CN102532499A - Cation dyeable flame-retardant polyester and application thereof - Google Patents
Cation dyeable flame-retardant polyester and application thereof Download PDFInfo
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- CN102532499A CN102532499A CN2010106035896A CN201010603589A CN102532499A CN 102532499 A CN102532499 A CN 102532499A CN 2010106035896 A CN2010106035896 A CN 2010106035896A CN 201010603589 A CN201010603589 A CN 201010603589A CN 102532499 A CN102532499 A CN 102532499A
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- flame retardant
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Abstract
The invention relates to cation dyeable flame-retardant polyester, which is prepared by reacting a dicarboxylic acid monomer or derivatives thereof, poly alkylene glycol, and metal sulphonate-containing isophthalic acid and derivatives thereof in the presences of a phosphorus flame retardant, a catalyst and an aid, wherein the phosphorus flame retardant is a reactive type and blend additive type phosphorus flame retardant, and the total adding amount of a phosphorus element is 2,000-12,000ppm based on the total amount of the polyester; and the polyester has the hue b value of less than 8 and the light fastness of over 4 grade. The obtained polyester polymer has good reactivity, excellent hue, high light fastness, and high spinnability, and is environment-friendly.
Description
Technical field
The present invention relates to a kind of cation dyeable flame retardant polyester and uses thereof.
Background technology
Polyester, particularly polyethylene terephthalate have outstanding performance, are widely used in fields such as fiber, film, extremely people's favor.
But because its molecular structure of PET is regular, is prone to crystallization, and is not prone to dye functional group, though under HTHP, can dye by enough dispersed dye, working condition is harsh, and production cost is high.Because the limiting oxygen index(LOI) of common PET is 20～24, can burn under usual conditions in the flame retardant resistance aspect, therefore just exist and meet the naked light stability problem.
In the research of present flame retardant cationic dyeable polyester, mainly contain following technology.Chinese patent CN1103185.9 relates to a kind of flame retardant cationic dye chromophil polyester staple fiber method of manufacture, adopts the method for transesterify to add the cation-dyeable composition in the transesterify stage, transesterification reaction after or polymerization stage interpolation reactive flame retardant.Chinese patent 200410084108.X relates to a kind of method of manufacture of flame retardant cationic dye chromophil polyester, adopts the direct esterification method to prepare polyester, esterification after or polymerization stage interpolation reactive flame retardant.Chinese patent 200510043752.7 relates to a kind of flame retardant polyester section of normal atmosphere cation-dyeable, comprises reactive flame retardant in the polymkeric substance.Chinese patent 200810211851.5 relates to a kind of flame retardant polyester multipolymer of normal atmosphere cation-dyeable, comprises reactive flame retardant in the multipolymer.There are shortcomings such as color variation, the photostabilization of polymkeric substance is poor, reactivity worth is low when the fire retardant volume is added in the polymkeric substance that aforesaid method obtains.
Summary of the invention
The object of the present invention is to provide that a kind of reactivity is good, tone is excellent, light fastness is good, the cation dyeable flame retardant polyester environmentally friendly, that spinning properties is good.
Technical solution of the present invention is following:
A kind of cation dyeable flame retardant polyester; Under phosphorus flame retardant, catalyzer and auxiliary agent condition, react and obtain by the m-phthalic acid or derivatives thereof of monomer di-carboxylic acid or derivatives thereof, aklylene glycol and containing metal sulphonate; Phosphorus flame retardant is response type and blend addition type phosphorus flame retardant, and the interpolation total amount of phosphoric is 2000ppm～12000ppm with respect to the polyester total amount; The tone b value of polyester is below 8, light fastness is more than 4 grades.
The structural formula of said response type phosphorus flame retardant suc as formula 1 or formula 2 shown in, the structural formula of said blend addition type phosphorus flame retardant is suc as formula shown in 3,
formula 1
R in the formula 1
1, R
2It is the hydroxy alkylidene of Wasserstoffatoms or C1～C10;
R in the formula 2
3Be the alkyl of C1～C6 or the aryl of C6～C9; R
4It is the alkylidene group of C1～C6; R
5And R
6It is the hydroxy alkylidene of Wasserstoffatoms or C2～C4;
formula 3
N in the formula 3 is 1～3 integer.
Said di-carboxylic acid or derivatives thereof is terephthalic acid, phthalic acid, m-phthalic acid, naphthalic acid, biphenyl dicarboxylic acid or cyclohexane dicarboxylic acid or their verivate; Aklylene glycol is a terepthaloyl moietie, 1, ammediol, Ucar 35 or 1,4-butyleneglycol.
Said catalyzer is a titanium catalyst, and the chemical formula of the titanium compound in the titanium catalyst is suc as formula shown in 4:
R
7O-[Ti (OR
8) (OR
9)-O-] m-R
10Formula 4
R wherein
7, R
8, R
9And R
10Be respectively the alkyl or phenyl of C2～C10, can be the same or different, m is 1～6 integer; The addition of titanium elements is 0.5～30ppm with respect to the polyester total amount.
The structural formula of the m-phthalic acid or derivatives thereof of said containing metal sulphonate is suc as formula shown in 5:
Wherein, R
11, R
12Be open chain or the cyclic alkyl of H or C1～C15, M is alkali metallic sodium, lithium or potassium; The addition of element sulphur is 0.01～0.5wt% with respect to the polyester total amount in the m-phthalic acid or derivatives thereof of containing metal sulphonate.
Said auxiliary agent is phosphorus compound and basic cpd; Phosphorus compound is phosphorous acid, phosphoric acid, phosphorous acid ester or SULPHOSUCCINIC ACID ESTER, and the addition of its phosphoric is 5～60ppm with respect to the polyester total amount; Basic cpd is sodium-acetate, Potassium ethanoate or Lithium Acetate, and the addition of its alkaline element is 10～100ppm with respect to the polyester total amount.
The limiting oxygen index(LOI) of polyester is 29～33, and terminal carboxyl(group) COOH content is that 35 equivalents/below the t, glycol ether DEG content is below the 2.5wt%.
Polyester of the present invention can pass through the direct polymerization method, and the DMT manufactured can also be passed through batchwise polymerization method, successive polymerization manufactured.In addition, copolyesters of the present invention can be processed fiber and then form fabric through known method.
The present invention adopts response type and blend additive flame retardant; Shortcomings such as the polymerization reaction time length of having avoided common response type fire retardant volume to add causing, polymkeric substance tonal difference; Add the blend additive flame retardant under the prerequisite that does not influence polymerization reaction time, avoided the blend additive flame retardant in the ununiformity in blend stage, improved the light fastness of fabric.
The prepared polyester product of the present invention has excellent tone and good photostabilization; And polymerization process is used titanium catalyst, and little to environmental influence, the pollution that in spinning process, spinning plate surface is caused is little, and the filter pressure is difficult for rising, fracture of wire is few, helps carrying out smoothly of spinning like this.
Embodiment
Below in conjunction with specific embodiment the present invention is described further.In addition, the measuring method of each index of embodiment and comparative example is following:
(1) limiting viscosity [η] (IV)
Under 25 ℃, test as solvent with ortho chloro phenol.
(2) (the equivalent/ton) of the terminal group carboxy CO OH in the polymkeric substance
, measure on automatic titration device (COM-550 of flat natural pond industry manufactured) with the NaOH aqueous solution of concentration 0.02mol/L down as solvent with Ortho Cresol at 25 ℃.
(3) DEG test
The 1g polyester is added in the 3ml thanomin, under 240 ℃ of conditions, dissolve.Be neutralized to neutrality with the 4-5g terephthalic acid then, in gc, test.
(4) tone L/b value
Measure by GB GB/T 14190-1993.
(5) flame retardant resistance test
With the polyester pelletizing, spun yarn, through knitting, washing, after the alkali decrement treatment, limit of utilization oxygen index (LOI) test.The testing method of limiting oxygen index(LOI) is according to GB5454-1997.
(6) cationic dye capable of dyeing property testing
With the polyester pelletizing, spun yarn with cationic dyestuff (positively charged ion is blue) dyeing at normal temperatures, detects by an unaided eye.
Zero: dye in the expression satisfactory for result, and color and luster homogeneous relatively
△: it is general to dye effect in the expression, the color and luster homogeneous
*: dye weak effect in the expression, and color and luster heterogeneity phenomenon occurs
(7) colour fastness to light
Testing method is tested the colour fastness of anti-artificial light xenon arc according to the GB/T8427-2008 textile color stability, grade has below three grades, three grades, more than three grades, below the level Four or the like.
Reactive flame retardant can be fire retardant A, B or C in embodiment and the comparative example.
Fire retardant A is suc as formula shown in 6:
formula 6
Fire retardant B is suc as formula shown in 7:
formula 7
Fire retardant C is suc as formula shown in 8:
Blend additive flame retardant D is suc as formula shown in 9:
formula 9
The concrete numerical value of each embodiment and comparative example is seen table 1.
Embodiment 1
A certain amount of polyester raw material DMT. Dimethyl p-benzenedicarboxylate and terepthaloyl moietie, the compound of containing metal sulphonate, catalyzer, auxiliary agent are added first reactive tank; Carry out 4～6 hours reaction; The reaction product that reaction is obtained moves into second reactive tank; Add response type and blend addition type phosphorus flame retardant, begin decompression after 20 minutes, heat up.Temperature rises to 290 ℃, pressure by 250 ℃ and reduces to 40Pa.Reach end reaction temperature, pressure after 90 minutes.After arriving certain stirring extent, import nitrogen to reaction system and be back to normal pressure, stop polyreaction.Polymkeric substance is strip and spues, cooling back section in tank.
Make its moisture rate remain on 50ppm the chip drying that obtains, melt-spinning under 290 ℃ spinning temperature then, portion spues from filament spinning component, batches with the pulling speed of 3000m.The amount of catalyzer, relevant rerum natura result see table 1 in the resulting polymers.
Embodiment 2～embodiment 10
Prepare polyester with embodiment 1 method, change the amount of additive, catalyzer and auxiliary agent in the polyester.The addition and the result of concrete catalyzer and additive see table 1.
Comparative example 1～3
Prepare polyester with embodiment 1 method, just change fire retardant among the embodiment into reactive flame retardant and add separately.Concrete addition transitivity result sees table 1.
Claims (8)
1. cation dyeable flame retardant polyester; Under phosphorus flame retardant, catalyzer and auxiliary agent condition, react and obtain by the m-phthalic acid or derivatives thereof of monomer di-carboxylic acid or derivatives thereof, aklylene glycol and containing metal sulphonate; It is characterized in that: phosphorus flame retardant is response type and blend addition type phosphorus flame retardant, and the interpolation total amount of phosphoric is 2000ppm～12000ppm with respect to the polyester total amount; The tone b value of polyester is below 8, light fastness is more than 4 grades.
2. cation dyeable flame retardant polyester according to claim 1 is characterized in that: the structural formula of said response type phosphorus flame retardant suc as formula 1 or formula 2 shown in, the structural formula of said blend addition type phosphorus flame retardant is suc as formula shown in 3,
R in the formula 1
1, R
2It is the hydroxy alkylidene of Wasserstoffatoms or C1～C10;
R in the formula 2
3Be the alkyl of C1～C6 or the aryl of C6～C9; R
4It is the alkylidene group of C1～C6; R
5And R
6It is the hydroxy alkylidene of Wasserstoffatoms or C2～C4;
N in the formula 3 is 1～3 integer.
3. cation dyeable flame retardant polyester according to claim 1 and 2 is characterized in that: said di-carboxylic acid or derivatives thereof is terephthalic acid, phthalic acid, m-phthalic acid, naphthalic acid, biphenyl dicarboxylic acid or cyclohexane dicarboxylic acid or their verivate; Aklylene glycol is a terepthaloyl moietie, 1, ammediol, Ucar 35 or 1,4-butyleneglycol.
4. cation dyeable flame retardant polyester according to claim 1 and 2 is characterized in that: said catalyzer is a titanium catalyst, and the chemical formula of the titanium compound in the titanium catalyst is suc as formula shown in 4:
R
7O-[Ti (OR
8) (OR
9)-O-] m-R
10Formula 4
R wherein
7, R
8, R
9And R
10Be respectively the alkyl or phenyl of C2～C10, can be the same or different, m is 1～6 integer; The addition of titanium elements is 0.5～30ppm with respect to the polyester total amount.
5. cation dyeable flame retardant polyester according to claim 1 and 2 is characterized in that: the structural formula of the m-phthalic acid or derivatives thereof of said containing metal sulphonate is suc as formula shown in 5:
Wherein, R
11, R
12Be open chain or the cyclic alkyl of H or C1～C15, M is alkali metallic sodium, lithium or potassium; The addition of element sulphur is 0.01～0.5wt% with respect to the polyester total amount in the m-phthalic acid or derivatives thereof of containing metal sulphonate.
6. cation dyeable flame retardant polyester according to claim 1 and 2 is characterized in that: said auxiliary agent is phosphorus compound and basic cpd; Phosphorus compound is phosphorous acid, phosphoric acid, phosphorous acid ester or SULPHOSUCCINIC ACID ESTER, and the addition of its phosphoric is 5～60ppm with respect to the polyester total amount; Basic cpd is sodium-acetate, Potassium ethanoate or Lithium Acetate, and the addition of its alkaline element is 10～100ppm with respect to the polyester total amount.
7. cation dyeable flame retardant polyester according to claim 1 and 2 is characterized in that: the limiting oxygen index(LOI) of polyester is 29～33, and terminal carboxyl(group) content is that 35 equivalents/below the t, glycol ether content is below the 2.5wt%.
8. the application of the described cation dyeable flame retardant polyester of claim 1 in the preparation fiber.
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| CN2010106035896A CN102532499A (en) | 2010-12-16 | 2010-12-16 | Cation dyeable flame-retardant polyester and application thereof |
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| CN2010106035896A CN102532499A (en) | 2010-12-16 | 2010-12-16 | Cation dyeable flame-retardant polyester and application thereof |
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| CN102532499A true CN102532499A (en) | 2012-07-04 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107880257A (en) * | 2016-09-29 | 2018-04-06 | 财团法人纺织产业综合研究所 | Flame-retardant material with high refractive index, manufacturing method thereof and flame-retardant polymer with high refractive index |
| CN115806660A (en) * | 2023-02-07 | 2023-03-17 | 江苏恒力化纤股份有限公司 | Preparation of ionic copolymerized flame-retardant polyester master batch and application of ionic copolymerized flame-retardant polyester master batch in fibers |
-
2010
- 2010-12-16 CN CN2010106035896A patent/CN102532499A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107880257A (en) * | 2016-09-29 | 2018-04-06 | 财团法人纺织产业综合研究所 | Flame-retardant material with high refractive index, manufacturing method thereof and flame-retardant polymer with high refractive index |
| CN115806660A (en) * | 2023-02-07 | 2023-03-17 | 江苏恒力化纤股份有限公司 | Preparation of ionic copolymerized flame-retardant polyester master batch and application of ionic copolymerized flame-retardant polyester master batch in fibers |
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Application publication date: 20120704 |