CN102924701A - Hydrophilic polyester and preparation method thereof - Google Patents
Hydrophilic polyester and preparation method thereof Download PDFInfo
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- CN102924701A CN102924701A CN2012104663029A CN201210466302A CN102924701A CN 102924701 A CN102924701 A CN 102924701A CN 2012104663029 A CN2012104663029 A CN 2012104663029A CN 201210466302 A CN201210466302 A CN 201210466302A CN 102924701 A CN102924701 A CN 102924701A
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Abstract
The invention provides a hydrophilic polyester and a preparation method of the hydrophilic polyester. The hydrophilic polyester is characterized in that the molecular chain comprises two chain segments like -COC6H4COOCH2CH2O- and -COC6H4COOCH2CH(OH)CH(OH)CH(OH)CH(OH)CH2O- with a quantitative proportion of 100:0.1-2.0; the intrinsic viscosity is 0.50-0.85g/dl and the melting temperature is 210-265 DEG C. The introduction of the hydrophilic groups into the polyester macromolecular chain and the change of the polyester crystal structure by increasing an amorphous zone are beneficial to the enterance of the water molecules, thereby increasing the hydrophilicity of the polyester, and the surface contact angle of the polyester chip is 40-65 degrees. The spun fiber has higher moisture regain rate and can be used for underwear, sporting suit, liner and the like. The method provided by the invention applys trace additive for the modification of the polyester, the additive has a few effects on the polymerization process, polyester quality and spinnability owing to the small addition amount. The obtained polyester has good modification effect and is especially suitable for melt direct spinning. The method provided by the invention reduces the development cost of the product and is easy to realize industrial production.
Description
Technical field
The present invention relates to a kind of hydrophilic polyester and preparation method thereof.
Background technology
Polyester and trevira have stepped into from 20 century 70s since the heavy industrialization, and tempo is far longer than other synthetic materialss and synthon, and China's trevira output was 2,513 ten thousand tons in 2010, accounted for 81% of China's chemical fibre output;
Account for 70% of Polyester fiber production.10 years from now on, Polyester and trevira will keep the speed increment more than 3%, and trevira will account for more than 60% of world's fiber product total amount.The physical and mechanical properties of trevira all can better satisfy the needs of various uses such as brute force, wear resistance, rebound resilience and dimensional stability.But trevira is a kind of typical hydrophobic fibre, and moisture regain only has 0.4%, and as the skintight suit material, its snugness of fit is very poor, and in high humidity, the condition of high temperature, the clothes that people wear synthon have feeling of oppression and heat, and mood is had the fidgets; Under humid tropical condition, human body and check room frictional force increase, and sense of heaviness increases, on people's psychology and the not very big impact of physiological change generation.Simultaneously, the trevira wetting ability is very poor, also gives to weave and brings series of problems.As easily gather static, easily to inhale dust, wipe oil stain difficult etc.For this reason, people have done a large amount of research work aspect the trevira hydrophilicity improving.Developed country is since the eighties in last century, the future development of natural fiber and textiles is progressively caught up with or surmounted to trevira and textiles thereof towards performance, quality and economic target, the developing goal that the super emulation synthon with features such as high function, high-quality, less energy-consumption and low emissions are synthon and textiles thereof.Simultaneously, moisture absorption, the perspire of raising synthetic fabrics also are one of following textiles developing direction.
The hydrophilic method that changes polyester is to adopt the means of copolymerization to introduce hydrophilic radical at normal polyester, strengthens the avidity with water.The kind of hydrophilic radical and the quantity of hydrophilic radical are very important, and polar group such as hydroxyl, amino, amide group, carboxyl etc. have stronger avidity to water molecules.The water-absorbent of much utilizing water-soluble polyester to improve trevira is arranged at present, but because the manufacturing cost of " water-soluble polyester " is higher, composite spinning technology is not only complicated and yield poorly, and the fiber price is higher, so limited its development and application.Such as polymer masterbatch and the synthetic method (patent No. 200710118744) thereof of domestic patent for the preparation of high moisture absorption and high moisture exclusion polyester textile, preparation method's (patent No. 200710178879) of a kind of acidic dyeable polyester and this acidic dyeable polyester and fiber thereof, produce continuously the method and apparatus (patent No. 200610039096) of damp absorbent polyester, cationic dye deep dyeing copolyester at normal pressure and preparation method thereof (patent No. 200410060520.8), water absorbability copolyester and with the moisture-absorbing fibre (patent No. 96104374) of its manufacturing, a kind of isophthalate modified poly terephthalic acid 1, the preparation method of 2-propyl alcohol copolyesters (patent No. 200910101792.0) etc.
Less about the polyester modification research that contains sorbyl alcohol, as take Isosorbide (product behind the sorbyl alcohol catalytic dehydration), ethylene glycol, terephthalic acid as raw material, adopt the PTA legal system standby the Isosorbide massfraction be 20% atactic polyester have good thermostability and spinning property.But utilize sorbyl alcohol to prepare the research that polyester carries out micro-modification and have no report.Method of the present invention, the addition of sorbyl alcohol and polyoxyethylene glycol is few, and is less on polymerization and the impact of polyester quality when guaranteeing modified effect.Adopt the method for in-situ polymerization, avoid the functional defect of reuniting and causing owing to wetting ability, flexibility group.The method cost increases few, and modified effect is good, is particularly suitable for fused mass directly spinning technique.
Summary of the invention
The purpose of this invention is to provide a kind of hydrophilic polyester and preparation method thereof, utilize sorbyl alcohol to prepare polyester and carry out micro-modification, to improve the hydrophilicity of polyester.
In order to achieve the above object, the invention provides a kind of hydrophilic polyester, it is characterized in that: comprise in its molecular chain-COC
6H
4COOCH
2CH
2O-and
Segment, and the quantitative proportion of two kinds of segments is 100: 0.1～2.0; Limiting viscosity is 0.50～0.85g/dl, and melt temperature is 210～265 ℃.
Further, after described hydrophilic polyester was made section, the surface contact angle of section was 45～60 °.
The present invention also provides the preparation method of above-mentioned hydrophilic polyester, it is characterized in that, concrete steps are:
The first step: terephthalic acid is mixed the preparation slurry with ethylene glycol according to 1: 1.05～2.0 mol ratio;
Second step: the slurry of the first step gained is added reaction kettle of the esterification carries out the first esterification, the by product collecting amount reach theoretical value 82%～95% the time, add sorbyl alcohol and polyoxyethylene glycol, carry out the second esterification;
The 3rd step: after finishing the second esterification, send the carboxylate of gained to batch condensation polymerization reactor and carry out polycondensation, make hydrophilic polyester.
Preferably, in the described second step, the first esterification is reacted under 225～250 ℃, the condition of 0～0.4MPa, and the reaction times is 0.5～4h.
Preferably, in the described second step, the second esterification is reacted under 240～260 ℃, the condition of normal pressure, and the reaction times is 0.5～1h.
Preferably, in the described second step, the add-on of sorbyl alcohol is 0.1～2.0% of the terephthalic acid mole number described in the first step, polyoxyethylene glycol is PEG-2000, PEG-4000 or PEG-6000, and the add-on of polyoxyethylene glycol is 0.05～0.2% of the terephthalic acid mole number described in the first step.
Preferably, in the described second step, before the slurry adding reaction kettle of the esterification with the first step gained carries out the first esterification, first with itself and catalyst mix, described catalyzer is Titanium series catalyst, antimony-based catalyst or their composition, the add-on of catalyzer is 120～550ppm, and radix is the quality of the terephthalic acid described in the first step.
More preferably, described Titanium series catalyst is titanium dioxide or tetrabutyl titanate, and described antimony-based catalyst is antimonous oxide, antimony acetate or antimony glycol.
Preferably, in the described second step, before the slurry adding reaction kettle of the esterification with the first step gained carries out the first esterification, first it is mixed with thermo-stabilizer and antioxidant.
More preferably, the add-on of described thermo-stabilizer is 0～0.02wt% of the terephthalic acid described in the first step, and the add-on of antioxidant is 0～0.03wt% of the terephthalic acid described in the first step.
More preferably, described antioxidant is one or more the mixture in antioxidant 1010, antioxidant 168 and the antioxidant 616; Described thermo-stabilizer is one or more the mixture in trimethyl phosphite 99, alkylphosphonic acid carboxylic acid diester and three (nonyl phenyl) phosphorous acid ester.
Preferably, in the described second step, described by product is water, in the first esterification reaction process, by separation column with moisture from out collecting, with graduated cylinder measurement collection amount, calculate theoretical value according to reaction formula.
Preferably, in described the 3rd step, the temperature of polycondensation remains on 260～290 ℃, and polycondensation comprises prepolymerization reaction and the poly-reaction of final minification, and the prepolymerization reaction time is 0.5～2h, and the poly-reaction times of final minification is 1～2h.
Preferably, in described the 3rd step, before carrying out polycondensation, batch condensation polymerization reactor is vacuumized small molecules.
Preferably, described each concrete steps adopt intermittent type, semi continuous or continous way production technique.
Because sorbyl alcohol contains great amount of hydroxy group, introduces hydrophilic radical in the macromolecular chain for polyester, changes simultaneously the crystalline texture of polyester, increase the pars amorpha, be conducive to entering of water molecules, thereby improve the hydrophilicity of polyester.Because this polyester introduced hydrophilic radical, so the hydrophilicity of polyester slice improves greatly, and the surface contact angle of section is 45～60 °, and the fiber that spins also has higher moisture regain, can be used for underwear, sweat shirt, lining etc.The inventive method has reduced product development cost, realizes easily suitability for industrialized production.Owing to introduced sorbyl alcohol in the polycondensation process of the present invention, polycondensation there is certain impact, the present invention has finally adopted Titanium series catalyst and/or antimony-based catalyst to carry out efficient catalytic through a large amount of experiments.Comprehensive, the present invention adopts indium addition that polyester is carried out modification, and because addition is few, so less on the spinning property impact of polyester, modified effect is good, is particularly suitable for fused mass directly spinning technique.
By a large amount of experimental verifications, the catalyzer that esterification system of the present invention adopts is Titanium series catalyst and/or antimony-based catalyst, Titanium series catalyst is titanium dioxide, tetrabutyl titanate etc., and described antimony-based catalyst is antimonous oxide, antimony acetate and antimony glycol etc.The add-on of catalyzer is 120～550ppm, and radix is the quality of described terephthalic acid.Esterification system of the present invention also can contain thermo-stabilizer and antioxidant, the add-on of thermo-stabilizer is 0～0.02wt% of the terephthalic acid described in the first step, and the add-on of antioxidant is 0～0.03wt% of the terephthalic acid described in the first step.Described antioxidant is one or more the mixture in antioxidant 1010, antioxidant 168 and the antioxidant 616; Described thermo-stabilizer is one or more the mixture in trimethyl phosphite 99, alkylphosphonic acid carboxylic acid diester and three (nonyl phenyl) phosphorous acid ester.
Sorbyl alcohol contains six hydroxyls, has very strong water absorbing properties, and polyoxyethylene glycol also often is used to improve wetting ability and the feel of polyester.The present invention adds sorbyl alcohol and polyoxyethylene glycol in the second esterification stage.Sorbyl alcohol under the second esterification condition with terephthaldehyde's acid-respons, generate
The segment of structure, because space steric effect, the features such as distortion, nonplanar structure of the hydroxyl activation energy difference that links to each other of coordination and segment not, and by control the second esterification reaction temperature and pressure, guarantee that 2,3,4,5 hydroxyls that sorbyl alcohol links to each other with carbon atom do not react.When esterification is finished, gamma value reaches more than 99.4% so that the macromolecular chain of ensuing polycondensation does not occur is crosslinked, be exposed to the molecular chain surface-OH can stop tightly packed between the molecular chain, increase the free volume of polymkeric substance, thereby guarantee the wetting ability of polyester;-OH itself has stronger avidity to water molecules, can be combined with airborne moisture, improves the wetting ability of polyester;
In-existence of OH reduces symmetry and the regularity of molecular chain to a certain extent, and so that degree of crystallinity reduces, molecule closely regular arrangement reduces, and grain surface is long-pending to be increased, and the hydrophilic radical that grain surface does not become bond to close is also many, thereby wetting ability improves; The water molecules in conjunction with between water and the unformed area molecular chain of-OH self combination has formed stratiform and has transferablely had a gradient hydrophilic layer, forms existing hydrophile function in the polymkeric substance, again the hydrophilic-structure of conducting moisture function is arranged.
The thermostability of polyoxyethylene glycol is relatively poor, adds in the second esterification stage, has reduced the residence time of polyoxyethylene glycol in still, avoids polyoxyethylene glycol to degrade, and the impact reaction reduces the side reactions such as glycol ether generation.The adding of polyoxyethylene glycol has improved flexibility and the wetting ability of polyester simultaneously.
Preparation method of the present invention, the addition of sorbyl alcohol and polyoxyethylene glycol is few, and is less on polymerization and the impact of polyester quality when guaranteeing modified effect.Adopt the method for in-situ polymerization, avoid the functional defect of reuniting and causing owing to wetting ability, flexibility group.The method cost increases few, and modified effect is good, is particularly suitable for fused mass directly spinning technique.
Compared with prior art, the invention has the beneficial effects as follows:
(1) the present invention adopts and adds the hydrophilicity that sorbyl alcohol improves polyester, and sorbyl alcohol contains six hydroxyls, adds sorbyl alcohol in the second esterification stage and guarantees that the hydroxyl on its side chain does not react, and generates
The segment of structure.And the existing hydrophile function in the formation polymkeric substance, again the hydrophilic-structure of conducting moisture function is arranged, greatly improve the hydrophilicity of polyester.
(2) the present invention has also added a certain amount of polyoxyethylene glycol, and the existence of polyoxyethylene glycol has increased the kindliness of polyester macromolecule segment, reduces the fusing point of polyester, simultaneously the wetting ability of polyester is increased.Add polyoxyethylene glycol in the second esterification stage, reduced the residence time of polyoxyethylene glycol in still, avoid polyoxyethylene glycol to degrade, the impact reaction reduces the side reactions such as glycol ether generation.
(3) addition of the sorbyl alcohol of the present invention's adding and polyoxyethylene glycol is little, does not affect polymerization process and polyester quality when guaranteeing modified effect.Method of the present invention, technique is simple, can carry out modification production at existing device.Cost increases few, is fit to large-scale production, especially is fit to fused mass directly spinning technique.
(4) surface contact angle of section of the present invention is 45～60 °, and the fiber that spins also has higher moisture regain, can be used for underwear, sweat shirt, lining etc.
(5) hydrophilic polyester that makes of the present invention can use by various ordinary methods, as can with the inorganic reinforcement compound use, inorganic reinforcement can be used for various long fibres and short fiber.Hydrophilic polyester of the present invention can also use the polyester working method of various routines to process, such as single screw extrusion machine, twin screw extruder, Banbury mixer.Hydrophilic polyester of the present invention is used for the various fields such as fiber, film, makes various subsequent products.
Description of drawings
Fig. 1 is the FTIR spectrogram of the hydrophilic polyester of embodiment 1 gained;
Fig. 2 is the nucleus magnetic resonance figure of the hydrophilic polyester of embodiment 1 gained.
Embodiment
Below in conjunction with embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Terephthalic acid is mixed in proportion the preparation slurry with ethylene glycol.The slurry for preparing and catalyzer metatitanic acid four butyl esters are mixed in proportion rear adding reaction kettle of the esterification carry out the first esterification, the first esterification reaction temperature is 225 ℃, and the time of reaction is 4h, and the relative pressure of reaction is 0MPa.By separation column water byproduct is separated and to be collected, with graduated cylinder measurement collection amount, calculate theoretical value according to reaction formula, the collecting amount of water reach theoretical value 82% the time, add sorbyl alcohol and polyoxyethylene glycol (PEG-2000) and carry out the second esterification, the second esterification reaction temperature is 240 ℃, and pressure is normal pressure, and reaction time of esterification is 1h.After finishing esterification, carboxylate is delivered to batch condensation polymerization reactor, vacuumize, carry out the poly-reaction of precondensation and final minification, prepolymerization reaction carries out under the rough vacuum condition, and final minification gathers under high vacuum condition and carries out, the temperature of polycondensation remains on 260 ℃, the prepolymerization reaction time is 2h, and the poly-reaction times of final minification is 2h, makes hydrophilic polyester.The preparation method adopts the intermittence type polymerization production technique.Comprise in the molecular chain of the hydrophilic polyester of gained-COC
6H
4COOCH
2CH
2O-and
Two kinds of segment quantitative proportions are 100: 0.1; The limiting viscosity of described hydrophilic polyester is 0.50g/dl, and melt temperature is 210 ℃.After making section, the surface water contact angle of section is 45 degree.
Fourier's infrared tester (FTIR) of the NEXUS-670 model of employing U.S. Nicolet company development is at wave number 500-3500cm
-1Test.As shown in Figure 1,3435cm
-1The representation hydroxy peak, peak at place, i.e. poly-hydroxy structure in the sorbyl alcohol (PET is herein without any peak); 2957cm
-1The vibration absorption peak of C-H in the bimodal representative polyester at place; At 1716cm
-1The strong absorption peak at place should be carbonyl (C=O) stretching vibration to be caused; 1400-1600cm
-1The weak peak at place is the characteristic absorbance band spectrum of phenyl ring; At 1245cm
-1And 1096cm
-12 of the place wide absorption peaks by force and are that the asymmetrical stretching vibration by the C-O-C key in the ester causes; 1017cm
-1And 873cm
-1The vibration of C-H in-plane deformation and the outer formation vibration of face on the corresponding Isosorbide-5-Nitrae substituted benzene ring of peak difference at place; At 725cm
-1Narrow and the strong absorption peak at place is to be caused by the C-H flexural vibration in the aromatic ring.
Nuclear-magnetism characterizes and adopts the Switzerland Avance400 of Bruker company nuclear magnetic resonance spectrometer to carry out,
1The vibrational frequency of HNMR is 400mHz, tests under 25 ℃ condition, uses the solvent deuterium for trifluoroacetic acid (CF
3COOD) calibration.From
1See among the HNMR, as shown in Figure 2, solvent C F
3The skew peak of COOD can see in multipolymer at δ=8.10ppm place a peak occurring that this peak is the H peak on the phenyl ring at the 11.5ppm place.Methylene radical H peak in that δ=4.70ppm occurs is PET molecular chain-COC
6H
4COOCH
2CH
2H peak in the methylene radical on the O-.The H peak that δ in spectrogram=3.9-4.2ppm occurs, for
H in the middle pure unit, and all the other H except methylene radical and benzene ring hydrogen in the main chain.
Embodiment 2
Terephthalic acid is mixed in proportion the preparation slurry with ethylene glycol.The slurry for preparing and antimony glycol, antioxidant 1010 and trimethyl phosphite 99 are mixed in proportion rear adding reaction kettle of the esterification carry out the first esterification, the first esterification reaction temperature is 250 ℃, and the time of reaction is 0.5h, and the relative pressure of reaction is 0.4MPa.By separation column with moisture from out collecting, with graduated cylinder measurement collection amount, calculate theoretical value according to reaction formula, the collecting amount of water byproduct reach theoretical value 95% the time, add sorbyl alcohol and polyoxyethylene glycol (PEG-4000) and carry out the second esterification, the second esterification reaction temperature is 260 ℃, and pressure is normal pressure, and reaction time of esterification is 0.5h.After finishing esterification, carboxylate is delivered to batch condensation polymerization reactor, vacuumize, carry out the poly-reaction of precondensation and final minification, prepolymerization reaction carries out under the rough vacuum condition, and final minification gathers under high vacuum condition and carries out, the temperature of polycondensation remains on 290 ℃, the prepolymerization reaction time is 0.5h, and the poly-reaction times of final minification is 1h, makes hydrophilic polyester; The preparation method adopts half continuous formula polymerization process.Comprise in the molecular chain of this hydrophilic polyester-COC
6H
4COOCH
2CH
2O-and
Two kinds of segment quantitative proportions are 100: 2.0; The limiting viscosity of described hydrophilic polyester is 0.85g/dl, and melt temperature is 265 ℃.After making section, the surface water contact angle of section is 50 degree.
Embodiment 3
Terephthalic acid is mixed in proportion the preparation slurry with ethylene glycol.The slurry for preparing and antimonous oxide and tetrabutyl titanate mixture, antioxidant 168 and alkylphosphonic acid carboxylic acid diester are mixed in proportion rear adding reaction kettle of the esterification carry out the first esterification, the first esterification reaction temperature is 240 ℃, the time of reaction is 3h, and the relative pressure of reaction is 0.3MPa.By separation column with moisture from out collecting, with graduated cylinder measurement collection amount, calculate theoretical value according to reaction formula, the collecting amount of water byproduct reach theoretical value 92% the time, add sorbyl alcohol and polyoxyethylene glycol (PEG-6000) and carry out the second esterification, the second esterification reaction temperature is 250 ℃, and pressure is normal pressure, and reaction time of esterification is 1h.After finishing esterification, carboxylate is delivered to batch condensation polymerization reactor, vacuumize, carry out the poly-reaction of precondensation and final minification, prepolymerization reaction carries out under the rough vacuum condition, and final minification gathers under high vacuum condition and carries out, the temperature of polycondensation remains on 280 ℃, the prepolymerization reaction time is 1h, and the poly-reaction times of final minification is 1h, makes hydrophilic polyester; The preparation method adopts the continous way polymerization process.Comprise in the molecular chain of this hydrophilic polyester-COC
6H
4COOCH
2CH
2O-and
Two kinds of segment quantitative proportions are 100: 1.0; The limiting viscosity of described hydrophilic polyester is 0.65g/dl, and melt temperature is 255 ℃.After making section, the surface water contact angle of section is 55 degree.
Terephthalic acid is mixed in proportion the preparation slurry with ethylene glycol.The mixture of the slurry for preparing and tetrabutyl titanate, antioxidant 616, trimethyl phosphite 99 and three (nonyl phenyl) phosphorous acid ester is mixed in proportion rear adding reaction kettle of the esterification carries out the first esterification, the first esterification reaction temperature is 230 ℃, the time of reaction is 2.5h, and the relative pressure of reaction is 0.25MPa.By separation column with moisture from out collecting, with graduated cylinder measurement collection amount, calculate theoretical value according to reaction formula, the collecting amount of water byproduct reach theoretical value 85% the time, add sorbyl alcohol and polyoxyethylene glycol (PEG-2000) and carry out the second esterification, the second esterification reaction temperature is 245 ℃, and pressure is normal pressure, and reaction time of esterification is 0.5h.After finishing esterification, carboxylate is delivered to batch condensation polymerization reactor, vacuumize, carry out the poly-reaction of precondensation and final minification, prepolymerization reaction carries out under the rough vacuum condition, and final minification gathers under high vacuum condition and carries out, the temperature of polycondensation remains on 265 ℃, the prepolymerization reaction time is 1h, and the poly-reaction times of final minification is 1.5h, makes hydrophilic polyester; Comprise in the molecular chain of this hydrophilic polyester-COC
6H
4COOCH
2CH
2O-and
Two kinds of segment quantitative proportions are 100: 0.6; The limiting viscosity of described hydrophilic polyester is 0.55g/dl, and melt temperature is 220 ℃.After making section, the surface water contact angle of section is 60 degree.
Embodiment 5
Terephthalic acid is mixed in proportion the preparation slurry with ethylene glycol.The slurry for preparing and antimony acetate, antioxidant 1010, antioxidant 168 and three (nonyl phenyl) phosphorous acid ester are mixed in proportion rear adding reaction kettle of the esterification carry out the first esterification, the first esterification reaction temperature is 230 ℃, the time of reaction is 3h, and the relative pressure of reaction is 0.35MPa.By separation column with moisture from out collecting, with graduated cylinder measurement collection amount, calculate theoretical value according to reaction formula, the collecting amount of water byproduct reach theoretical value 88% the time, add in proportion sorbyl alcohol and polyoxyethylene glycol (PEG-4000) and carry out the second esterification, the second esterification reaction temperature is 250 ℃, and pressure is normal pressure, and reaction time of esterification is 0.5h.After finishing esterification, carboxylate is delivered to batch condensation polymerization reactor, vacuumize, carry out the poly-reaction of precondensation and final minification, prepolymerization reaction carries out under the rough vacuum condition, and final minification gathers under high vacuum condition and carries out, the temperature of polycondensation remains on 265 ℃, the prepolymerization reaction time is 1.5h, and the poly-reaction times of final minification is 1.5h, makes hydrophilic polyester; Comprise in the molecular chain of this hydrophilic polyester-COC
6H
4COOCH
2CH
2O-and
Two kinds of segment quantitative proportions are 100: 0.8; The limiting viscosity of described hydrophilic polyester is 0.60g/dl, and melt temperature is 235 ℃.After making section, the surface water contact angle of section is 50 degree.
Terephthalic acid is mixed in proportion the preparation slurry with ethylene glycol.With slurry and the antimonous oxide for preparing, antioxidant 1010, antioxidant 168 and antioxidant 616 mixtures, trimethyl phosphite 99, alkylphosphonic acid carboxylic acid diester and three (nonyl phenyl) phosphite mixture are mixed in proportion rear adding reaction kettle of the esterification and carry out the first esterification, the first esterification reaction temperature is 240 ℃, the time of reaction is 3h, and the relative pressure of reaction is 0.35MPa.By separation column with moisture from out collecting, with graduated cylinder measurement collection amount, calculate theoretical value according to reaction formula, the collecting amount of water byproduct reach theoretical value 90% the time, add in proportion sorbyl alcohol and polyoxyethylene glycol (PEG-6000) and carry out the second esterification, the second esterification reaction temperature is 255 ℃, and pressure is normal pressure, and reaction time of esterification is 1h.After finishing esterification, carboxylate is delivered to batch condensation polymerization reactor, vacuumize, carry out the poly-reaction of precondensation and final minification, prepolymerization reaction carries out under the rough vacuum condition, and final minification gathers under high vacuum condition and carries out, the temperature of polycondensation remains on 285 ℃, the prepolymerization reaction time is 1.5h, and the poly-reaction times of final minification is 1.5h, makes hydrophilic polyester; Comprise in the molecular chain of this hydrophilic polyester-COC
6H
4COOCH
2CH
2O-and
Two kinds of segment quantitative proportions are 100: 1.2; The limiting viscosity of described hydrophilic polyester is 0.65g/dl, and melt temperature is 240 ℃.After making section, the surface water contact angle of section is 50 degree.
Claims (10)
1. a hydrophilic polyester is characterized in that: comprise in its molecular chain-COC
6H
4COOCH
2CH
2O-and
Segment, and the quantitative proportion of two kinds of segments is 100: 0.1～2.0; Limiting viscosity is 0.50～0.85g/dl, and melt temperature is 210～265 ℃.
2. hydrophilic polyester as claimed in claim 1, it is characterized in that: after making section, the surface contact angle of section is 45～60 °.
3. the preparation method of hydrophilic polyester claimed in claim 1 is characterized in that, concrete steps are:
The first step: terephthalic acid is mixed the preparation slurry with ethylene glycol according to 1: 1.05～2.0 mol ratio;
Second step: the slurry of the first step gained is added reaction kettle of the esterification carries out the first esterification, the by product collecting amount reach theoretical value 82%～95% the time, add sorbyl alcohol and polyoxyethylene glycol, carry out the second esterification;
The 3rd step: after finishing the second esterification, send the carboxylate of gained to batch condensation polymerization reactor and carry out polycondensation, make hydrophilic polyester.
4. the preparation method of hydrophilic polyester as claimed in claim 3 is characterized in that, in the described second step, the first esterification is reacted under 225～250 ℃, the condition of 0～0.4MPa, and the reaction times is 0.5～4h.
5. the preparation method of hydrophilic polyester as claimed in claim 3 is characterized in that, in the described second step, the second esterification is reacted under 240～260 ℃, the condition of normal pressure, and the reaction times is 0.5～1h.
6. the preparation method of hydrophilic polyester as claimed in claim 3, it is characterized in that, in the described second step, the add-on of sorbyl alcohol is 0.1～2.0% of the terephthalic acid mole number described in the first step, described polyoxyethylene glycol is PEG-2000, PEG-4000 or PEG-6000, and the add-on of polyoxyethylene glycol is 0.05～0.2% of the terephthalic acid mole number described in the first step.
7. the preparation method of hydrophilic polyester as claimed in claim 3, it is characterized in that, in the described second step, before the slurry adding reaction kettle of the esterification with the first step gained carries out the first esterification, first with itself and catalyst mix, described catalyzer is Titanium series catalyst, antimony-based catalyst or their composition, and the add-on of catalyzer is 120～550ppm, and radix is the quality of the terephthalic acid described in the first step.
8. the preparation method of hydrophilic polyester as claimed in claim 3 is characterized in that, in the described second step, before the slurry adding reaction kettle of the esterification with the first step gained carries out the first esterification, first it is mixed with thermo-stabilizer and antioxidant.
9. the preparation method of hydrophilic polyester as claimed in claim 3 is characterized in that, in the described second step, by product is water, in the first esterification reaction process, by separation column with moisture from out collecting, with graduated cylinder measurement collection amount, calculate theoretical value according to reaction formula.
10. the preparation method of hydrophilic polyester as claimed in claim 3, it is characterized in that, in described the 3rd step, the temperature of polycondensation remains on 260～290 ℃, polycondensation comprises prepolymerization reaction and the poly-reaction of final minification, the prepolymerization reaction time is 0.5～2h, and the poly-reaction times of final minification is 1～2h.
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| CN201210466302.9A Active CN102924701B (en) | 2012-11-16 | 2012-11-16 | Hydrophilic polyester and preparation method thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103469628A (en) * | 2013-09-16 | 2013-12-25 | 上海大学 | Method for dyeing polyether type high-hydrophilicity polyester fiber |
| CN103789865A (en) * | 2014-01-26 | 2014-05-14 | 东华大学 | Preparation method of easily dyed polyester fiber with high hydrophilicity |
| CN103788350A (en) * | 2014-01-26 | 2014-05-14 | 东华大学 | Preparation method of polyhydric flexible polyester |
| CN103910862A (en) * | 2014-03-27 | 2014-07-09 | 泗阳宝源塑胶材料有限公司 | High-color fastness hydrophilic copolyester master batch and preparation method thereof |
| CN107936237A (en) * | 2017-11-13 | 2018-04-20 | 东华大学 | A kind of bio-based biodegradable polyester fiber and preparation method thereof |
| CN108003332A (en) * | 2016-10-28 | 2018-05-08 | 中国石油化工股份有限公司 | A kind of easy hydrolysis degradable polyester and its synthetic method |
| CN111117544A (en) * | 2020-01-03 | 2020-05-08 | 东华大学 | Biodegradable pressure-sensitive adhesive and preparation method thereof |
| CN111116887A (en) * | 2019-12-31 | 2020-05-08 | 上海慧翌新材料科技有限公司 | Preparation method of hydrophilic polyester |
| CN111154080A (en) * | 2020-01-19 | 2020-05-15 | 浙江万凯新材料有限公司 | Extrusion blow-molded PET resin and preparation method thereof |
| CN111875787A (en) * | 2020-07-07 | 2020-11-03 | 浙江恒澜科技有限公司 | High-heat-resistance degradable copolyester and preparation method thereof |
Families Citing this family (1)
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| CN107987263B (en) * | 2017-11-06 | 2020-07-03 | 中纺院（天津）科技发展有限公司 | Hydrophilic polyester and preparation method thereof |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103469628A (en) * | 2013-09-16 | 2013-12-25 | 上海大学 | Method for dyeing polyether type high-hydrophilicity polyester fiber |
| CN103789865A (en) * | 2014-01-26 | 2014-05-14 | 东华大学 | Preparation method of easily dyed polyester fiber with high hydrophilicity |
| CN103788350A (en) * | 2014-01-26 | 2014-05-14 | 东华大学 | Preparation method of polyhydric flexible polyester |
| CN103789865B (en) * | 2014-01-26 | 2016-04-06 | 东华大学 | A kind of preparation method of high hydrophilic easy-to-dye polyester fiber |
| CN103910862A (en) * | 2014-03-27 | 2014-07-09 | 泗阳宝源塑胶材料有限公司 | High-color fastness hydrophilic copolyester master batch and preparation method thereof |
| CN103910862B (en) * | 2014-03-27 | 2016-03-30 | 泗阳宝源塑胶材料有限公司 | A kind of high color fastness hydrophilic copolyester master batch and preparation method thereof |
| CN108003332B (en) * | 2016-10-28 | 2022-02-08 | 中国石油化工股份有限公司 | Easily hydrolyzed polyester and synthesis method thereof |
| CN108003332A (en) * | 2016-10-28 | 2018-05-08 | 中国石油化工股份有限公司 | A kind of easy hydrolysis degradable polyester and its synthetic method |
| CN107936237A (en) * | 2017-11-13 | 2018-04-20 | 东华大学 | A kind of bio-based biodegradable polyester fiber and preparation method thereof |
| CN111116887A (en) * | 2019-12-31 | 2020-05-08 | 上海慧翌新材料科技有限公司 | Preparation method of hydrophilic polyester |
| CN111117544A (en) * | 2020-01-03 | 2020-05-08 | 东华大学 | Biodegradable pressure-sensitive adhesive and preparation method thereof |
| CN111154080A (en) * | 2020-01-19 | 2020-05-15 | 浙江万凯新材料有限公司 | Extrusion blow-molded PET resin and preparation method thereof |
| CN111154080B (en) * | 2020-01-19 | 2022-07-05 | 万凯新材料股份有限公司 | Extrusion blow-molded PET resin and preparation method thereof |
| CN111875787A (en) * | 2020-07-07 | 2020-11-03 | 浙江恒澜科技有限公司 | High-heat-resistance degradable copolyester and preparation method thereof |
| CN111875787B (en) * | 2020-07-07 | 2022-07-08 | 浙江恒逸石化研究院有限公司 | High-heat-resistance degradable copolyester and preparation method thereof |
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