CN101376738B - Flame-retardant polyester composition for preparing industrial polyester fibre - Google Patents
Flame-retardant polyester composition for preparing industrial polyester fibre Download PDFInfo
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- CN101376738B CN101376738B CN2007100453868A CN200710045386A CN101376738B CN 101376738 B CN101376738 B CN 101376738B CN 2007100453868 A CN2007100453868 A CN 2007100453868A CN 200710045386 A CN200710045386 A CN 200710045386A CN 101376738 B CN101376738 B CN 101376738B
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Abstract
The invention relates to a flame-retardant polyester compound used for manufacturing industrial polyester fiber which includes the components as follows: a) the polyester of a reaction type flame-retardant which comprises a structural formula I is formed by the copolycondensation of terephthalic acid, glycol, pentaerythritol and the flame-retardant. In the formula I, R1 refers to the C1-C4 alkylidene ; R2 and R3 respectively refer to H or C2-C4 hydroxyalkyl, the content of the pentaerythritol in the polyester is 0.01 to 0.10wt percent, the content of the flame-retardant in the polyester is 2 to 10wt percent, the characteristic viscidity of the polyester is 0.60 to 0.75 dl/g; and b) a nucleating agent which relates to the grain of nano-Kaolin with an average grain diameter of 200 to 600nm. The nucleating agent is uniformly stored in the polyester compound and the content of the nucleating agent is 0.06 to 1.0wt percent. The departure on the thermal transformation performance existed between the flame-retardant polyester compound and the normal polyester is remarkably reduced; the manufacturing industrial polyester fiber can be produced by adopting the normal polyester fiber manufacture device and technique.
Description
Technical field
The present invention relates to a kind of flame retardant polyester composition, particularly be used for process industry with trevira, contain the flame retardant polyester composition that phosphorus is organic reaction type fire retardant.
Background technology
Polyester development in recent years with flame retardant properties is rapid, the Application Areas of product relates to civilian and industrial, wherein the application of fire-retardant polyester fibre is then extensive, especially consumption is just at the indusrial polyester fiber of sustainable growth, and possessing excellent flame-retardant performance becomes its basic performance requriements gradually.The fire retardant that flame retardant polyester adopts mainly comprises three types: addition type, copolyreaction type and back arrangement type, comparatively speaking, copolyreaction type flame retardant polyester finally is present on the macromolecular chain of polyester because of fire retardant, so flame retardant properties is more stable and long-acting.Phosphorus is the flame retardant properties excellence of reactive flame retardant, and environmental friendliness, is acknowledged as one of optimal polyester flame-retardant agent, uses the flame retardant polyester product of this based flame retardant also to become the main flow of research and development.
Employing phosphorus is that the flame retardant polyester of reactive flame retardant also can be described as phosphorous copolyester, the introducing of fire retardant has destroyed the regularity of macromolecular structure, thereby cause its heat deflection performance that tangible change has taken place, the change of this heat deflection performance is particularly outstanding to the manufacturing processing adverse effect of indusrial polyester fiber.In order to obtain higher modulus, be used for process industry and pass through its limiting viscosity of the incompatible increase of solid polycondensation again with the common needs of the polyester of trevira, just because the change of heat deflection performance, in carrying out drying crystalline and solid state polymerization processes, serious adhesion caking phenomenon can take place in phosphorous copolyester, makes that drying crystalline and solid state polymerization processes are difficult to carry out smoothly.In the prior art, people have to by taking to reduce pre-Tc, drying temperature, slow down temperature rise rate, prolong time of drying, using the intermittent type vacuum drum drying plant that falls behind, reduce measures such as solid phase polymerization temperature and prolongation polymerization time and overcome, this has just increased production cost greatly and has reduced production efficiency.The change of this heat deflection performance disadvantageous effect that manufacturing brings to fiber also is present in the spinning drafting process, and it is stable that it will make that the drawing-off operating procedure is difficult for.
In the prior art, the technical scheme release that much is intended to improve the phosphorous copolyester thermal characteristics is arranged.Introduce by in flame retardant polyester, adding inorganic additive as Chinese patent 02133602.4, Chinese patent application 200510021959.4 and can improve its thermal characteristics, can obviously reduce the generation of melt drippage after the flame retardant polyester fusion.But it is bigger that existing these methods add the amount of inorganic additivess, and additive level reaches 5wt% and just brings about tangible results when above in the polyester, the highest even reach 10wt% or 30wt%.This has been similar in fact, and the adding inorganic filler improves its thermal characteristics in phosphorous copolyester, it is little for making the influence of film or other moulded product to mix the higher inorganic particulate matter of content in the polymer melt, but to spinning processing obviously is disadvantageous, causes broken end, filament spinning component life cycle to shorten during as spinning easily; Yielding stress reduces and influences macromolecular orientation degree etc. during drawing-off, and the latter will directly influence the mechanical property of fiber product.
Existing technical scheme all proposes to attempt to dwindle departing from that phosphorous copolyester and normal polyester exist clearly on the heat deflection performance, and for the manufacturing firm of trevira, dwindling phosphorous copolyester and normal polyester departing from the heat deflection performance should expect the most, because the manufacturing difficulty of processing that this will reduce fiber greatly reduces production costs effectively.
Summary of the invention
The invention provides a kind of process industry that is used for the flame retardant polyester composition of trevira, its technical problem to be solved is to dwindle flame retardant polyester and departing from that normal polyester produces on the heat deflection performance, thereby overcomes the defective of prior art existence.Simultaneously, require the technical measures itself solve the problems of the technologies described above can the performance of the manufacturing of fire-retardant polyester fibre or the product that makes not to be had a negative impact.
Below be the technical scheme that the present invention solves the problems of the technologies described above:
A kind of flame retardant polyester composition that is used for process industry with trevira, the component of said composition comprises:
A) contain the polyester of reactive flame retardant, this polyester is formed by terephthalic acid, ethylene glycol, tetramethylolmethane and fire retardant copolycondensation, and fire retardant is the compound with following structural formula:
R wherein
1Be the alkylidene group of C1～C4, R
2And R
3Respectively the do for oneself hydroxyalkyl of H or C2～C4,
The content of tetramethylolmethane in polyester is 0.01～0.10wt%, and the content of fire retardant in polyester is 2～10wt%, and the limiting viscosity of polyester is 0.60～0.75dl/g;
B) nucleator, this nucleator are the nano kaoline particle, and its median size is 200～600nm;
Nucleator is present in the polymer blend equably, and the content in polymer blend is 0.06～1.0wt%.
Above-mentioned nucleator nano kaoline particulate median size is preferably 200～500nm; The content of nucleator in polymer blend is preferably 0.2～0.9wt%; The limiting viscosity of polyester is preferably 0.60～0.70dl/g.
Existing studies show that, Chang Gui polyester relatively, the second-order transition temperature T of phosphorous copolyester
g, fusing point T
mReduce, and cold crystallization peak temperature T
HcRaising, fusion-crystallization peak temperature T
CcReduce, this crystallizing power that is indicating phosphorous copolyester descends, be that crystallization rate descends, and the change of this crystal property should be to cause phosphorous copolyester to be difficult for stable main and direct reason at drying crystalline, solid state polymerization processes generation adhesion caking, drawing-off operating procedure.The contriver has given one's full attention to this point, and has finished technical scheme of the present invention in view of the above.
Key of the present invention is to adjust its heat deflection performance by introduce a kind of suitable nucleator in phosphorous copolyester, really, in superpolymer, introduce nucleator in right amount and can promote the crystalline generation and accelerate crystallization rate to be well-known, yet, will find a kind of suitable and ideal nucleator pointedly is not apparent also, and this relates to the dispersibility of nucleator in polyester, nucleator is as the ability of nucleus to promoting that crystal generates, the negative impact that the introducing of nucleator may bring spinning and post-treatment performance, the problems such as possibility that cause the form and aspect variation.
The contriver screens the multiple material that may possess nucleogenesis by a large amount of experiments, finds that finally above-mentioned nano kaoline is ideal as the nucleator of above-mentioned phosphorous copolyester, and this also is the place of another key of the present invention.Characteristics such as this nucleator has easy dispersion, and is easy to operate generate, accelerate crystallization rate to the crystal that promotes above-mentioned phosphorous copolyester and have very ideal effect.Required add-on is very little, thereby can make the various negative impacts that introducing produced by nucleator be controlled at minimum degree.Know by experimental result, when the add-on of nucleator is 0.2wt% when above, the second-order transition temperature T of phosphorous copolyester
g, fusing point T
m, that crystallization rate etc. characterizes the critical index and the normal polyester of heat deflection performance is very approaching.Production application by reality is also found, the drying crystalline that adopts general continuous drying equipment and adopt conventional section drying process condition to cut into slices, and adopt conventional processing condition to carry out solid state polymerization, the adhesion caking phenomenon obviously reduces even disappears, and post-treatment processes such as spinning process and drawing-off are also highly stable.
The adition process of nucleator is comparatively easy, can be earlier the dibasic alcohol of one of monomer of itself and polyester be mixed with slurry, and being milled, to disperse redilution be the nucleator annex solution.Annex solution can add system with other raw material before esterification is carried out, also can be before esterification finishes aftercondensated reaction and carries out the adding system.Nucleator adopts mixing of reaction process with polyester, is uniformly distributed in the polyester with can guaranteeing the nucleator high dispersing.
Raw material as spinning, the various additives that also can add other in the above-mentioned flame retardant polyester composition as required, as matting agent, be used to prevent that polyester from producing the pyrolysated stablizer, adjusting the toning agent of form and aspect etc., this and prior art are identical, and are known by those of ordinary skill in the art.
Compared with prior art, departing from obviously that flame retardant polyester composition provided by the invention and normal polyester exist on the heat deflection performance dwindled, and can satisfy fiber manufacturing firm fully and adopt conventional trevira producing apparatus and technology to come the requirement of manufacture usefulness fire-retardant polyester fibre stably.Simultaneously, just, make the decline of fibrous mechanical property also be improved owing to dwindling that the heat deflection performance departs from.On the other hand, because the add-on of nucleator is very low, itself is little of the degree that can ignore fully in the negative impact that the spinning processing process produces to polyester.
Below will the invention will be further described by specific embodiment, because essence of the present invention is to have introduced a kind of nucleator in phosphorous copolyester, other parts and prior art are basic identical.And those skilled in the art can predict, and other parts change back the present invention can obtain identical effect equally, because the possible variation of other parts will only be the identical replacement of proterties.One of monomer in polyester tetramethylolmethane is the chainextender of solid state polymerization, helps the increase of limiting viscosity, and this also is known in prior art.So embodiment will pay attention to enumerating and describing of nucleator especially.
Embodiment
[embodiment 1～8]
Be used for the flame retardant polyester composition of process industry with trevira, its component comprises:
A) contain the polyester of reactive flame retardant, form by terephthalic acid, ethylene glycol, tetramethylolmethane and fire retardant copolycondensation.Fire retardant is the compound with following structural formula:
Wherein, R
1Be methylene radical, R
2, R
3Be hydroxyethyl;
The content of tetramethylolmethane in polyester is controlled to be 0.05～0.10wt%, and the limiting viscosity of polyester is controlled to be 0.60～0.70dl/g, and the content of fire retardant in polyester sees Table 1;
B) nucleator is the nano kaoline particle, and median size is 200～500nm, and nucleator is present in the polymer blend equably, and the content of nucleator in polymer blend sees Table 1.
[comparative example 1]
Do not add nucleator in the flame retardant polyester composition, other is with embodiment 1～8.
[comparative example 2]
By the normal polyester that terephthalic acid and ethylene glycol polycondensation form, limiting viscosity is controlled to be 0.60～0.70dl/g.
Measure the physical index that embodiment and comparative example flame retardant polyester composition or normal polyester reflect heat change performance, and other main quality index, data see Table 2.
Table 1.
| Nucleator content (wt%) in the polymer blend | Flame retardant agent content in the polyester (wt%) | |
| Embodiment 1 | 0.6 | 8 |
| Embodiment 2 | 0.5 | 5 |
| Embodiment 3 | 0.4 | 3 |
| Embodiment 4 | 1.0 | 10 |
| Embodiment 5 | 0.2 | 5 |
| Embodiment 6 | 0.8 | 8 |
| Embodiment 7 | 0.06 | 2 |
| Embodiment 8 | 0.9 | 8 |
| Comparative example 1 | - | 8 |
| Comparative example 2 | - | - |
Table 2.
Annotate: T
gBe second-order transition temperature; T
mBe fusing point; t
1/2Be the hypocrystalline time.
By the data of table 2 as seen, the flame retardant polyester composition of the foregoing description obviously dwindles with the conventional deviation of polyester (comparative example 2) on the heat deflection performance, particularly directly reflects the t of crystallization rate
1/2Very approaching with the data of normal polyester.
The flame retardant polyester composition of the foregoing description adopts conventional trevira producing apparatus and technology process industry trevira, the adhesion caking phenomenon does not all appear in chip drying crystallization, solid state polymerization processes, post-treatment such as spinning process and drawing-off process is also highly stable, and making fiber number is the DTY industrial filament of 167dtex/36f.The fabric of making is tested according to GB GB/T5454-1997, GB/T 5455-1997, and limiting oxygen index(LOI) (LOI) reaches more than 32%, and combustionproperty reaches " difficult combustion " B1 grade standard.
Claims (4)
1. one kind is used for the flame retardant polyester composition that process industry is used trevira, and the component of said composition comprises:
A) contain the polyester of reactive flame retardant, this polyester is formed by terephthalic acid, ethylene glycol, tetramethylolmethane and fire retardant copolycondensation, and fire retardant is the compound with following structural formula:
R wherein
1Be the alkylidene group of C1～C4, R
2And R
3Respectively the do for oneself hydroxyalkyl of H or C2～C4,
The content of tetramethylolmethane in polyester is 0.01～0.10wt%, and the content of fire retardant in polyester is 2～10wt%, and the limiting viscosity of polyester is 0.60～0.75dl/g;
B) nucleator, this nucleator are the nano kaoline particle, and its median size is 200～600nm,
Nucleator is present in the polymer blend equably, and the content in polymer blend is 0.06～1.0wt%.
2. flame retardant polyester composition according to claim 1 is characterized in that described nucleator nano kaoline particulate median size is 200～500nm.
3. flame retardant polyester composition according to claim 1 is characterized in that the content of described nucleator in polymer blend is 0.2～0.9wt%.
4. flame retardant polyester composition according to claim 1, the limiting viscosity that it is characterized in that described polyester is 0.60～0.70dl/g.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100453868A CN101376738B (en) | 2007-08-30 | 2007-08-30 | Flame-retardant polyester composition for preparing industrial polyester fibre |
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|---|---|---|---|
| CN2007100453868A CN101376738B (en) | 2007-08-30 | 2007-08-30 | Flame-retardant polyester composition for preparing industrial polyester fibre |
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| CN101376738B true CN101376738B (en) | 2011-07-20 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1127764A (en) * | 1995-11-21 | 1996-07-31 | 南亚塑胶工业股份有限公司 | Method for modification of colour of flame retardant polyester |
| US5955565A (en) * | 1996-12-28 | 1999-09-21 | Eastman Chemical Company | Polyesters from terephthalic acid, 2,2,4,4-tetramethyl-1,3-cyclobutanediol and ethylene glycol |
-
2007
- 2007-08-30 CN CN2007100453868A patent/CN101376738B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1127764A (en) * | 1995-11-21 | 1996-07-31 | 南亚塑胶工业股份有限公司 | Method for modification of colour of flame retardant polyester |
| US5955565A (en) * | 1996-12-28 | 1999-09-21 | Eastman Chemical Company | Polyesters from terephthalic acid, 2,2,4,4-tetramethyl-1,3-cyclobutanediol and ethylene glycol |
Non-Patent Citations (1)
| Title |
|---|
| JP特开2006-169359A 2006.06.29 |
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