CN103122058A - Antistatic polyester, preparation method and application of antistatic polyester - Google Patents
Antistatic polyester, preparation method and application of antistatic polyester Download PDFInfo
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- CN103122058A CN103122058A CN 201110366746 CN201110366746A CN103122058A CN 103122058 A CN103122058 A CN 103122058A CN 201110366746 CN201110366746 CN 201110366746 CN 201110366746 A CN201110366746 A CN 201110366746A CN 103122058 A CN103122058 A CN 103122058A
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Abstract
The invention discloses antistatic polyester, a preparation method and application of the antistatic polyester. The antistatic polyester comprises polyether with amino end groups and sulphonate. The polyether with the amino end groups overcomes the defect of easy hydrolyzation of polyether with hydroxyl end groups, so that the antistatic performance can be still maintained after the antistatic polyester is dyed or reduced. By aid of the sulphonate, the additive amount of the polyether with the amino end groups is reduced to guarantee the spinnability of the antistatic polyester. The antistatic polyester can be widely applied to fibers.
Description
Technical field
The present invention relates to a kind of antistatic polyester and production method thereof and purposes.
Background technology
Specific inductivity and the electroconductibility of conventional macromolecular material are all very low, and the fiber made from macromolecular material easily produces static when rubbing, and this brings difficulty for the weaving post-treatment, and can produce the problems such as easy contamination, binding dust in the use procedure of fabric.Therefore, give these macromolecular material static resistances and become more and more important.
The method of improving at present material electroconductibility has and static inhibitor is coated in the products formed surface or uses in the synthetic process of polyester or add static inhibitor or the conducting particles with antistatic effect during in blend.But, for a kind of front method, along with the static inhibitor that extends surface-coated duration of service also can slowly come off, there is no permanent static resistance; A kind of rear method, the general lower molecular weight static inhibitor that uses are easily separated out from material in post-processed and are not had an antistatic property.
Patent 200880010957.7 adopts polyether ester amides as the core shift part, make the good conjugated fibre of a kind of static resistance, water-absorbent and contact coldness, its core is to adopt polyether block amide copolymer, the multipolymer that the polyamide units by having the reactive terminal base and the polyether units copolymerization condensation with reactive terminal make.This method adopts core sheath composite spinning method to make, but polyetheramides itself is easy to change, and adding does not have static resistance very little, adds influential to dyeing too much.
Patent CN200910163800.4 discloses the antistatic polyester that adopts polyoxyethylene glycol and the preparation of Sulfonates static inhibitor.In this polyester, after fiber being carried out post-treatment such as decrement or dyeing and processing, the decomposition of the ester bond that forms due to polyoxyethylene glycol and polyester causes the stripping of polyoxyethylene glycol, makes the anlistatig effect of fiber forfeiture.
Summary of the invention
The object of the present invention is to provide a kind of after adding water treatment the static resistance retentivity good, the simple antistatic polyester of production technique.
Technical solution of the present invention is as follows:
A kind of antistatic polyester,
(1) end that contains in described polyester segment as shown in Equation 1 is the polyether structure unit of imino-, and its content is 1%～20% with respect to the polyester gross weight:
-NH-(R
1O)
n-R
1-NH-formula 1
Wherein, R
1Be the straight-chain alkyl-sub-of carbonatoms 2～4, n is 10～500 integer;
(2) contain in described polyester suc as formula 2 or formula 3 shown in sulfonate in one or more, its content is 0.1%～10% with respect to the polyester gross weight:
Wherein, R
2For the straight chain of carbonatoms 2～22 or with the alkyl chain of side chain, m is 1 or 2, M
1Be metal;
Wherein, R
3For the straight chain of carbonatoms 3～20 or with the alkyl chain of side chain, x is 1 or 2, M
2Be metal.
Use in the present invention two ends to be the polyethers of amino, after reacting, the terminal carboxyl(group) with polyester forms amide group, the hydrolytic resistance of amide group is stronger than ester group, thereby has reduced polyethers because of the loss of polyester after dyeing or decrement treatment, keeps the antistatic property of polyester.
In polyester, end is that the polyether structure unit of imino-accounts for 1%～20% of polyester gross weight, and lower than 1% the time, polyester does not reach anlistatig effect when its content; Higher than 20% the time, the spinning properties of gained polyester descends when its content.This content preferred 3%～15%.
Above-mentioned end is that the molecular weight of the polyether structure unit of imino-is 1000～20000g/mol, preferred 4000～20000g/mol.
Can affect the spinning property of polyester due to the increase of polyether units content in polyester, so improve its antistatic property when keeping the spinning property of polyester, also contain in described polyester contain in described polyester suc as formula 2 or formula 3 shown in sulfonate in one or more, play the booster action that strengthens antistatic effect.The content of described sulfonate accounts for 0.1%～10% of polyester gross weight, if the content of sulfonate during lower than 0.1wt%, the gained polyester does not have antistatic effect; If the content of sulfonate is higher than 10wt%, the antistatic effect of polyester can't be significantly improved, and also can raise the cost simultaneously.Above-mentioned content preferred 0.2%～6%.
Above-mentioned M
1And M
2Difference preferred as alkali, alkaline-earth metal or zinc, more preferably sodium and magnesium.
The production method of the described antistatic polyester of a kind of claim 1, by dibasic alcohol and diprotic acid or its esterified derivative carry out esterification or transesterify, polycondensation makes, it is characterized in that:
(1) finish rear or add the end as shown in Equation 4 that accounts for final polyester gross weight 1%～25% before polycondensation to be amino polyethers in esterification or transesterification reaction:
H
2N-(R
1O)
n-R
1-NH
2Formula 4
Wherein, R
1Be the straight-chain alkyl-sub-of carbonatoms 2～4, n is 10～500 integer;
(3) add after esterification or transesterification reaction or before polymerization account for final polyester gross weight 0.1%～12% suc as formula 2 or formula 3 shown in sulfonate in one or more:
Wherein, R
2For the straight chain of carbonatoms 2～22 or with the alkyl chain of side chain, m is 1 or 2, M
1Be metal;
Wherein, R
3For the straight chain of carbonatoms 3～20 or with the alkyl chain of side chain, x is 1 or 2, M
2Be metal.
The resulting polyester of the present invention has good antistatic property, and the frictional electrification pressure energy of the fabric that it is made enough reaches below 3000v, and still can keep the friction belt voltage of this scope after adding water treatment, and the static resistance retentivity is good.And the production method of antistatic polyester of the present invention is simple, with low cost, does not need more equipment investment.
Embodiment
The present invention is further described below in conjunction with embodiment, but do not limit content of the present invention.
Testing method:
(1) static resistance (friction belt voltage/V):
Be that 60T/8f, intensity are the conjugated fibre of 3.0cn/dtex with rugosity, utilize level and smooth weave to weave, refining is after 30 minutes in the YS51 of 0.2% concentration refining agent with the cloth that obtains, and 170 ℃ of lower heat setting types made fabric in 1 minute.Measure according to JIS L-1094-1997 friction belt attenuation measurement method:
Friction belt voltage is measured: electrostatic tester,
Friction cloth: wool, cotton,
Frictional direction: athwartship plane,
Humiture: 20 ℃ * 40%RH.
(2) condition is dyed in vacation: behind 130 ℃ of water-bath * 30 minute, 170 ℃ of heat setting type is 1 minute.
(3) polyethers testing method: hydrogen spectrum nucleus magnetic resonance.
(4) testing method of sulphur atom: fluorescent X-ray spectroscopy.
Embodiment 1
Bishydroxyethyl terephthalate is added the esterification layer, keep 250 ℃ of temperature, pressure 1.2 * 10
5Pa joined gradually the esterification layer with the TPA (terephthalic acid) of 10 weight parts and EG (ethylene glycol) slurry of 4.5 weight parts, then carries out the esterification of 1 hour in 4 hours.Get at last 12.3 weight parts and join the polycondensation layer from the reactant of esterification that obtains.
esterification reaction product is remained on 250 ℃, under normal pressure, add the defoamer (methyl-silicone oil) that is equivalent to weight polyester 0.01% and the phosphoric acid that is equivalent to weight polyester 18ppm in phosphorus atom, stir and add the antimonous oxide that is equivalent to weight polyester 230ppm in antimony atoms after 5 minutes, the Cobaltous diacetate that is equivalent to weight polyester 15ppm in cobalt atom, reach the ethylene glycol slurry mix that contains Titanium particles that is equivalent to weight polyester 0.3wt% in the Titanium particles amount, stir again after 5 minutes and to add the Y-4000 that is equivalent to weight polyester 5wt% (structure as shown in Equation 4, R1 is ethylidene, molecular weight 4000g/mol), wait to stir and add again the Sodium dodecylbenzene sulfonate (DBS) that is equivalent to weight polyester 0.5wt%.Begin decompression after 5 minutes, heat up, temperature rises to 290 ℃, Pressure Drop to 40Pa by 250 ℃, reaches outlet temperature, resulting pressure after 60 minutes.After arriving certain stirring extent, import nitrogen in the reaction system and be back to normal pressure, stop polycondensation.Polyester is strip and spues, cooling rear section in tank.The intrinsic viscosity of gained polyester is 0.67.With its static resistance of test after the standby one-tenth of this polyester fiber.
Embodiment 2
Add the Y-10000 be equivalent to weight polyester 5wt% (structure as shown in Equation 4, R in polycondensation
1Be ethylidene, molecular weight 10000g/mol), other are with embodiment 1.
Embodiment 3
Add the Y-4000 that is equivalent to weight polyester 15wt% in polycondensation, other are with embodiment 1.
Embodiment 4
Add the Y-20000 be equivalent to weight polyester 10wt% (structure as shown in Equation 4, R in polycondensation
1Be ethylidene, molecular weight 20000g/mol), add again the carbonatoms be equivalent to weight polyester 3wt% and be 10～18 alkyl sodium sulfonate salt mixture A (CAS:68037-49-0) after stirring, other are with embodiment 1.
Embodiment 5
Add in polycondensation and be equivalent to weight polyester Y-1000 (structure as shown in Equation 4, R
1Be propylidene, molecular weight 1000g/mol) and 3wt% to own Phenylsulfonic acid magnesium B, other are with embodiment 4.
Embodiment 6
187 weight part ethylene glycol and 303 weight part dimethyl terephthalate (DMT) (DMT) are added in reactor, add simultaneously catalyzer, with respect to weight polyester addition antimonous oxide 300ppm, calcium acetate 900ppm, antioxidant (IR1010) 0.1wt%, defoamer methyl-silicone oil 0.1wt%, carry out transesterification reaction, the transesterify outlet temperature is controlled at 240～250 ℃, go out the complete stablizer trimethyl phosphite 99 that is equivalent to weight polyester 0.043wt% that adds of methyl alcohol to transesterify, then steam ethylene glycol under normal pressure and add the Sodium dodecylbenzene sulfonate (DBS) that is equivalent to weight polyester 5wt% after 30 minutes, stir and finish after 15 minutes to react to obtain the polymerization oligopolymer.
With above resulting polymerization oligopolymer and the Y-2000 (structure shown in formula 4, the R that are equivalent to weight polyester 8wt%
1Be butylidene, molecular weight 2000g/mol) add in reactor, be decompressed to 40Pa in 60 minutes, temperature is controlled at carries out conventional polymerization under 270～290 ℃, and termination reaction during to the discharging viscosity that reaches regulation obtains anti-electrostatic polymer.With its static resistance of test after the standby one-tenth of this polyester fiber.
Embodiment 7
The terephthalic acid of 6.0 weight parts and the butyleneglycol of 4.9 weight parts are added in esterifying kettle, add simultaneously catalyzer, with respect to weight polyester, add Mono-n-butyltin 0.042wt%, antioxidant (IR1010) 0.2wt%, defoamer methyl-silicone oil 0.13wt% adds Y-100008wt% simultaneously.Stir under 150 ℃ of constant temperature and add the tetrabutyl titanate that is equivalent to weight polyester 0.045wt% after 10 minutes, then temperature reaction, constant temperature is 30 minutes after the esterification outlet temperature reaches 225～230 ℃, add the DBS that is equivalent to weight polyester 1.5wt% after water reaches theoretical amount, stir and finish after 15 minutes to react to obtain the polymerization oligopolymer.
Above polymerization oligopolymer is added in the polycondensation vessel of 230 ℃ of constant temperature, be warming up to after adding and add the phosphoric acid that is equivalent to weight polyester 190ppm after 250 ℃, stir and add the tetrabutyl titanate that is equivalent to weight polyester 0.045wt% after 5 minutes, keep 250 ℃ of beginning vacuum after 5 minutes, be decompressed to 40Pa in 60 minutes, termination reaction during to the discharging viscosity that reaches regulation obtains anti-electrostatic polymer.With its static resistance of test after the standby one-tenth of this polyester fiber.
Comparative example 1
Do not add DBS, other are with embodiment 1.
Comparative example 2
It is 4000 polyoxyethylene glycol (PEG4000) that the polycondensation stage is added the molecular weight be equivalent to weight polyester 5wt%, and other are with embodiment 1.
The concrete data of each embodiment and comparative example see Table 1.
Claims (7)
1. antistatic polyester is characterized in that:
(1) end that contains in described polyester segment as shown in Equation 1 is the polyether structure unit of imino-, and its content is 1%～20% with respect to the polyester gross weight:
-NH-(R
1O)
n-R
1-NH-formula 1
Wherein, R
1Be the straight-chain alkyl-sub-of carbonatoms 2～4, n is 10～500 integer;
(2) contain in described polyester suc as formula 2 or formula 3 shown in sulfonate in one or more, its content is 0.1%～10% with respect to the polyester gross weight:
Formula 2
Wherein, R
2For the straight chain of carbonatoms 2～22 or with the alkyl chain of side chain, m is 1 or 2, M
1Be metal;
Wherein, R
3For the straight chain of carbonatoms 3～20 or with the alkyl chain of side chain, x is 1 or 2, M
2Be metal.
2. antistatic polyester according to claim 1 is characterized in that: described end is that the molecular weight of the polyether structure unit of imino-is 1000～20000g/mol.
3. antistatic polyester according to claim 1, is characterized in that: described M
1And M
2Be respectively basic metal, alkaline-earth metal or zinc.
4. antistatic polyester according to claim 1 and 2 is characterized in that: described end is that the polyether structure unit of imino-accounts for 3%～15% of polyester gross weight.
5. according to claim 1 or 3 described antistatic polyesters, it is characterized in that: described sulfonate accounts for 0.2%～6% of polyester gross weight.
6. the production method of the described antistatic polyester of claim 1, by dibasic alcohol and diprotic acid or its esterified derivative carry out esterification or transesterify, polycondensation makes, it is characterized in that:
(1) finish rear or add the end as shown in Equation 4 that accounts for final polyester gross weight 1%～25% before polycondensation to be amino polyethers in esterification or transesterification reaction:
H
2N-(R
1O)
n-R
1-NH
2Formula 4
Wherein, R
1Be the straight-chain alkyl-sub-of carbonatoms 2～4, n is 10～500 integer;
(2) add after esterification or transesterification reaction or before polymerization account for final polyester gross weight 0.1%～12% suc as formula 2 or formula 3 shown in sulfonate in one or more:
Formula 2
Wherein, R
2For the straight chain of carbonatoms 2～22 or with the alkyl chain of side chain, m is 1 or 2, M
1Be metal;
Wherein, R
3For the straight chain of carbonatoms 3～20 or with the alkyl chain of side chain, x is 1 or 2, M
2Be metal.
7. the application of antistatic polyester claimed in claim 1 in the preparation fiber.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104231249A (en) * | 2013-06-21 | 2014-12-24 | 东丽纤维研究所（中国）有限公司 | Modified polyester as well as preparation method and application thereof |
| CN104480564A (en) * | 2014-12-31 | 2015-04-01 | 江苏恒力化纤股份有限公司 | Super-bright light trefoil irregular FDY fiber and preparation method thereof |
| CN107059243A (en) * | 2017-05-02 | 2017-08-18 | 深圳市新纶科技股份有限公司 | A kind of antistatic viscose rayon non-woven fabrics and preparation method thereof |
-
2011
- 2011-11-18 CN CN 201110366746 patent/CN103122058A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104231249A (en) * | 2013-06-21 | 2014-12-24 | 东丽纤维研究所（中国）有限公司 | Modified polyester as well as preparation method and application thereof |
| CN104231249B (en) * | 2013-06-21 | 2018-05-18 | 东丽纤维研究所（中国）有限公司 | A kind of modified poly ester and its preparation method and application |
| CN104480564A (en) * | 2014-12-31 | 2015-04-01 | 江苏恒力化纤股份有限公司 | Super-bright light trefoil irregular FDY fiber and preparation method thereof |
| CN107059243A (en) * | 2017-05-02 | 2017-08-18 | 深圳市新纶科技股份有限公司 | A kind of antistatic viscose rayon non-woven fabrics and preparation method thereof |
| CN107059243B (en) * | 2017-05-02 | 2019-10-29 | 深圳市新纶科技股份有限公司 | A kind of antistatic viscose rayon non-woven fabrics and preparation method thereof |
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Application publication date: 20130529 |