CN100355831C - Phosphorus containing fire retardant copolyester/barium sulphate nano-composite material and its preparation method - Google Patents
Phosphorus containing fire retardant copolyester/barium sulphate nano-composite material and its preparation method Download PDFInfo
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Abstract
The present invention relates to a phosphatic flame resistant copolyester / barium sulfate nanometer composite material which comprises phosphatic flame resistant copolyester. The phosphatic flame resistant copolyester / barium sulfate nanometer composite material is characterized in that the content of the phosphatic flame resistant copolyester is 90 to 99.5 wt%, the content of the barium sulfate contained in the composite material is 0.5 to 10 wt%, and the particle diameter is at most 100 nm. The present invention also relates to a preparation method of the nanometer composite materials comprise that the nanometer composite material is prepared with a direct esterification method or an indirect esterification method by mixing raw material monomers, a catalyst and phosphatic flame resistant comonomers. The preparation method is characterized in that 0.5 to 10 wt% of nanometer barium sulfate suspension is added before an esterification reaction or after the esterification reaction and before a polycondensation reaction. Because the nanometer barium sulfate of the material is added in a suspension mode, and an in-situ polymerization technology is adopted, the obtained composite material can overcome the defects of thermal property reduction, mechanical property reduction, melting dropping, etc. of common flame resistant polyester. In addition, the material has good spinnability and is suitable for high-speed spinning, and obtained fiber can meet the requirements of civil fibre.
Description
One, technical field
The invention belongs to phosphor-containing flame-proof polymer/inorganic salt nano composite material and preparation method thereof technical field, be specifically related to a kind of phosphor-containing flame-retardant copolyester/barium sulphate nano-composite material and preparation method thereof.Because the nano barium sulfate in this material adds with form of suspension, and the technology that adopts in-situ polymerization obtains a kind ofly can overcoming the thermal characteristics that common flame retardant polyester exists and mechanical property reduces and the flame-proof composite material of the excellent property of shortcomings such as fusion drippage, and this material good spinnability, be suitable for high speed spinning.
Two, background technology
Polyethylene terephthalate (abbreviation polyester) has plurality of advantages such as high-modulus, high strength, snappiness, conformality and good heat resistance because of it, be most widely used general, synthon kind that consumption is maximum in the textile field.But, make it requiring the application aspect the special trade working suit such as used finishing material in fire-retardant aviation, railway, highway and other transport facility, hotel, restaurant, place of public amusement and fire-fighting to be subjected to certain restriction because this fiber species belongs to combustiblematerials.Therefore fire-retardantization of this class material caused worldwide extensive concern more.
Since the seventies, the research of fire-retardant polyester fibre is a focus of polyester research always.Constantly flame retardant polyester that comes out and fiber thereof generally are to adopt addition type or reactive flame retardant to make material obtain flame retardant resistance.These fire retardants mainly are halogen-containing and the phosphorated fire retardant.Halogen-containing fire retardant has pungency and corrosive hydrogen halide and smog because of it can discharge in combustion processes, not only contaminate environment also can threaten to people's life security, and some halogen containing flame-retardant is by some country's forbidding.Though the phosphorus in the phosphorated fire retardant there are some researches show (Wang Yuzhong work, " design of fire-retardantization of trevira ", Sichuan science and technology press, 1994), for polyester, it is the most effective ignition-proof element, even but existing be the flame-retardant modified phosphorous copolyester that obtains of matrix with the polyethylene terephthalate, all having the lot of valuable attribute with sacrifice or reduction material is the problem of cost, as thermal characteristics or mechanical properties decrease, trevira itself also has at high temperature the fusion drippage of when taking place (or fire) in addition, causes the problem of disaster and loss of life and personal injury, thereby has limited its application in some fields.So simultaneously polyester is carried out fire-retardantization and refractory drips modification, particularly halogen-free flameproofization and no molten drop modification have become this field important problem of concern both at home and abroad.
The research of the polymer/inorganic thing nano composite material that the late 1980s and the beginning of the nineties rise is for flame retarded polymeric material has been opened up new approach.At present, people after deliberation multiple polymers/inorganic nano composite material, the Comell university of the U.S., Michigan state university, chemistry institute of the Chinese Academy of Sciences etc. has all carried out big quantity research, having prepared with polyethylene terephthalate (PET) etc. is polymeric matrix, with layered silicate (LS) is the nano composite material of inorganics, and a series of progress have been obtained in its basic theory and application facet, especially after adding nano-complex, the thermostability and the flame retardant properties of material improve a lot, it is fewer to add its addition, thereby less to the mechanics and the physicals influence of material.But what prior art was used mainly is inorganic nanometer powder, inevitably there is agglomeration in these powders, therefore must use the external force bigger particle of will reuniting to open before using, so not only need to consume a lot of energy, and some agglomerated particles can't be opened at all, after external force stopped simultaneously, the particle after opening was reunited again very easily once more.Because the poor stability of this powder, big, the skewness of powder granularity, its particle diameter is generally between 300～600nm, cause particle particle diameter in polymkeric substance also bigger, aggregated particle is many, spinning property is poor, the spinning equipment serious wear has also influenced the raising of material property simultaneously to a certain extent.
The inventor for make polyethylene terephthalate/laminated nm-silicate composite material not only mechanical property be significantly improved, flame retardant properties satisfies the practicality requirement, and can also slow down the fusion drippage significantly, a kind of phosphor-containing flame-proof polyethylene terephthalate/laminated nm-silicate composite material was once disclosed in ZL0213602.4.This material needs to add organic intercalation agent in preparation process, carry out in-situ polymerization after the interlamellar spacing that has enlarged layered silicate again.Though the above-mentioned goal of the invention of this material can reach, because of the existence of silicate lamella structure, this material is a monodimension nanometer material, and only thickness is nano level, causes in spinning process spinning property poor.
Three, summary of the invention
The objective of the invention is deficiency at prior art, a kind of phosphor-containing flame-retardant copolyester/barium sulphate nano-composite material is provided, it not only can overcome thermal characteristics and the shortcomings such as mechanical property reduction and fusion drippage that common flame retardant polyester exists, and has good spinning property.
Another object of the present invention provides the preparation method of above-mentioned nano composite material.
Phosphor-containing flame-retardant copolyester/barium sulphate nano-composite material provided by the invention, wherein contain phosphor-containing flame-retardant copolyester, the content that it is characterized in that phosphor-containing flame-retardant copolyester is 90～99.5% by weight percentage, and the barium sulfate that contains in this matrix material is 0.5～10% by weight percentage, preferred 1～8%, more preferably 3～8%, its particle diameter≤100nm, preferred≤90nm.
The preparation method of above-mentioned nano composite material provided by the invention is with terephthalic acid or dimethyl terephthalate (DMT), ethylene glycol, catalyzer and phosphorus containing fire retardant copolyester monomer add reactor together, and adopt conventional direct esterification method or indirect esterification process to carry out caseation, polycondensation is prepared from, wherein terephthalic acid or dimethyl terephthalate (DMT), ethylene glycol, the proportioning of catalyzer is conventional polymeric proportioning, it is characterized in that before esterification or the esterification aftercondensated before, adding is 0.5～10% nano barium sulfate suspension by weight percentage, and the phosphorus containing fire retardant copolyester monomer that adds should make it account for 1～20% by weight percentage in matrix material.
Before esterification or before the esterification aftercondensated, preferred adding is 1～8% nano barium sulfate suspension by weight percentage, and the phosphorus containing fire retardant copolyester monomer that adds should make it account for 5～15% by weight percentage in matrix material.
Before esterification or before the esterification aftercondensated, more preferably adding is 3～8% nano barium sulfate suspension by weight percentage, and the phosphorus containing fire retardant copolyester monomer that adds should make it account for 5～15% by weight percentage in matrix material.
Adopt conventional direct esterification method and indirect esterification process as follows in the inventive method:
The direct esterification method adds terephthalic acid, ethylene glycol, phosphorus containing fire retardant copolyester monomer, catalyzer and nano barium sulfate suspension by proportioning in reactor, pressurize and be warming up to 245～269 ℃ and carry out esterification, reaction time of esterification 2～3 hours; After esterification finishes, rough vacuum polycondensation 1～1.5 hour, 269～283 ℃ of temperature; Continue to be warming up to 283～290 ℃ then, and under high vacuum condition, carry out polycondensation 1～2 hour, get final product.
Esterification process adds dimethyl terephthalate (DMT), ethylene glycol, phosphorus containing fire retardant copolyester monomer, catalyzer and nano barium sulfate suspension by proportioning in reactor indirectly, is warming up to 230～269 ℃ under the normal pressure and carries out transesterification reaction 3～4 hours; After transesterification reaction finishes, rough vacuum polycondensation 1～1.5 hour, 269～283 ℃ of temperature; Continue to be warming up to 280～290 ℃ then, and under high vacuum condition, carry out polycondensation 1～2 hour, get final product.
In order to mate the glycolic suspension that added nano barium sulfate suspension is nano barium sulfate in the above method better with reaction system.
If the glycolic suspension with nano barium sulfate before esterification adds reaction system, consider that esterification temperature is higher, barium sulfate time lengthening at high temperature, the system formation changes in the esterification process in addition, causing barium sulfate that part takes place easily reunites, influence its spinning property, so preferred version of the present invention is to adopt after esterification finishes, add nano barium sulfate suspension before the polycondensation, so just can reduce the barium sulfate particle residence time at high temperature, thereby reduced the reunion probability of barium sulfate particle, reduced the quantity of aggregated particle in the copolymerization section, improved the section spinning property.Simultaneously,, reduce inner residual activity group, thereby improve the intensity, toughness, thermotolerance etc. of polymer materials because the ultra micro dimensional effect and the surfactivity effect of nano grade inorganic particle can be carried out fabulous modification to the polymer materials subsurface defect.
Used phosphorus containing fire retardant copolyester monomer is the compound with following formula in the aforesaid method:
Wherein, R is C
1～C
15Aliphatic group, aryl radical or fatty aryl radical, R
1Be alkyl or C
6Above aryl or benzyl; The phosphorus containing fire retardant copolyester monomer also can be has 9 of following structure, and the 10-dihydro-9-oxy is mixed-the assorted luxuriant and rich with fragrance compounds of 10-phosphono:
R
2Be C
3～C
15Aliphatic group, aryl radical or fatty aryl radical, X and Y are hydroxyl or carboxyl, can be identical, also can be inequality.
Used catalyzer is selected from any in antimony glycol, the antimonous oxide in the aforesaid method.
For the particle diameter of the nano barium sulfate that guarantees to add below 100nm, the glycolic suspension of used nano barium sulfate directly prepares according to ZL 01107744.1 disclosed method in the aforesaid method.
Four, description of drawings
Fig. 1 has added the transmission electron microscope photo of 1% nano barium sulfate matrix material section for the present invention;
Fig. 2 has added the transmission electron microscope photo of 3% nano barium sulfate matrix material section for the present invention;
Fig. 3 has added the transmission electron microscope photo of 5% nano barium sulfate matrix material section for the present invention;
Fig. 4 has added the transmission electron microscope photo of 8% nano barium sulfate matrix material section for the present invention;
Fig. 5 is the contrast transmission electron microscope photo that has added 3% powder nano barium sulfate matrix material section.
Five, 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 present technique field professional is made according to the invention described above content should belong to protection scope of the present invention.
Embodiment 1
Measure ethylene glycol 732mL, take by weighing terephthalic acid 2308g, 9, the 10-dihydro-9-oxy is mixed-the assorted phenanthrene of 10-phosphinylidyne-Succinic Acid 333g, the concentration for preparing in advance is that the nano barium sulfate glycolic suspension 600g of 5wt% joins in the reactor, The catalytic antimony trioxide 1.0g joins in the pure terephthalic acid's slurry that modulates, and pressurization 0.36Mpa also is warming up to 248 ℃, esterification 2.5 hours; After esterification finished, polycondensation was 1.5 hours under vacuum tightness 150Pa, 275 ℃ of temperature; Continue to be warming up to 288 ℃ then, and polycondensation 1.5 hours under vacuum tightness 50Pa, can obtain wherein that the phosphorus containing fire retardant copolyester monomer is 10wt%, nano barium sulfate is phosphor-containing flame-retardant copolyester/barium sulphate nano-composite material of 1wt%.
Embodiment 2
Measure ethylene glycol 1245mL, take by weighing terephthalic acid 2256g, 9, the 10-dihydro-9-oxy is assorted-and the assorted phenanthrene of 10-phosphinylidyne-Succinic Acid 333g joins in the reactor, The catalytic antimony trioxide 1.0g joins in the pure terephthalic acid's slurry that modulates, pressurization 0.36Mpa also is warming up to 248 ℃, esterification 2.5 hours; After esterification finishes, take by weighing the nano barium sulfate glycolic suspension 900g of the concentration 10wt% for preparing in advance, join in the esterification products, polycondensation is 1.5 hours under vacuum tightness 150Pa, 275 ℃ of temperature; Continue to be warming up to 288 ℃ then, and polycondensation 1.5 hours under vacuum tightness 50Pa, can obtain wherein that the phosphorus containing fire retardant copolyester monomer is 10wt%, nano barium sulfate is phosphor-containing flame-retardant copolyester/barium sulphate nano-composite material of 3wt%.
Embodiment 3
Measure ethylene glycol 1240mL, take by weighing terephthalic acid 2204g, 9, the 10-dihydro-9-oxy is assorted-and the assorted phenanthrene of 10-phosphinylidyne-Succinic Acid 333g joins in the reactor, catalyst glycol antimony 0.8g joins in the pure terephthalic acid's slurry that modulates, pressurization 0.36Mpa also is warming up to 248 ℃, caseation reaction 2.5 hours; After esterification finishes, take by weighing the nano barium sulfate glycolic suspension 1500g of the concentration 10wt% for preparing in advance, join in the esterification products, polycondensation is 1 hour under vacuum tightness 150Pa, 275 ℃ of temperature; Continue to be warming up to 285 ℃ then, and polycondensation 1 hour under vacuum tightness 50Pa, can obtain wherein that the phosphorus containing fire retardant copolyester monomer is 10wt%, nano barium sulfate is phosphor-containing flame-retardant copolyester/barium sulphate nano-composite material of 5wt%.
Embodiment 4
Measure ethylene glycol 1235mL, take by weighing terephthalic acid 2126g, 9, the 10-dihydro-9-oxy is assorted-and the assorted phenanthrene of 10-phosphinylidyne-Succinic Acid 333g joins in the reactor, The catalytic antimony trioxide 0.8g joins in the pure terephthalic acid's slurry that modulates, pressurization 0.36Mpa also is warming up to 248 ℃, esterification 2.5 hours; After esterification finishes, take by weighing the nano barium sulfate glycolic suspension 1600g of the concentration 15wt% for preparing in advance, join in the esterification products, polycondensation is 1 hour under vacuum tightness 150Pa, 275 ℃ of temperature; Continue to be warming up to 285 ℃ then, and polycondensation 1 hour under vacuum tightness 50Pa, can obtain wherein that the phosphorus containing fire retardant copolyester monomer is 10wt%, nano barium sulfate is phosphor-containing flame-retardant copolyester/barium sulphate nano-composite material of 8wt%.
Embodiment 5
Measure ethylene glycol 1230mL, take by weighing terephthalic acid 2075g, 9, the 10-dihydro-9-oxy is assorted-and the assorted phenanthrene of 10-phosphinylidyne-Succinic Acid 333g joins in the reactor, The catalytic antimony trioxide 0.8g joins in the pure terephthalic acid's slurry that modulates, pressurization 0.36Mpa also is warming up to 248 ℃, esterification 2.5 hours; After esterification finishes, take by weighing the nano barium sulfate glycolic suspension 2000g of the concentration 15wt% for preparing in advance, join in the esterification products, polycondensation is 1 hour under vacuum tightness 150Pa, 275 ℃ of temperature; Continue to be warming up to 283 ℃ then, and polycondensation 1 hour under vacuum tightness 50Pa, can obtain wherein that the phosphorus containing fire retardant copolyester monomer is 10wt%, nano barium sulfate is phosphor-containing flame-retardant copolyester/barium sulphate nano-composite material of 10wt%.
Embodiment 6
Measure ethylene glycol 1163mL, take by weighing terephthalic acid 2334g, 9, the 10-dihydro-9-oxy is assorted-and the assorted phenanthrene of 10-phosphinylidyne-Succinic Acid 166g joins in the reactor, The catalytic antimony trioxide 1.0g joins in the pure terephthalic acid's slurry that modulates, pressurization 0.36Mpa also is warming up to 247 ℃, esterification 2.5 hours; After esterification finishes, take by weighing the nano barium sulfate glycolic suspension 1500g of the concentration 10wt% for preparing in advance, join in the esterification products, polycondensation is 1 hour under vacuum tightness 150Pa, 275 ℃ of temperature; Continue to be warming up to 285 ℃ then, and polycondensation 1 hour under vacuum tightness 50Pa, can obtain wherein that the phosphorus containing fire retardant copolyester monomer is 5wt%, nano barium sulfate is phosphor-containing flame-retardant copolyester/barium sulphate nano-composite material of 5wt%.
Embodiment 7
Measure ethylene glycol 1173mL, take by weighing terephthalic acid 2127g, 9, the 10-dihydro-9-oxy is assorted-and the assorted phenanthrene of 10-phosphinylidyne-Succinic Acid 499g joins in the reactor, The catalytic antimony trioxide 1.4g joins in the pure terephthalic acid's slurry that modulates, pressurization 0.36Mpa also is warming up to 248 ℃, esterification 3 hours; After esterification finishes, take by weighing the nano barium sulfate glycolic suspension 900g of the concentration 10wt% for preparing in advance, join in the esterification products, polycondensation is 1 hour under vacuum tightness 150Pa, 280 ℃ of temperature; Continue to be warming up to 289 ℃ then, and polycondensation 1.5 hours under vacuum tightness 50Pa, can obtain wherein that the phosphorus containing fire retardant copolyester monomer is 15wt%, nano barium sulfate is phosphor-containing flame-retardant copolyester/barium sulphate nano-composite material of 3wt%.
Embodiment 8
Measure ethylene glycol 1110mL, take by weighing terephthalic acid 2334g, hydroxybenzene phosphine oxide vinylformic acid 164g joins in the reactor, and The catalytic antimony trioxide 1.0g joins in the pure terephthalic acid's slurry that modulates, pressurization 0.36Mpa also is warming up to 245 ℃, esterification 2.5 hours; After esterification finishes, take by weighing the nano barium sulfate glycolic suspension 1500g of the concentration 10wt% for preparing in advance, join in the esterification products, polycondensation is 1.5 hours under vacuum tightness 150Pa, 270 ℃ of temperature; Continue to be warming up to 283 ℃ then, and polycondensation 1.5 hours under vacuum tightness 50Pa, can obtain wherein that the phosphorus containing fire retardant copolyester monomer is 5wt%, nano barium sulfate is phosphor-containing flame-retardant copolyester/barium sulphate nano-composite material of 5wt%.
Embodiment 9
Measure ethylene glycol 1000mL, take by weighing terephthalic acid 2075g, hydroxybenzene phosphine oxide vinylformic acid 328g joins in the reactor, and catalyst glycol antimony 1.2g joins in the pure terephthalic acid's slurry that modulates, pressurization 0.36Mpa also is warming up to 245 ℃, esterification 2.5 hours; After esterification finishes, take by weighing the nano barium sulfate glycolic suspension 3000g of the concentration 10wt% for preparing in advance, join in the caseation product, polycondensation is 1.5 hours under vacuum tightness 150Pa, 270 ℃ of temperature; Continue to be warming up to 283 ℃ then, and polycondensation 2 hours under vacuum tightness 50Pa, can obtain wherein that the phosphorus containing fire retardant copolyester monomer is 10wt%, nano barium sulfate is phosphor-containing flame-retardant copolyester/barium sulphate nano-composite material of 10wt%.
Embodiment 10
Measure ethylene glycol 275mL, take by weighing terephthalic acid 2127g, hydroxybenzene phosphine oxide vinylformic acid 491g, the concentration for preparing in advance is that the nano barium sulfate glycolic suspension 900g of 10wt% joins in the reactor, catalyst glycol antimony 1.2g joins in the pure terephthalic acid's slurry that modulates, pressurization 0.36Mpa also is warming up to 245 ℃, esterification 3 hours; After esterification finished, polycondensation was 1.5 hours under vacuum tightness 150Pa, 270 ℃ of temperature; Continue to be warming up to 283 ℃ then, and polycondensation 2 hours under vacuum tightness 50Pa, can obtain wherein that the phosphorus containing fire retardant copolyester monomer is 15wt%, nano barium sulfate is phosphor-containing flame-retardant copolyester/barium sulphate nano-composite material of 3wt%.
Embodiment 11
Measure ethylene glycol 1250mL, take by weighing dimethyl terephthalate (DMT) 2697g, 9, the 10-dihydro-9-oxy is assorted-and the assorted phenanthrene of 10-phosphinylidyne-Succinic Acid 333g adds in the reactor; Catalyst glycol antimony 1.2g joins in the pure terephthalic acid's dimethyl ester slurry that modulates, and is warming up to 235 ℃ under the normal pressure and carries out transesterification reaction 2.5 hours; After transesterification reaction finishes, take by weighing the nano barium sulfate glycolic suspension 3000g of the 10wt% for preparing in advance, add in the ester exchange offspring, rough vacuum 150Pa polycondensation 1 hour, 275 ℃ of temperature, high vacuum 50Pa polycondensation 1.5 hours, 285 ℃ of temperature, can obtain wherein that the phosphorus containing fire retardant copolyester monomer is 10wt%, nano barium sulfate is phosphor-containing flame-retardant copolyester/barium sulphate nano-composite material of 10wt%.
In order to show progressive of the present invention, the limiting viscosity of embodiment of the invention synthetic part nano composite material, glycol ether, fusing point, aggregated particle, spinning property etc. are measured, and contrast with the copolyesters and the conventional flame-proof copolyester that add powder barium sulfate, the results are shown in Table 1.
The mensuration of the limiting viscosity of all material, glycol ether, fusing point, aggregated particle is pressed the test of GB/T 14190-93 specific fibre grade polyester chip analytical procedure; The spinning property quality during mainly from spinning several angles such as strainer, unit replacement cycle, pre-oriented yarn (POY) full-rolling rate investigate, its grade standard is: strainer replacement cycle 〉=72 hour, unit replacement cycle 〉=20 day, the POY full-rolling rate is " good " more than 90%; Strainer replacement cycle 〉=60 hour, unit replacement cycle 〉=15 day, the POY full-rolling rate is " better " more than 90%; Strainer replacement cycle≤48 hour, unit replacement cycle≤12 day, the POY full-rolling rate is " generally " more than 90%; Strainer replacement cycle≤10 hour, unit replacement cycle≤7 day, the POY full-rolling rate is " poor " below 85%;
Table 1
| Material | Project | Comparative Examples | The present invention's (direct esterification) | |||||
| Blank | Powder | 1 | 2 | 3 | 4 | 5 | ||
| Barium sulfate | Content (%) | 0 | 3 | 1 | 3 | 5 | 8 | 10 |
| Particle diameter (nm) | 0 | ≥600 | ≤40 | ≤60 | ≤70 | ≤90 | ≤100 | |
| The copolymerization section | Limiting viscosity (dl/g) | 0.645 | 0.638 | 0.638 | 0.641 | 0.637 | 0.651 | 0.612 |
| Fusing point (℃) | 240 | 248 | 240 | 245 | 246 | 249 | 251 | |
| Second-order transition temperature (℃) | 65 | 70 | 76 | 77 | 76 | 80 | 78 | |
| Melt crystallization peak temperature (℃) | 175 | 182 | 195 | 198 | 205 | 202 | 203 | |
| End carboxyl (mmol/kg) | 27.5 | 28.1 | 27.2 | 27.6 | 28.1 | 27.1 | 27.5 | |
| Glycol ether content (%) | 3.1 | 2.8 | 3.2 | 2.7 | 2.6 | 2.3 | 2.1 | |
| Aggregated particle (individual/mg) | 0 | 7.300 | 0.000 | 0.000 | 0.000 | 0.025 | 0.500 | |
| Fiber | Spinning property | Good | Difference | Good | Good | Good | Better | Generally |
By table 1 as seen, along with barium sulfate adds the increase of concentration, its particle diameter in the copolyesters matrix increases, and spinning property descends, and mainly is that (particle diameter 〉=10um) the number increase causes because of the aggregated particle in the matrix material; But than the matrix material that adds powder barium sulfate, even if the weight percent concentration of adding reaches 8%, this matrix material still has spinning property preferably, and aggregated particle content is still very low.
In addition, for thermal characteristics, mechanical property and the flame retardant properties of investigating matrix material of the present invention, the present invention has also carried out test to the prepared phosphorous copolyester nano composite material of part embodiment, and it the results are shown in Table 2,3,4 (data of table 3 and table 4 are to adopt the standard batten of injection moulding to obtain).
Table 2
| Embodiment | Nano-inorganic substance content (%) | Heat decomposition temperature (℃) | Fusing point Tm (℃) | Melt crystallization peak temperature Tc (℃) | ΔT＝Tm-Tc (℃) |
| A | 0 | 396 | 240 | 175 | 65 |
| 1 | 1 | 398 | 240 | 195 | 45 |
| 2 | 3 | 405 | 245 | 198 | 47 |
| 3 | 5 | 408 | 246 | 205 | 41 |
| 4 | 8 | 416 | 249 | 202 | 47 |
| 5 | 10 | 421 | 251 | 203 | 48 |
Annotate: A is the blank Comparative Examples in the table 1, wherein is added with 9 of 10wt%, and the 10-dihydro-9-oxy is mixed-the assorted fire-retardant monomer of phenanthrene-Succinic Acid of 10-phosphinylidyne.
Table 3
| Embodiment | Nano-inorganic substance content (%) | Notched Izod impact strength (JM -1) | Tensile strength (MPa) | Extension at break (%) | Flexural strength (MPa) | Modulus in flexure (MPa) |
| A | 0 | 23 | 33 | 6 | 82 | 1600 |
| 1 | 1 | 31 | 37 | 10 | 95 | 2140 |
| 2 | 3 | 33 | 38 | 12 | 93 | 2356 |
| 3 | 5 | 26 | 34 | 11 | 86 | 2650 |
| 4 | 8 | 23 | 32 | 9 | 78 | 3465 |
| 5 | 10 | 18 | 26 | 5 | 81 | 3680 |
| 9 | 10 | 24 | 28 | 6 | 87 | 3390 |
| 11 | 10 | 20 | 24 | 5 | 80 | 3686 |
Annotate: A is the blank Comparative Examples in the table 1, wherein is added with 9 of 10wt%, and the 10-dihydro-9-oxy is mixed-the assorted fire-retardant monomer of phenanthrene-Succinic Acid of 10-phosphinylidyne.
The result of table 2 shows, heat decomposition temperature is progressively brought up to 421 ℃ with the increase of nano barium sulfate content, and fusing point also increases, and illustrates that the thermal characteristics of nano composite material of copolyester improves, the numerical value of Δ T is minimum reduces to 41 ℃, shows that crystal property improves simultaneously.
The result of table 3 shows that under the situation of nano barium sulfate low levels (below 3%), the mechanical property of nano composite material is improved preferably; But after content increased, except that modulus in flexure increased, other mechanical properties were by in various degree reduction.
Table 4
| Embodiment | Nano-inorganic substance content (%) | Vertical combustion rank (UL-94) | Oxygen index (%) | Molten drop number (twice ignite) |
| A | 0 | V-2 | 32 | 20 |
| 1 | 1 | V-2 | 32 | 18 |
| 2 | 3 | V-2 | 30 | 10 |
| 3 | 5 | V-0 | 28.5 | 3 |
| 4 | 8 | V-0 | 28 | 3 |
| 5 | 10 | V-0 | 27 | 0 |
| 9 | 10 | V-0 | 28.5 | 0 |
| 11 | 10 | V-0 | 27 | 0 |
Annotate: A is the blank Comparative Examples in the table 1, wherein is added with 9 of 10wt%, the assorted fire-retardant monomer of phenanthrene-Succinic Acid of assorted-10 phosphinylidynes of 10-dihydro-9-oxy.
By table 4 as seen, increase along with nano barium sulfate weight percent in matrix material, its oxygen index reduces gradually, but still can reach practical requirement, the vertical combustion rank increases, and when content is 5%, can arrive the highest level V-0 level of material vertical combustion, and the molten drop number obviously reduces, even molten drop no longer.
Table 5 is the physicals test result of pre-oriented yarn (POY) fiber of embodiment 1～7.Spinning speed 2800m/min, the position twin screw composite spinning machine that spinning equipment is produced with U.S. Hills company carry out spinning test, screw diameter 38mm, length-to-diameter ratio 30.Used detecting instrument is that the STATIMATM type that German Textechna company produces is stretched instrument by force, the dried instrument of USTER TESTER 3 type bars that Uster, Switzerland company produces.Fibrous physics index test standard is respectively GB/T14343-1993 filament of synthetic fibre and textured filament linear density experimental technique, GB/T14344-1993 filament of synthetic fibre and textured filament ultimate strength and extension at break experimental technique, GB/T14343-1993 chemical fiber filament electronics bar is done uneven rate experimental technique.
Table 5
| Embodiment | Linear density (dtex)/cv (%) | Breaking tenacity (cN/dtex)/(%) | Extension at break (%)/cv (%) | Bar is done uneven rate U (%) |
| 1 | 110.3/1.53 | 1.56/4.78 | 156.23/7.96 | 2.15 |
| 2 | 110.9/1.32 | 1.67/2.24 | 134.25/2.63 | 1.13 |
| 3 | 110.8/1.45 | 1.65/3.53 | 125.36/5.0 1 | 1.25 |
| 4 | 110.2/0.95 | 1.59/6.01 | 109.53/4.35 | 1.25 |
| 5 | 110.6/1.12 | 1.46/2.53 | 135.54/7.56 | 0.95 |
| 9 | 110.4/1.64 | 1.48/4.62 | 132.52/3.29 | 1.12 |
| 11 | 110.8/1.19 | 1.51/3.30 | 134.52/4.36 | 1.19 |
By table 5 as seen, its basic physical performance index of the POY fiber of each matrix material changes little, can reach the requirement of civilian fiber.
Claims (7)
1, a kind of phosphor-containing flame-retardant copolyester/barium sulphate nano-composite material, wherein contain phosphor-containing flame-retardant copolyester, it is characterized in that phosphor-containing flame-retardant copolyester is to be formed through esterification, polycondensation by terephthalic acid or dimethyl terephthalate (DMT), ethylene glycol and phosphorus containing fire retardant copolyester monomer, its content is 90～99.5% by weight percentage, and wherein used phosphorus containing fire retardant copolyester monomer is the compound with following formula:
Wherein, R is C
1～C
15Aliphatic group, aryl radical or fatty aryl radical, R
1Be alkyl or C
6Above aryl or benzyl; Or for having 9 of following formula, the 10-dihydro-9-oxy is mixed-the assorted luxuriant and rich with fragrance compounds of 10-phosphono:
R wherein
2Be C
3～C
15Aliphatic group, aryl radical or fatty aryl radical, X and Y are hydroxyl or carboxyl, can be identical, also can be inequality, and the barium sulfate that contains in this matrix material is 0.5～10% by weight percentage, its particle diameter≤100nm.
2,, it is characterized in that the barium sulfate that contains is 1～8% by weight percentage in this matrix material, its particle diameter≤90nm according to the described phosphor-containing flame-retardant copolyester/barium sulphate nano-composite material of claim 1.
3,, it is characterized in that the barium sulfate that contains is 3～8% by weight percentage in this matrix material, its particle diameter≤90nm according to the described phosphor-containing flame-retardant copolyester/barium sulphate nano-composite material of claim 1.
4, preparation method according to each described phosphor-containing flame-retardant copolyester/barium sulphate nano-composite material of claim 1～3, phosphor-containing flame-retardant copolyester is with terephthalic acid or dimethyl terephthalate (DMT) in this method, ethylene glycol, catalyzer and phosphorus containing fire retardant copolyester monomer add reactor together, and adopt conventional direct esterification method or indirect esterification process to carry out esterification, polycondensation is prepared from, wherein terephthalic acid or dimethyl terephthalate (DMT), ethylene glycol, the proportioning of catalyzer is conventional polymeric proportioning, it is characterized in that before esterification or the esterification aftercondensated before, adding is 0.5～10% nano barium sulfate suspension by weight percentage, and the phosphorus containing fire retardant copolyester monomer that adds should make it account for 1～20% by weight percentage in matrix material, and used phosphorus containing fire retardant copolyester monomer is the compound with following formula:
Wherein, R is C
1～C
15Aliphatic group, aryl radical or fatty aryl radical, R
1Be alkyl or C
6Above aryl or benzyl; Or for having 9 of following formula, the 10-dihydro-9-oxy is mixed-the assorted luxuriant and rich with fragrance compounds of 10-phosphono:
R
2Be C
3～C
15Aliphatic group, aryl radical or fatty aryl radical, X and Y are hydroxyl or carboxyl, can be identical, also can be inequality.
5, according to the preparation method of the described phosphor-containing flame-retardant copolyester/barium sulphate nano-composite material of claim 4, it is characterized in that before esterification or the esterification aftercondensated before, adding is 1～8% nano barium sulfate suspension by weight percentage, and the phosphorus containing fire retardant copolyester monomer that adds should make it account for 5～15% by weight percentage in matrix material.
6, according to the preparation method of the described phosphor-containing flame-retardant copolyester/barium sulphate nano-composite material of claim 4, it is characterized in that before esterification or the esterification aftercondensated before, adding is 3～8% nano barium sulfate suspension by weight percentage, and the phosphorus containing fire retardant copolyester monomer that adds should make it account for 5～15% by weight percentage in matrix material.
7,, it is characterized in that used catalyzer is selected from any in antimony glycol, the antimonous oxide according to the preparation method of claim 4 or 5 or 6 described phosphor-containing flame-retardant copolyester/barium sulphate nano-composite materials.
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| CN101376700B (en) * | 2007-08-30 | 2011-04-06 | 中国石化上海石油化工股份有限公司 | Preparation of flame-retardant polyester for preparing industrial yarn |
| CN101376694B (en) * | 2007-08-30 | 2011-07-20 | 中国石化上海石油化工股份有限公司 | Preparation of flame-retardant polyester for preparing industrial fibre |
| CN101532189B (en) * | 2009-04-07 | 2011-01-12 | 江苏中鲈科技发展股份有限公司 | Flame retardant PTT polyester fiber and production method thereof |
| CN101851811B (en) * | 2010-06-03 | 2011-09-21 | 江阴博伦化纤有限公司 | Method for preparing flame-retardant and anti-dripping polyester fiber |
| JP6005070B2 (en) * | 2012-01-27 | 2016-10-12 | 株式会社クラレ | Polyester composite fiber with excellent heat insulation and color development |
| CN104045821B (en) * | 2014-06-17 | 2016-04-06 | 四川大学 | Phosphoric flame-proof copolyester ionomer/nano composite material and preparation method thereof |
| CN106243332B (en) * | 2016-08-31 | 2018-08-31 | 浙江省现代纺织工业研究院 | A kind of manufacturing method of enhanced flame-proof anti-aging polyester film |
| CN115594833A (en) * | 2021-07-08 | 2023-01-13 | 中国石油天然气股份有限公司（Cn） | Flame-retardant matte polyethylene glycol terephthalate composite material and preparation method thereof |
| CN114957636B (en) * | 2022-06-14 | 2023-05-16 | 四川轻化工大学 | Phosphorus-containing flame-retardant copolymerization type PBS (Poly Butylene succinate) and preparation method thereof |
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|---|---|---|---|---|
| CN1192444A (en) * | 1998-02-20 | 1998-09-09 | 华南理工大学 | Method for preparing polymer nanometre composite material |
| DE19828536A1 (en) * | 1998-06-26 | 1999-12-30 | Bayer Ag | Fire-resistant polycarbonate-graft copolymer molding material, useful for the production of molded products, e.g. housings for monitors, printers, copiers etc. |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1192444A (en) * | 1998-02-20 | 1998-09-09 | 华南理工大学 | Method for preparing polymer nanometre composite material |
| DE19828536A1 (en) * | 1998-06-26 | 1999-12-30 | Bayer Ag | Fire-resistant polycarbonate-graft copolymer molding material, useful for the production of molded products, e.g. housings for monitors, printers, copiers etc. |
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