CN101376688B - Flame-retardant polyester composition for preparing fibre - Google Patents
Flame-retardant polyester composition for preparing fibre Download PDFInfo
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- CN101376688B CN101376688B CN2007100453745A CN200710045374A CN101376688B CN 101376688 B CN101376688 B CN 101376688B CN 2007100453745 A CN2007100453745 A CN 2007100453745A CN 200710045374 A CN200710045374 A CN 200710045374A CN 101376688 B CN101376688 B CN 101376688B
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Abstract
A flame-retardant polyester combination used for manufacturing fiber comprises the following components: a) polyester, containing a reactive flame retardant having a structural formula I, and being formed by polycondensating phthalic acid, dihydric alcohol and a flame retardant, wherein the phthalic acid is ethylene glycol, 1,3-propanediol or 1,4-butanediol, R1 in the structural formula I is C1-C4 alkylidene, R2 and R3 are respectively H or C2-C4 hydroxyalkyl, the content of the flame retardant in the polyester is 2 wt% to 10 wt%, and the intrinsic viscosity of the polyester is 0.60 to 0.75 dl/g; and b) a nucleating agent which is nano kaolin particles with the average particle diameter being 200 to 600 nm, and uniformly exists in the polyester combination with the content being 0.05 wt% to 0.9 wt%. The deviation of the thermal transformation performance existing between the conventional polyester and the flame-retardant polyester combination is obviously reduced, so that the conventional polyester fiber manufacturing equipment and the manufacturing process thereof can be adopted to reliably manufacture the flame-retardant polyester fiber.
Description
Technical field
The present invention relates to a kind of flame retardant polyester composition, particularly be used to make fiber, 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, and the Application Areas of product relates to civilian and industrial, and wherein the application of fire-retardant polyester fibre is then extensive.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, and the introducing of fire retardant has destroyed the regularity of macromolecular structure, thereby causes its heat deflection performance that tangible change has taken place.The change of this heat deflection performance has brought adverse influence to the manufacturing of trevira processing, apparent in view is polyester slice drying and the crystallisation process caking that very easily sticks together before spinning.In the prior art, people have to by taking to reduce pre-Tc, drying temperature and slow down temperature rise rate, prolong time of drying, use the measures such as intermittent type vacuum drum drying plant that fall behind to overcome the adhesion caking phenomenon of section, and 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 will make the drawing-off operating procedure be difficult to stablize.
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 this will help using conventional trevira producing apparatus and technology stably to produce fire-retardant fibre.
Summary of the invention
The invention provides a kind of flame retardant polyester composition that is used to make fiber, its technical problem to be solved is to dwindle departing from that flame retardant polyester and normal polyester produce on the heat deflection performance, so that its easier trevira producing apparatus and technology by routine is stably made the fire-retardant fibre product, 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 to make fiber, the component of said composition comprises:
A) contain the polyester of reactive flame retardant, this polyester is formed by terephthalic acid, dibasic alcohol and fire retardant polycondensation, and dibasic alcohol is an ethylene glycol, 1, ammediol or 1, and 4-butyleneglycol, fire retardant are 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 fire retardant in polyester is 2～10wt%, 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 0.05～0.9wt%.
Above-mentioned polyester is preferably formed by terephthalic acid, ethylene glycol and fire retardant polycondensation; 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 process 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, even the drying that adopts general continuous drying equipment and adopt conventional section drying process condition to cut into slices, do not produce the adhesion caking phenomenon yet, post-treatment such as spinning process and drawing-off process is also highly stable, and makes the course of processing and adopted and the essentially identical processing parameter of normal polyester.
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 the requirement that fiber manufacturing firm adopts conventional trevira producing apparatus and technology stably to produce fire-retardant fibre fully.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.So embodiment will only pay attention to enumerating and describing of nucleator.
Embodiment
[embodiment 1～8]
Be used to make the flame retardant polyester composition of fiber, its component comprises:
A) contain the polyester of reactive flame retardant, form by terephthalic acid, ethylene glycol and fire retardant polycondensation.Fire retardant is the compound with following structural formula:
Wherein, R
1Be methylene radical, R
2, R
3Be hydroxyethyl;
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 | 0.9 | 8 |
| Embodiment 2 | 0.9 | 10 |
| Embodiment 3 | 0.5 | 5 |
| Embodiment 4 | 0.6 | 5 |
| Embodiment 5 | 0.2 | 5 |
| Embodiment 6 | 0.05 | 2 |
| Embodiment 7 | 0.5 | 8 |
| Embodiment 8 | 0.8 | 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 to make fire-retardant polyester fibre, the adhesion caking phenomenon does not appear when chip drying, post-treatment such as spinning process and drawing-off process is also highly stable, and making fiber number is the DTY silk of 167dtex/36f.The fabric of making is tested according to GB GB/T 5454-1997, GB/T 5455-1997, and limiting oxygen index(LOI) (LOI) reaches more than 32%, and combustionproperty reaches " difficult combustion " B1 grade standard.
Claims (5)
1. flame retardant polyester composition that is used to make fiber, the component of said composition comprises:
A) contain the polyester of reactive flame retardant, this polyester is formed by terephthalic acid, dibasic alcohol and fire retardant polycondensation, and dibasic alcohol is an ethylene glycol, 1, ammediol or 1, and 4-butyleneglycol, fire retardant are 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 fire retardant in polyester is 2～10wt%, 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 0.05～0.9wt%.
2. flame retardant polyester composition according to claim 1 is characterized in that described polyester is formed by terephthalic acid, ethylene glycol and fire retardant polycondensation.
3. flame retardant polyester composition according to claim 1 is characterized in that described nucleator nano kaoline particulate median size is 200～500nm.
4. 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%.
5. 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 |
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| CN2007100453745A CN101376688B (en) | 2007-08-30 | 2007-08-30 | Flame-retardant polyester composition for preparing fibre |
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| CN2007100453745A CN101376688B (en) | 2007-08-30 | 2007-08-30 | Flame-retardant polyester composition for preparing fibre |
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| CN101376688B true CN101376688B (en) | 2011-07-20 |
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| CN110396181B (en) * | 2018-04-24 | 2021-12-07 | 中国石油化工股份有限公司 | Fast crystallization polyester and preparation method of hot-filling polyester bottle chip thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1894456A (en) * | 2003-12-17 | 2007-01-10 | 东洋纺织株式会社 | Non-woven fabric for manufacturing vehicle formed article and use thereof |
| CN101709137A (en) * | 2009-11-25 | 2010-05-19 | 四川大学 | Phosphorus-containing PTT fire-resistant copolyesters/ nano composite material and preparation method thereof |
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- 2007-08-30 CN CN2007100453745A patent/CN101376688B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1894456A (en) * | 2003-12-17 | 2007-01-10 | 东洋纺织株式会社 | Non-woven fabric for manufacturing vehicle formed article and use thereof |
| CN101709137A (en) * | 2009-11-25 | 2010-05-19 | 四川大学 | Phosphorus-containing PTT fire-resistant copolyesters/ nano composite material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| JP特开2005-296825A 2005.10.27 |
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