CN1552752A - Modified polyester and preparing method thereof - Google Patents
Modified polyester and preparing method thereof Download PDFInfo
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- CN1552752A CN1552752A CNA031122426A CN03112242A CN1552752A CN 1552752 A CN1552752 A CN 1552752A CN A031122426 A CNA031122426 A CN A031122426A CN 03112242 A CN03112242 A CN 03112242A CN 1552752 A CN1552752 A CN 1552752A
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Abstract
An easily soluble modified polyester is prepared from the terephthalic acid (or dimethyl terephthalato) and glycol. Its preparing process features that in its esterifying or ester exchanging step the meta-naphthalic acid is added and in the esterifying (or ester exchange) or polycondensation step, the meta-naphthalic acid component containing the metallic sulfonate and polyalkylene diol are added for block copolymerizing.
Description
Technical field
The present invention relates to a kind of processable polyester and manufacture method thereof, particularly a kind of caustic solubility can be good, the spinning property excellence, the processable polyester of silk stable physical property, and can high-level efficiency, the preparation method of low cost production processable polyester.
Background technology
Sea-island fibre is a kind of conjugated fibre, and this conjugated fibre can access in the world today one of fiber the thinnest in the commercialization through post-treatment, arrangement, is the desirable feedstock of producing articles for use such as high-grade fabric, high-grade decorating cloth, high-grade Wiping material.Islands-in-sea bicomponent fibre is to adopt composite spinning technology, form a kind of composition among being embedded in another kind of processable polymkeric substance marine facies (Sea Phase) by a kind of polymkeric substance with superfine island phase (Island Phase), adopt dissolving technology through aftertreatment, with the marine facies dissolving, just can obtain ultra-fine fibre.This conjugated fibre is used to make to have well-pressed style, imitate high-density woven fabrics, the cloth of chamois leather effect or has the graceful gloss and the thin,tough silk class cloth of soft feel etc.
Japan's clock spins a kind of modified poly ester once was provided, its main repeating unit is an ethylene glycol terephthalate, the m-phthalic acid composition that in sour composition, contains 2.0～3.0% moles containing metal sulphonate-base, the molecular-weight average that contains 9.0～13.0% weight in polymkeric substance is 1000～10000 polyalkylene glycol, in glycol component, contained glycol ether (DEG) is 4.7～5.7% moles, the ratio 1.0～1.02 of the maximum value of limiting viscosity and minimum value.Though adopt this method to produce alkali soluble polyester with continuous processing, high viscosity of its product (about 0.70) and low-solubility (90min) have determined this product to have defective at aspects such as becoming silk, painted, the molten speed of alkali; And aspect facility investment, the cost of continuous processing device is more than the twice of intermittently device; Simultaneously, its quantity-produced technology also is unfavorable for changing product category or adjusting product style according to the market requirement, especially when corrective maintenance maintenance or abnormal conditions occur, causes the bigger wasting of resources easilier.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, a kind of sufficient alkali lye solvability that has is provided, the polyester of dyeability and spinning property excellence, can reduce the equipment input cost, improved the use value of the finished product greatly, make it on composite spinning machine, make sea island fiber, after alkali lye is handled, obtain ultra-fine fibre as a component and terylene (PET) or polyamide fibre melt-spinnable polymers such as (PA).
The technical solution adopted for the present invention to solve the technical problems is: a kind of modified poly ester, adopt terephthalic acid (or dimethyl terephthalate (DMT)), ethylene glycol to form for the basic raw material copolymerization, it is to contain 0～25.0% mole m-phthalic acid, the modified poly ester that 1.0～15.0% mole the m-phthalic acid composition that contains the metal organic sulfonate base, 2.0～15.0% weight, molecular-weight average are 500～10000 polyalkylene glycol copolymerization to form.
Aforesaid modified poly ester, the dissolution time of its ester grain (4mm*4mm*2.5mm) is in 100 minutes, limiting viscosity is 0.40～0.60 deciliter/gram, content of carboxyl end group is less than 30.0 moles/ton, 210 ℃～240 ℃ of fusing points, the b value is less than 14.0, and the L value is greater than 40.0, ash is less than 2.0%, and glycol ether (DEG) content is in 2.0～6.0% weight.
Aforesaid modified poly ester, wherein the molecular-weight average of polyalkylene glycol is 500～10000.
Aforesaid modified poly ester, its alkali dissolution are that the ester grain is boiled with 5% sodium hydroxide solution, are estimated by its consoluet time.
A kind of preparation method of aforesaid modified poly ester, be to adopt terephthalic acid (or dimethyl terephthalate (DMT)), ethylene glycol, the m-phthalic acid composition that contains the metal organic sulfonate base, polyalkylene glycol is a raw material, carry out direct esterification (or transesterify) reaction, polyester is made in polycondensation, dicarboxylic acid composition and ethylene glycol are made into slurry, be to carry out esterification (or transesterify) reaction under 1.1～1.5 the condition in total mol ratio, the m-phthalic acid composition and the polyalkylene glycol that contain the metal organic sulfonate base can add in esterification (or transesterify) or polycondensation phase, carboxylate imports polymeric kettle with batch form, carries out polyreaction under reduced pressure.
The preparation method of aforesaid a kind of modified poly ester also can include m-phthalic acid in the wherein said raw material.
The preparation method of aforesaid a kind of modified poly ester, wherein said esterification (or transesterify) is reflected under the normal pressure to be carried out, and temperature is 130～245 ℃, and the time is 4～14 hours.
The preparation method of aforesaid a kind of modified poly ester, in the wherein said polycondensation rough vacuum stage, temperature is 245～265 ℃, the time is 0.5～3 hour.
The preparation method of aforesaid a kind of modified poly ester, wherein said polycondensation high vacuum stage of Fig, the still internal pressure is below 0.3 holder, and temperature is 265～285 ℃, and the time is 1～3 hour.
A kind of device that is used to prepare aforesaid modified poly ester, it comprises:
The melt self-circulation system its role is to make the reaction mass homogeneity to be guaranteed;
Melt Pump its role is to accomplish in the vacuum state bottom discharge;
One esterification, two polycondensation vessels, still plays poising action in the middle of its role is to make, to enhance productivity to greatest extent;
Three monomers configurations still its role is to produce specially the compound (SIPE) that spent glycol and dimethyl ester carry out transesterify, with avoid SIPE transport, inconvenience aspect the storage.
In actual use, in joining stock tank, pure terephthalic acid and ethylene glycol are made into slurry, in the input port of joining stock tank, drop into m-phthalic acid, then this slurry is added in the esterifying kettle, dimethyl terephthalate (DMT) (DMT) or pure terephthalic acid's (or pure terephthalic acid (PTA)) route hot mother liquor (PTA) that prepared beforehand is arranged in esterifying kettle, and carry out esterification (or transesterify) and react the formation oligopolymer, esterification (or transesterify) is reflected under the normal pressure to be carried out, temperature is at 130～245 ℃, time is 4～14 hours, according to esterification water (or methyl alcohol) amount of steaming decision reaction end; The oligopolymer that generates is imported middle still, add m-phthalic acid composition and the polyalkylene glycol that contains the metal organic sulfonate base in the input port of middle still, material imports in the polymeric kettle, and carries out polyreaction under vacuum state continuously; In the polycondensation rough vacuum stage, temperature is controlled at 245～265 ℃, and the time is 0.5～3 hour; High vacuum stage of Fig is pressed in the still below 0.3 holder, and temperature is controlled at 265～285 ℃, and the time is 1～3 hour, grasps reaction end according to reactor beater motor power situation; Polyester fondant is extruded into the cooling bath from discharge port, by cutting device with the ester bar granulation of extruding.
The dissolution time of its ester grain (4mm*4mm*2.5mm) is in 100 minutes, limiting viscosity is 0.40～0.60 deciliter/gram, content of carboxyl end group is less than 30.0 moles/ton, 210 ℃～240 ℃ of fusing points, the b value is less than 14.0, the L value is greater than 40.0, and ash is less than 2.0%, and glycol ether (DEG) content is in 2.0～6.0% weight.
The invention has the beneficial effects as follows, because having adopted terephthalic acid (or dimethyl terephthalate (DMT)), ethylene glycol is basic raw material, in esterification (or transesterify), can add m-phthalic acid, and esterification (or transesterify) or polycondensation phase to add the m-phthalic acid composition that contains the metal organic sulfonate base and molecular-weight average be 500～10000 polyalkylene glycol with batch form carry out block copolymerization and make modified poly ester; This modified poly ester has good alkali lye processable, the concentration of alkali lye is 5%, the solvability of test section under boiling state, can dissolve fully with interior in 100 minutes, its dyeability and spinning property excellence, the silk stable physical property has improved the use value of the finished product greatly, can on composite spinning machine, make sea island fiber as a component and terylene (PET) or polyamide fibre melt-spinnable polymers such as (PA), after alkali lye is handled, obtain ultra-fine fibre.And the melt self-circulation system that is adopted can make the reaction mass homogeneity be guaranteed, and, Melt Pump can accomplish in the vacuum state bottom discharge by being set, thereby avoid because polymer-extruded timeliness changes, and produce the polymer viscosity when beginning to extrude and extrude the polymer viscosity difference when finishing, the big problem of polymer physics performance difference between each batch, and, still played poising action in the middle of the flow process of one esterification, two polycondensation vessels made, can enhance productivity to greatest extent, its virtual rating is wanted obvious device at intermittence greater than equal scale.The manufacture method of this batchwise polymerization can high-level efficiency, low cost production goes out the processable polyester, making technology is easy to adjust, can adjust product style at any time according to customer need, especially when overhaul of the equipments maintenance or abnormal conditions occur, can avoid tremendous loss.
Description of drawings
Below in conjunction with drawings and Examples the present invention is described in further detail; But a kind of modified poly ester of the present invention and preparation method thereof is not limited to embodiment.
Fig. 1 is a step of manufacturing synoptic diagram of the present invention.
Nomenclature among the figure: 1 joins stock tank; 2 esterifying kettles; Still in the middle of 3; 4 polymeric kettles; A, b charging opening; The c discharge port
Embodiment
A kind of modified poly ester of the present invention, be to adopt terephthalic acid (or dimethyl terephthalate (DMT)), ethylene glycol to form for the basic raw material copolymerization, it is to contain 0～25.0% mole m-phthalic acid, the modified poly ester that 1.0～15.0% mole the m-phthalic acid composition that contains the metal organic sulfonate base, 2.0～15.0% weight, molecular-weight average are 500～10000 polyalkylene glycol copolymerization to form.
This modified poly ester, the dissolution time of its ester grain (4mm*4mm*2.5mm) is in 100 minutes, limiting viscosity is 0.40～0.60 deciliter/gram, content of carboxyl end group is less than 30.0 moles/ton, 210 ℃～240 ℃ of fusing points, the b value is less than 14.0, and the L value is greater than 40.0, ash is less than 2.0%, and glycol ether (DEG) content is in 2.0～6.0% weight.
The compound (hereinafter referred to as SIPE) that the m-phthalic acid composition that contains the metal organic sulfonate base that uses in the present invention adopts 5-sulfonic acid metal matrix-dimethyl isophthalate (hereinafter referred to as SIPM) or spent glycol and SIPM to carry out transesterify; If the SIPM that drops into is excessive, will make the slurry deterioration in physical properties, so preferably adopt SIPE in slurry; Metal among SIPM or the SIPE can use sodium, potassium, lithium etc., but sodium most preferably; SIPM can be provided with a special transesterification reactor and produce SIPE, avoids the inconvenience of SIPE aspect transportation, storage.The add-on of SIPE is set in the sour composition of polymkeric substance 1.0～15.0% moles better, during less than 1.0% mole, can not obtain sufficient alkali dissolution, during greater than 15.0% mole, will produce tackify, gelation because of the charge effect of SIPE in the melt-spinning operation, the spinning property transitivity of section significantly descends.
The present invention can add m-phthalic acid (IPA) in esterification (or transesterify), add-on is set in the sour composition of polymkeric substance 0～25.0% mole, the adding of m-phthalic acid (IPA) is suitably to reduce the consumption of SIPE, under the prerequisite that guarantees alkali dissolution, improve because SIPE adds the difficulty that causes to polymerization.
The present invention must add polyalkylene glycol and carry out block copolymerization, and polyalkylene glycol can be used general expression HO (CnH
2NO) mH (wherein n, m are positive integer) expression, the polyoxyethylene glycol during n=2 (hereinafter referred to as PEG) is widely used and is optimal.
PEG molecular-weight average used in the present invention is 500～10000, if molecular weight less than 500, will cause the hydrolysis reaction of modified poly ester when melt-spinning easily, the thermotolerance of polyester is insufficient, sticks together between polyester granulate, in twisting operation generation efflorescence, and,, will lack polymerisation reactivity if molecular weight surpasses 10000, because difficulty is copolymerized to PEG in the molecular chain of polyester, so the scale resistance variation of polyester.
The add-on of PEG need be 2.0～15.0% weight of polymkeric substance.Be lower than at 2.0% o'clock, the buck solubility property is just insufficient, if surpass 15.0% weight, the thermotolerance of polymkeric substance, scale resistance are with regard to variation.
The modified poly ester that the present invention makes, content of carboxyl end group be less than 30.0,210 ℃～240 ℃ of fusing points, and the b value is less than 14.0, and the L value is greater than 40.0, and ash is less than 2.0%; Glycol ether (DEG) content is in 2.0～6.0% weight, this glycol ether (DEG) is to generate because of the side reaction in the polymerization, if less than 2.0% weight, the buck solubility property is with regard to variation, if surpass 6.0% weight, the thermotolerance of polymkeric substance, scale resistance be with regard to variation, the remarkable variation of the operability during melt-spinning; Limiting viscosity must be lower than 0.40 deciliter/gram in 0.40～0.60 deciliter/gram, can not guarantee fibre strength, is higher than 0.60 deciliter/gram, and difficulty in spinning can not make qualified fiber.
Below the measuring method of above-mentioned modified poly ester eigenwert is explained as follows:
(1) limiting viscosity IV
The sample collecting that the limiting viscosity IV of section measures usefulness is performed as follows, and begins to extrude and extrude the polyester grain of firm end for each batch polymerization thing, and in extrusion, gather suitable polymerization grain and with it as sample; In the mixed solvent of phenol/tetrachloroethane=1: 1 (weight ratio), under 25 ℃ of conditions, with the automatic viscosity apparatus working sample of AVSPRO.
(2) glycol ether (DEG) amount
With regard to the glycol ether amount, the polyester grain is dissolved transesterify with 1,6 hexylene glycol-methanol solution under 280 ℃, take out cooling after 2 hours, carrying out gas chromatographic analysis again can get.
(3) yellowish-white degree b, L value
Sample is placed in the cuvette, use color difference meter directly to measure.
(4) ash content
Claim in the porcelain crucible of constant weight sample to be positioned over earlier and burn on the electric furnace that it is moved in 400 ℃ the High Temperature Furnaces Heating Apparatus calcination to 800 ℃, putting into the moisture eliminator constant weight after the taking-up can record again to not smoldering.
(5) fusing point
Directly record with DSC (Different scanning calorimetry) differential thermal analyzer (U.S. TA company 2010 types) or fusing point instrument.The DSC test condition: nitrogen atmosphere, gas flow rate 40ml/min takes by weighing the 10mg sample respectively and puts into the sample chamber with reference substance heat up 10 ℃/min of temperature rise rate in sample box.
(6) content of carboxyl end group
Take by weighing example weight (g), add phenol-chloroform solvent heating for dissolving, again it is washed with phenol-chloroform, use 702 SM automatical potentiometric titrimeters to calculate.
(7) alkali dissolution
Polyester granulate boiled with 5% sodium hydroxide solution carry out alkali dissolution test, estimate by its consoluet time.
(8) thermostability
With thermogravimetric analyzer (U.S. TA company's T GAQ-500 type) the polyester grain is analyzed.Test condition: nitrogen atmosphere, the heavily about 10mg of gas flow rate 40ml/min, sample, temperature rise rate: 20 ℃/min.
The preparation method of modified poly ester of the present invention, be to adopt terephthalic acid (or dimethyl terephthalate (DMT)), ethylene glycol, the m-phthalic acid composition that contains the metal organic sulfonate base, polyalkylene glycol is a raw material, carry out direct esterification (or transesterify) reaction, polyester is made in polycondensation, dicarboxylic acid composition and ethylene glycol are made into slurry, be to carry out esterification (or transesterify) reaction under 1.1～1.5 the condition in total mol ratio, the m-phthalic acid composition and the polyalkylene glycol that contain the metal organic sulfonate base can add in esterification (or transesterify) or polycondensation phase, carboxylate imports polymeric kettle with batch form, carries out polyreaction under reduced pressure.
In said process, wherein;
Also can include m-phthalic acid in the raw material; Esterification (or transesterify) is reflected under the normal pressure to be carried out, and temperature is 130～245 ℃, and the time is 4～14 hours; In the polycondensation rough vacuum stage, temperature is 245～265 ℃, and the time is 0.5～3 hour; The polycondensation high vacuum stage of Fig, the still internal pressure is below 0.3 holder, and temperature is 265～285 ℃, and the time is 1～3 hour.
The device that is used to prepare modified poly ester of the present invention, it comprises:
The melt self-circulation system its role is to make the reaction mass homogeneity to be guaranteed;
Melt Pump its role is to accomplish in the vacuum state bottom discharge;
One esterification, two polycondensation vessels, still plays poising action in the middle of its role is to make, to enhance productivity to greatest extent;
Three monomers configurations still its role is to produce specially the compound (SIPE) that spent glycol and dimethyl ester carry out transesterify, with avoid SIPE transport, inconvenience aspect the storage.
Describe the preparation process of modified poly ester of the present invention in detail below in conjunction with accompanying drawing:
As shown in Figure 1, in joining stock tank 1, pure terephthalic acid and ethylene glycol are made into slurry, drop into m-phthalic acid to joining stock tank 1 from input port a, then this slurry is added in esterifying kettle 2 DMT or the PTA route hot mother liquor of prepared beforehand (in have) and carry out esterification (or transesterify) reaction and form oligopolymer; Esterification (or transesterify) is reflected under the normal pressure to be carried out, and temperature is at 130～245 ℃, and the time is 4～14 hours, according to esterification water (or methyl alcohol) amount of steaming decision reaction end.
The oligopolymer that generates is imported middle still 3, add m-phthalic acid composition and the polyalkylene glycol that contains the metal organic sulfonate base at input port b, material imports in the polymeric kettle 4, and carries out polyreaction under vacuum state continuously; In the polycondensation rough vacuum stage, temperature is controlled at 245～265 ℃, and the time is 0.5～3 hour; High vacuum stage of Fig is pressed in the still below 0.3 holder, and temperature is controlled at 265～285 ℃, and the time is 1～3 hour, grasps reaction end according to reactor beater motor power situation; Polyester fondant is extruded into the cooling bath from discharge port c, by cutting device with the ester bar granulation of extruding.
At this, the m-phthalic acid that contains the metal organic sulfonate base is become to be dispensed into slurry or adds at charging opening b all is feasible, but in batch technology, for the lower SIPE ethylene glycol solution of concentration, not only can suppress to have the caused gel of electric charge from charging opening b interpolation because of SIPE, also avoided exceeding standard because of the ethylene glycol too high levels causes DEG, fusing point is too low, is unfavorable for the problem of post-treatment; If the ethylene glycol solution concentration of SIPE is higher, then it is evenly added in the slurry of prior synthetic terephthalic acid and ethylene glycol, can avoid oligopolymer polymerization degree height because of the esterification end, influence the dispersed of SIPE and produce the problem of cohesion.
The present invention adopts manganese acetate and calcium acetate, also can be that zinc acetate, Cobaltous diacetate, magnesium acetate etc. are done transesterification catalyst, and add-on is 0.01～0.1% (with respect to dimethyl terephthalate (DMT)), can add in slurry.
For preventing that DEG content from increasing, add sodium-acetate in esterification (or transesterify) stage, also can be that Lithium Acetate, Potassium ethanoate, sodium-chlor, Sodium Benzoate etc. are done anti-ether agent, add-on be 0.01～0.1% (with respect to pure terephthalic acid or dimethyl terephthalate (DMT)).Adopting antimonous oxide, also can be that germanium dioxide, tetra-n-butyl titanate etc. are done polycondensation catalyst, adopts triphenylphosphate, " 1222 ", triphenyl phosphite, trimethyl phosphite 99 etc. to make stablizer.
In the present invention, the total mol ratio in the time of need be with esterification (or transesterify) is set at 1.1～1.5, if this mol ratio surpasses 1.5, will generate DEG in a large number, the physicals of infringement polymkeric substance; And, if less than 1.1 because the amount of ethylene glycol is insufficient, just can not normally be carried out esterification (or transesterify), polyreaction.
The b that the input of PEG is preferably in Fig. 1 carries out, the standard that drops into is that the esterification yield of oligopolymer is more than 80%, under this esterification yield, even produce boiling phenomenon because of the input of PEG, but because the amount of free ethylene glycol seldom, so can suppress intrasystem foamed phenomenon.
As the purpose of improving various physicalies, can in polyester of the present invention, add photostabilizer, heat-resistant agent, matting agent etc., the input of these additives can be carried out in any operation in manufacturing process.
The modified poly ester that the present invention makes has good alkali lye processable, and the concentration of alkali lye is 5%, the solvability of test section under boiling state, and 100min can dissolve fully with interior.Its dyeability and spinning property excellence, the silk stable physical property has improved the use value of the finished product greatly, can make sea island fiber on composite spinning machine as melt-spinnable polymers such as a component and PET or PA, obtains ultra-fine fibre after the alkali lye processing.The manufacture method of this batchwise polymerization can high-level efficiency, low cost production goes out the processable polyester, making technology is easy to adjust, can adjust product style at any time according to customer need, especially when overhaul of the equipments maintenance or abnormal conditions occur, can avoid tremendous loss.
Below by three groups of embodiment modified poly ester and preparation process thereof are described in more detail:
Earlier terephthalic acid (or dimethyl terephthalate (DMT)), ethylene glycol input are joined and be made into slurry in the stock tank, to wherein adding m-phthalic acid, sodium acetate trihydrate, then slurry is added in the esterifying kettle hot mother liquor of prepared beforehand (in have) and stir, keep 130～245 ℃ of esterification (or transesterify) temperature, treat esterification water (or methyl alcohol) when quantity of distillate reaches theoretical value, esterification is finished; Carboxylate is moved in the polymeric kettle, adding SIPE, PEG, antimonous oxide, triphenylphosphate stir, be warming up to 245～265 ℃ after the normal pressure polycondensation gradually, and progressively decompression, polycondensation is 0.5～3 hour under rough vacuum, carries out the high vacuum polycondensation again 1～3 hour, and still is pressed 0.3 holder, 265～285 ℃ of temperature are judged reaction end according to the power of stirring motor.
Table 1 has been put down in writing the three groups of embodiment 1,2,3 that carry out under the different condition, this only is preferred embodiment of the present invention, be not that the present invention is done any pro forma restriction, every foundation technical spirit of the present invention all still belongs in the scope of technical solution of the present invention any simple modification, equivalent variations and modification that above embodiment did.
Table 1
| Embodiment | ????1(0214) | ????2(0213) | ????3(0130) |
| Polymerization process | PTA intermittently | PTA intermittently | DMT intermittently |
| SIPE (mole %) | ????5.94 | ????5.94 | ????5.94 |
| PEG (weight %/molecular weight) | ????4.37/2000 | ????4.37/600 | ????4.37/2000 |
| M-phthalic acid addition (mole %) | ????3 | ????3 | ????0 |
| Sodium acetate trihydrate addition (ppm) | ????200 | ????200 | ????200 |
| Antimonous oxide addition (ppm) | ????250 | ????250 | ????250 |
| Triphenylphosphate addition (mole %) | ????0 | ????0 | ????0.03 |
| Total mol ratio | ????1.5 | ????1.5 | ????1.5 |
| Limiting viscosity (dl/g) | ????0.503 | ????0.467 | ????0.439 |
| Glycol ether content (w.t%) | ????4.72 | ????5.59 | ????5.88 |
| Content of carboxyl end group (mol/t) | ????11.32 | ????12.8 | ????12.2 |
| Fusing point (℃) | ????227.94 | ????220.76 | ????233.54 |
| B | ????8.8 | ????9.9 | ????8.4 |
| L | ????62 | ????60 | ????43.4 |
| Ash content (%) | ????1.65 | ????1.71 | ????1.44 |
| Alkali lye solvability (min) | ????52 | ????＜67 | ????50 |
| Thermostability | Good | Good | Good |
Claims (10)
1. modified poly ester, adopt terephthalic acid (or dimethyl terephthalate (DMT)), ethylene glycol to form for the basic raw material copolymerization, it is characterized in that: it is to contain 0～25.0% mole m-phthalic acid, the modified poly ester that 1.0～15.0% mole the m-phthalic acid composition that contains the metal organic sulfonate base, 2.0～15.0% weight, molecular-weight average are 500～10000 polyalkylene glycol copolymerization to form.
2. modified poly ester according to claim 1, it is characterized in that: described modified poly ester, the dissolution time of its ester grain (4mm*4mm*2.5mm) is in 100 minutes, limiting viscosity is 0.40～0.60 deciliter/gram, and content of carboxyl end group is less than 30.0 moles/ton, 210 ℃～240 ℃ of fusing points, the b value is less than 14.0, the L value is greater than 40.0, and ash is less than 2.0%, and glycol ether (DEG) content is in 2.0～6.0% weight.
3. modified poly ester according to claim 1 is characterized in that: wherein the molecular-weight average of polyalkylene glycol is 500～10000.
4. modified poly ester according to claim 1 is characterized in that: its alkali dissolution is that the ester grain is boiled with 5% sodium hydroxide solution, is estimated by its consoluet time.
5. the preparation method of an aforesaid modified poly ester, it is characterized in that: be to adopt terephthalic acid (or dimethyl terephthalate (DMT)), ethylene glycol, the m-phthalic acid composition that contains the metal organic sulfonate base, polyalkylene glycol is a raw material, carry out direct esterification (or transesterify) reaction, polyester is made in polycondensation, dicarboxylic acid composition and ethylene glycol are made into slurry, be to carry out esterification (or transesterify) reaction under 1.1～1.5 the condition in total mol ratio, the m-phthalic acid composition and the polyalkylene glycol that contain the metal organic sulfonate base can add in esterification (or transesterify) or polycondensation phase, carboxylate imports polymeric kettle with batch form, carries out polyreaction under reduced pressure.
6. the preparation method of modified poly ester according to claim 5 is characterized in that: also can include m-phthalic acid in the described raw material.
7. the preparation method of modified poly ester according to claim 5, it is characterized in that: described esterification (or transesterify) is reflected under the normal pressure to be carried out, and temperature is 130～245 ℃, and the time is 4～14 hours.
8. the preparation method of modified poly ester according to claim 5, it is characterized in that: in the described polycondensation rough vacuum stage, temperature is 245～265 ℃, and the time is 0.5～3 hour.
9. the preparation method of modified poly ester according to claim 5 is characterized in that: described polycondensation high vacuum stage of Fig, and the still internal pressure is below 0.3 holder, and temperature is 265～285 ℃, and the time is 1～3 hour.
10. device that is used to prepare aforesaid modified poly ester, it is characterized in that: it comprises:
Can make the guaranteed melt self-circulation system of reaction mass homogeneity, can accomplish Melt Pump in the vacuum state bottom discharge, still plays an esterification two polycondensation vessel flow processs of poising action in the middle of can making, and is used for producing specially spent glycol and disposes still with three monomers that SIPM carries out the compound (SIPE) of transesterify.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100415795C (en) * | 2006-06-23 | 2008-09-03 | 江苏江南高纤股份有限公司 | Alkali soluble polyester and its preparation method |
| CN102161751A (en) * | 2011-01-12 | 2011-08-24 | 江南大学 | Method for producing polyester sizing agent |
| CN101200536B (en) * | 2006-12-13 | 2011-11-23 | 东丽纤维研究所（中国）有限公司 | Basic aqueous easily-soluble modified polyesters and preparation method |
| CN102352027A (en) * | 2011-08-08 | 2012-02-15 | 张大省 | Cationic dye dyeable polyester and superfine fibers thereof |
| CN102086261B (en) * | 2009-12-07 | 2012-10-17 | 上海联吉合纤有限公司 | Preparation method of polyol copolyester |
| CN101570596B (en) * | 2009-04-30 | 2013-07-17 | 江苏江南高纤股份有限公司 | Method for preparing cationic-dyeable copolyester |
| CN103243399A (en) * | 2013-04-24 | 2013-08-14 | 浙江古纤道股份有限公司 | Preparation method of dark island polyester fully drawn yarn |
| CN103833994A (en) * | 2012-11-22 | 2014-06-04 | 东丽纤维研究所（中国）有限公司 | Alkali-soluble copolyester and its production method and use |
| CN107602832A (en) * | 2017-09-27 | 2018-01-19 | 宜昌中盈合成材料有限公司 | A kind of island section of low alkali fibrillation and its production method |
| WO2023203975A1 (en) * | 2022-04-22 | 2023-10-26 | 東洋紡エムシー株式会社 | Copolymer polyester resin |
| CN117343301A (en) * | 2023-12-06 | 2024-01-05 | 安徽国风新材料股份有限公司 | Low-melting-point cationic dye easy-to-color PET resin and preparation method and application thereof |
-
2003
- 2003-05-30 CN CN 03112242 patent/CN1253486C/en not_active Expired - Lifetime
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100415795C (en) * | 2006-06-23 | 2008-09-03 | 江苏江南高纤股份有限公司 | Alkali soluble polyester and its preparation method |
| CN101200536B (en) * | 2006-12-13 | 2011-11-23 | 东丽纤维研究所（中国）有限公司 | Basic aqueous easily-soluble modified polyesters and preparation method |
| CN101570596B (en) * | 2009-04-30 | 2013-07-17 | 江苏江南高纤股份有限公司 | Method for preparing cationic-dyeable copolyester |
| CN102086261B (en) * | 2009-12-07 | 2012-10-17 | 上海联吉合纤有限公司 | Preparation method of polyol copolyester |
| CN102161751A (en) * | 2011-01-12 | 2011-08-24 | 江南大学 | Method for producing polyester sizing agent |
| CN102352027A (en) * | 2011-08-08 | 2012-02-15 | 张大省 | Cationic dye dyeable polyester and superfine fibers thereof |
| CN102352027B (en) * | 2011-08-08 | 2013-02-06 | 张大省 | Cationic dye dyeable polyester and superfine fibers thereof |
| CN103833994A (en) * | 2012-11-22 | 2014-06-04 | 东丽纤维研究所（中国）有限公司 | Alkali-soluble copolyester and its production method and use |
| CN103243399A (en) * | 2013-04-24 | 2013-08-14 | 浙江古纤道股份有限公司 | Preparation method of dark island polyester fully drawn yarn |
| CN103243399B (en) * | 2013-04-24 | 2015-09-02 | 浙江古纤道股份有限公司 | A kind of preparation method of aterrimus island polyester fullly drawn yarn (FDY) |
| CN107602832A (en) * | 2017-09-27 | 2018-01-19 | 宜昌中盈合成材料有限公司 | A kind of island section of low alkali fibrillation and its production method |
| WO2023203975A1 (en) * | 2022-04-22 | 2023-10-26 | 東洋紡エムシー株式会社 | Copolymer polyester resin |
| CN117343301A (en) * | 2023-12-06 | 2024-01-05 | 安徽国风新材料股份有限公司 | Low-melting-point cationic dye easy-to-color PET resin and preparation method and application thereof |
| CN117343301B (en) * | 2023-12-06 | 2024-02-02 | 安徽国风新材料股份有限公司 | Low-melting-point cationic dye easy-to-color PET resin and preparation method and application thereof |
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| CN1253486C (en) | 2006-04-26 |
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Effective date of registration: 20090619 Address after: Fujian province Xiamen City Haicang Taiwan investment area LKeng village postal code: 361026 Co-patentee after: Dragon Special Resin (Xiamen) Co.,Ltd. Patentee after: XIAMEN XIANGLU CHEMICAL FIBER CO.,LTD. Address before: Fujian city of Xiamen province haicanginvestmentzone Xianglu polyester textile fibers (Xiamen) Co., Ltd. postcode: 361026 Patentee before: XIAMEN XIANGLU CHEMICAL FIBER CO.,LTD. |
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Assignee: Dragon Special Resin (Xiamen) Co.,Ltd. Assignor: Dragon Special Resin (Xiamen) Co.,Ltd.|XIAMEN XIANGLU CHEMICAL FIBER CO.,LTD. Contract fulfillment period: 2009.9.25 to 2014.9.25 Contract record no.: 2009351000075 Denomination of invention: Modified polyester and preparing method thereof Granted publication date: 20060426 License type: Exclusive license Record date: 20091102 |
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