CN101376698B - Preparation of flame-retardant polyester for preparing fibre - Google Patents
Preparation of flame-retardant polyester for preparing fibre Download PDFInfo
- Publication number
- CN101376698B CN101376698B CN2007100453853A CN200710045385A CN101376698B CN 101376698 B CN101376698 B CN 101376698B CN 2007100453853 A CN2007100453853 A CN 2007100453853A CN 200710045385 A CN200710045385 A CN 200710045385A CN 101376698 B CN101376698 B CN 101376698B
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- polycondensation
- retardant polyester
- polyester
- add
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A method for preparing flame-retardant polyester for manufacturing fiber comprises the following steps: 1) carrying out the esterification of monomer terephthalic acid and ethylene glycol; and 2) adding a reactive flame retardant having a structural formula I to the esterification products, and sequentially carrying out the pre-polymerization reaction and the polycondensation reaction in the presence of a polycondensation catalyst to obtain the polycondensation product, that is, the flame-retardant polyester, wherein R in the structural formula I is hydroxyalkyl or carboxyalkyl of C1 to C4. Nano kaolin particles which serve as a flame-retardant polyester crystallization nucleating agent are added to the reaction system, wherein the nano kaolin particles are added before the esterificationor before the pre-polymerization reaction, and the adding amount by the content of the nano kaolin particles existing in the polycondensation products at the end is 0.05 wt% to 1.0 wt%. The deviationof the thermal transformation performance existing between the conventional polyester and the prepared flame-retardant polyester 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 fiber.
Description
Technical field
The present invention relates to a kind of preparation method of flame retardant polyester, particularly be used to make fiber, contain the preparation method that phosphorus is the flame retardant polyester of 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 is linked 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 preparation method who makes fiber with flame retardant polyester, its technical problem to be solved is that the flame retardant polyester that makes is dwindled and departing from that normal polyester produces on the heat deflection performance, thereby make its easier trevira producing apparatus and technology stably make the fire-retardant fibre product by routine, simultaneously, the technical measures itself that require to solve the problems of the technologies described above can not produce adverse influence to the manufacturing of fire-retardant polyester fibre or the product performance that make.
Below be the technical scheme that the present invention solves the problems of the technologies described above:
A kind of preparation method who makes fiber with flame retardant polyester, this method may further comprise the steps:
1) monomers terephthalic acid and ethylene glycol carry out esterification, and the monomeric charge mol ratio is a terephthalic acid: ethylene glycol=100: 110～200, temperature of reaction are 260～280 ℃, and reaction pressure is 100～300kPa, and reactant residence time is 1.5～4 hours;
2) add reactive flame retardant in the esterification products, carry out prepolymerization reaction and polycondensation successively and obtain the polycondensation product flame retardant polyester in the presence of polycondensation catalyst, reactive flame retardant is the compound with following structural formula:
R is hydroxyalkyl or the carboxyalkyl of C1～C4 in the structural formula, the add-on of reactive flame retardant is a benchmark with the charging capacity of monomers terephthalic acid, the weight ratio of terephthalic acid and reactive flame retardant is 100: 1.40～7.50, the making beating of reactive flame retardant spent glycol mixes, add in the esterification products after being mixed with the slurry that concentration is 20～45wt%
Prepolymerization reaction and polycondensation are all carried out under negative pressure, temperature of reaction is 270～285 ℃, reactant residence time respectively is 1～3 hour, the vacuum tightness of prepolymerization reaction is 1.0～2.0kPa, the vacuum tightness of polycondensation is 0.1～0.2kPa, and the limiting viscosity of polycondensation product is controlled to be 0.60～0.75dl/g.
In reactive system, add nano kaoline particle as the flame retardant polyester crystallization nucleating agent, nano kaoline particulate median size is 200～600nm, its adding mode is for adding before esterification or adding before prepolymerization reaction, and nano kaoline particulate add-on is counted 0.05～1.0wt% with the content that it finally is present in the polycondensation product.
Above-mentioned nano kaoline particulate median size is preferably 200～500nm; Nano kaoline particulate add-on is preferably 0.3～1.0wt% in the content that it finally is present in the polycondensation product.
The limiting viscosity of polycondensation product preferably is controlled to be 0.60～0.70dl/g.
When nano kaoline particulate adding mode is fashionable for adding before esterification, the nano kaoline particle can be pulled an oar with the raw material of esterification and mix back adding reactive system; Before nano kaoline particulate adding mode is prepolymerization reaction, add fashionable, the nano kaoline particle can be pulled an oar with reactive flame retardant and ethylene glycol and be hybridly prepared into the slurry that total concn is 20～45wt%, the nano kaoline particle adds reactive system with reactive flame retardant.
Above-mentioned polycondensation catalyst can be taken from any in antimony glycol, antimony acetate or the antimonous oxide; The consumption of polycondensation catalyst is a benchmark with monomers terephthalic acid weight, in antimony ion, is 120～300mg/kg.
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 that the process in esterification or polycondensation has added an amount of nano kaoline in system, makes and introduces a kind of suitable crystallization nucleating agent in the phosphorous copolyester that makes, and then adjust its heat deflection performance.Can promote the crystalline generation and accelerate crystallization rate to be well-known though in superpolymer, introduce nucleator in right amount, yet, will find a kind of suitable and ideal nucleator pointedly is not apparent also, and this relates to the negative impact that the dispersibility of nucleator in polyester, nucleator may bring spinning and post-treatment performance the introducing of the ability that promotes crystal to generate, nucleator as nucleus, 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.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 can be controlled at minimum degree.Know that by experimental result the nucleator in being present in phosphorous copolyester is 0.3wt% 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 adding of nucleator 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.
Should say that except adding an amount of nano kaoline particle as the crystallizing polyester nucleator in esterification or polycondensation process, other parts and prior art in the technical solution of the present invention are basic identical in system.And as the raw material of spinning, the various additives that also can add other in the above-mentioned flame retardant polyester 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., everything is those of ordinary skill in the art and knows.
Compared with prior art, departing from obviously that flame retardant polyester that the present invention makes 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 because dwindling of departing from of heat deflection performance, make the decline of mechanical property of fiber also be improved.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 added in system in esterification or polycondensation process a kind of crystallization nucleating agent of polyester, and 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.So embodiment will pay attention to relating in the technical solution of the present invention description of nucleator partial content.
Embodiment
[embodiment 1～4]
One, esterification process:
Monomers terephthalic acid and ethylene glycol carry out esterification, and the monomeric charge mol ratio is a terephthalic acid: ethylene glycol=100: 110～200, temperature of reaction are 260～280 ℃, and reaction pressure is 100～300kPa, and reactant residence time is 1.5～4 hours.
The adding mode of nano kaoline adds before being chosen in esterification.When raw material pulping mixes, the nano kaoline particle of aequum is joined in the esterification feed, nano kaoline particulate median size is 200～500nm.The concrete nano kaoline batch sizes of particles of each embodiment is pressed in the flame retardant polyester product nano kaoline content and is determined that nano kaoline content sees Table 1 in the flame retardant polyester product of each embodiment;
Two, precondensation and polycondensation process:
Add the reactive flame retardant of aequum in the esterification products, in the presence of polycondensation catalyst, carry out prepolymerization reaction and polycondensation successively and obtain the polycondensation product flame retardant polyester.
Reactive flame retardant is the compound with following structural formula:
The add-on of reactive flame retardant is a benchmark with the charging capacity of monomers terephthalic acid, and the weight ratio of terephthalic acid and reactive flame retardant is 100: 1.40～7.50, and flame retardant agent content sees Table 1 in the concrete data of each embodiment and the flame retardant polyester product.Reactive flame retardant mixes with the ethylene glycol making beating, is mixed with the slurry that concentration is 20～45wt%, adds reactive system by the oligopolymer pipeline then.
Prepolymerization reaction and polycondensation are all carried out under negative pressure, and temperature of reaction all is controlled to be 270～285 ℃, and reactant residence time respectively is controlled to be 1～3 hour.The vacuum degree control of prepolymerization reaction is 1.0～2.0kPa, and the vacuum degree control of polycondensation is 0.1～0.2kPa.
Polycondensation catalyst adopts antimony glycol, and consumption is a benchmark with monomers terephthalic acid weight, in antimony ion, is controlled to be 120～300mg/kg.
Polycondensation promptly gets the polycondensation product flame retardant polyester product after finishing, and its limiting viscosity is controlled to be 0.60～0.70dl/g.
[embodiment 5～8]
The adding mode of nano kaoline changes into before polycondensation and adding, the nano kaoline particle is mixed with reactive flame retardant and ethylene glycol making beating, be mixed with the slurry that total concn is 20～45wt%, add reactive system by the oligopolymer pipeline with reactive flame retardant then.All the other are with embodiment 1～4.
[comparative example 1]
Do not add nano kaoline in the reactive system, other is with embodiment 1～4.
[comparative example 2]
Terephthalic acid and ethylene glycol are made normal polyester through esterification, precondensation and polycondensation, and limiting viscosity is controlled to be 0.60～0.70dl/g.
Get flame retardant polyester composition or normal polyester that embodiment and comparative example make, measure physical index and other main quality index that its reflect heat changes performance, data see Table 2.
Table 1.
| Nucleator nano kaoline content (wt%) in the product | Terephthalic acid: reactive flame retardant (weight ratio) | Flame retardant agent content in the product (wt%) | |
| Embodiment 1 | 0.8 | 100∶7.27 | 5 |
| Embodiment 2 | 1.0 | 100∶7.27 | 5 |
| Embodiment 3 | 0.05 | 100∶1.45 | 1 |
| Embodiment 4 | 0.6 | 100∶4.36 | 3 |
| Embodiment 5 | 0.3 | 100∶2.91 | 2 |
| Embodiment 6 | 0.7 | 100∶7.27 | 5 |
| Embodiment 7 | 0.5 | 100∶5.81 | 4 |
| Embodiment 8 | 0.9 | 100∶7.27 | 5 |
| Comparative example 1 | — | 100∶5.81 | 4 |
| Comparative example 2 | — | — | — |
Table 2.
| T g(℃) | T m(℃) | t 1/2min | Glycol ether content (wt%) | Content of carboxyl end group (mol/t) | Form and aspect (B value) | |
| Embodiment 1 | 76 | 256 | 1.358 | 2.89 | 26 | 3.9 |
| Embodiment 2 | 77 | 256 | 1.332 | 2.88 | 28 | 4.0 |
| Embodiment 3 | 79 | 260 | 1.317 | 2.48 | 26 | 2.0 |
| Embodiment 4 | 79 | 258 | 1.365 | 2.50 | 27 | 2.9 |
| Embodiment 5 | 80 | 258 | 1.380 | 2.49 | 29 | 3.0 |
| Embodiment 6 | 76 | 256 | 1.370 | 2.90 | 27 | 4.1 |
| Embodiment 7 | 78 | 257 | 1.398 | 2.51 | 27 | 3.4 |
| Embodiment 8 | 77 | 256 | 1.342 | 2.88 | 28 | 3.9 |
| Comparative example 1 | 74 | 250 | 2.019 | 2.50 | 26 | 3.4 |
| Comparative example 2 | 79 | 259 | 1.32 | 2.60 | 26 | 2.0 |
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/T5454-1997, GB/T5455-1997, and limiting oxygen index(LOI) (LOI) reaches more than 32%, and combustionproperty reaches " difficult combustion " B1 grade standard.
Claims (7)
1. make the preparation method that fiber is used flame retardant polyester for one kind, this method may further comprise the steps:
1) monomers terephthalic acid and ethylene glycol carry out esterification, and the monomeric charge mol ratio is a terephthalic acid: ethylene glycol=100: 110～200, temperature of reaction are 260～280 ℃, and reaction pressure is 100～300kPa, and reactant residence time is 1.5～4 hours;
2) add reactive flame retardant in the esterification products, carry out prepolymerization reaction and polycondensation successively and obtain the polycondensation product flame retardant polyester in the presence of polycondensation catalyst, reactive flame retardant is the compound with following structural formula:
R is hydroxyalkyl or the carboxyalkyl of C1～C4 in the structural formula, the add-on of reactive flame retardant is a benchmark with the charging capacity of monomers terephthalic acid, the weight ratio of terephthalic acid and reactive flame retardant is 100: 1.40～7.50, the making beating of reactive flame retardant spent glycol mixes, add in the esterification products after being mixed with the slurry that concentration is 20～45wt%
Prepolymerization reaction and polycondensation are all carried out under negative pressure, temperature of reaction is 270～285 ℃, reactant residence time respectively is 1～3 hour, the vacuum tightness of prepolymerization reaction is 1.0～2.0kPa, the vacuum tightness of polycondensation is 0.1～0.2kPa, the limiting viscosity of polycondensation product is controlled to be 0.60～0.75dl/g
It is characterized in that in reactive system, adding nano kaoline particle as the flame retardant polyester crystallization nucleating agent, nano kaoline particulate median size is 200～600nm, its adding mode is for adding before esterification or adding before prepolymerization reaction, and nano kaoline particulate add-on is counted 0.05～1.0wt% with the content that it finally is present in the polycondensation product.
2. system fiber according to claim 1 is characterized in that with the preparation method of flame retardant polyester in described nano kaoline particulate median size be 200～500nm.
3. system fiber according to claim 1 is characterized in that counting 0.3～1.0wt% in described nano kaoline particulate add-on with the content that it finally is present in the polycondensation product with the preparation method of flame retardant polyester.
4. system fiber according to claim 1 is characterized in that being controlled to be 0.60～0.70dl/g in the limiting viscosity of described polycondensation product with the preparation method of flame retardant polyester.
5. use the preparation method of flame retardant polyester according to claim 1,2,3 or 4 described system fibers, it is characterized in that in described nano kaoline particulate adding mode that for before esterification, to add the nano kaoline particle is pulled an oar with the raw material of esterification and mixed the back and add reactive system.
6. system fiber according to claim 1 is with the preparation method of flame retardant polyester, it is characterized in that described polycondensation catalyst takes from any in antimony glycol, antimony acetate or the antimonous oxide.
7. system fiber according to claim 6 is characterized in that with the preparation method of flame retardant polyester the consumption of described polycondensation catalyst is a benchmark with monomers terephthalic acid weight, in antimony ion, is 120～300mg/kg.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100453853A CN101376698B (en) | 2007-08-30 | 2007-08-30 | Preparation of flame-retardant polyester for preparing fibre |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100453853A CN101376698B (en) | 2007-08-30 | 2007-08-30 | Preparation of flame-retardant polyester for preparing fibre |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101376698A CN101376698A (en) | 2009-03-04 |
| CN101376698B true CN101376698B (en) | 2011-04-13 |
Family
ID=40420442
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007100453853A Active CN101376698B (en) | 2007-08-30 | 2007-08-30 | Preparation of flame-retardant polyester for preparing fibre |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101376698B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1306020A (en) * | 2000-03-03 | 2001-08-01 | 仪征化纤股份有限公司 | Process for preparing high-concentration phosphorus-contained copolyester |
| CN1332201A (en) * | 2000-06-22 | 2002-01-23 | 帝人株式会社 | Resin composition for optical fiber loose concentrated pipe and optical fiber loose concentrated pipe |
| US6500881B1 (en) * | 1998-02-11 | 2002-12-31 | Rhodia Engineering Plastics S.R.L. | Flame-proofed polyamide composition |
| EP1541611A1 (en) * | 2002-08-07 | 2005-06-15 | Goo Chemical Co., Ltd. | Water-soluble flame-retardant polyester resin, resin composition containing the resin, and fabric product treated with the resin composition |
-
2007
- 2007-08-30 CN CN2007100453853A patent/CN101376698B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6500881B1 (en) * | 1998-02-11 | 2002-12-31 | Rhodia Engineering Plastics S.R.L. | Flame-proofed polyamide composition |
| CN1306020A (en) * | 2000-03-03 | 2001-08-01 | 仪征化纤股份有限公司 | Process for preparing high-concentration phosphorus-contained copolyester |
| CN1332201A (en) * | 2000-06-22 | 2002-01-23 | 帝人株式会社 | Resin composition for optical fiber loose concentrated pipe and optical fiber loose concentrated pipe |
| EP1541611A1 (en) * | 2002-08-07 | 2005-06-15 | Goo Chemical Co., Ltd. | Water-soluble flame-retardant polyester resin, resin composition containing the resin, and fabric product treated with the resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101376698A (en) | 2009-03-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103739832B (en) | A kind of manufacture method of cationic dye capable of dyeing fire retardant polyester resin | |
| CN103145957A (en) | Method for producing low-melting-point renewable polyester for sheath-core polyester through glycol degradation | |
| CN108003332B (en) | Easily hydrolyzed polyester and synthesis method thereof | |
| CN100355831C (en) | Phosphorus containing fire retardant copolyester/barium sulphate nano-composite material and its preparation method | |
| CN107189062A (en) | A kind of low melting point fire-resistant copolyesters nylon and preparation method thereof | |
| CN102532546A (en) | Preparation and application of hydroxyl modified poly-p-phenylene benzo imidazolinyl resin | |
| CN101376690B (en) | Preparation of flame-retardant polyester for preparing fiber | |
| CN101376689B (en) | Preparation of flame-retardant polyester for preparing fiber | |
| CN104559100A (en) | Functional cyclodextrin flame-retarding polylactic acid composite material and preparation method thereof | |
| CN101376691B (en) | Preparation of flame-retardant polyester for preparing industrial yarn | |
| CN103145958A (en) | Method for producing low-melting-point renewable polyester for sheath-core polyester through methanol degradation | |
| CN107881580B (en) | Continuous production method of flame-retardant polyester fiber | |
| CN101376699B (en) | Preparation of flame-retardant polyester for preparing industrial yarn | |
| CN103145959A (en) | Method for producing low-melting-point recycled polyester for sheath-core type polyester through hydrolytic degradation | |
| CN101392050A (en) | Fire retardation copolyester polymer, preparation method thereof and fire retardation copolyester fiber | |
| CN101376694B (en) | Preparation of flame-retardant polyester for preparing industrial fibre | |
| CN101376693B (en) | Preparation of flame-retardant polyester for preparing industrial fibre | |
| CN101376692B (en) | Preparation of flame-retardant polyester for preparing industrial yarn | |
| CN101376700B (en) | Preparation of flame-retardant polyester for preparing industrial yarn | |
| CN101376698B (en) | Preparation of flame-retardant polyester for preparing fibre | |
| CN101376697B (en) | Preparation of flame-retardant polyester for preparing fibre | |
| CN101376696B (en) | Preparation of flame-retardant polyester for preparing industrial yarn | |
| CN110511368B (en) | Vinyl nano-silicon sphere compounded high-temperature self-crosslinking flame-retardant anti-dripping copolyester and preparation method thereof | |
| CN101376695B (en) | Preparation of flame-retardant polyester for preparing industrial yarn | |
| CN114574995B (en) | Flame-retardant low-melting-point polyester fiber and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |