CN104120504B - A kind of hydrolysis-resistant polyester fiber and preparation method thereof - Google Patents
A kind of hydrolysis-resistant polyester fiber and preparation method thereof Download PDFInfo
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- CN104120504B CN104120504B CN201310144895.1A CN201310144895A CN104120504B CN 104120504 B CN104120504 B CN 104120504B CN 201310144895 A CN201310144895 A CN 201310144895A CN 104120504 B CN104120504 B CN 104120504B
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Abstract
The invention discloses a kind of hydrolysis-resistant polyester fiber and preparation method thereof, oligomer first is made by esterification or ester exchange reaction in aromatic acid or its carboxylate and aliphatic diol, gained oligomer is subjected to polycondensation, and add silicon compound in the polycondensation reaction stage, reach discharge, cooling and dicing after required polymer viscosity, then solid phase is carried out, then obtains after melt spinning and deep processing hydrolysis-resistant polyester fiber.In gained polyester fiber silicon-containing compound in terms of element silicon relative to the construction unit formed in fiber by aromatic acid or its carboxylate 0.01~0.5mol%.The polyester has excellent hydrolytic Resistance, available for radial, the field such as fishing net.
Description
Technical field
The present invention relates to the preparation method of a kind of hydrolysis-resistant polyester fiber and the fiber.
Background technology
It is moist because ester bond can react and cause the fracture of ester bond with water in polyester fiber in moist environment
Environment temperature is higher, and ester linkage breaking speed is faster, meanwhile, the acid system of hydrolysis formation more promotes polyester fiber
Hydrolysis process, causes the properties such as polyester fiber mechanics drastically to deteriorate.Therefore, people enter to the hydrolytic Resistance of polyester fiber
Many researchs are gone.Chinese patent CN 200810019423.2 discloses one kind by hydrolysis-resisting agent carbodiimides and polyester
Mixing carries out hydrolysis-resistant polyester fiber made from melt spinning again.But, directly mixing hydrolysis-resisting agent can be to polyester in the polyester
The other performance of fiber has a negative impact, and complex and cost is high relative to general technology this method.In addition, using
The hydrolysis fiber of the carbodiimides manufacture of higher addition may produce more harmful substances in decomposable process and
Severe contamination environment.
The content of the invention
It is an object of the invention to provide a kind of polyester fiber of excellent hydrolysis resistance and preparation method thereof, pass through one kind
The silicon compound of copolymerization can be carried out with aromatic acid or its carboxylate and aliphatic dihydroxy alcohol, polyester can be effectively reduced fine
The end carboxyl group content of dimension, while promoting the densification of fiber molecule chain, and then makes polyester fiber obtain quite excellent hydrolysis
Performance.
The present invention technical solution be：
A kind of hydrolysis-resistant polyester fiber, wherein containing silicon-containing compound as shown in Equation 1, its content is relative in terms of element silicon
0.01~0.5mol% of the construction unit formed in fiber by aromatic acid or its carboxylate,
Formula 1
Wherein, R1、R2、R3The respectively alkyl of polyester molecule chain or carbon number 1~6, R1、R2And R3In at least one
For polyester molecule chain；R4For the alkylidene of carbon number 0~6, preferably methylene；R5For the alkylene of carbon number 2~10, ammonia
Base, imino group, epoxy radicals or aromatic radical, or be the alkyl or thiol base of carbon number 2~25, preferably anilino-.
The degree of stretching of heretofore described hydrolysis-resistant polyester fiber is 8~50%.Such degree of the stretching scope of selection, is mainly examined
Consider two aspects of practicality and feature of the hydrolysis-resistant polyester fiber.In terms of practicality, the fiber is primarily as industry
Fiber is used, using having little significance when degree of stretching is less than 8%；And feature in terms of, if the fiber degree of stretching has been more than 50%, i.e., its
The densification degree of interior molecules chain is abundant not enough, and easily intrusion causes anti-hydrolytic performance to be had a greatly reduced quality to hydrone.
Analyzed with dynamic mechanical（DMA）Tan (delta) temperature of the hydrolysis-resistant polyester fiber measured by method is
135~180 DEG C.The temperature reflects the complexity of molecular chain movement, the reaction of the higher explanation molecule of tan (delta) temperature
Activity is lower, and the hydrolytic resistance of polyester fiber is better.
The content of heretofore described silicon-containing compound as shown in Equation 1 in terms of element silicon relative in fiber by aromatic series
0.01~the 0.5mol%, preferably 0.05~0.3mol% of binary acid or the construction unit of its carboxylate formation.If as shown in Equation 1
The content of silicon-containing compound is less than 0.01mol%, then gained polyester fiber cannot get excellent anti-hydrolytic performance；And if the change
The content of compound is more than 0.5mol%, and the heat resistance of polyester fiber is deteriorated, while also can largely influence the mechanics of fiber
Performance.
A kind of preparation method of heretofore described hydrolysis-resistant polyester fiber comprises the following steps：
（1）Aromatic acid or its carboxylate and aliphatic dihydroxy alcohol are obtained oligomeric by esterification or ester exchange reaction
Thing, then carries out melt polycondensation by oligomer, and silicon compound as shown in Equation 2 is added in the melt polycondensation reaction stage, and it is added
Measure equivalent to aromatic acid or 0.02~0.6mol% of its carboxylate, preferably 0.06~0.4mol%,
R5-R4-Si-( R6)3Formula 2
R in formula 24For the alkylidene of carbon number 0~6, preferably methylene, R5For the alkylene of carbon number 2~10, ammonia
Base, imino group, epoxy radicals or aromatic radical, or carbon number 2~25 alkyl or thiol base, preferably anilino-, R6For carbon
The alkoxy of atomicity 1~6；
（2）By step（1）Obtained melt polycondensation thing carries out solid phase and obtains polyester, and the temperature of solid phase is 220
~240 DEG C；
（3）Spinning after polyester is dried, obtains hydrolysis-resistant polyester fiber after final deep processing.
Why select to use silicon compound as shown in Equation 2 in the present invention as copolymer composition, be because such chemical combination
Three alkoxy grp R of thing end6It can be reacted in copolymerization with the carboxyl or ester group of aromatic acid or its carboxylate, and
And ultimately form the polyester molecule chain with bridging structure.It is such to be advantageous in that, both reduced containing for terminal carboxyl group in polyester
Amount, slows down its catalytic hydrolysis reaction, makes strand be more prone to form compact texture after extension again, prevents invading for hydrone
Enter.In addition, the silicon compound used in the present invention just can be with the excellent hydrolysis of extraordinary imparting polyester in a small amount of addition
Performance, and the silicon compound Stability Analysis of Structures, it is not degradable, it is also more friendly to human body and environment.
Catalyst used in polymerization stage can be various conventional pet reaction catalyst in the present invention, such as in ester
Inorganic antimony compounds and organic acid manganese compound can be added as catalyst in change or ester exchange reaction.
The above-mentioned preferred antimony oxide of inorganic antimony compounds, most preferably antimony pentoxide, antimony oxide.Wherein antimony element
Addition is 80~500ppm, preferably 200~400ppm relative to polyester total amount.So, preferably catalysis effect can either be realized
Really, it will not cause to generate substantial amounts of foreign matter in polymer because of excessive antimony element again, influence the quality of polymer.
Above-mentioned organic acid manganese compound can be manganese acetate, manganese benzoate etc., preferably manganese acetate.Wherein manganese element addition
It is 30~200ppm, preferably 100~190ppm relative to polyester total amount.Organic acid manganese compound is used as esterification or ester exchange reaction
Catalyst, how many pairs of esterifications of its content or ester exchange reaction speed and the heat resistance of copolyesters have a certain impact.When
During too high levels, the heat resistance of gained copolyesters is deteriorated；When content is too low, then the reaction rate of esterification or ester exchange can be reduced.
In order to prevent the generation of foreign matter in pet reaction from causing the pressure oscillation of follow-up spinning engineering, preferably in polycondensation reaction
Stage add stabilizer phosphorus compound, its addition in terms of P elements equivalent to polyester total amount 5~500ppm, preferably 30~
300ppm.Stabilizer phosphorus compound preferably phosphoric acid.
It is the terminal carboxyl group of further reduction energy catalyzing hydrolysis process in the present invention using the purpose of solid phase technology
Content, while improving the intrinsic viscosity IV of polymer, makes it very excellent beneficial to preparation mechanical property and anti-hydrolytic performance
Polyester fiber.The end carboxyl group content of hydrolysis-resistant polyester in the present invention after solid phase is between 4~12eq/t, intrinsic viscosity
IV is between 0.90~1.20dl/g.The intrinsic viscosity IV of the hydrolysis-resistant polyester fiber finally given is 0.6~1.0dl/g.
Heretofore described spining technology can use any method commonly known in the art, be said as an example below
It is bright.
By after solid phase hydrolysis-resistant polyester cut into slices at 150 DEG C be dried in vacuo, make its moisture rate reach 50ppm with
Under, then the melt spinning under 295~305 DEG C of spinning temperature, is batched with 2000~4000m/min hauling speed, obtained
Do not extend silk.
Heretofore described deep processing can be one section of extension or two sections of extensions, and during one section of extension, a heat roller temperature is set
Be set to 70~100 DEG C, two heat roller temperatures be set as 120~150 DEG C, extension ratio is 1.5~6.5 times；During two sections of extensions, a heat
Roll temperature is 80~120 DEG C, two heat roller temperatures are 130~160 DEG C, and three heat roller temperatures are between 170~230 DEG C, one, two hot-rollings
Extension ratio be 3.0~5.0 times, the extension ratio between two, three hot-rollings is 1.5~2.0 times.Fiber after deep processing
Gap between strand is greatly reduced, and strand arrangement of the strand arrangement particularly with bridging structure is more densified,
So that hydrone is difficult intrusion to suppress the generation of hydrolysis.
Method of testing involved in the present invention is described as follows：
（1）Silicon compound content
Precise 2g fibers, after being cleared up using concentrated nitric acid/hydrogen peroxide in 100 DEG C~160 DEG C, according to required
Concentration be diluted it is quantitative.Then tested with ICP-MS analyzers, with reference to the advance inspection amount made using standard sample
Line, measures the content of element silicon, and then determine the content of silicon compound.Experiment test precision 0.5ppm.
（2）Fibrous fracture intensity and degree of stretching
Cupping machine：Model RTC-1225A INTEC.CO.LTD
Extend silk（DT）：Filament length 20cm draw speed 200m/min,
Preoriented yarn（POY）：Filament length 5cm draw speeds 400m/min.
（3）Fiber hydrolytic resistance index
A certain amount of fiber samples are taken to be put into sealed hydrolysis system for handling, in 155 DEG C, 0.46MPa vapor bar
Handled under part 4 hours, the sample after processing is then placed in 20 DEG C of temperature, about 24 hours in the environment of humidity 65%, finally by such as
Lower metrics evaluation anti-hydrolytic performance：
A）The end carboxyl group content of hydrolysis before and after the processing is determined, carboxyl variable is calculated,
Δ COOH (eq/t)=COOHAfter processing- COOHBefore processing,
B）The fracture strength and elongation at break of hydrolysis before and after the processing are determined, strength and elongation product conservation rate is calculated,
。
（4）Carboxyl-content
Using optics titration measuring, sample is dissolved in the mixed liquor of o-cresol and chloroform（Weight compares 70:30）In, plus
Enter bromthymol blue indicator, then titrated with the ethanol solution of 0.05N potassium hydroxide.
（5）Intrinsic viscosity (IV)（dL/g）
1.6 grams of polyester is dissolved in 20ml ortho-chloro phenol solution, its inherent viscosity is determined at 25 DEG C（IV）.
（6）Tan (delta) temperature measuring
Using dynamic mechanical analytic approach（DMA methods）Determine.A certain amount of fiber is taken, makes its total fiber number about 200dtex,
3~4cm of length, and every monofilament of fiber is closely spaced in same plane, then fiber two ends are respectively fixed to dynamic
Determination of viscoelasticity device（TA company systems, model Q800）Upper and lower ends, be measured by following basic condition：
Temperature：Room temperature~200 DEG C, heating rate：5 DEG C/min, frequency：40Hz, Poisson's ratio：0.35；
Tan (delta) temperature is the corresponding temperature of peak-peak on tan (delta)-temperature curve.
Embodiment
The part of compounds being related in the embodiment included in the present invention is as follows：
1. dimethyl terephthalate (DMT)（It is abbreviated as DMT）；
2. terephthalic acid (TPA)（It is abbreviated as TPA）；
3. ethylene glycol（It is abbreviated as EG）；
4. butanediol（It is abbreviated as BDO）；
5. terephthalic acid (TPA) diethyl diester（It is abbreviated as BHT）
6. antimony oxide（It is abbreviated as AO）；
7. manganese acetate（It is abbreviated as MN）；
8. phosphoric acid（It is abbreviated as PA）；
9. the specifically used silicon compound arrived is as follows in the present invention：
Formula A,
Formula B,
Formula C；
10. the silicon compound being related in comparative example is as follows：
The formula D of n=100.
Illustrate present disclosure by the following examples, but the invention is not limited in content listed by embodiment.
Embodiment 1
By dimethyl terephthalate (DMT)（DMT）And ethylene glycol（EG）It is placed in 1 ︰ 1.8 mol ratio poly- equipped with rectifying column
Close in flask, ester exchange reaction is carried out at a temperature of 140 DEG C.In ester-exchange reaction, addition is suitable in terms of antimony element
In the catalytic antimony trioxide of polyester total amount 80~500（AO）, in terms of manganese element equivalent to 30~200ppm's of polyester total amount
Manganese acetate（MN）Mixed, reacted at ambient pressure.After reaction terminates, by obtained terephthalic acid (TPA) diethyl diester
（BHT）Oligomer, which is transferred in polymeric kettle, carries out polycondensation reaction.Added into polymeric kettle in terms of P elements equivalent to polyester total amount 5
~500ppm stabilizer phosphoric acid（PA）, the silicon compound equivalent to DMT0.2mol% is added after 5 minutes（Formula A）, addition terminates
Start to depressurize, heat up within 5 minutes afterwards, whole course of reaction is 1~3 hour, reaching and spue, cool down after required polymer viscosity
Pelletizing, then solid phase is carried out at 230 DEG C, hydrolysis-resistant polyester section is made.
Obtained polyester slice makes its moisture rate be maintained at below 50ppm, then under 295~305 DEG C of spinning temperature
Melt spinning, is batched with 2000~4000m/min hauling speed, and obtained undrawn yarn carries out one section of extension, a hot-rolling temperature
Degree is 70~100 DEG C, two heat roller temperatures are 120~130 DEG C, and extension ratio D is 3.5 times, obtains hydrolysis-resistant polyester fiber.
The anti-hydrolytic performance Δ COOH and strength and elongation product conservation rate of test gained fiber, concrete numerical value see attached list 1.
Embodiment 2
The silicon compound equivalent to aromatic dicarboxylic acrylate structure unit 0.02mol% in polyester is added in polycondensation process
（Formula A）, during one section extends, extension ratio D is 1.5 times, other step be the same as Examples 1.
Embodiment 3
The silicon compound equivalent to aromatic dicarboxylic acrylate structure unit 0.6mol% in polyester is added in polycondensation process
（Formula B）, during one section extends, extension ratio D is 6.5 times, other step be the same as Examples 1.
Embodiment 4
One section of extension is changed to two sections of extensions, and a heat roller temperature is 80~120 DEG C, two heat roller temperatures are 130~160 DEG C, three
Heat roller temperature is the extension ratio D between 170~230 DEG C, one, two hot-rollings12For 4.0 times, the extension ratio between two, three hot-rollings
D23For 1.7 times, other step be the same as Examples 1.
Embodiment 5
The silicon compound equivalent to aromatic dicarboxylic acrylate structure unit 0.4mol% in polyester is added in polycondensation process
（Formula C）, one section of extension is changed to two sections of extensions, and a heat roller temperature is 80~120 DEG C, two heat roller temperatures are 130~160 DEG C, three heat
Roll temperature is the extension ratio D between 170~230 DEG C, one, two hot-rollings12For 3.0 times, the extension ratio between two, three hot-rollings
D23For 2.0 times, other step be the same as Examples 1.
Embodiment 6
The silicon compound equivalent to aromatic dicarboxylic acrylate structure unit 0.1mol% in polyester is added in polycondensation process
（Formula A）, the temperature of solid phase is 240 DEG C, and one section of extension is changed to two sections of extensions, and a heat roller temperature is 80~120 DEG C, two hot-rollings
Temperature is 130~160 DEG C, and three heat roller temperatures are the extension ratio D between 170~230 DEG C, one, two hot-rollings12For 5.0 times, two,
Extension ratio D between three hot-rollings23For 1.5 times, other step be the same as Examples 1.
Embodiment 7
By DMT and butanediol（BDO）It is placed in 1 ︰ 2.0 mol ratio in the polymerization flask equipped with rectifying column, at 140 DEG C
At a temperature of carry out ester exchange reaction, other step be the same as Examples 1.
Embodiment 8
By terephthalic acid (TPA) diethyl diester at 250 DEG C（BHT）As bed material, 166 weights are added after bed material is melted completely
Measure the terephthalic acid (TPA) of part（TPA）With the ethylene glycol of 72 parts by weight（EG）（That is EG and TPA mol ratio is 1.15 ︰ 1）Carry out ester
Change reaction, by the output of water byproduct, reactivity to be esterified reaches more than 97%, by obtained new terephthalic acid (TPA) two
Second diester（BHT）Oligomer is transferred in polymeric kettle.Added successively into polymeric kettle in terms of P elements equivalent to polyester total amount 5~
500ppm stabilizer phosphoric acid（PA）, buffer sodium dihydrogen phosphate in terms of P elements equivalent to polyester total amount 60ppm
（NaH2PO4·2H2O）, equivalent to the catalytic antimony trioxide of polyester total amount 80~500 in terms of antimony element（AO）, with manganese element
Count the manganese acetate equivalent to 30~200ppm of polyester total amount（MN）Mixed, added after 5 minutes equivalent to TPA0.2mol%'s
Silicon compound（Formula A）, add and start to depressurize, heat up within 5 minutes after terminating, whole course of reaction is 1~3 hour, required for reaching
Polymer viscosity after spue, cooling and dicing, then carry out at 220 DEG C solid phase, hydrolysis-resistant polyester section be made.
Obtained polyester slice makes its moisture rate be maintained at below 50ppm, then under 295~305 DEG C of spinning temperature
Melt spinning, is batched with 2000~4000m/min hauling speed, and obtained undrawn yarn carries out one section of extension, a hot-rolling temperature
Degree is 70~100 DEG C, two heat roller temperatures are 120~130 DEG C, and extension ratio D is 2 times, obtains hydrolysis-resistant polyester fiber.
The anti-hydrolytic performance Δ COOH and strength and elongation product conservation rate of test gained fiber, concrete numerical value see attached list 1.
Comparative example 1
Without silicon compound, other step be the same as Examples 1.
Comparative example 2
Formula A silicon compounds are replaced into accepted way of doing sth D silicon compounds, addition is constant, other step be the same as Examples 1.
Comparative example 3
Solid phase in embodiment 1 is without other step be the same as Examples 1.
Comparative example 4
Extension line project in embodiment 1 is without other step be the same as Examples 1.
Claims (6)
1. a kind of preparation method of hydrolysis-resistant polyester fiber, it is characterized in that：This method comprises the following steps：
（1）Aromatic acid or its carboxylate and aliphatic dihydroxy alcohol are obtained into oligomer by esterification or ester exchange reaction,
Then oligomer is subjected to melt polycondensation, silicon compound as shown in Equation 2, its addition phase is added in the melt polycondensation reaction stage
When in 0.02~0.6mol% of aromatic acid or its carboxylate,
R5-R4-Si-(R6)3Formula 2,
R in formula 24For the alkylidene of carbon number 0~6, R5For the alkylene of carbon number 2~10, amino, imino group, epoxy radicals
Or aromatic radical, or carbon number 2~25 alkyl or thiol base, R6For the alkoxy of carbon number 1~6；
（2）By step（1）Obtained melt polycondensation thing carries out solid phase and obtains polyester, and the temperature of solid phase is 220~240
℃；
（3）Spinning after polyester is dried, obtains hydrolysis-resistant polyester fiber after final deep processing；
In the fiber contain silicon-containing compound as shown in Equation 1, its content in terms of element silicon relative in fiber by aromatic series two
0.01~0.5mol% of first acid or the construction unit of its carboxylate formation,
Formula 1
Wherein, R1、R2、R3The respectively alkyl of polyester molecule chain or carbon number 1~6, R1、R2And R3In at least one be poly-
Ester molecule chain；
The degree of stretching of the fiber is 8~50%；Tan (delta) temperature of the fiber measured with dynamic mechanical analytic approach is
135~180 DEG C.
2. the preparation method of hydrolysis-resistant polyester fiber according to claim 1, it is characterized in that：The R4For methylene, R5For
Phenylamino.
3. the preparation method of hydrolysis-resistant polyester fiber according to claim 1, it is characterized in that：The silicon-containing compound is with silicon
0.05~0.3mol% of the element meter relative to the construction unit formed in fiber by aromatic acid or its carboxylate.
4. the preparation method of hydrolysis-resistant polyester fiber according to claim 1, it is characterized in that：Silication shown in the formula 2 is closed
The addition of thing is equivalent to aromatic acid or 0.06~0.4mol% of its carboxylate.
5. the preparation method of hydrolysis-resistant polyester fiber according to claim 1, it is characterized in that：The deep processing is one section and prolonged
Stretch, a heat roller temperature is 70~100 DEG C, two heat roller temperatures are 120~150 DEG C, extension ratio is 1.5~6.5 times.
6. the preparation method of hydrolysis-resistant polyester fiber according to claim 1, it is characterized in that：The deep processing is two sections and prolonged
Stretch, a heat roller temperature is 80~120 DEG C, two heat roller temperatures are 130~160 DEG C, three heat roller temperatures are 170~230 DEG C, one, two
Extension ratio between hot-rolling is that the extension ratio between 3.0~5.0 times, two, three hot-rollings is 1.5~2.0 times.
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| CN113801309A (en) * | 2020-06-12 | 2021-12-17 | 东丽纤维研究所（中国）有限公司 | Hydrolysis-resistant high-strength cation dyeable polyester composition and preparation method and application thereof |
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| CN101469108A (en) * | 2007-12-24 | 2009-07-01 | 东丽纤维研究所（中国）有限公司 | Production method of hydrolysis resistant polyester composition |
| CN102485770A (en) * | 2010-12-06 | 2012-06-06 | 东丽纤维研究所（中国）有限公司 | Polyester and its production method |
| CN102702699A (en) * | 2012-07-06 | 2012-10-03 | 上海日之升新技术发展有限公司 | Glass-fiber-reinforced hydrolysis-resistant polyester material and preparation method thereof |
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| CN101469108A (en) * | 2007-12-24 | 2009-07-01 | 东丽纤维研究所（中国）有限公司 | Production method of hydrolysis resistant polyester composition |
| CN102485770A (en) * | 2010-12-06 | 2012-06-06 | 东丽纤维研究所（中国）有限公司 | Polyester and its production method |
| CN102702699A (en) * | 2012-07-06 | 2012-10-03 | 上海日之升新技术发展有限公司 | Glass-fiber-reinforced hydrolysis-resistant polyester material and preparation method thereof |
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