CN1834131A - Water-soluable sizing material polyester and prepn. thereof - Google Patents
Water-soluable sizing material polyester and prepn. thereof Download PDFInfo
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- CN1834131A CN1834131A CN 200610017686 CN200610017686A CN1834131A CN 1834131 A CN1834131 A CN 1834131A CN 200610017686 CN200610017686 CN 200610017686 CN 200610017686 A CN200610017686 A CN 200610017686A CN 1834131 A CN1834131 A CN 1834131A
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Abstract
This invention relates to polyester materials. The extracted aqueous soluble polyester paste comprises terephthalic acid and some other dicarboxylic acids, glycol and some other diols, some inorganic salt additives and at least two species of polyglycol with a structural formula shown below: H-(OCH2CH2)n-OH where n is not less than 2 and not more than 4 or not less than 45 and not more than 136. The method to prepare aqueous soluble polyester paste is direct esterification polycondensation during which modification ingredients including sulphonate, inorganic salts and polyglycol are added so that products are eligible for the requirements of sizing production in spinning. The aqueous soluble polyester not only performs good adhesion to dacron yarns and good miscibility to starch and other polymer paste, but also has the advantages of environmental friendliness and easy de-sizing.
Description
Technical field
The present invention relates to the polyester macromolecule material, mainly propose a kind of water-soluable sizing material polyester and preparation method and relate to and be applied to terylene and polyester-cotton blend starching.
Background technology
At present, PVA (polyvinyl alcohol) commonly used in the slurry is a slurry feedstock preferably, and its film-forming properties is very good, often is described as " hard and tough ".Yet the PVA slurry has a problem of environmental pollution can not solve well in using always, and the U.S. just proposes this problem in the early 1980s, and some countries (Germany etc.) in Europe also ban use of recently, and PVA is called as " unclean slurry "; In addition, PVA is general to the adhesivity of fiber, and its purposes is had certain limitation.Although another kind of spinning slurry main raw material starch has been done a large amount of improvement, because the film-forming properties that itself exists is poor, defectives such as toughness deficiency can not be used for yarn sizing separately, also need to use with other mixed with polymers.
It is well known in the art adopting sulfonic group dicarboxylic acid and polyoxyethylene glycol that the polymkeric substance of terephthalic acid and ethylene glycol is carried out having certain water dispersible after the modification.For example, the water-soluble copolyester that sea-island fibre commonly used is used, Chinese patent 200510038276.X has introduced such polyester, make the 3rd monomer with sulfonic group dicarboxylic acid such as 5-sodium sulfo isophthalates, adopt PTA route or the copolycondensation of DMT route to prepare water-soluble copolyester, product that makes and normal polyester section blending make sea-island fibre.But this polymkeric substance can only be with pH value greater than dissolving in 12 the water, and gained solution belongs to small molecules solution, and solution does not have cohesiveness and film-forming properties.Chinese patent 99815831.3 has been told about such polyester equally, and is to be used for textile mills' slurry application facet, and the polymerization degree that this patent discloses used polyoxyethylene glycol is 2～20, that is to say that molecular weight is 106～900.Products obtained therefrom is because the component that is added contains sodium group, very easily combine and be created on the calcium salt that is insoluble in water such as calcium sulphonate etc. with calcium ions and magnesium ions in the water, form a large amount of flosss or form comparatively compact isolating layer of one deck in surface of polyester, make polymkeric substance be difficult to be dissolved in the water fully, therefore this patent proposition product must be dissolved in the deionized water, because the deionized water price is higher and obtain difficulty, it is very inconvenient so a lot of spinning milies being used.
Therefore, when needing that still product improved the adhesive power of product and wear resistance, multipolymer is dissolved in the process water that conveniently is easy to get at an easy rate.
We are in the process of sintetics, a kind of inorganic salt have been added, make polymkeric substance simultaneously at dissolved, reduced the hardness of water quality, that is to say that the dirty metal ion (mainly being calcium ions and magnesium ions) that causes to being free in the water carries out complexing, its effect to polymkeric substance is weakened significantly, so, just make product can be dissolved in easily in hardness higher the general industry water and domestic water.
Summary of the invention
The objective of the invention is to propose a kind of water-soluable sizing material polyester and preparation method who is used for terylene and polyester-cotton blend yarn sizing, make the water-soluble polyester of acquisition not only have good adhesive force to spun polyester thread, good with starch and the high molecular compatibility of other slurry, but also have advantages such as environmental protection and destarch be easy.
The water-soluable sizing material polyester that the present invention proposes, it comprises:
(1), terephthalic acid or its derivative;
(2), at least account for the minimum 3mol% of di-carboxylic acid total mole number, and at least a di-carboxylic acid except that terephthalic acid or its derivative of maximum 25mol%;
(3), one or more dibasic alcohol and must contain ethylene glycol, wherein glycol content accounts for dibasic alcohol total mole number 80mol% at least;
(4), mole number is the minimum 0.3mol% of di-carboxylic acid total mole number, and at least two kinds of polyoxyethylene glycol with following structural formula of 1.5mol% at most:
H-(O CH
2CH
2)
n-OH
2≤n≤4 and 45≤n≤136 wherein
(5), mole number is the minimum 10mol% of di-carboxylic acid total mole number, and the phthalic acid sulfonate or derivatives thereof of 20mol% at most;
(6) weight is the 0.3wt% at least of di-carboxylic acid gross weight, and the inorganic salt of maximum 2.5wt%.
The carboxyl and the hydroxyl that contain equivalent in the water-soluable sizing material polyester.About 0.125g polymkeric substance is dissolved in 25ml phenol/tetrachloroethane 50/50 solvent, and the limiting viscosity of the water-soluble polyester of measuring under 25 ℃ of conditions of the present invention is 0.25dL/g at least, the highest 0.52dL/g.
The second-order transition temperature of water-soluble polyester of the present invention is at least 20 ℃, and is the highest 68 ℃, and the better products second-order transition temperature is at least 30 ℃ to 60 ℃, and best is 38 ℃ to 54 ℃.
Water-soluable sizing material polyester of the present invention provides the inorganic additives of eliminating interim hardness and permanent hardness in the process water, make product in dissolution process, in advance carry out complexing and generate water-soluble complex compound with the dirty metal ion (mainly being calcium ions and magnesium ions) that causes that is free in the water, thus make calcium ions and magnesium ions no longer with polymkeric substance in sodium sulfonate produce replacement(metathesis)reaction and generate insoluble or be insoluble in the material of water.
The polyoxyethylene glycol component provides the wetting ability of water-soluble polyester but has not produced ion, thereby can avoid negative impact because of water hardness, except the hydrophilic advantage that can increase water-soluble polyester, use polyoxyethylene glycol also to have many other advantages, for example can improve the cohesive force of slurry and yarn and the wear resistance of increase yarn etc.
Water-soluable sizing material polyester of the present invention provides hydrophilic bifunctional sulfonate monomer to be: 1,3 rutgers-5-sodium sulfonate; 1,3 phthalic acid binaryglycol ester-5-potassium sulfonate; Dimethyl terephthalate (DMT), the 2-sodium sulfonate; Diglycol terephthalate, the 2-potassium sulfonate; Adding above-mentioned comonomer can make the hydrophobic polyester resin of original demonstration have can be scattered under proper condition and form the high molecular aqueous solution in the water.
Di-carboxylic acid except that terephthalic acid can be a m-phthalic acid; 1, the 6-hexanodioic acid; ω-nonane diacid; ω-sebacic acid etc.
Inorganic salt can be phosphate polymers, hexametaphosphate, hydrophosphate polymkeric substance.Optionally material has SODIUM PHOSPHATE, MONOBASIC, potassium primary phosphate, sodium acid phosphate, tripoly phosphate sodium STPP, Potassium tripolyphosphate, Sodium hexametaphosphate 99, hexa metaphosphoric acid potassium, trisodium phosphate, sodium acid pyrophosphate etc.
The inorganic salt that add are because the part functional group in its molecule is adsorbed on the active site on crystal (nucleus) surface that causes dirty metallic salt and forming by electrostatic force, suppress crystal growing, thereby make many crystal of formation remain on microcrystalline state, this has equaled to increase the solubleness that causes in the dirty metallic salt big flood; Owing to be adsorbed in functional group on the plane of crystal and be the part functional group in the Scale inhibitors molecule, those do not participate in the functional group of absorption, will present ionic to crystal, make crystal be in dispersion state because of the repulsive force of electric charge increases, make to cause dirty metal ion and no longer combine and produce floss with sodium sulfonate in the polymkeric substance.
The inorganic salt that add are because granularity is bigger, if directly sneak into polymkeric substance, make that the homogeneity of product is too poor not only to influence product appearance, and discontinuity appears in the effect of inorganic salt, thereby do not reach the ideal purpose.With high-speed shearing equipment inorganic salt are carried out adding in the polymkeric substance after fragmentation, the dispersion again earlier, making product appearance can not produce bigger variation and effect can be desirable more.Used dispersion medium adopts the dibasic alcohol of main reaction raw material and less water to form, because the polarity of water is stronger, its existence reaches can quicken rate of dispersion and the dispersion effect of inorganic salt in dibasic alcohol under the high speed shear effect, final water and dibasic alcohol are discharged from outside the system under the effect of vacuum in reaction process, inorganic salt with polymer formation the system of relative homogeneous.
The adding of polyoxyethylene glycol can provide the wetting ability of polymkeric substance and equally because it is the non-ionic type component, can be owing to the one-tenth in water quality dirt metal ion produce precipitation, and the snappiness and the wear resistance of product can be provided.But the kindliness that is it equally is better, and the crystallization velocity of product is improved, and crystallization increases the density of product, and structure is finer and close, thereby can make aqueous solvent be difficult to swollen polymer, also just makes the product solvability be subjected to certain placing restrictions on.Second-order transition temperature owing to itself is too low in addition, and the polymerization degree is more little, and second-order transition temperature is low more, if consumption is too big, will certainly makes product in use produce " moisture absorption is sticking again " phenomenon, thereby influence product performance.In order to obtain best product performance, adopted by low polymerization degree polyoxyethylene glycol and high-polymerization degree polyoxyethylene glycol and phthalic acid sulfonate collocation use, reach water miscible purpose jointly and have better comprehensive performance.
The preparation of water-soluable sizing material polyester of the present invention:
1, by di-carboxylic acid and diol reaction, by the direct esterification reaction, obtain intermediate compound I, be used for following polycondensation.
2, by phthalic acid sulfonate or its derivative and ethylene glycol by transesterification reaction, obtain intermediate II, be used for following polycondensation.
3, with the high speed shear diverting device inorganic additives is sheared dispersion, make it reach aim of even dispersion, thereby satisfy the quality product requirement, products obtained therefrom is component III, is used for following polycondensation.
4, by intermediate compound I, intermediate II, component III and the polycondensation of polyoxyethylene glycol process normal pressure, rough vacuum and high vacuum polymerization, finally synthesize target product.
Obtain intermediate compound I by di-carboxylic acid and dibasic alcohol by the direct esterification reaction, be one of means commonly used in the polyester industrial, its detailed process is:
A, in stainless steel preparation still, di-carboxylic acid and dibasic alcohol are modulated into slurry, under the effect of slurry supply pump, continuously slurry is sent in the stainless steel reaction kettle of the esterification that has chuck then, the temperature that keeps reactor is at 220～275 ℃, pressure remains on 0.20～0.35Mpa, reacted 1～8 hour, be preferable over 240～265 ℃, pressure remains on 0.25～0.35Mpa, residence time of material 3～4.5 hours.Material in the still to be prepared is all sent in the reaction kettle of the esterification, and esterification water quantities received reaches theoretical value ± 5%, and force value is tending towards 0, and the fractionation column top temperature can judge that reaction finishes when being lower than 100 ℃.
B, di-carboxylic acid can be terephthalic acid, m-phthalic acid, 1, and two or more composition in 6-hexanodioic acid, ω-nonane diacid, ω-sebacic acid etc. and these acid wherein must comprise terephthalic acid.
Wherein, it is 75% that terephthalic acid accounts for the ratio of mole of total di-carboxylic acid minimum, maximum 97%, other di-carboxylic acid except that terephthalic acid account for total di-carboxylic acid mole ratio be at least 3%, maximum 25%.
In addition, the ratio control of the mole of dibasic alcohol and di-carboxylic acid is 1.25～1.8 in the reaction: 1, and dibasic alcohol can be an ethylene glycol, 1, ammediol, 1,4-butyleneglycol, 1, the 6-hexylene glycol, one or more compositions in the neopentyl glycol wherein must contain ethylene glycol, and the ratio that accounts for the mole of total alcohol is at least 80%.The unnecessary dibasic alcohol that adds in this process can be discharged in system under the condition of vacuum and heating at polycondensation step, finally makes product keep the ratio of the mole of dibasic alcohol and di-carboxylic acid to be approximate 1: 1,
Synthesize intermediate II by phthalic acid sulfonate or its derivative and ethylene glycol by transesterification reaction, its process is similarly one of means commonly used in the polyester industrial, and its detailed process is:
A, in the stainless steel jacket reactor, add based on the phthalic acid sulfonate of the 10mol%～20mol% of di-carboxylic acid mole number or its derivative, add auxiliary agents such as ethylene glycol and catalyzer, anti-ether agent simultaneously, then in anaerobic atmosphere, in carrying out under 140～260 ℃ 1.5～5 hours and being preferable over and carrying out under 170～200 ℃ 1.5～4 hours, when the overhead product quantities received reaches theoretical value ± 5%, can judge that reaction finishes.
Phthalic acid sulfonate or its derivative in b, the reaction component can be 1,3 rutgers-5-sodium sulfonates; 1,3 rutgers-5-potassium sulfonate; Dimethyl terephthalate (DMT)-2-sodium sulfonate; At least a or several in dimethyl terephthalate (DMT)-2-potassium sulfonate.
The mol ratio of ethylene glycol in the reaction and phthalic acid sulfonate or its derivative is controlled at 2.1～2.6: 1, the same unnecessary ethylene glycol that adds in this process can be discharged in system under the condition of vacuum and heating at polycondensation step, finally make product keep the ratio of the mole of dibasic alcohol and di-carboxylic acid to be approximate 1: 1
Can add calcium acetate and sodium-acetate in the reaction as transesterification catalyst, sodium-acetate can play the effect that prevents the dibasic alcohol etherificate again simultaneously.
The process that component III is obtained is illustrated:
A, in the high speed shear diverting device, adding is based on the inorganic salt of the 0.3wt～%2.5% of di-carboxylic acid gross weight, and dispersion medium and deionized water, earlier by stirring at low speed, the inorganic salt particle tentatively is distributed in the dispersion medium, forms the relatively suspension of homogeneous.Improve rotating speed then, the highest 5600rpm that is no more than with the further broken dispersion of inorganic salt particle, thereby reaches the mixture system that visual inspection is homogeneous, can judge that preparation finishes.
The weight ratio of b, inorganic salt shared mixture (by inorganic salt, dispersion medium and deionized water are formed) in preparation process is minimum to be 10%, and is no more than 30% at most, and all the other are dispersion medium and small amount of deionized water.Dispersion medium is made up of ethylene glycol, and the content of deionized water is 2%～5% of mixture total weight amount.Glycol content is 65%～88% of a mixture weight.
To by intermediate compound I, intermediate II, component III and polyoxyethylene glycol be through the normal pressure polycondensation, rough vacuum and high vacuum polymerization, the process that finally synthesizes target product is illustrated:
In the stainless steel jacket reactor, add intermediate compound I in proportion, intermediate II, component III and polyoxyethylene glycol carry out the condensation polymerization at intermittence under the condition that stirs and progressively reduce pressure.Under vacuum state, the ethylene glycol in the reaction system and the boiling point lowering of water, excess glycol and water that aforementioned each step is added go out in the system to separate under heating and vacuum condition, thus the molar ratio that reaches di-carboxylic acid and dibasic alcohol approached 1: 1.At 235～295 ℃, polymerization 2.5～6 hours is preferable over 255～285 ℃ of polyase 13 .0～5.5 hour, when vacuum tightness reaches absolute pressure less than 133Pa, Nei Wen and stir current reach processing requirement value ± 5% o'clock, can judge that reaction finishes, through cast bar, granulation, air-dry packing product.
Above preparation process adopts suitable catalyzer can promote the reaction of each step, when with terephthalic acid and ethylene glycol direct esterification, because the self-catalysis of terephthalic acid can not selected catalyzer for use, selects catalyzer the carrying out of fast response more for use.The polycondensation catalyst system therefor includes but not limited to: metal oxide, Alkyzin compound, organic carboxylate, alkoxy titanium compound and Si oxide etc., its consumption is 200～400ppm of polymkeric substance total amount.According to the characteristics of each reactions steps, do not add anti-ether agent, thermal oxidation stabilizer in addition, toning agents etc. do not influence successful reaction and carry out, and are that the product that is obtained can reduce fusing point, the color jaundice, adding aforementioned various auxiliary agent can have the auxiliary effect that improves to product appearance and performance.
The water-soluble polyester that is used for terylene or polyester-cotton blend yarn sizing that the present invention proposes, it not only has good adhesive force to spun polyester thread, and is good with starch and the high molecular compatibility of other slurry, but also has environmental protection and the easy characteristics of destarch.
Water-soluble polyester provided by the invention, its repeating unit mainly is terephthalic acid and ethylene glycol, the structural unit that has " similar " from structure to PET, principle according to polymkeric substance " similar mixing ", " mixing " property of product and PEET strengthens greatly, it is easy also to have destarch in addition, the condition characteristic of simple, and the destarch waste liquid alleviates greatly to the pressure of environment.According to the water feature in cotton mill, but add the material of calcium ions and magnesium ions in the complexing water quality in the product, make its can not form precipitation and not with product in sodium sulfonate form and be insoluble in the material of water, thereby make the product that obtains can be widely used in various water quality.
Description of drawings:
Fig. 1 is a production craft step synoptic diagram of the present invention.
Among the figure: 1, high-shear dispersing technology, 2, esterification reaction tech, 3, trans-esterification processes, 4, polymerization process, 5 underwater cutpellet production technique.
Embodiment:
The invention provides following examples in order to the present invention is further specified, but the present invention is not limited to these embodiment.
Embodiment one:
1, with the TA of 30.1mol, 4.1mol IA, and by the mol ratio of dibasic alcohol/di-carboxylic acid 1.6 ethylene glycol 54.7mol, thermal oxidation stabilizer TMP (trimethyl phosphite 99) by sour weight 0.04% drops in the preparation still of band stirring, stir into slurries, drop into the 30L stainless steel chuck esterifying kettle of band fractionation plant then, behind the nitrogen replacement, airtight, stir, slowly be warming up to 220 ℃ with the speed of 10 ℃/min, control fractionation column top temperature is at 120 ℃, the reactor pressure-controlling is at 0.25Mpa, along with the slowly rising of temperature continuation in the reactor of carrying out of reaction.
React 6 hours to the reactor temperature reach 255 ℃, temperature slowly is reduced to below 100 ℃ in the capital, reactor pressure slowly is reduced to and is tending towards 0, when receiving the water yield and press the about 1230g of 2 times of di-carboxylic acid total mole number, the esterification end obtains intermediate compound I.
2,580g ethylene glycol input band is stirred and the transesterification reactor of fractionation plant in, under agitation condition, drop into SIPM (1,3-rutgers-5-benzene sulfonic acid sodium salt) 4.7mol several times, drop into 0.4% the Ca (AC) that presses the SIPM weight ratio
2(calcium acetate), press 0.06% NaAC (sodium-acetate) of SIPM weight ratio., start and stir and progressively heat up after the ester interchange vessel displacement with high pure nitrogen, when the fractionation column top temperature rises to 62 ℃, the control rate of heating, column top temperature is stabilized in minimumly is not less than 60 ℃, the highlyest be no more than 90 ℃, interior temperature is progressively by rising to 180 ℃, react 4.5 hours when the overhead product quantities received reaches about 300g, reaction finishes, and stops to stir cooling, obtain intermediate II, it is standby to pour finished product into beaker.
3, use 200ml ethylene glycol, 5ml deionized water and sodium polyphosphate 29 gram that accounts for di-carboxylic acid total amount 0.5wt% are put into the beaker of 500ml, shear with the high-shear dispersion machine, treat that solution is when homogeneous transparent is little to turn blue, component III.
4, with intermediate compound I, intermediate II, component III, account for the PEG3350 that the di-carboxylic acid mol ratio is 0.4mol% (the 3350th, the number-average molecular weight of polyoxyethylene glycol, down with), account for the DEG that the di-carboxylic acid mol ratio is 0.3mol%, account for the Sb of di-carboxylic acid total amount 0.04wt%
2O
3(antimonous oxide), the thermal oxidation stabilizer TMP that accounts for di-carboxylic acid total amount 0.05wt% put in the 30L stainless steel chuck batch condensation polymerization reactor.Slowly be warming up to 245 ℃ after the high pure nitrogen displacement, dish is moving to be stirred, if can move more than the week in very light domain, can slowly start the frequency conversion agitator motor from low to high, and, in 45min, pressure is reduced in the 667Pa, and finally keeps below the high vacuum of 133Pa simultaneously progressively to system decompression and slow elevated temperature, treat that temperature reaches 275 ℃ in the polycondensation, get final product when stir current reaches 0.11A.Stop stirring and stop to vacuumize and with high purity nitrogen releasing vacuum, rising pressure is to 0.25Mpa, from the end of extruded band cast bar, enter water quench after, be a granulated into the finished product water-soluable sizing material polyester with dicing machine.
The products obtained therefrom limiting viscosity is 0.385dl/g, second-order transition temperature is 52 ℃, in the solution of dissolving back micro-floss is arranged, not influencing sizing uses, do not precipitate in miscible 96 hours with PVA1799 (polyvinyl alcohol), compatibility is good, and the film wear resistance that makes on sheet glass is good, breaking tenacity and extension at break and spun polyester thread quite, the rate of begining a theatrical performance has raising by a relatively large margin during the gained sizing for weaving.
Embodiment two:
1, with the TA of 30.1mol, 3.0mol IA, 1.5mol AA, and by the mol ratio of glycol/diacid 1.5 ethylene glycol 51.9mol, thermal oxidation stabilizer TMP (trimethyl phosphite 99) by sour weight 0.04% drops in the preparation still of band stirring, stir into slurries, drop into the 30L stainless steel chuck esterifying kettle of band fractionation plant then, behind the nitrogen replacement, airtight, stir, speed with 15 ℃/min slowly is warming up to 240 ℃, control the fractionation column top temperature at 135 ℃, the reactor pressure-controlling is at 0.35Mpa, along with the slowly rising of temperature continuation in the reactor of carrying out of reaction.
React 4.5 hours to the reactor temperature reach 265 ℃, temperature slowly is reduced to below 100 ℃ in the capital, and reactor pressure slowly is reduced to and is tending towards 0, when quantities received is pressed the about 1250g of 2 times the water yield of di-carboxylic acid total mole number, esterification finishes, and obtains intermediate compound I.
2,750g ethylene glycol input band is stirred and the transesterification reactor of fractionation plant in, under agitation condition, drop into SIPM (1,3-rutgers-5-benzene sulfonic acid sodium salt) 5.2mol several times, drop into 0.4% the Ca (AC) that presses the SIPM weight ratio
2(calcium acetate), press 0.06% NaAC (sodium-acetate) of SIPM weight ratio., start and stir and progressively heat up after the ester interchange vessel displacement with high pure nitrogen, when the fractionation column top temperature rises to 65 ℃, the control rate of heating, column top temperature is stabilized in minimumly is not less than 60 ℃, the highlyest be no more than 90 ℃, interior temperature progressively rises to 190 ℃, when the overhead product quantities received reaches about 330g, reaction finishes, and stops to stir cooling, obtain intermediate II, it is standby to pour finished product into beaker.
3, use 300ml ethylene glycol, 10ml deionized water and the Sodium hexametaphosphate 99 34g that accounts for diprotic acid total amount 0.6wt% put into the beaker of 500ml, shear with the high-shear dispersion machine, treat that solution is when homogeneous transparent is little to turn blue, component III.
4, with intermediate compound I, intermediate II, component III, account for PEG2000 that the di-carboxylic acid mol ratio is 0.4mol%, account for the DEG that the di-carboxylic acid mol ratio is 0.2mol%, account for the Sb of di-carboxylic acid total amount 0.04wt%
2O
3(antimonous oxide), the thermal oxidation stabilizer TMP that accounts for di-carboxylic acid total amount 0.05wt% put in the 30L stainless steel chuck batch condensation polymerization reactor.Slowly be warming up to 265 ℃ after the high pure nitrogen displacement, dish is moving to be stirred, if can move more than the week in very light domain, can slowly start the frequency conversion agitator motor from low to high, and, in 40min, pressure is reduced in the 667Pa, and finally keeps below the high vacuum of 133Pa simultaneously progressively to system decompression and slow elevated temperature, treat that temperature reaches 285 ℃ in the polycondensation, get final product when stir current reaches 0.11A.Stop stirring and stop to vacuumize and with high purity nitrogen releasing vacuum, rising pressure is to 0.25Mpa, from the end of extruded band cast bar, enter water quench after, be a granulated into the finished product water-soluable sizing material polyester with dicing machine.
The products obtained therefrom limiting viscosity is 0.420dl/g, second-order transition temperature is 44 ℃, in the solution of dissolving back micro-floss is arranged, not influencing sizing uses, do not precipitate in miscible 96 hours with PVA1799 (polyvinyl alcohol), compatibility is good, and the film wear resistance that makes on sheet glass is good, breaking tenacity and extension at break and spun polyester thread are suitable, and the rate of begining a theatrical performance has raising by a relatively large margin during the gained sizing for weaving.
Embodiment three:
1, TA with 30.1mol, 3.3mol AA, by the mol ratio of ethylene glycol/diprotic acid 1.5 ethylene glycol 50.1mol, and by the mol ratio of neopentyl glycol/diprotic acid 0.12 neopentyl glycol (NPG) 4.0mol, thermal oxidation stabilizer TMP (trimethyl phosphite 99) by sour weight 0.04% drops in the preparation still of band stirring, stir into slurries, drop into the 30L stainless steel chuck esterifying kettle of band fractionation plant then, behind the nitrogen replacement, airtight, stir, speed with 10 ℃/min slowly is warming up to 230 ℃, control fractionation column top temperature is at 130 ℃, and the reactor pressure-controlling is at 0.30Mpa, and temperature slowly raises in the reactor.
React 4 hours to the reactor temperature reach 255 ℃, temperature slowly is reduced to below 100 ℃ in the capital, reactor pressure slowly is reduced to and is tending towards 0, when quantities received press the about 1200g of 2 times the water yield of di-carboxylic acid total mole number, the esterification end obtained intermediate compound I.
2,805g ethylene glycol input band is stirred and the transesterification reactor of fractionation plant in, under agitation condition, drop into STPM (dimethyl terephthalate (DMT)-2-benzene sulfonic acid sodium salt) 5.9mol several times, drop into 0.5% the Ca (AC) that presses the SIPM weight ratio
2(calcium acetate), press 0.1% NaAC (sodium-acetate) of SIPM weight ratio., start and stir and progressively heat up after the ester interchange vessel displacement with high pure nitrogen, when the fractionation column top temperature rises to 62 ℃, the control rate of heating, column top temperature is stabilized in minimumly is not less than 60 ℃, the highlyest be no more than 90 ℃, interior temperature progressively rises to 185 ℃, when the overhead product quantities received reaches about 380g, reaction finishes, and stops to stir cooling, obtain intermediate II, it is standby to pour finished product into beaker.
3, use 350ml ethylene glycol, 15ml deionized water and sodium polyphosphate 98 gram that accounts for di-carboxylic acid total amount 1.8wt% are put into the beaker of 500ml, shear with the high-shear dispersion machine, treat that solution is when homogeneous transparent is little to turn blue, component III.
4, with intermediate compound I, intermediate II, component III, account for DEG that the di-carboxylic acid mol ratio is 1.1mol%, account for the Sb of di-carboxylic acid total amount 0.04wt%
2O
3(antimonous oxide), the thermal oxidation stabilizer TMP that accounts for di-carboxylic acid total amount 0.04wt% put in the 30L stainless steel chuck batch condensation polymerization reactor.Slowly be warming up to 245 ℃ after the high pure nitrogen displacement, dish is moving to be stirred, if can move more than the week in very light domain, can slowly start the frequency conversion agitator motor from low to high, and, in 45min, pressure is reduced in the 667Pa, and finally keeps below the high vacuum of 133Pa simultaneously progressively to system decompression and slow elevated temperature, treat that temperature reaches 278 ℃ in the polycondensation, get final product when stir current reaches 0.12A.Stop stirring and stop to vacuumize and with high purity nitrogen releasing vacuum, rising pressure is to 0.25Mpa, from the end of extruded band cast bar, enter water quench after, be a granulated into the finished product water-soluable sizing material polyester with dicing machine.
The products obtained therefrom limiting viscosity is 0.366dl/g, second-order transition temperature is 48 ℃, in the solution of dissolving back micro-floss is arranged, not influencing sizing uses, do not precipitate in miscible 120 hours with PVA1799 (polyvinyl alcohol), compatibility is outstanding, and the film wear resistance that makes on sheet glass is good, breaking tenacity and extension at break and spun polyester thread are suitable, and the rate of begining a theatrical performance has raising by a relatively large margin during the gained sizing for weaving.
Embodiment four:
1, TA with 30.1mol, 2.2mol IA, 1.3mol SA, by 1, the mol ratio of 4-butyleneglycol/di-carboxylic acid be 0.09 1,4-butyleneglycol 3.0mol, and be 1.6 ethylene glycol 53.7mol by the mol ratio of ethylene glycol/di-carboxylic acid, thermal oxidation stabilizer TMP (trimethyl phosphite 99) by sour weight 0.04% drops in the preparation still of band stirring, stir into slurries, drop into the 30L stainless steel chuck esterifying kettle of band fractionation plant then, behind the nitrogen replacement, airtight, stir, slowly be warming up to 235 ℃ with the speed of 10 ℃/min, control fractionation column top temperature is at 130 ℃, the reactor pressure-controlling is at 0.30Mpa, and temperature slowly raises in the reactor.
React 4.5 hours to the reactor temperature reach 245 ℃, temperature slowly is reduced to below 100 ℃ in the capital, reactor pressure slowly is reduced to and is tending towards 0, when receiving the water yield and press the about 1200g of 2 times of di-carboxylic acid total mole number, the esterification end obtains intermediate compound I.
2,1370g ethylene glycol input band is stirred and the transesterification reactor of fractionation plant in, under agitation condition, drop into SIPM (1,3-rutgers-5-benzene sulfonic acid sodium salt) 10.0mol several times, drop into 0.4% the Ca (AC) that presses the SIPM weight ratio
2(calcium acetate), press 0.06% NaAC (sodium-acetate) of SIPM weight ratio., start and stir and progressively heat up after the ester interchange vessel displacement with high pure nitrogen, when the fractionation column top temperature rises to 64 ℃, the control rate of heating, column top temperature is stabilized in minimumly is not less than 60 ℃, the highlyest be no more than 90 ℃, interior temperature progressively rises to 187 ℃, when the overhead product quantities received reaches about 640g, reaction finishes, and stops to stir cooling, obtain intermediate II, it is standby to pour finished product into beaker.
3, use 300ml ethylene glycol, 5ml deionized water and sodium polyphosphate 34 gram that accounts for di-carboxylic acid total amount 0.6wt% are put into the beaker of 500ml, shear with the high-shear dispersion machine, treat that solution is when homogeneous transparent is little to turn blue, component III.
4, with intermediate compound I, intermediate II, component III, account for PEG2000 that the di-carboxylic acid mol ratio is 2.4mol%, account for the Sb of di-carboxylic acid total amount 0.04wt%
2O
3(antimonous oxide), the thermal oxidation stabilizer TMP that accounts for di-carboxylic acid total amount 0.05wt% put in the 30L stainless steel chuck batch condensation polymerization reactor.Slowly be warming up to 247 ℃ after the high pure nitrogen displacement, dish is moving to be stirred, if can move more than the week in very light domain, can slowly start the frequency conversion agitator motor from low to high, and, in 45min, pressure is reduced in the 667Pa, and finally keeps below the high vacuum of 133Pa simultaneously progressively to system decompression and slow elevated temperature, treat that temperature reaches 278 ℃ in the polycondensation, get final product when stir current reaches 0.11A.Stop stirring and stop to vacuumize and with high purity nitrogen releasing vacuum, rising pressure is to 0.25Mpa, from the end of extruded band cast bar, enter water quench after, be a granulated into the finished product water-soluable sizing material polyester with dicing machine.
The products obtained therefrom limiting viscosity is 0.377dl/g, second-order transition temperature is 52 ℃, in the solution of dissolving back the trace floss is arranged, do not precipitate in miscible 144 hours with PVA1799 (polyvinyl alcohol), compatibility is outstanding, the film wear resistance that makes on sheet glass is good, breaking tenacity and extension at break and spun polyester thread quite, the rate of begining a theatrical performance has raising by a relatively large margin during the gained sizing for weaving.
Comparative example five:
1, with the TA of 30.1mol, 4.1mol IA, and by the mol ratio of ethylene glycol/di-carboxylic acid 1.6 ethylene glycol 54.7mol, the thermal oxidation stabilizer TMP (trimethyl phosphite 99) that presses diprotic acid weight 0.04% drops in the preparation still of band stirring, stir into slurries, drop into the 30L stainless steel chuck esterifying kettle of band fractionation plant then, behind the nitrogen replacement, airtight, pressurize 0.1～0.25Mpa stirs, speed with 10 ℃/min slowly is warming up to 230 ℃, control fractionation column top temperature is at 130 ℃, and the reactor pressure-controlling is at 0.30Mpa, and temperature slowly raises in the reactor.
React 4.5 hours to the reactor temperature reach 250 ℃, temperature slowly is reduced to below 100 ℃ in the capital, reactor pressure slowly is reduced to and is tending towards 0, when receiving the water yield and press the about 1230g of 2 times of di-carboxylic acid total mole number, the esterification end obtains intermediate compound I.
2,560g ethylene glycol input band is stirred and the transesterification reactor of fractionation plant in, under agitation condition, drop into SIPM (1,3-rutgers-5-benzene sulfonic acid sodium salt) 1.0mol several times, drop into 0.4% the Ca (AC) that presses the SIPM weight ratio
2(calcium acetate), press 0.06% NaAC (sodium-acetate) of SIPM weight ratio., start and stir and progressively heat up after the ester interchange vessel displacement with high pure nitrogen, when the fractionation column top temperature rises to 60 ℃, the control rate of heating, column top temperature is stabilized in minimumly is not less than 60 ℃, the highlyest be no more than 90 ℃, interior temperature progressively rises to 180 ℃, when the overhead product quantities received reaches about 300g, reaction finishes, and stops to stir cooling, obtain intermediate II, it is standby to pour finished product into beaker.
3, with intermediate compound I, intermediate II, account for PEG3350 that the di-carboxylic acid mol ratio is 4.4mol%, account for the DEG that the di-carboxylic acid mol ratio is 6.1mol%, account for the Sb of di-carboxylic acid total amount 0.04wt%
2O
3(antimonous oxide), the thermal oxidation stabilizer TMP that accounts for di-carboxylic acid total amount 0.05wt% put in the 30L stainless steel chuck batch condensation polymerization reactor.Slowly be warming up to 245 ℃ after the high pure nitrogen displacement, dish is moving to be stirred, if can move more than the week in very light domain, can slowly start the frequency conversion agitator motor from low to high, and, in 45min, pressure is reduced in the 667Pa, and finally keeps below the high vacuum of 133Pa simultaneously progressively to system decompression and slow elevated temperature, treat that temperature reaches 282 ℃ in the polycondensation, get final product when stir current reaches 0.12A.Stop stirring and stop to vacuumize and with high purity nitrogen releasing vacuum, rising pressure is to 0.25Mpa, from the end of extruded band cast bar, enter water quench after, be a granulated into the finished product water-soluable sizing material polyester with dicing machine.
The products obtained therefrom limiting viscosity is 0.483dl/g, and second-order transition temperature is 35 ℃, particle deliquescingization during dissolving, but the surface generates one deck white mass, and particle all the time can not swelling and is dissolved in the medium, therefore can not be used for textile sizing.
Comparative example six:
1, with the TA of 30.1mol, and by the mol ratio of dibasic alcohol/di-carboxylic acid 1.6 ethylene glycol 48.2mol, thermal oxidation stabilizer TMP (trimethyl phosphite 99) by sour weight 0.04% drops in the preparation still of band stirring, stir into slurries, drop into the 30L stainless steel chuck esterifying kettle of band fractionation plant then, behind the nitrogen replacement, airtight, stir, speed with 10 ℃/min slowly is warming up to 235 ℃, control fractionation column top temperature is at 130 ℃, and the reactor pressure-controlling is at 0.35Mpa, and temperature slowly raises in the reactor.
React 3.5 hours to the reactor temperature reach 255 ℃, temperature slowly is reduced to below 100 ℃ in the capital, reactor pressure slowly is reduced to and is tending towards 0, when receiving the water yield and press the about 1080g of 2 times of di-carboxylic acid total mole number, the esterification end obtains intermediate compound I.
2,2500g ethylene glycol input band is stirred and the transesterification reactor of fractionation plant in, under agitation condition, drop into SIPM (1,3-rutgers-5-benzene sulfonic acid sodium salt) 17.8mol several times, drop into 0.4% the Ca (AC) that presses the SIPM weight ratio
2(calcium acetate), press 0.06% NaAC (sodium-acetate) of SIPM weight ratio., start and stir and progressively heat up after the ester interchange vessel displacement with high pure nitrogen, when the fractionation column top temperature rises to 70 ℃, the control rate of heating, column top temperature is stabilized in minimumly is not less than 60 ℃, the highlyest be no more than 90 ℃, interior temperature progressively rises to 190 ℃, when the overhead product quantities received reaches about 1140g, reaction finishes, and stops to stir cooling, obtain intermediate II, it is standby to pour finished product into beaker.
3, with intermediate compound I, intermediate II, account for PEG2000 that the di-carboxylic acid mol ratio is 12.0mol%, account for the Sb of di-carboxylic acid total amount 0.04wt%
2O
3(antimonous oxide), the thermal oxidation stabilizer TMP that accounts for di-carboxylic acid total amount 0.05wt% put in the 30L stainless steel chuck batch condensation polymerization reactor.Slowly be warming up to 245 ℃ after the high pure nitrogen displacement, dish is moving to be stirred, if can move more than the week in very light domain, can slowly start the frequency conversion agitator motor from low to high, and, in 50min, pressure is reduced in the 667Pa, and finally keeps below the high vacuum of 133Pa simultaneously progressively to system decompression and slow elevated temperature, treat that temperature reaches 284 ℃ in the polycondensation, get final product when stir current reaches 0.10A.Stop stirring and stop to vacuumize and with high purity nitrogen releasing vacuum, rising pressure is to 0.25Mpa, from the end of extruded band cast bar, enter water quench after, be a granulated into the finished product water-soluable sizing material polyester with dicing machine.
The products obtained therefrom limiting viscosity is 0.211dl/g, second-order transition temperature is 37 ℃, product can be dissolved in (40 ℃) in the warm water, in the solution of dissolving back more floss is arranged, do not precipitate in miscible 96 hours with PVA1799 (polyvinyl alcohol), compatibility is good, product does not have film-forming properties, and stronger water absorbability is arranged after drying, and there is " it is sticking again to inhale temperature " tendency in product, can not test breaking tenacity and extension at break and wear resistance.
Comparative example seven:
1, with the TA of 30.1mol, 4.1mol IA, and by the mol ratio of dibasic alcohol/di-carboxylic acid 1.6 ethylene glycol 54.7mol, thermal oxidation stabilizer TMP (trimethyl phosphite 99) by sour weight 0.04% drops in the preparation still of band stirring, stir into slurries, drop into the 30L stainless steel chuck esterifying kettle of band fractionation plant then, behind the nitrogen replacement, airtight, stir, slowly be warming up to 240 ℃ with the speed of 10 ℃/min, control fractionation column top temperature is at 135 ℃, the reactor pressure-controlling is at 0.35Mpa, and temperature slowly raises in the reactor.
2,580g ethylene glycol input band is stirred and the transesterification reactor of fractionation plant in, under agitation condition, drop into SIPM (1,3-rutgers-5-benzene sulfonic acid sodium salt) 4.7mol several times, drop into 0.4% the Ca (AC) that presses the SIPM weight ratio
2(calcium acetate), press 0.06% NaAC (sodium-acetate) of SIPM weight ratio., start and stir and progressively heat up after the ester interchange vessel displacement with high pure nitrogen, when the fractionation column top temperature rises to 75 ℃, the control rate of heating, column top temperature is stabilized in minimumly is not less than 60 ℃, the highlyest be no more than 90 ℃, interior temperature progressively rises to 190 ℃, when the overhead product quantities received reaches about 300g, reaction finishes, and stops to stir cooling, obtain intermediate II, it is standby to pour finished product into beaker.
4, with intermediate compound I, intermediate II, account for PEG3350 that the di-carboxylic acid mol ratio is 5.2mol%, account for the TEG that the di-carboxylic acid mol ratio is 7.3mol% (Triethylene glycol), account for the Sb of di-carboxylic acid total amount 0.03wt%
2O
3(antimonous oxide), the thermal oxidation stabilizer TMP that accounts for di-carboxylic acid total amount 0.05wt% put in the 30L stainless steel chuck batch condensation polymerization reactor.Slowly be warming up to 240 ℃ after the high pure nitrogen displacement, dish is moving to be stirred, if can move more than the week in very light domain, can slowly start the frequency conversion agitator motor from low to high, and, in 50min, pressure is reduced in the 667Pa, and finally keeps below the high vacuum of 133Pa simultaneously progressively to system decompression and slow elevated temperature, treat that temperature reaches 277 ℃ in the polycondensation, get final product when stir current reaches 0.12A.Stop stirring and stop to vacuumize and with high purity nitrogen releasing vacuum, rising pressure is to 0.25Mpa, from the end of extruded band cast bar, enter water quench after, be a granulated into the finished product water-soluable sizing material polyester with dicing machine.
The products obtained therefrom limiting viscosity is 0.436dl/g, second-order transition temperature is 24 ℃, be elastomerics under the product normal temperature, in the solution of dissolving back more floss is arranged, influential slightly to sizing, do not precipitate in miscible 96 hours with PVA1799 (polyvinyl alcohol), compatibility is good, the film wear resistance that makes on sheet glass is good, and much lower bigger with extension at break than breaking tenacity with spun polyester thread, the rate of begining a theatrical performance has raising during the gained sizing for weaving.
Above embodiment and comparative example are as shown in Table 1 raw materials used:
The raw materials used table look-up of table one: embodiment and comparative example
| Example | Di-carboxylic acid (dihydroxy ethyl ester), mol | Phosphoric acid salt g | Dibasic alcohol mol | ||||||||||
| TA | IA | AA | SA | SIPE | STPE | EG | DEG | PEG | TEG | NPG | BG | ||
| Embodiment one | 30.1 | 4.1 | / | / | 4.7 | / | 29 | 35.5 | 0.11 | 0.13 | / | / | / |
| Embodiment two | 30.1 | 3.0 | 1.5 | / | 5.2 | / | 34 | 35.4 | 0.07 | 0.14 | / | / | / |
| Embodiment three | 30.1 | / | 3.3 | / | / | 5.9 | 98 | 34.1 | 1.1 | / | / | 4.0 | / |
| Embodiment four | 30.1 | 2.2 | / | 1.3 | 10.0 | / | 34 | 39.2 | / | 1.2 | / | / | 3.0 |
| Comparative example five | 30.1 | 4.1 | / | / | 1.0 | / | 30.8 | 2.1 | 1.5 | / | / | / | |
| Comparative example six | 30.1 | / | / | / | 17.8 | / | 42.3 | / | 3.6 | / | / | / | |
| Comparative example seven | 30.1 | 4.1 | / | / | 4.7 | / | 24.6 | / | 1.8 | 2.5 | / | / | |
The TA-terephthalic acid; The IA-m-phthalic acid; AA-ω-hexanodioic acid; SA-ω-sebacic acid; SIPE-1, the two hydroxyl ethyl esters of 3-phthalic acid-5-sodium sulfonate; STPE-bishydroxyethyl terephthalate-5-sodium sulfonate; EG-ethylene glycol; The DEG-glycol ether; The TEG-Triethylene glycol; The PEG-polyoxyethylene glycol; NPG-2,2-dimethyl-1, ammediol; BG-1, the 4-butyleneglycol;
Above embodiment and comparative example product performance are as shown in Table 2:
Table two: embodiment and comparative example product performance table look-up
| Example | Phosphoric acid salt | Tg，℃① | [η]，dl/ | Solvability | 3. | Compatibility 4. | Wear resistance | Serous coat |
| Embodiment one | √ | 52 | 0.385 | The trace wadding | Excellent | Very | In | |
| Embodiment two | √ | 44 | 0.42 | The trace wadding | Very | Excellent | Very | |
| Embodiment three | √ | 48 | 0.366 | The trace wadding | Excellent | In | In | |
| Embodiment four | √ | 52 | 0.377 | The trace wadding | Excellent | Excellent | In | |
| Comparative example five | √ | 35 | 0.483 | Insoluble | / | / | / | |
| Comparative example six | × | 37 | 0.211 | Cold water is molten | Very | Difference | Difference | |
| Comparative example seven | × | 24 | 0.436 | A small amount of wadding | Very | Difference | Difference |
Remarks: 1. DSC is adopted in the Tg test; 2. the Ubbelohde viscometer method is adopted in limiting viscosity [η] test; 3. the solvability test is with detecting by an unaided eye after the dispersion medium water dissolution; 4. compatibility is to dissolve the back simultaneously with PVA1799 and product of the present invention to contrast with single component.
Claims (6)
1, a kind of water-soluable sizing material polyester is characterized in that, comprises:
(1), terephthalic acid or its derivative;
(2), at least account for the minimum 3mol% of di-carboxylic acid total mole number, and at least a di-carboxylic acid except that terephthalic acid or its derivative of maximum 25mol%;
(3), one or more dibasic alcohol and must contain ethylene glycol, wherein glycol content accounts for dibasic alcohol total mole number 80mol% at least;
(4), mole number is the minimum 0.3mol% of di-carboxylic acid total mole number, and at least two kinds of polyoxyethylene glycol with following structural formula of 1.5mol% at most:
H-(OCH
2CH
2)
n-OH
2≤n≤4 and 45≤n≤136 wherein
(5), mole number is the minimum 10mol% of di-carboxylic acid total mole number, and the phthalic acid sulfonate or derivatives thereof of 20mol% at most;
(6) weight is the 0.3wt% at least of di-carboxylic acid gross weight, and the inorganic salt of maximum 2.5wt%.
2, according to the preparation method of the described water-soluable sizing material polyester of claim 1, it is characterized in that:
(1), by di-carboxylic acid and diol reaction, by direct esterification reaction, obtain intermediate compound I, be used for following polycondensation.
(2), by phthalic acid sulfonate or its derivative and ethylene glycol by transesterification reaction, obtain intermediate II, be used for following polycondensation.
(3), inorganic additives is sheared dispersion, make it reach aim of even dispersion, thereby satisfy the quality product requirement, products obtained therefrom is component III, is used for following polycondensation with the high speed shear diverting device.
(4), by intermediate compound I, intermediate II, component III and polyoxyethylene glycol through normal pressure polycondensation, rough vacuum and high vacuum polymerization, finally synthesize target product.
3, according to the described water-soluable sizing material polyester of claim 1, it is characterized in that: described di-carboxylic acid except that terephthalic acid or its derivative is a m-phthalic acid, 1,6-hexanodioic acid, ω-nonane diacid, ω-sebacic acid.
4, according to the described water-soluable sizing material polyester of claim 1, it is characterized in that: described phthalic acid sulfonate is 1,3 rutgers-5-sodium sulfonate; 1,3 rutgers-5-potassium sulfonate; Dimethyl terephthalate (DMT)-2-sodium sulfonate; Dimethyl terephthalate (DMT)-2-potassium sulfonate.
5, according to the described water-soluable sizing material polyester of claim 1, it is characterized in that: described inorganic salt are phosphate polymer, hexametaphosphate, hydrophosphate polymkeric substance.
6, according to claim 1 or 5 described water-soluable sizing material polyesters, it is characterized in that: described inorganic salt are SODIUM PHOSPHATE, MONOBASIC, potassium primary phosphate, sodium acid phosphate, tripoly phosphate sodium STPP, Potassium tripolyphosphate, Sodium hexametaphosphate 99, hexa metaphosphoric acid potassium, trisodium phosphate, sodium acid pyrophosphate.
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| CN102086261B (en) * | 2009-12-07 | 2012-10-17 | 上海联吉合纤有限公司 | Preparation method of polyol copolyester |
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| CN102079812A (en) * | 2010-11-16 | 2011-06-01 | 苏州瀚海化学有限公司 | Water-soluble copolyester and preparation method thereof |
| CN102079812B (en) * | 2010-11-16 | 2012-12-26 | 苏州瀚海化学有限公司 | Water-soluble copolyester and preparation method thereof |
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| CN105064028A (en) * | 2015-07-29 | 2015-11-18 | 湖北佳特纺织浆料有限公司 | Water soluble polyester slurry for sizing DTY polyester low elastic filaments and preparation method thereof |
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| CN111676546A (en) * | 2020-07-07 | 2020-09-18 | 上海市合成纤维研究所有限公司 | Use of modified copolyesters as sea material for sea-island fibers |
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