A kind of copolyester section of modification or fiber and preparation method thereof
Technical field
The present invention relates to a kind of polyester fiber (polyester fiber) and preparation thereof, specifically a kind of copolyester section of aliphatic dihydroxy alcohol (or its alkoxide) modification that contains side chain or fiber and preparation method thereof.
Background technology
Polyester fiber has outstanding performance, as high-modulus, high strength, resilience, light resistance, ABRASION RESISTANCE, heat resistance, chemicals-resistant is good and advantage such as with low cost, can be used for numerous areas such as dress ornament, decoration and industry.Yet this excellent physical and mechanical properties of polyester fiber depends on molecular structure that it is regular and higher degree of crystallinity, but this has also brought the difficulty of dyeing simultaneously to polyester fiber, can only utilize DISPERSE DYES under High Temperature High Pressure, to dye, and dyefastness is low, of light color, its equipment and specification requirement height, contaminated environment.
The method of improving the polyester fiber dyeability is a lot, and widely used is to add the method that modified monomer carries out copolymerization.Modified monomer commonly used can be divided into following three kinds: (1) cationic dye capable of dyeing monomer, as metal sulfamate sodium (or potassium) class; (2) disperse dyes can dye monomer, as have the M-phthalic acid of a bit architecture, have the polyethylene glycol of flexible structure and decanedioic acid etc.; (3) acid-dyeable monomer is as amine group containing.
Wherein add CATION and dye the copolyesters of seat, its good dyeability obtains the extensive concern of various countries, du pont company was in order to improve the stainability of polyester fiber in 1958, adopt the SIPE that adds 2mol% to produce CDP as the 3rd component and DMT, ethylene glycol (EG) copolymerization, because its excellent dyeability and cheap dyeing cost make it become the main representative of polyester fiber new varieties.But its structure still relatively closely dyes under the boiling dyeing at normal pressure condition, and dye-uptake is low, so dyeing also need be carried out under high-temperature and high-pressure conditions, this has just brought energy consumption big, shortcomings such as equipment complexity, and can not with the blending or the dyeing that interweave such as wool, silk.The ECDP fiber that people develop on the CDP basis, this fiber not only normal pressure can dye dark color, and color and luster is more bright-coloured than CDP fiber.But owing in the copolyesters macromolecular chain, introduced ehter bond, make the heat endurance of copolyesters descend, cause the spinning temperature adjustable range narrow, shortcomings such as spinnability difference.Entered since the nineties, beautiful, developed countries such as day are by improving SIP content, developed the product HCDP of a collection of brand-new characteristic, this kind fiber has dye-uptake and COLOR FASTNESS preferably, and increase along with SIP content, its hygroscopicity, antistatic behaviour increases greatly, but owing to the content of polymerization stage with SIP increases, the interaction of ionic group strengthens, cause melt viscosity sharply to increase, make polymerisation be difficult to carry out, the molecular weight that increase polymer becomes very difficult, so the molecular weight of HCDP is generally lower, high viscosity during fusion also causes the product processing difficulties, mechanical properties decrease, these all become the key factor that limits the further application of this class modified copolyester.
On the basis of the present invention's cation-modified polyester more than comprehensively, by introducing the 4th new monomer, develop a kind of copolyester section or fiber of the novel aliphatic dihydroxy alcohol that contains side chain (or its alkoxide) modification, and had good market using value.
Summary of the invention
The purpose of this invention is to provide a kind of copolyester section of aliphatic dihydroxy alcohol (or its alkoxide) modification that contains side chain or fiber and preparation method thereof, this copolyester section or fiber can be under normal pressures, all can dye dark color to cation dyes and disperse dyes, and ultra-soft feel, gloss are soft, highly shrinkable, potential little crimpiness, its preparation manipulation is simple, cost is low, is fit to suitability for industrialized production.
The copolyester section of a kind of aliphatic dihydroxy alcohol (or its alkoxide) modification that contains side chain of the present invention or fiber (being called for short MCDP section or fiber), by following four kinds of monomer copolymerizations:
(1) terephthalic acid (TPA),
(2) ethylene glycol,
Benzene binary acid dibasic ester sodium sulfonate (or potassium) (3),
(4) contain the aliphatic dihydroxy alcohol (or its alkoxide) of side chain.
The described aliphatic dihydroxy alcohol (being abbreviated as M) that contains side chain is made up of 4 to 25 carbon atoms, can be 2-methyl isophthalic acid, ammediol, 2,2-dimethyl-1,3 propylene glycol, 2-methyl isophthalic acid, 4-butanediol, 2,3-dimethyl-1,4-butanediol, 3-ethyl-1,5-pentanediol, 2-methyl isophthalic acid, 5-pentanediol, 3,3-dimethyl-1,5-pentanediol or 3-methyl-3-ethyl-15-pentanediol.
It is as follows that the described alkoxide that contains the aliphatic dihydroxy alcohol of side chain has following molecular structural formula:
Wherein: the aliphatic dihydroxy alcohol that contains side chain that the M representative is made up of 4 to 25 carbon atoms, x and y are relatively independent integer, and satisfy 1≤x+y≤5.
A kind of preparation method of copolyester section of modification comprises the following steps:
(1) ethylene glycol is mixed the formation mixed alcohol with the aliphatic dihydroxy alcohol that contains side chain (or its alkoxide), the aliphatic dihydroxy alcohol (or its alkoxide) that wherein contains side chain accounts for 1~50mol% of mixed alcohol, add catalyst and stabilizing agent, and add terephthalic acid (TPA) and mixed alcohol carries out esterification under 220 ℃~260 ℃;
(2) after esterification finishes, adding with respect to benzene binary acid dibasic ester sodium sulfonate (or potassium) between terephthalic acid (TPA) molar weight 1~9mol% as the 3rd monomer, under 250 ℃~300 ℃, carry out polycondensation reaction, finally make the aliphatic dihydroxy alcohol that contains side chain or the copolyester section of its alkoxide modification.
A kind of preparation method of copolyester fiber of modification comprises the following steps:
(1) ethylene glycol is mixed the formation mixed alcohol with the aliphatic dihydroxy alcohol that contains side chain (or its alkoxide), the aliphatic dihydroxy alcohol (or its alkoxide) that wherein contains side chain accounts for 1~50mol% of mixed alcohol, add catalyst and stabilizing agent, and add terephthalic acid (TPA) and mixed alcohol carries out esterification under 220 ℃~260 ℃;
(2) after esterification finishes, adding with respect to benzene binary acid dibasic ester sodium sulfonate (or potassium) between terephthalic acid (TPA) molar weight 1~9mol% as the 3rd monomer, under 250 ℃~300 ℃, carry out polycondensation reaction, finally make the aliphatic dihydroxy alcohol that contains side chain or the copolyester section of its alkoxide modification;
(3) the prepared copolyester section of step (2) can be spun section 100~170 ℃ of dry acquisitions, 280~320 ℃ of extruder temperatures, spinning speed 400~1500m/min, 70~160 ℃ of drawing temperatures, under the condition that drafting multiple is 2~4 times, make the copolyester fiber of modification.
Catalyst described in the step 1 is the acetate compound of Metal Zn, Sb, Mn, Ca or the Co of divalence or trivalent, and consumption is 0.01~0.08wt% of terephthalic acid (TPA).
Stabilizing agent described in the step 1 is trimethyl phosphate or triphenyl phosphate, and consumption is 0.02~0.06wt% of terephthalic acid (TPA).
With the described copolyester section of step (2) through super-dry as a kind of component, a kind of with in polyester (PET), polyamide 6 (PA6), polyamide 66 (PA66), polypropylene (PP), the high-load cation dyeable copolyester (HCDP) as another kind of component, adopt parallel type or tangerine lobe type composite spinneret to carry out melt spinning, spinning speed 400~1500m/min, 70~160 ℃ of drawing temperatures, under 2~4 times of conditions of drafting multiple, make the copolyesters composite fibre of modification, wherein spinning temperature is respectively 280~300 ℃ of polyester; 285~315 ℃ of high-load cation dyeable copolyesters; 270~290 ℃ of polyamide; 270~290 ℃ of polypropylene.
With polyester (PET) or polyamide 6 (PA6) or polyamide 66 (PA66) or polypropylene (PP) or high-load cation dyeable copolyester (HCDP) is matrix, the copolyester section that adds the described modification of step (2) carries out blend, cut into slices then through 100~170 ℃ of dryings, 280~320 ℃ of extruder temperatures, spinning speed 400~1500m/min, 70~160 ℃ of drawing temperatures, 2~4 times of drafting multiples, make the polyester blending fiber of modification, wherein polyester, polyamide 6, polyamide 66 or polypropylene content are 10~80wt% of copolyester section or fiber.
Copolyester fiber provided by the present invention has been introduced the side chain alkane group again in the introducing sulfonate groups in its macromolecular chain, make copolyester fiber can dye dark color for cation dyes and disperse dyes under normal pressure.
This is because after the common polyester fiber process spinning drawing-off, its big molecules align is tight and degree of crystallinity is high, the glass transition temperature height, and after fiber immerses dye liquor, need be under high-temperature and high-pressure conditions, the side make dye molecule infiltrated fiber inside, finishes dyeing.And the HCDP copolyesters is introduced sodiosulfoisophthalic acid (or potassium) group on polyester macromolecule, make the fiber that is spinned to carry out cationic dyeing, and because sodiosulfoisophthalic acid (or potassium) group volume is bigger, destroy macromolecular regularity of fiber and crystallinity, made the HCDP fiber under normal pressure, can dye.
In view of the foregoing, the present invention is in the process of preparation copolyesters, introduce sulfonate groups and introduce the aliphatic dihydroxy alcohol (or its alkoxide) that contains side chain simultaneously again, make this copolyester fiber under normal pressure, not only to cation dyes and can all have good Color to disperse dyes.This be because between benzene binary acid sodium sulfonate (or potassium) group and contain side chain the bulky joint effect of side-chain radical of aliphatic dihydroxy alcohol (or its alkoxide), and number is more, make this kind copolyester fiber structure more loose, crystal property and vitrification point all descend, thereby the fiber macromolecular chain is easier moving in the normal pressure dye bath, produce more spaces, make cation dyes molecule and disperse dyes molecule be easier to enter intramolecule and combine with dying, obtain darker Color.
The copolyester fiber of the aliphatic dihydroxy alcohol that contains side chain (or its alkoxide) modification of the present invention preparation be by purely spin, co-blended spinning, composite spinneret design, multiple modification technologies such as control spinning and draft process obtain, therefore except having cation dyes or dyed easily by disperse dye, also with super soft feel, excellent specific properties such as gloss is soft, highly shrinkable, potential crimping property.The copolyester fiber of the aliphatic dihydroxy alcohol that contains side chain (or its alkoxide) modification of the present invention preparation in addition, its manufacture process does not have specific (special) requirements to equipment, can on import or homemade conventional equipment, produce, and cost price is cheap, easily realizes suitability for industrialized production.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described 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 institute restricted portion equally.
Terephthalic acid (TPA) of the present invention is abbreviated as PTA; Ethylene glycol is abbreviated as EG; The 2-methyl isophthalic acid, ammediol is abbreviated as MPD; Ethylene m-phthalate-5-sodium sulfonate (or potassium) is abbreviated as SIPE, and copolymer is abbreviated as MCDP.
Embodiment 1
Adopt intermittence type polymerization equipment, with 2.117mol PTA, after 3.403mol EG and 0.142mol are equivalent to the MPD mixed together of EG and MPD mixed alcohol 4mol% molar weight, add in the reaction system, add the antimony acetate catalyst of 0.01wt% and the triphenyl phosphate (with respect to PTA) of 0.02wt% simultaneously, 230 ~ 240 ℃ of temperature, pressure 0.0 ~ 0.5Mpa stirs 1.5h down, when treating that esterification finishes, add the SIPE that is equivalent to PTA 3mol% molar weight, enter polycondensation phase, control reaction temperature is at 240 ~ 280 ℃, be decompressed to vacuum<130pa gradually, polycondensation 2h finally makes and contains MPD unit 4mol%, the MCDP copolyester section of SIPE unit 3mol%.The copolyesters inherent viscosity is 0.512,235 ℃ of fusing points.
Embodiment 2
Adopt intermittence type polymerization equipment, add PTA 150kg, EG 70.6kg, and the MPD that is equivalent to EG and MPD mixed alcohol 10mol% molar weight, the triphenyl phosphate (with respect to PTA) that adds catalyst 0.01wt% antimony acetate catalyst and 0.02wt%, 230 ~ 240 ℃ of temperature, pressure 0.0 ~ 0.5Mpa stirs 3h down, when treating that esterification finishes, add and be equivalent to PTA 3mol% molar weight SIPE, control reaction temperature is at 240 ~ 280 ℃, be decompressed to vacuum<130pa gradually, polycondensation 4h makes and contains MPD unit 10mol%, the MCDP copolyester section of SIPE unit 3mol%.The copolyesters inherent viscosity is 0.486,214 ℃ of fusing points.
Embodiment 3
Adopt intermittence type polymerization equipment, add PTA 150kg, EG 66.7kg, and the MPD that is equivalent to EG and MPD mixed alcohol 15mol% molar weight, the triphenyl phosphate (with respect to PTA) that adds catalyst 0.01wt% antimony acetate catalyst and 0.02wt%, under 230 ~ 240 ℃ of pressure 0.0 ~ 0.5Mpa of temperature, stir 4h, when treating that esterification finishes, under 0.1 ~ 0.01Mpa system, add and be equivalent to PTA 3mol% molar weight SIPE, control reaction temperature is at 240 ~ 280 ℃, be decompressed to vacuum<130pa gradually, polycondensation 4h makes and contains MPD unit 15mol%, the MCDP copolyester section of SIPE unit 3mol%.The copolyesters inherent viscosity is 0.476,209 ℃ of fusing points.
Comparative example 4
After 2.117mol PTA, 3.544mol EG mixing, add in the reaction system, add the antimony acetate catalyst of 0.01wt% and the triphenyl phosphate (with respect to PTA) of 0.02wt% simultaneously, when treating out that esterification finishes, add the SIPE that is equivalent to the PTA3mol% molar weight, finally make the HCDP copolyester section that contains SIPE unit 3mol%.The copolyesters inherent viscosity is 0.512,241 ℃ of fusing points.
Embodiment 5
The MCDP copolyester section places in the vacuum drum drier, steam pressure 0.2Mpa, and vacuum≤0Mpa, 100 ~ 120 ℃ of temperature, time 8 ~ 12h is warming up to 120 ~ 140 ℃ again, and control time 12 ~ 16h obtains the dried section of moisture content less than 50PPM.
Embodiment 6
To contain the MPD unit is that the MCDP copolyester section of 10mol% is a raw material, adopt Japanese ABE composite spinning machine, extruder temperature is 285 ~ 305 ℃, and pump is for amount 45g/min, winding speed 1000m/min, adopt the Barmag drawing machine, 75 ~ 160 ℃ of heat dish, hot plate temperatures, 2 ~ 4 times of drafting multiples, making fiber number is 138dtex/36F, fracture strength 2.2dtex/cN, the copolyesters long filament of the aliphatic dihydroxy alcohol that contains side chain of extension at break 31% (or its alkoxide) modification.
Embodiment 7
To contain the MPD unit is that the MCDP copolyester section of 15mol% is a raw material, adopt Japanese ABE composite spinning machine, extruder temperature is 285 ~ 305 ℃, and pump is for amount 45g/min, winding speed 1000m/min, adopt the Barmag drawing machine, 75 ~ 160 ℃ of heat dish, hot plate temperatures, 2 ~ 4 times of drafting multiples, making fiber number is 138dtex/36F, fracture strength 2.0dtex/cN, the copolyesters long filament of the aliphatic dihydroxy alcohol that contains side chain of extension at break 31% (or its alkoxide) modification.
Embodiment 8
To contain MCDP copolyesters that the MPD unit is 15mol% and the hybrid slicing of HCDP is raw material (weight ratio is 2: 1), adopt Japanese ABE composite spinning machine, extruder temperature is 280 ~ 320 ℃, pump is for amount 45g/min, winding speed 1000m/min, adopt the Barmag drawing machine, 70 ~ 150 ℃ of heat dish, hot plate temperatures, 2 ~ 4 times of drafting multiples, making fiber number is 133dtex/36F, fracture strength 2.4dtex/cN, the copolyesters long filament of the aliphatic dihydroxy alcohol that contains side chain of extension at break 31% (or its alkoxide) modification.
Embodiment 9
To contain MCDP copolyesters that the MPD unit is 10mol% and the hybrid slicing of PET is raw material (weight ratio is 3: 2), adopt Japanese ABE composite spinning machine, extruder temperature is 280 ~ 320 ℃, pump is for amount 45g/min, winding speed 800m/min, adopt the Barmag drawing machine, 70 ~ 150 ℃ of heat dish, hot plate temperatures, 2 ~ 4 times of drafting multiples, making fiber number is 139dtex/36F, fracture strength 3.2dtex/cN, the copolyesters long filament of the aliphatic dihydroxy alcohol that contains side chain of extension at break 17% (or its alkoxide) modification.
Embodiment 10
To contain MCDP copolyesters that the MPD unit is 15mol% and the hybrid slicing of PET is raw material (weight ratio is 2: 3), adopt Japanese ABE composite spinning machine, extruder temperature is 280 ~ 320 ℃, pump is for amount 45g/min, winding speed 800m/min, adopt the Barmag drawing machine, 70 ~ 150 ℃ of heat dish, hot plate temperatures, 2 ~ 4 times of drafting multiples, making fiber number is 144dtex/36F, fracture strength 3.3dtex/cN, the copolyesters long filament of the aliphatic dihydroxy alcohol that contains side chain of extension at break 21% (or its alkoxide) modification.
Comparative example 11
With the HCDP copolyester section that contains 3mol% is raw material, adopt Japanese ABE composite spinning machine, extruder temperature is 285 ~ 315 ℃, and pump is for amount 45g/min, winding speed 1000m/min, adopt the Barmag drawing machine, 70 ~ 150 ℃ of heat dish, hot plate temperatures, 2 ~ 4 times of drafting multiples, making fiber number is 138dtex/36F, fracture strength 2.9dtex/cN, the high-load cation dyeable copolyester long filament of extension at break 28%.
Embodiment 12
To contain MCDP copolyester section and the HCDP section that the MPD unit is 15mol% is raw material, adopt Japanese ABE composite spinning machine and parallel type composite spinneret, extruder temperature is controlled to be respectively: 285 ~ 305 ℃ of MCDP, 285 ~ 315 ℃ of HCDP, pump is controlled to be respectively for amount: MCDP 16g/min, HCDP 16g/min, winding speed 800m/min, adopt the Barmag drawing machine, the heat dish, 70 ~ 150 ℃ of hot plate temperatures, 2 ~ 4 times of drafting multiples, making fiber number is 140dtex/36F, fracture strength 2.2dtex/cN, the copolyesters parallel type bicomponent filament yarn of the aliphatic dihydroxy alcohol that contains side chain of extension at break 31% (or its alkoxide) modification.
Embodiment 13
To contain MCDP copolyester section and the PA6 section that the MPD unit is 10mol% is raw material, adopt Japanese ABE composite spinning machine and tangerine lobe type composite spinneret, extruder temperature is controlled to be respectively: 285 ~ 305 ℃ of MCDP, 270 ~ 290 ℃ of PA6, pump is controlled to be respectively for amount: MCDP 16g/min, PA6 16g/min, winding speed 800m/min, adopt the Barmag drawing machine, the heat dish, 70 ~ 150 ℃ of hot plate temperatures, 2 ~ 4 times of drafting multiples, making fiber number is 136dtex/36F, fracture strength 2.3dtex/cN, the copolyesters tangerine lobe type bicomponent filament yarn of the aliphatic dihydroxy alcohol that contains side chain of extension at break 35% (or its alkoxide) modification.