CN115961373B - Preparation method of modified PTT fiber with deformation memory function - Google Patents
Preparation method of modified PTT fiber with deformation memory function Download PDFInfo
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- 230000006386 memory function Effects 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 35
- 238000005886 esterification reaction Methods 0.000 claims abstract description 24
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000009987 spinning Methods 0.000 claims abstract description 16
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims abstract description 15
- 229940119545 isobornyl methacrylate Drugs 0.000 claims abstract description 15
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 14
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 36
- 239000003054 catalyst Substances 0.000 claims description 30
- NMYFVWYGKGVPIW-UHFFFAOYSA-N 3,7-dioxabicyclo[7.2.2]trideca-1(11),9,12-triene-2,8-dione Chemical compound O=C1OCCCOC(=O)C2=CC=C1C=C2 NMYFVWYGKGVPIW-UHFFFAOYSA-N 0.000 claims description 23
- 238000006068 polycondensation reaction Methods 0.000 claims description 23
- 239000003999 initiator Substances 0.000 claims description 19
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 18
- 230000032050 esterification Effects 0.000 claims description 17
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- 230000003078 antioxidant effect Effects 0.000 claims description 15
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical group COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 12
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 12
- KRXBVZUTZPDWQI-UHFFFAOYSA-N ethane-1,2-diol;titanium Chemical compound [Ti].OCCO KRXBVZUTZPDWQI-UHFFFAOYSA-N 0.000 claims description 11
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 11
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 claims description 10
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 8
- 229940035437 1,3-propanediol Drugs 0.000 claims description 8
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 8
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical group CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- -1 terephthalic acid propylene glycol ester Chemical class 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
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- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000009477 glass transition Effects 0.000 abstract description 26
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- 239000005020 polyethylene terephthalate Substances 0.000 description 14
- 229920000139 polyethylene terephthalate Polymers 0.000 description 13
- NOJQSZZIXRYAFK-UHFFFAOYSA-N propane-1,2-diol;terephthalic acid Chemical compound CC(O)CO.OC(=O)C1=CC=C(C(O)=O)C=C1 NOJQSZZIXRYAFK-UHFFFAOYSA-N 0.000 description 11
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- 210000002268 wool Anatomy 0.000 description 2
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Artificial Filaments (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention provides a preparation method of modified PTT fiber with a deformation memory function, which comprises esterification reaction, ternary polymerization and spinning. The glass transition temperature of the PTT is 45-65 ℃ which is not in accordance with the use temperature in daily life of clothing, and the modified PTT polymer is prepared by adding a certain proportion of isobornyl methacrylate and isobutyl acrylate for ternary polymerization through material modification, so that the glass transition temperature of the PTT is reduced to 30-40 ℃, and the PTT is more suitable for the wearing environment of human bodies. The modified PTT fiber and the nylon filament yarn prepared by the invention are prepared into the modified PTT/PA6 cool sense covering yarn, and can be used as summer body shaping sportswear fabric. Because the glass transition temperature of the modified PPT polymer is 30-40 ℃, when the environmental temperature is lower than the glass transition temperature of the modified PPT polymer in summer and high temperature, the fabric is conformal; when the ambient temperature is higher than the glass transition temperature, the modulus of the material is reduced sharply, the fabric is deformed, and the air heat insulation layer is led in, so that the human body generates cool feeling.
Description
Technical Field
The invention belongs to the technical field of PTT fibers, and particularly relates to a preparation method of modified PTT fiber with a deformation memory function.
Background
Poly (trimethylene terephthalate) (PTT) and poly (ethylene terephthalate) (PET), which are the polyesters, were synthesized in the laboratory in 1941, wherein PET has been industrially produced in the 50 th century of 20, and PTT has been commercialized by the Shell chemical company of the United states until 90 because of the difficulty and high cost of the preparation of the main synthetic monomer 1, 3-Propanediol (PDO). The PTT fiber has the advantages of terylene and chinlon, and can be prepared by a biological method to have resource advantages, and accords with the sustainable development and the future industrial development direction based on people, so the PTT fiber is known as a synthetic fiber with great potential in the 21 st century.
In terms of chemistry and macromolecular chain structure, PET and PTT belong to the polyester series, and a rigid chain benzene ring and a flexible methylene (-CH 2-) exist in the molecular chain at the same time, and are connected by an ester group (-CO-O-) to form a typical rigid-flexible coexisting linear macromolecule. The main difference of the chemical structures of the two is that: two methylene groups are on the PET molecular chain links, and three methylene groups are on the PTT molecular chain links; the three methylene groups of the PTT molecular chain enable the PTT molecular chain to have an odd carbon effect, the molecular chain presents a spiral structure similar to a wool protein molecular chain, has obvious Z-shaped conformation, leads the macromolecular chain to have the deformation and deformation recovery capability similar to a spring, is easy to elongate under the action of longitudinal external force, and returns to the original state after the external force is removed, thus endowing the PTT molecular chain with excellent rebound resilience.
In terms of crystallization and orientation structure, PET and PTT belong to high-speed melt spinning orientation induced crystallization, but the crystal domain modulus of PET fiber is as high as 108GPa, while the PTT crystal domain modulus is only 3.16GPa, which is basically close to the modulus value of an amorphous domain. This results in a PTT fiber whose modulus does not vary with draft ratio, being substantially constant. Due to the low modulus, various functional powder, color master batch and the like are easier to add in the PTT spinning process, so that the functional PTT and the stock solution coloring PTT are obtained.
In terms of thermal properties, PTT fibers have a lower glass transition temperature (45 to 65 ℃) and melting temperature (228 ℃) and a higher boiling water shrinkage (about 14%) than PET fibers. The PTT fiber can be dyed at normal pressure due to the lower glass transition temperature, and the dyeing is recommended to be carried out at 100-110 ℃, so that the dye-uptake is higher than that of PET, and the energy conservation and emission reduction of factories are facilitated; the low melting temperature requires that the temperature is lower than that of the PET fabric in the shaping process of the PTT fabric, and the temperature is recommended to be about 160 ℃; the difference in boiling water shrinkage indicates that the PTT fiber has a large unorientation capability, and by utilizing the point, the PTT and the PET are subjected to composite spinning, so that the elastic fiber with permanent curl can be obtained.
In terms of mechanical properties, PTT has superior rebound properties, lower tensile modulus, and higher elongation at break than other polyester fibers due to its unique structural characteristics. The elastic recovery rate, young's modulus and elongation at break of the PTT fiber are respectively 22%, 22.01cN/dtex and 55%, while the PET fiber is respectively about 4%, 81.56cN/dtex and 27%. But the Young's modulus of PTT fiber is similar to that of wool fiber (20-30 cN/dtex).
Creep and stress relaxation experiments of the fiber show that PTT has better elasticity than PET and is equivalent to chinlon (PA). The advantages of elasticity and wear resistance of PTT can replace high-price PA66 and PA6 to be used as carpets and clothing fabrics.
Shape memory polymers are those that are capable of recovering their permanent shape from a temporary shape upon application of an appropriate stimulus, such as electricity, temperature, magnetism, light, temperature, force, solvent, etc. When the shape memory polymer is subjected to external stimulus under the initial shape, the shape memory polymer is shaped into a temporary shape under the action of external force, and the external stimulus is removed at the moment, so that the shape memory polymer is fixed into the temporary shape; when the polymer is stimulated again by the outside, the fixed temporary shape spontaneously returns to the original shape under the condition of no external force, and the process is macroscopic shape memory effect.
The main process of a typical shape memory cycle for a temperature responsive shape memory polymer material is as follows:
(1) Heating and shaping: the successfully prepared temperature responsive shape memory polymer having a permanent shape is first placed under room temperature conditions, where the polymer shape is referred to as the initial shape. The polymer material is heated to a temperature above the glass transition temperature (Ttrans) to change the material from a glassy state to a rubbery state, and an external force is applied to the material to fix the shape memory polymer in a desired shape, where the polymer shape is referred to as a temporary shape.
(2) Cooling and solidifying: the temperature of the polymer material is reduced below its glass transition temperature (Ttrans) under the condition of keeping the external force unchanged, at this time, the temporary shape of the polymer shape is fixed, and the temporary shape is not changed when the external force is removed to restrict the temporary shape.
(3) Shape recovery: and (3) raising the temperature of the shape memory polymer with the temporary shape to be higher than Ttrans again, wherein the shape memory polymer spontaneously returns to the original shape from the temporary shape under the stimulation of temperature, so that the shape memory polymer completes a shape memory cycle.
The PTT shape memory fabric prepared in the prior art has unique fabric shaping property and crease recovery property, so the PTT shape memory fabric is usually made into radian modeling fabrics, automobile interiors and the like, but the glass transition temperature of PTT is 45-65 ℃ which is not in accordance with the use temperature in daily life of clothing, thereby restricting the development of PTT in the clothing field.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of modified PTT with a deformation memory function, which realizes the aim of modifying PTT polymer to ensure that the PTT polymer also has the deformation memory function when being worn by a daily human body.
In order to solve the technical problems, the invention adopts the following technical scheme:
A preparation method of modified PTT fiber with deformation memory function comprises the following steps:
S1, esterification reaction
Adding 1, 3-propylene glycol and refined terephthalic acid into a reaction kettle according to a certain proportion, adding an esterification catalyst, heating to 210-250 ℃, reacting for 2-3 hours under the pressure of 0.2-0.5 MPa, wherein the esterification rate is more than 98%, and ending the reaction to obtain the propylene glycol terephthalate.
Preferably, the effective content of the 1, 3-propanediol is 99.9%, which is purchased from the chemical industry limited company of the kylhaa of Guangzhou city; the effective content of the purified terephthalic acid is 99%, and the purified terephthalic acid is purchased from Xiamen Yude chemical products limited company.
Further, the molar ratio of the 1, 3-propanediol to the refined terephthalic acid is 1.7-2: 1.
Preferably, the esterification catalyst is one or more of TiO 2-SiO2 catalyst, tetrabutyl titanate, ethylene glycol titanium, potassium fluotitanate, dibutyl tin oxide and stannous octoate, and the adding amount is 260-280 mg of the catalyst added in each Kg of refined terephthalic acid.
More preferably, the esterification catalyst is ethylene glycol titanium and stannous octoate, and the mass ratio of the ethylene glycol titanium to the stannous octoate is 3-5:1.
S2, ternary polymerization
Adding a polycondensation catalyst, a stabilizer and an antioxidant into the trimethylene terephthalate prepared in the step S1, performing polycondensation reaction at the temperature of 250-265 ℃, adding a certain amount of isobornyl methacrylate, isobutyl acrylate and an initiator, and continuously reacting for 0.5-2 h at the temperature of 270-280 ℃ to obtain the modified PPT polymer.
Preferably, the polycondensation is carried out by reacting at 0.1-0.5 MPa for 0.5-1 h, and then at 40-100 Pa for 1.5-2 h.
Preferably, the polycondensation catalyst is tetrabutyl titanate and antimony acetate, and the addition amount is 220-240 mg of the polycondensation catalyst is correspondingly added into each Kg of the terephthalic acid propylene glycol ester; the mass ratio of the tetrabutyl titanate to the antimony acetate is 1.5-2: 1.
Preferably, the stabilizer is trimethylolpropane or triphenyl phosphite, and the adding amount is 120-160 mg in each Kg of the trimethylene terephthalate; the antioxidant is antioxidant 1010, and the adding amount is 300-400 mg of the antioxidant added into each Kg of the trimethylene terephthalate.
Preferably, the molar ratio of the propylene glycol terephthalate, the isobornyl methacrylate and the isobutyl acrylate is 1.6-2:0.8-1:1.1-1.4.
Preferably, the addition amount of the initiator is 0.6 to 1.5 weight percent of the trimethylene terephthalate; the initiator is cumene hydroperoxide and di-tert-butyl peroxide, and the mass ratio of the cumene hydroperoxide to the di-tert-butyl peroxide is 1:2 to 3. The cumene hydroperoxide and the di-tert-butyl peroxide are used as the initiator in a matching way, the addition amount is controlled to be 0.6-1.5 wt%, so that the copolymerization reaction is promoted, and meanwhile, the copolymerization stability is promoted; the addition of the stabilizer reduces side reaction of polymerization, avoids the color degradation of the modified PPT polymer, and the addition of the antioxidant avoids the thermal degradation of the polymerized monomer.
The glass transition temperature of the modified PPT polymer is 30-40 ℃, the hue b value is 3.7-5, and the intrinsic viscosity is 0.85-0.94 dL/g.
S3, spinning
Granulating the modified PPT polymer to prepare modified PPT slices, and carrying out melt spinning by a screw extruder, wherein the temperature of each spinning area is 250-270 ℃, thus obtaining the modified PTT fiber.
The modified PTT fiber and the nylon filament yarn prepared by the invention are adopted to prepare the modified PTT/PA6 cool feel core spun yarn by adopting a spinning frame and taking the modified PTT fiber as a core and the nylon filament yarn as a covering yarn, and the modified PTT/PA6 cool feel core spun yarn can be used as a body shaping sportswear fabric in summer.
By adopting the technical scheme, the invention has the following technical effects:
the breaking strength of the modified PTT fiber prepared by the invention is 3.8-4.3 cN/dex, the breaking elongation is 37-44%, and the mechanical property is good, thus the modified PTT fiber can be applied to the textile industry.
2. The glass transition temperature of the PTT is 45-65 ℃ which is not in accordance with the use temperature in daily life of clothing, and the modified PTT polymer is prepared by adding a certain proportion of isobornyl methacrylate and isobutyl acrylate for ternary polymerization through material modification, so that the glass transition temperature of the PTT is reduced to 30-40 ℃, and the PTT is more suitable for the wearing environment of human bodies; meanwhile, the isobornyl methacrylate, isobutyl acrylate and PTT have good copolymerization property, the modified PTT has good color phase, the intrinsic viscosity is 0.85-0.94 dL/g, and the commercial PTT has the intrinsic viscosity of 0.7-1.2 dL/g, so the modified PTT is also suitable for melt spinning.
3. The modified PTT fiber and the nylon filament yarn prepared by the invention are adopted to prepare the modified PTT/PA6 cool feel core spun yarn by adopting a spinning frame and taking the modified PTT fiber as a core and the nylon filament yarn as a covering yarn, and the modified PTT/PA6 cool feel core spun yarn can be used as a body shaping sportswear fabric in summer. Because the glass transition temperature of the modified PPT polymer is 30-40 ℃, when the environmental temperature is lower than the glass transition temperature of the modified PPT polymer in summer and high temperature, the fabric is conformal; when the ambient temperature is higher than the glass transition temperature, the modulus of the material is reduced sharply, the fabric is deformed, and the air heat insulation layer is led in, so that the human body generates cool feeling.
4. The cumene hydroperoxide and the di-tert-butyl peroxide are used as the initiator in a matching way, so that the copolymerization reaction is promoted, the copolymerization stability is promoted, and the self-polymerization phenomenon of the monomer is avoided; when the initiator is used in a small amount, the copolymerization reaction is incomplete, and when the initiator is excessive, the copolymerization reaction is easy to cause too fast, and the stability of a polymerization system is affected, so that the use amount is controlled to be 0.6-1.5 wt%.
5. The esterification catalyst is ethylene glycol titanium and stannous octoate, the catalytic performance is better, and the molar ratio of 1, 3-propanediol to refined terephthalic acid is preferably 1.7-2: 1, under the action of an esterification catalyst, the esterification rate is up to more than 98 percent.
6. The addition of the stabilizer reduces side reaction of polymerization, avoids the color degradation of the modified PPT polymer, and the addition of the antioxidant avoids the thermal degradation of the polymerized monomer.
Detailed Description
The invention will be further illustrated with reference to specific examples.
Example 1a method for preparing modified PTT fiber with deformation memory function comprises the following steps:
S1, esterification reaction
Adding 1, 3-propylene glycol and refined terephthalic acid into a reaction kettle according to a certain proportion, adding an esterification catalyst, heating to 235 ℃, reacting for 2.5 hours at the pressure of 0.4MPa, and ending the reaction to obtain the propylene glycol terephthalate.
The molar ratio of the 1, 3-propanediol to the refined terephthalic acid is 1.9:1.
The esterification catalyst is ethylene glycol titanium and stannous octoate, and the adding amount is 270mg of the catalyst added correspondingly per Kg of refined terephthalic acid; the mass ratio of the ethylene glycol titanium to the stannous octoate is 4:1.
S2, ternary polymerization
Adding a polycondensation catalyst, a stabilizer and an antioxidant into the propylene glycol terephthalate prepared in the step S1, performing polycondensation reaction at 260 ℃, adding a certain amount of isobornyl methacrylate, isobutyl acrylate and an initiator, and continuously reacting for 1h at 275 ℃ to obtain the modified PPT polymer.
The polycondensation reaction is carried out for 0.5h at 0.4MPa and then for 2h at 70 Pa.
The polycondensation catalyst is tetrabutyl titanate and antimony acetate, and the addition amount is 230mg correspondingly added into each Kg of trimethylene terephthalate; the mass ratio of the tetrabutyl titanate to the antimony acetate is 1.5:1.
The stabilizer is triphenyl phosphite, and the addition amount is 150mg of the stabilizer is correspondingly added into each Kg of the trimethylene terephthalate; the antioxidant is antioxidant 1010, and the addition amount is 350mg per Kg of the trimethylene terephthalate.
The molar ratio of the propylene glycol terephthalate, the isobornyl methacrylate and the isobutyl acrylate is 1.8:0.9:1.2.
The addition amount of the initiator is 1.2wt% of the trimethylene terephthalate; the initiator is cumene hydroperoxide and di-tert-butyl peroxide, and the mass ratio of the cumene hydroperoxide to the di-tert-butyl peroxide is 1:2.
The glass transition temperature of the modified PPT polymer is 34 ℃, the hue b value is 4.2, and the intrinsic viscosity is 0.89dL/g.
S3, spinning
Granulating the modified PPT polymer to prepare modified PPT slices, and carrying out melt spinning by a screw extruder, wherein the temperature of each spinning area is 250-270 ℃, thus obtaining the modified PTT fiber.
The modified PTT fiber prepared in example 1 had a breaking strength of 4.3cN/dex and an elongation at break of 37%.
Example 2a method for preparing modified PTT fiber with deformation memory function comprises the following steps:
S1, esterification reaction
Adding 1, 3-propylene glycol and refined terephthalic acid into a reaction kettle according to a certain proportion, adding an esterification catalyst, heating to 210 ℃, controlling the pressure to 0.2MPa, reacting for 3 hours, controlling the esterification rate to 98%, and ending the reaction to obtain the propylene glycol terephthalate.
The molar ratio of the 1, 3-propanediol to the refined terephthalic acid is 1.7:1.
The esterification catalyst is ethylene glycol titanium and stannous octoate, and the adding amount is 260mg added correspondingly per Kg of refined terephthalic acid; the mass ratio of the ethylene glycol titanium to the stannous octoate is 3:1.
S2, ternary polymerization
Adding a polycondensation catalyst, a stabilizer and an antioxidant into the propylene glycol terephthalate prepared in the step S1, performing polycondensation reaction at the temperature of 250 ℃, adding a certain amount of isobornyl methacrylate, isobutyl acrylate and an initiator, and continuously reacting for 2 hours at the temperature of 270 ℃ to obtain the modified PPT polymer.
The polycondensation reaction is carried out for 1h at 0.1MPa and then for 2h at 40 Pa.
The polycondensation catalyst is tetrabutyl titanate and antimony acetate, and the addition amount is 220mg added into each Kg of trimethylene terephthalate; the mass ratio of the tetrabutyl titanate to the antimony acetate is 2:1.
The stabilizer is trimethylolpropane, and the addition amount is 120mg of the stabilizer is correspondingly added into each Kg of the trimethylene terephthalate; the antioxidant is antioxidant 1010, and the adding amount is 300mg per Kg of the trimethylene terephthalate.
The molar ratio of the propylene glycol terephthalate, the isobornyl methacrylate and the isobutyl acrylate is 1.6:1:1.1.
The addition amount of the initiator is 0.6wt% of the trimethylene terephthalate; the initiator is cumene hydroperoxide and di-tert-butyl peroxide, and the mass ratio of the cumene hydroperoxide to the di-tert-butyl peroxide is 1:3.
The glass transition temperature of the modified PPT polymer is 40 ℃, the hue b value is 5, and the intrinsic viscosity is 0.85dL/g.
S3, spinning
Granulating the modified PPT polymer to prepare modified PPT slices, and carrying out melt spinning by a screw extruder, wherein the temperature of each spinning area is 250-270 ℃, thus obtaining the modified PTT fiber.
The modified PTT fiber prepared in example 2 had a breaking strength of 3.8cN/dex and an elongation at break of 44%.
Example 3a method for preparing modified PTT fiber with deformation memory function, comprising the following steps:
S1, esterification reaction
Adding 1, 3-propylene glycol and refined terephthalic acid into a reaction kettle according to a certain proportion, adding an esterification catalyst, heating to 250 ℃, controlling the pressure to 0.5MPa, reacting for 2 hours, controlling the esterification rate to 98.5%, and ending the reaction to obtain the propylene glycol terephthalate.
The molar ratio of the 1, 3-propylene glycol to the refined terephthalic acid is 2:1.
The esterification catalyst is ethylene glycol titanium and stannous octoate, and the adding amount is 280mg of the catalyst added for each Kg of refined terephthalic acid; the mass ratio of the ethylene glycol titanium to the stannous octoate is 5:1.
S2, ternary polymerization
Adding a polycondensation catalyst, a stabilizer and an antioxidant into the propylene glycol terephthalate prepared in the step S1, performing polycondensation reaction at 265 ℃, adding a certain amount of isobornyl methacrylate, isobutyl acrylate and an initiator, and continuously reacting for 0.5h at 280 ℃ to obtain the modified PPT polymer.
The polycondensation reaction is carried out for 0.5h at 0.5MPa and then for 1.5h at 100 Pa.
The polycondensation catalyst is tetrabutyl titanate and antimony acetate, and the addition amount is 240mg in each Kg of trimethylene terephthalate; the mass ratio of the tetrabutyl titanate to the antimony acetate is 1.5:1.
The stabilizer is triphenyl phosphite, and the addition amount is 160mg of the stabilizer is correspondingly added into each Kg of the trimethylene terephthalate; the antioxidant is antioxidant 1010, and the adding amount is 400mg per Kg of the trimethylene terephthalate.
The molar ratio of the propylene glycol terephthalate, the isobornyl methacrylate and the isobutyl acrylate is 2:0.8:1.4.
The addition amount of the initiator is 1.5wt% of the trimethylene terephthalate; the initiator is cumene hydroperoxide and di-tert-butyl peroxide, and the mass ratio of the cumene hydroperoxide to the di-tert-butyl peroxide is 1:3.
The glass transition temperature of the modified PPT polymer is 30 ℃, the hue b value is 3.7, and the intrinsic viscosity is 0.94dL/g.
S3, spinning
Granulating the modified PPT polymer to prepare modified PPT slices, and carrying out melt spinning by a screw extruder, wherein the temperature of each spinning area is 250-270 ℃, thus obtaining the modified PTT fiber.
The modified PTT fiber prepared in example 3 had a breaking strength of 4.1cN/dex and an elongation at break of 40%.
The modified PTT fiber and the nylon filament yarn prepared in the examples 1-3 are adopted by a spinning frame, the modified PTT fiber is taken as a core, the nylon filament yarn is taken as a covering yarn, and the modified PTT/PA6 cool sense covering yarn is prepared and can be used as a summer body shaping sportswear fabric. Since the glass transition temperature of the modified PPT polymer prepared in the embodiment 1-3 is 30-40 ℃, the fabric is conformal when the ambient temperature is smaller than the glass transition temperature of the modified PPT polymer in the high-temperature environment in summer; when the ambient temperature is higher than the glass transition temperature, the modulus of the material is reduced sharply, the fabric is deformed, and the air heat insulation layer is led in, so that the human body generates cool feeling.
Comparative example 1
Representative example 1 was selected, the ternary polymerization was removed, and a polycondensation catalyst, a stabilizer and an antioxidant were directly added to the trimethylene terephthalate obtained in S1, and a PTT polymer was obtained by polycondensation reaction at 260℃in the same manner as in example 1, except that the comparative example 1 was obtained.
The PTT polymer prepared in comparative example 1 had a glass transition temperature of 54℃and a hue b value of 4.1 and an intrinsic viscosity of 0.84dL/g; the prepared PTT fiber has a breaking strength of 4.5cN/dex and an elongation at break of 35%. The PTT fiber prepared in the comparative example 1 and the nylon filament are prepared into PTT/PA6 core spun yarn by a spinning frame, and the glass transition temperature of the PTT polymer prepared in the comparative example 1 is 54 ℃, so when the fabric prepared by the PTT/PA6 core spun yarn in the comparative example 1 is worn on the body, the PTT in the fabric in the comparative example 1 is not deformed to generate an air heat insulation layer and thus is not cool.
The glass transition temperature of the PTT is 45-65 ℃, and a certain proportion of isobornyl methacrylate and isobutyl acrylate ternary polymerization is added to modify the PTT to prepare a modified PTT polymer, so that the glass transition temperature of the PTT is reduced to 30-40 ℃, and the modified PTT polymer is more suitable for the wearing environment of human bodies; meanwhile, the copolymerization characteristics of the isobornyl methacrylate and the isobutyl acrylate with the PTT are good, the color phase of the modified PTT is good, the intrinsic viscosity is 0.85-0.94 dL/g, the breaking strength of the prepared modified PTT fiber is 3.8-4.3 cN/dex, the breaking elongation is 37-44%, and the mechanical property is also good; the commercial PTT intrinsic viscosity is 0.7-1.2 dL/g, and the PTT polymer prepared in comparative example 1 has an intrinsic viscosity of 0.83dL/g, so that the addition of isobornyl methacrylate and isobutyl acrylate has substantially no effect on the PTT properties.
The proportions are mass proportions, and the percentages are mass percentages, unless otherwise specified; the raw materials are all commercially available.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the technical solutions described in the foregoing embodiments, or equivalents may be substituted for some of the technical features thereof. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. The preparation method of the modified PTT fiber with the deformation memory function is characterized by comprising esterification reaction, ternary polymerization and spinning;
The esterification reaction, 1, 3-propanediol and refined terephthalic acid are added into a reaction kettle according to a certain proportion, an esterification catalyst is added, the temperature is raised to 210-250 ℃, the pressure is 0.2-0.5 MPa, and after 2-3 hours of reaction, the reaction is finished to obtain the trimethylene terephthalate;
adding a polycondensation catalyst, a stabilizer and an antioxidant into the trimethylene terephthalate for polycondensation reaction at the temperature of 250-265 ℃, and then adding a certain amount of isobornyl methacrylate, isobutyl acrylate and an initiator for continuous reaction at the temperature of 270-280 ℃ for 0.5-2 h to obtain a modified PPT polymer;
the molar ratio of the terephthalic acid propylene glycol ester to the methacrylic acid isobornyl ester to the acrylic acid isobutyl ester is 1.6-2:0.8-1:1.1-1.4;
The addition amount of the initiator is 0.6 to 1.5 weight percent of the trimethylene terephthalate; the initiator is cumene hydroperoxide and di-tert-butyl peroxide, and the mass ratio of the cumene hydroperoxide to the di-tert-butyl peroxide is 1:2 to 3.
2. The method for preparing modified PTT fiber with deformation memory function according to claim 1, wherein the molar ratio of the 1, 3-propanediol to the refined terephthalic acid is 1.7-2: 1.
3. The preparation method of the modified PTT fiber with the deformation memory function according to claim 1, wherein the esterification catalyst is one or more of a TiO 2-SiO2 catalyst, tetrabutyl titanate, ethylene glycol titanium, potassium fluotitanate, dibutyl tin oxide and stannous octoate, and the adding amount is 260-280 mg per Kg of refined terephthalic acid.
4. The method for producing a modified PTT fiber having a deformation memory function according to claim 1, wherein the polycondensation is carried out at 0.1 to 0.5MPa for 0.5 to 1 hour and at 40 to 100Pa for 1.5 to 2 hours.
5. The preparation method of the modified PTT fiber with the deformation memory function according to claim 1, wherein the polycondensation catalyst is tetrabutyl titanate and antimony acetate, and the addition amount is 220-240 mg in each Kg of trimethylene terephthalate; the mass ratio of the tetrabutyl titanate to the antimony acetate is 1.5-2: 1.
6. The method for preparing modified PTT fiber with deformation memory function according to claim 1, wherein the stabilizer is trimethylolpropane or triphenyl phosphite, and the adding amount is 120-160 mg in each Kg of trimethylene terephthalate; the antioxidant is antioxidant 1010, and the adding amount is 300-400 mg of the antioxidant added into each Kg of the trimethylene terephthalate.
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| CN102850536A (en) * | 2012-09-18 | 2013-01-02 | 江苏柏鹤涂料有限公司 | Silicon-containing acrylate-polyester resin, and finish coat and application thereof |
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| CN102093544A (en) * | 2009-12-14 | 2011-06-15 | 上海杰事杰新材料(集团)股份有限公司 | 1, 2-propanediol copolyester polyterephthalate with high 1, 2-propanediol content and preparation method thereof |
| CN102850536A (en) * | 2012-09-18 | 2013-01-02 | 江苏柏鹤涂料有限公司 | Silicon-containing acrylate-polyester resin, and finish coat and application thereof |
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