100 | 0.686 | 63.5 | 85.5 | 28.6 | 108 | 86.4 | 430.2 | 250.2 | 10 | 22.5 | |
| C | 100 | 16 | 0.550 | 42.5 | 71.5 | 9.2 | 62 | - | 384.9 | 222 | 8.0 | 32.5 |
Annotate: A, B, C example are Comparative Examples.Phosphonium flame retardant in the A example is a hydroxybenzene phosphine oxide vinylformic acid, and the layered silicate in the B example is polynite, and the phosphonium flame retardant in the C example is 9, and the 10-dihydro-9-oxy is mixed-the assorted phenanthrene-Succinic Acid of 10-phosphinylidyne.
Claims (10)
1, a kind of phosphor-containing flame-proof polyethylene terephthalate/laminated nm-silicate composite material is characterized in that this matrix material feed composition and content (weight part) are:
30～100 parts of dimethyl terephthalate (DMT) or terephthalic acids
30～100 parts of ethylene glycol
0.5～30 part of layered silicate
0.3～20 part of response type phosphonium flame retardant
0.01～5.0 part of intercalator
10～800 parts in dispersion medium
0.001～0.05 part of catalyzer.
2, phosphor-containing flame-proof polyethylene terephthalate/laminated nm-silicate composite material according to claim 1 is characterized in that the response type phosphonium flame retardant is the compound with following formula:
Wherein R is C
1～C
15Open chain or cyclic alkyl alkene, aryl olefin or alkylaryl alkene, R ' is alkyl or C
6Above aryl or benzyl, or for having 9 of following structure, the 10-dihydro-9-oxy is mixed-the assorted phenanthrene-Succinic Acid of 10-phosphinylidyne:
Or for synthetic 9, the 10-dihydro-9-oxy is assorted-the following structure monomer of the assorted phenanthrene-Succinic Acid of 10-phosphinylidyne:
3, phosphor-containing flame-proof polyethylene terephthalate/laminated nm-silicate composite material according to claim 2, the response type phosphonium flame retardant that it is characterized in that used formula are any in hydroxybenzene phosphine oxide hexenoic acid, hydroxybenzene phosphine oxide vinylformic acid, hydroxymethyl phosphine oxide hexenoic acid, the hydroxymethyl phosphine oxide vinylformic acid.
4, according to claim 1 or 2 or 3 described phosphor-containing flame-proof polyethylene terephthalate/laminated nm-silicate composite materials, it is characterized in that layered silicate is polynite or Meccah stone, its cationic exchange total amount is 50～180meq/100g.
5, according to claim 1 or 2 or 3 described phosphor-containing flame-proof polyethylene terephthalate/laminated nm-silicate composite materials, it is characterized in that intercalator is a Dodecyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride or two ten alkyl-dimethyl ammonium chlorides, intercalator also can be 12～cetylamine, 1, the 6-hexanediamine, thanomin, diethanolamine or lauric acid amine, a time-like after intercalator adopts, need to add phosphoric acid, hydrochloric acid, sulfonic acid, protonating agent such as sulfuric acid or acetic acid, the add-on of protonating agent are 0.01～2.0 part (weight part).
6,, it is characterized in that dispersion medium is at least a in water, the ethylene glycol according to claim 1 or 2 or 3 described phosphor-containing flame-proof polyethylene terephthalate/laminated nm-silicate composite materials.
7,, it is characterized in that catalyzer is antimony acetate or antimonous oxide according to claim 1 or 2 or 3 described phosphor-containing flame-proof polyethylene terephthalate/laminated nm-silicate composite materials.
8, according to the preparation method of the described phosphor-containing flame-proof polyethylene terephthalate/laminated nm-silicate composite material of claim 1～7, after it is characterized in that above-mentioned formula constituent weighed respectively, earlier layered silicate is added the dispersion medium high speed and stir, form stable suspensoid; Again intercalator or intercalator and protonating agent are added and are warming up to 60～80 ℃ and fully stir, after the filtration with 2～3 centrifuge drippings of throw out washing; Add dimethyl terephthalate (DMT) and ethylene glycol, fully mix once more, be warming up to 160～230 ℃ and carried out transesterification reaction 2.5～4 hours; Add the response type phosphonium flame retardant then, catalyst mix is even, 245～275 ℃, below the pressure 60Pa, polymerization got final product in 2～3 hours.
9, according to the described phosphor-containing flame-proof polyethylene terephthalate/laminated nm-silicate composite material of claim 1～7, after it is characterized in that above-mentioned formula constituent weighed respectively, earlier layered silicate is added the dispersion medium high speed and stir, form stable suspensoid; Again intercalator or intercalator and protonating agent are added and are warming up to 60～80 ℃ and fully stir, after the filtration with 2～3 centrifuge drippings of throw out washing; Add terephthalic acid, ethylene glycol and response type phosphonium flame retardant, fully mix once more, be warming up to 160～230 ℃ and carried out esterification 1.5～3 hours; Add catalyzer then, and 245～275 ℃, below the pressure 60Pa, polymerization got final product in 2～3 hours.
10,, it is characterized in that this matrix material can be used for making the raw material of various flame retardant plastics goods, fire-retardant fibre according to the purposes of the described phosphor-containing flame-proof polyethylene terephthalate/laminated nm-silicate composite material of claim 1～7.
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| CN101974148A (en) * | 2010-09-17 | 2011-02-16 | 四川大学 | High-molecular weight phosphorous flame retardant random copolyester and preparation method thereof |
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