CN115304890B - Poly (2-methylpropanediol terephthalate) and polyethylene terephthalate blend composition - Google Patents

Poly (2-methylpropanediol terephthalate) and polyethylene terephthalate blend composition Download PDF

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CN115304890B
CN115304890B CN202110496158.2A CN202110496158A CN115304890B CN 115304890 B CN115304890 B CN 115304890B CN 202110496158 A CN202110496158 A CN 202110496158A CN 115304890 B CN115304890 B CN 115304890B
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blending
terephthalate
polyethylene terephthalate
temperature
blend composition
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CN115304890A (en
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郑虓
张晶
姚春海
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Beijing Shuimu Binhua Technology Co ltd
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Beijing Shuimu Binhua Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

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  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Artificial Filaments (AREA)

Abstract

The invention provides a blending composition, a preparation method thereof and a blending polyester fiber prepared from the blending composition, wherein the blending composition comprises poly (2-methyl propylene glycol) terephthalate and polyethylene terephthalate, and the blending composition has good crystallization property and spinnability, can reduce the spinning temperature of the fiber on the premise of keeping the good property of the prepared blending polyester fiber, and has good energy-saving benefit. Meanwhile, the prepared blend polyester fiber has good mechanical property and crystallization property.

Description

Poly (2-methylpropanediol terephthalate) and polyethylene terephthalate blend composition
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a blend composition of poly (2-methylpropanediol terephthalate) and poly (ethylene terephthalate).
Background
Polyethylene terephthalate (PET) is prepared by the transesterification of dimethyl terephthalate with ethylene glycol or by the esterification of terephthalic acid with ethylene glycol to synthesize dihydroxyethyl terephthalate and then by polycondensation. Belongs to crystalline saturated polyester, is a crystalline polymer, has excellent physical and mechanical properties in a wider temperature range, can reach 120 ℃ after long-term use, has excellent electrical insulation property, and has better electrical property even under high temperature and high frequency, but has poor corona resistance, and better creep resistance, fatigue resistance, friction resistance and dimensional stability.
The production of PET fiber in 2019 in China reaches 4000 ten thousand tons, belongs to the high-energy consumption industry, and can reduce the temperature for PET spinning by 5-10 ℃ by adding other polymers and auxiliaries into PET, thereby making an important contribution for reducing the energy consumption in the PET fiber industry, meeting the relevant national policies in terms of energy and having good market prospect.
The blend composition prepared from different polymers and PET has different properties, and if other polymers or auxiliary agents can be added into PET to prepare a composition or blend polyester, the blend composition not only has the excellent properties of PET, but also has other good properties, and the blend composition can make an important contribution to the development of the field of polyester materials.
Disclosure of Invention
Based on the technical background, the inventor makes a keen approach, and found that: the blend composition prepared from polyethylene terephthalate and polyethylene terephthalate-2-methylpropanediol has good compatibility with polyethylene terephthalate, and meanwhile, the blend composition has good crystallinity, spinnability and processability, and the blend polyester fiber prepared from the blend composition has good product performances, such as good application prospect.
A first aspect of the present invention is to provide a blend composition comprising poly-2-methylpropanediol terephthalate and polyethylene terephthalate, the mass ratio of poly-2-methylpropanediol terephthalate to polyethylene terephthalate being 1: (0.5-1000).
A second aspect of the present invention is to provide a method of preparing the blend composition according to the first aspect of the present invention, the method comprising the steps of:
step 1, drying polyethylene terephthalate-2-methyl propylene glycol ester, and pre-crystallizing and drying polyethylene terephthalate slices;
and 2, slicing and blending the pretreated poly-2-methylpropanediol terephthalate and polyethylene terephthalate.
A third aspect of the present invention is to provide a blended polyester fiber produced by spinning the blend composition of the first aspect of the present invention or the blend composition produced by the production method of the second aspect of the present invention.
The blend composition provided by the invention, the preparation method thereof and the blend polyester fiber prepared by spinning the blend composition have the following advantages:
(1) The blend composition provided by the invention has good compatibility with the polyethylene terephthalate and the polyethylene terephthalate, and meanwhile, the blend composition has good crystallinity, spinnability and post-processing property, and has good application prospects;
(2) The blended polyester fiber prepared by the blending composition can reduce the spinning temperature of the polyethylene terephthalate under the condition of keeping the mechanical properties of the polyethylene terephthalate basically unchanged, and the prepared blended polyester fiber has good mechanical properties.
Drawings
FIG. 1 shows thermal performance curves of the blend compositions prepared in examples 6-10 of the present invention during the warm-up process;
FIG. 2 shows thermal performance curves of the cooling process of the blend compositions prepared in examples 6 to 10 of the present invention;
FIG. 3 shows an X-ray diffraction pattern of the blend composition produced in example 7 of the present invention;
FIG. 4 shows an X-ray diffraction pattern of the blend composition produced in example 8 of the present invention;
FIG. 5 shows an X-ray diffraction pattern of the blend composition produced in example 9 of the present invention;
FIG. 6 shows the thermal decomposition performance graphs of the blend compositions prepared in examples 6 to 10 of the present invention;
FIG. 7 shows thermal performance curves of the temperature rise process of the blend compositions prepared in examples 1 to 5 of the present invention;
FIG. 8 shows thermal performance curves of the blend compositions prepared in examples 6-10 of the present invention during the warm-up process;
FIG. 9 shows the thermal performance curve of the temperature rising process of the blended polyester fiber prepared in Experimental example 5 of the present invention;
FIG. 10 shows the thermal performance curve of the cooling process of the blended polyester fiber prepared in Experimental example 5 of the present invention.
Detailed Description
The features and advantages of the present invention will become more apparent and evident from the following detailed description of the invention.
A first aspect of the present invention is to provide a blend composition comprising poly (2-methylpropanediol terephthalate) (i.e., MPTT, hereinafter MPTT, i.e., poly (2-methylpropanediol terephthalate)) and poly (ethylene terephthalate) (i.e., PET, hereinafter PET, i.e., ethylene terephthalate), the mass ratio of poly (2-methylpropanediol terephthalate) to poly (ethylene terephthalate) being 1: (0.5-1000).
Preferably, the mass ratio of MPTT to PET is 1: (1.5 to 99), more preferably the mass ratio is 1: (3-19).
Experiments show that the blend composition prepared from PET and MPTT with the mass ratio has good crystallization performance, and the blend composition can reduce spinning temperature and energy consumption under the condition of ensuring good performances of mechanical strength, dimensional stability and the like of the prepared fiber in the post-processing process, such as spinning process, saves cost and has good application prospect.
The poly (2-methylpropanediol terephthalate) (MPTT) is prepared from a 2-methyl-1, 3-propanediol Monomer (MPO) and a dicarboxylic acid monomer through a direct esterification and polycondensation reaction, and the poly (2-methylpropanediol terephthalate) is preferably prepared through the following steps:
step a, adding MPO and a dicarboxylic acid monomer into a reaction vessel for esterification reaction to obtain an esterification product;
the dicarboxylic acid is preferably terephthalic acid (i.e., TPA).
The molar ratio of MPO to dicarboxylic acid monomer is (1.2-1.8): 1, preferably (1.2 to 1.6): 1, more preferably (1.2 to 1.3): 1.
according to the invention, the temperature of the esterification reaction is 200 to 260 ℃, preferably 205 to 250 ℃, more preferably 220 to 248 ℃.
According to a preferred embodiment of the present invention, the esterification reaction temperature is 205 to 245 ℃, preferably 220 to 246 ℃, in a 2L polymerization reactor;
in a 30L polymerization reactor, the esterification reaction temperature is 220-250 ℃, preferably 245-247 ℃.
The initial pressure of the esterification reaction is 80 to 120kPa, preferably 90 to 110kPa, more preferably 100kPa.
According to the present invention, the pressure in the reaction vessel is controlled to be 200 to 330kPa, preferably 200 to 300kPa during the water discharge.
The esterification reaction time comprises positive pressure reaction time and normal pressure reaction time, wherein the positive pressure reaction time of the esterification reaction is 60-250 min, and the normal pressure reaction time is 30-200 min.
According to a preferred embodiment of the present invention, the positive pressure reaction time of the esterification reaction is 120 to 250 minutes and the normal pressure reaction time is 40 to 200 minutes in a 2L polymerization reaction vessel.
In the esterification process, an auxiliary agent is also added, and the auxiliary agent comprises one or more of a heat stabilizer, an antioxidant and the like.
The heat stabilizer is preferably one or more of trimethyl phosphate, triphenyl phosphite, triphenyl phosphate and trimethyl phosphite, and the antioxidant is an antioxidant 1010 or an antioxidant 168, preferably an antioxidant 1010.
In the invention, the addition of a heat stabilizer such as triphenyl phosphite prior to polycondensation is advantageous for improving the hue of MPTT.
According to the invention, the heat stabilizer is added in an amount of 0.1 to 0.5% by mass, preferably 0.2 to 0.4% by mass, based on TPA.
According to the invention, the antioxidant is added in an amount of 0.1 to 0.5% by mass, preferably 0.2 to 0.4% by mass, based on TPA.
Step b, polycondensation reaction: and (3) carrying out polycondensation reaction on the esterification product to obtain the poly (2-methylpropanediol terephthalate).
In the polycondensation process, a polycondensation catalyst is also added to catalyze the polycondensation reaction, wherein the polycondensation catalyst is a titanium catalyst, preferably one or more selected from tetrabutyl titanate, tetraethyl titanate, tetra-n-propyl titanate, tetraisopropyl titanate or tetraisooctyl titanate, and more preferably tetrabutyl titanate (TBT).
After the esterification reaction is finished, vacuumizing the system for 10-60 min, removing water in the system as much as possible, and adding a polycondensation catalyst.
The polycondensation catalyst is added in an amount of 0.1 to 1% by mass, preferably 0.3 to 0.8% by mass, for example 0.3% by mass, of TPA.
One or more of auxiliary agents, heat stabilizer, antioxidant and the like are added before polycondensation, and the heat stabilizer and the antioxidant can prevent thermal degradation and oxygen degradation of polyester.
According to the invention, the auxiliary agent for preventing the catalyst from hydrolyzing is preferably acetic acid, the heat stabilizer is preferably one or more of trimethyl phosphate, triphenyl phosphite, triphenyl phosphate and trimethyl phosphite, and the antioxidant is an antioxidant 1010 or an antioxidant 168, preferably an antioxidant 1010.
The amount of the heat stabilizer added is 0.1 to 0.5% by mass, preferably 0.2 to 0.4% by mass of TPA.
According to the invention, the antioxidant is added in an amount of 0.1 to 0.5% by mass, preferably 0.2 to 0.4% by mass, based on TPA.
The polycondensation reaction temperature is 210 to 280 ℃, preferably 210 to 260 ℃, more preferably 230 to 255 ℃.
According to a preferred embodiment of the invention, the polycondensation reaction temperature is 210 to 260℃and preferably 230 to 260℃in a 2L polymerization reactor.
According to a preferred embodiment of the invention, the polycondensation reaction temperature is 230 to 260℃and preferably 240 to 255℃in a 30L polymerization reactor.
The degree of vacuum in the polycondensation reaction is 10 to 100Pa, preferably 10 to 80Pa, and more preferably 10 to 60Pa.
The MPTT of the present invention has a discharge power of 5-90W, preferably 15-75W, more preferably 35-50W.
MPTT (poly-2-methylpropanediol terephthalate) has an intrinsic viscosity of 0.5 to 1.0 and a relative molecular mass of 14000 to 28000.
The inventors found that MPTT with an intrinsic viscosity of 0.5-1.0 and a relative molecular mass of 14000-28000 has good compatibility with PET, and the prepared blend composition has good crystallization property, spinnability and processability.
According to a preferred embodiment of the present invention, the MPTT has an intrinsic viscosity of 0.55 to 0.9, a relative molecular mass of 14000 to 26000, and more preferably, the MPTT has an intrinsic viscosity of 0.6 to 0.877. The intrinsic viscosity of the PET is 0.5-0.8.
The blending composition is prepared by blending raw materials comprising poly (2-methyl propylene glycol terephthalate) and polyethylene terephthalate.
The blending temperature of the blending composition is 255-300 ℃, preferably 260-290 ℃, and more preferably 270-280 ℃.
The blending temperature is higher than the melting temperature of each component, and experiments show that when blending is carried out at 270-280 ℃, the viscosity of each component in the mixed system is lower and the mixing is more uniform.
According to a preferred embodiment of the present invention, the blending composition is blended in a twin screw extruder, more preferably, the temperatures of the zones in the twin screw extruder are (260-280 ℃) to (250-270 ℃) to (245-265 ℃) to (240-260 ℃) to (230-260 ℃), respectively).
In the blending process, the blending temperature should be higher than the melting points of PET and MPTT during processing, and the melt viscosity is reduced along with the increase of the MPTT addition amount, so that the blending temperature is gradually reduced to improve the strength of the melt of the blending composition and ensure that the melt of the blending composition can be continuously cooled and granulated.
The blending time is 1 to 8 minutes, preferably 1 to 6 minutes, more preferably 2 to 4 minutes. The longer the blending time, the better the compatibility of the system.
The shear rate of the twin-screw extruder is 1000-3000 s -1 Preferably 1000 to 2500s -1 More preferably 1500 to 2000s -1 。
The shear viscosity of the blend composition decreases with increasing shear rate, which manifests itself as shear thinning, a pseudoplastic fluid. At the same addition level and shear rate, the shear viscosity of the blend composition decreases with increasing temperature; at the same temperature and the same shear rate, the shear viscosity of the blend composition decreases with increasing MPTT addition.
According to the invention, the thermal properties of the obtained blend composition are tested, and the thermal properties of the polymer determine the processing technology, the properties of the obtained product and the application field. The glass transition temperature of a polymer determines its softening temperature and the molecular chain slip temperature as the fiber is drawn.
The glass transition temperature (Tg) of the blend composition is 70-80 ℃ by test, and is slightly lower than that of PET. It is possible that the MPTT molecular chain and the PET molecular chain undergo partial transesterification during the blending process, and the non-crystallized MPTT contributes to the flexibility of the blending composition to a certain extent, so that Tg is slightly reduced, and the reduction of the glass transition temperature is beneficial to improving the toughness of the material.
The melting point of the blending composition is 240-260 ℃, the cold crystallization temperature is 120-140 ℃, the cold crystallization temperature is slightly increased compared with the cold crystallization temperature of PET, the cold crystallization temperature of the polymer determines the shaping processing temperature of the fiber, which indicates that MPTT molecular chains are dispersed among PET molecular chains to prevent the PET molecular chains from moving to crystal nuclei, and higher energy is required to be provided for the PET molecular chains to move to the crystal nuclei, so that the crystallization performance of the blending composition is slightly reduced due to the addition of MPTT, but the spinnability and the processing performance of the blending composition are not affected by the slight reduction of the crystallization performance, and the mechanical property of the polyester fiber prepared from the blending composition is not affected by the addition of MPTT.
The thermal crystallization temperature of the blending composition is 210-220 ℃, and is more reduced than that of PET, especially, the thermal crystallization temperature of the blending composition is increased along with the increase of the addition amount of MPTT with higher intrinsic viscosity, and partial transesterification of MPTT molecular chains and PET molecular chains possibly occurs in the blending process.
After the polymer is crystallized, the mechanical property, softening point and dimensional stability of the material can be improved, and the application range is enlarged, so that the crystallization property of the polymer is very important for the material.
The crystallinity of the blend composition is 20% -40%, and good crystallization property has very important significance for the application of the blend composition in the fiber field. The inventors found that the mass ratio of MPTT to PET is 1: (0.5-1000), the blend composition has good crystallization properties, further experiments have found that the higher the intrinsic viscosity of MPTT, the less the impact on the crystallization properties of the blend composition.
The blend composition has good spinning and fiber post-processing properties, and has good application prospect.
The blend composition of the present invention further comprises an antioxidant, a light stabilizer, a yellowing resistance agent, and a flame retardant.
The blend composition of the present invention is prepared by a preparation process comprising the steps of:
step 1, drying MPTT, and pre-crystallizing and drying PET slices;
and 2, blending the processed MPTT and PET slices.
A second aspect of the present invention is to provide a method of preparing the blend composition according to the first aspect of the present invention, the method comprising the steps of:
step 1, drying polyethylene terephthalate-2-methyl propylene glycol ester, and pre-crystallizing and drying polyethylene terephthalate slices;
and 2, slicing and blending the treated poly-2-methylpropanediol terephthalate and polyethylene terephthalate.
This step is specifically described and illustrated below.
Step 1, drying the poly-2-methyl propylene glycol terephthalate, and pre-crystallizing and drying the poly-ethylene glycol terephthalate slices.
The MPTT (poly (2-methylpropanediol terephthalate)) of the present invention has an intrinsic viscosity of 0.5 to 1.0, preferably 0.55 to 0.9, and more preferably 0.6 to 0.877. The intrinsic viscosity of PET in the present invention is 0.5 to 0.8.
The lower the intrinsic viscosity is, the lower the viscosity of the blend composition prepared by blending MPTT and PET can be carried out at a lower temperature in the post-processing or spinning process, so that the energy consumption in the post-processing process is reduced. However, the intrinsic viscosity is too small, which can affect the crystallization performance of the prepared blend composition, and further adversely affect the performance of the blend composition in the later processing product (such as fiber obtained by spinning), and has an influence on the application prospect of the blend composition.
The relative molecular weight of MPTT is 14000-28000, preferably 14000-26000.
The relative molecular mass of MPTT also affects the performance of the blend composition, and experiments show that after the MPTT with the relative molecular mass of 14000-28000 is blended with PET, the blend composition has good compatibility with PET.
The water content of each component in the blending process can influence the performance of the blending composition, MPTT has higher water content, and certain degradation can occur in the melt blending process to generate other small molecular substances, so that the crystallization performance, compatibility, thermal performance, pyrolysis performance and the like of the prepared blending composition are influenced, further the processing performance, mechanical performance and the like in the later stage of the blending composition are influenced, and the application prospect of the blending composition is influenced.
MPTT drying is carried out in a vacuum oven, since the softening point of MPTT is about 50 ℃, the drying temperature is preferably 50-75 ℃, more preferably 70 ℃.
The drying time is preferably 5 to 15 hours, more preferably 10 hours.
The inventor discovers that MPTT obtained after drying at the drying temperature and the drying time can meet the requirement on the water content of the blending process, and the blending composition prepared by blending the MPTT dried and PET has good spinnability and processability, and the fiber obtained after spinning has good mechanical property.
In the present invention, the pre-crystallization temperature of PET is 100 to 150 ℃, preferably 110 to 130 ℃, more preferably 120 ℃.
The pre-crystallization time is 1 to 5 hours, preferably 1.5 to 3 hours, more preferably 2 hours.
The amorphous PET is easy to be bonded at a high temperature, so that the feeding of a screw extruder is difficult, the blending effect is affected, the MPTT and the PET are unevenly mixed, the compatibility of each component in the blending composition is affected, and the crystallization performance and spinnability of the prepared blending composition are also affected. The pre-crystallization prior to drying is more advantageous in improving the compatibility of the components, as well as the properties of the blend composition such as crystallinity and processability.
The pre-crystallization is followed by drying, the PET drying temperature being 120 to 160 ℃, preferably 130 to 150 ℃, more preferably 140 ℃.
The PET drying time is 5 to 20 hours, preferably 8 to 15 hours, more preferably 10 hours.
MPTT and PET are both macromolecular structures connected by ester bonds, hydrolysis chain scission occurs in the melt processing process if the water content is high, and meanwhile, the mechanical properties of the blend composition prepared by the invention are also adversely affected if the water content is high, and even the blend composition cannot be processed into a required material under the condition of serious hydrolysis. Experiments show that the MPTT and PET can meet the requirement on the water content through the drying process, and the prepared blend composition has good crystallinity and other properties and has better application prospect.
And 2, slicing and blending the treated poly-2-methylpropanediol terephthalate and polyethylene terephthalate.
The mass ratio of the poly-2-methyl propylene glycol terephthalate to the polyethylene terephthalate is 1: (0.5-1000), preferably, the mass ratio of MPTT to PET is 1: (1.5 to 99), more preferably the mass ratio is 1: (3-19).
Experiments show that when the mass ratio of MPTT to PET is in the range, the prepared blend composition has good crystallization property and processability.
Further experiments have found that the thermal stability of the blend composition is slightly reduced after the addition of MPTT, when the mass ratio of MPTT to PET is in the above range, T 5wt％ The melt processability of the blend composition obtained by using MPTT and PET in the above-mentioned ranges is good because the spinning temperature of PET does not exceed 300℃because of a small drop in the temperature at which the weight loss reaches 5%.
The blending temperature of the poly (2-methylpropanediol terephthalate) and the poly (ethylene terephthalate) is 255-300 ℃, preferably 260-290 ℃, and more preferably 270-280 ℃.
According to a preferred embodiment of the invention, the blending is carried out in a twin-screw extruder.
The temperatures of the respective zones in the twin-screw extruder are (260 to 280 ℃ C.) - (260 to 280 ℃ C. - (250 to 270 ℃ C. - (245 to 265 ℃ C. - (240 to 260 ℃ C. - (230 to 260 ℃ C.).
According to a preferred embodiment of the invention, the temperatures of the zones are (265-275 ℃) to (260-265 ℃) to (250-260 ℃) to (245-260 ℃) to (235-260 ℃).
According to a further preferred embodiment of the invention, the temperature of each zone is 270 ℃ -270 ℃ -265 ℃ - (250-260 ℃) - (240-255 ℃), respectively.
The temperature of the die is 200 to 260 ℃, preferably 210 to 255 ℃, more preferably 230 to 250 ℃.
In the blending process of MPTT and PET, as the melting point of PET is 255 ℃, the temperature of the front two areas of the screw rod should be higher than the melting point of PET during processing, and as the adding amount of MPTT increases, the viscosity of the melt is reduced, and the temperature of the rear three areas of the screw rod and the die opening needs to be gradually reduced to improve the strength of the blend melt of MPTT and PET so as to ensure that the melt can be continuously cooled and granulated.
The blending effect is related to factors such as blending equipment, blending temperature and blending time, and the inventor discovers that excellent blending effect can be achieved by adopting the blending temperature in the blending equipment, and the obtained blending composition has good performance.
The rotational speed of the twin-screw extruder is 10 to 50r/min, preferably 20 to 40r/min, more preferably 30 to 40r/min.
The blending time is 1 to 8 minutes, preferably 1 to 6 minutes, more preferably 2 to 4 minutes.
The better the compatibility of each component in the blending system is, the more favorable the improvement of the processability of the blending system and the performance of the prepared material is, the compatibility is closely related to the processing technology, the higher the rotating speed (the higher the rotating speed is, the higher the shearing rate is) and the longer the blending time are adopted to be favorable for improving the compatibility of the blending composition, and especially for the MPTT and PET blending system which can generate chain exchange in the invention, the blending time and the rotating speed in the range are more favorable for improving the compatibility of the system. Too high moisture results in hydrolysis of the MPTT during melt blending, and if the blending time is too long, it is detrimental to the improvement of the properties of the blended composition.
A third aspect of the present invention is to provide a blended polyester fiber produced by spinning the blend composition of the first aspect of the present invention or the blend composition produced by the production method of the second aspect of the present invention.
According to a preferred embodiment of the present invention, specifically, after the blended polyester fiber is dried from the blending composition, the blended polyester fiber is discharged from a twin-screw extruder and a spinneret to obtain a wound yarn, and more preferably, the wound yarn is subjected to a drawing process to obtain the blended polyester fiber.
The fineness of the blended polyester fiber is 24-80 dtex/48f, the strength is 2-5 cN/dtex, and the elongation at break is 7-160%.
The crystallinity of the blended polyester fiber was tested to determine the dimensional stability of the fiber after processing, and thus the crystallinity of the fiber is very important for its usability. The crystallinity of the blended polyester fiber is 20-38%, preferably 25-33%. The blended polyester fiber obtained by spinning the blending composition prepared by the invention has good dimensional stability.
The thermal performance test is carried out on the blended polyester fiber, and only the glass transition temperature of PET appears in DSC curve, and the peak shape and peak width of cold crystallization peak, melting peak and thermal crystallization peak are not obviously changed, which proves that MPTT and PET in the blended polyester fiber prepared by spinning the blending composition have good compatibility, and the good compatibility is beneficial to the improvement of mechanical property of a blending system. It was further confirmed that the components in the blend composition of the present invention have good compatibility.
The blended polyester fiber according to the present invention is prepared by a preparation method comprising the steps of:
step a, pre-crystallizing and drying the blending composition;
and b, spinning the blend composition treated in the step a.
In step a, the pre-crystallization temperature is 100 to 150 ℃, preferably 110 to 130 ℃, more preferably 120 ℃.
The pre-crystallization time is 1 to 5 hours, preferably 1.5 to 3 hours, more preferably 2 hours.
The drying temperature is 100 to 160 ℃, preferably 120 to 140 ℃, more preferably 125 ℃.
The drying time is 3 to 10 hours, preferably 5 to 8 hours, more preferably 6 hours.
In the step b, the dried blend composition is placed in a screw extruder for melting and metering, and then is discharged through a spinneret plate.
The temperature of each region of the screw extruder is (240 to 275 ℃ C.) - (260 to 280 ℃ C.) - (255 to 290 ℃ C., preferably (245 to 270 ℃ C.) - (265 to 285 ℃ C.) - (260 to 285 ℃ C., more preferably (250 to 265 ℃ C.) - (270 to 278 ℃ C.) - (265 to 280 ℃ C.).
The melt channel temperature is 250 to 290 ℃, preferably 260 to 285 ℃, more preferably 265 to 280 ℃.
The spinning temperature is 230 to 280 ℃, preferably 240 to 275 ℃, more preferably 250 to 270 ℃.
On the premise of ensuring that the supply amount of a spinning pump and the pressure of a component are basically the same (the melt flow viscosity is approximately the same), compared with PET, the blend composition provided by the invention has the advantages that the spinning temperature and the spinning pressure are reduced, the spinning temperature is reduced by 5-25 ℃, and good energy-saving benefits are realized.
The invention has the beneficial effects that:
(1) The viscosity of the blending composition is reduced along with the increase of the shear rate, and the shear viscosity is shown as shear thinning, so that the blending composition is a pseudoplastic fluid;
(2) The blend composition has good crystallization property and spinnability, the glass transition temperature is 70-80 ℃, and the crystallinity is 20-40%;
(3) The blend composition has good melt fluidity and spinnability, the spinning temperature is lower than that of PET, and is reduced by about 5-25 ℃ compared with that of PET, so that the blend composition has good energy-saving benefit;
(4) The blended polyester fiber prepared by the blending composition has good mechanical properties, and compared with PET fiber, the blended polyester fiber prepared by the blending composition has the mechanical properties basically same as PET fiber, the fineness is 24-80 dtex/48f, the strength is 2-5 cN/dtex, the elongation at break is 7-160%, and the blended polyester fiber has good application prospect.
Examples
The invention is further illustrated by the following specific examples, which are intended to be illustrative of the invention and are not intended to limit the scope of the invention.
Example 1
Synthesis of MPTT in a 2L polymerization apparatus: the PTA (terephthalic acid) feeding amount is 700g, the molar ratio of 2-methyl-1, 3 propylene glycol to terephthalic acid feeding is 1.3, the esterification temperature is 240-245 ℃, the esterification drainage pressure is 240-270kPa, the pressurized esterification time is 160-180 min, and the normal pressure esterification time is 100-120min; after the esterification reaction is finished, vacuumizing for 10min, adding 540ppm of catalyst TBT (tetrabutyl titanate), and obtaining MPTT with the intrinsic viscosity of 0.742, wherein the polycondensation reaction temperature is 240-255 ℃, the vacuum degree is about 30-40 Pa, and the discharge power is 50W (50 Hz).
MPTT pellets with an intrinsic viscosity of 0.742 were dried in a vacuum oven at 70℃for 10 hours, PET (intrinsic viscosity 0.66) pellets were pre-crystallized in a vacuum oven at 120℃for 2 hours and then dried at 140℃for 10 hours.
And (3) slicing the dried MPTT and PET according to the mass ratio of 1:19 into a Poly OS twin screw extruder to blend, the temperatures of the zones and dies of the twin screw extruder were set to: 270 ℃ (one zone) -270 ℃ (two zones) -265 ℃ (three zones) -260 ℃ (four zones) -250 ℃ (five zones) -240 ℃ (six zones) -230 ℃ (die head), the speed of rotation of the twin screw extruder was 35r/min and the blending time was 3min. To obtain a blended composition.
Example 2
Blending with PET was performed in the same manner as in example 1, except that: the mass ratio of MPTT to PET is 1:9.
example 3
Blending with PET was performed in the same manner as in example 1, except that: the mass ratio of MPTT to PET is 15:85.
example 4
Blending with PET was performed in the same manner as in example 1, except that: the mass ratio of MPTT to PET is 1:4.
Example 5
Blending with PET was performed in the same manner as in example 1, except that: the mass ratio of MPTT to PET is 1:3.
Example 6
Synthesizing MPTT, PTA (terephthalic acid) with a feeding amount of 700g, a feeding mole ratio of 2-methyl-1, 3-propanediol to terephthalic acid of 1.3, an esterification temperature of 220-245 ℃, an esterification drainage pressure of 240-270kPa, a pressurized esterification time of 160-180 min and a normal pressure esterification time of 100-120min in a 2L polymerization device; after the esterification reaction is finished, vacuumizing for 10min, adding 540ppm of catalyst TBT, wherein the polycondensation reaction temperature is 240-255 ℃, the vacuum degree is about 30-40 Pa, and the discharge power is 38W (30 Hz), so as to obtain MPTT with the intrinsic viscosity of 0.877.
MPTT pellets with an intrinsic viscosity of 0.877 were dried in a vacuum oven at 70℃for 10 hours, PET (intrinsic viscosity 0.66) pellets were pre-crystallized in a vacuum oven at 120℃for 2 hours and then dried at 140℃for 10 hours.
And (3) slicing the dried MPTT and PET according to the mass ratio of 1:19 into a Poly OS twin screw extruder to blend, the temperatures of the zones and dies of the twin screw extruder were set to: 270 ℃ (one zone) -270 ℃ (two zones) -265 ℃ (three zones) -260 ℃ (four zones) -260 ℃ (five zones) -255 ℃ (six zones) -250 ℃ (die head), the speed of rotation of the twin screw extruder was 35r/min and the blending time was 3min. To obtain a blended composition.
Example 7
Blending with PET was performed in the same manner as in example 6, except that: the mass ratio of MPTT to PET is 1:9.
example 8
Blending with PET was performed in the same manner as in example 6, except that: the mass ratio of MPTT to PET is 15:85.
example 9
Blending with PET was performed in the same manner as in example 6, except that: the mass ratio of MPTT to PET is 1:4.
Example 10
Blending with PET was performed in the same manner as in example 6, except that: the mass ratio of MPTT to PET is 1:3.
Experimental example
Experimental example 1X ray diffraction (crystallization Property) test
The crystallization and orientation of the blend compositions prepared in examples 7, 8 and 9 were tested using a D8 DISCOVER two-dimensional wide angle X-ray diffraction tester from BRUKER, germany, light source wavelength was 0.154nm, collected by a two-dimensional area detector VANTEC-500, exposure time 300s, and sample-to-detector distance was 85.6mm. The test results are shown in fig. 3, 4 and 5, respectively.
As can be seen from fig. 3 to 5, the blend compositions prepared in example 7, example 8 and example 9 all have a distinct diffraction ring like PET, indicating that the blend compositions obtained by blending MPTT and PET have good crystallization properties. The blend composition has good crystallization property and has very important significance for application in the fiber field, which proves that the blend composition has good application prospect in the fiber field.
Experimental example 2 thermal performance test
The thermal properties of the blend compositions and PET prepared in examples 6 to 10 were tested by using a TA Q2000 DSC tester at a temperature ranging from 20 to 300℃and a heating rate of 10℃per minute under a nitrogen atmosphere. The temperature rise process test result is shown in fig. 1, and the temperature reduction process test result is shown in fig. 2.
As can be seen from fig. 1 and 2, only the glass transition temperature of PET appears in the heat and pressure test curve of DSC test, and the peak shapes and peak widths of the cold, melt and hot crystallization peaks of the blend composition do not significantly change, indicating good compatibility of MPTT and PET in the blend composition.
The thermal properties of the blend compositions prepared in examples 1 to 5 were tested according to the above method, and the results of the temperature increase and decrease tests are shown in fig. 7 and 8, respectively.
As can be seen from fig. 7 and 8, only the glass transition temperature of PET appears in the temperature rise test curve of DSC test, and the peak shapes and peak widths of the cold crystallization peak, the melting peak and the thermal crystallization peak of the blend composition do not significantly change, which proves that the MPTT and the PET in the blend composition of the present invention have good compatibility.
Experimental example 3 thermal decomposition Performance test
The thermal stability of the blend compositions and PET obtained in examples 6 to 10 was tested by using a German relaxation-resistant 209F1 type thermogravimetric analyzer at a temperature ranging from 30 to 700 ℃ and a temperature rising rate of 10 ℃/min under nitrogen atmosphere, and the test results are shown in FIG. 6. The thermal decomposition temperature and the residual rate are shown in Table 2.
TABLE 2
As can be seen from FIG. 6 and Table 2, the thermal stability of the blend composition prepared in accordance with the present invention was slightly lowered as compared with PET, and the blend composition T prepared in example 10 5wt％ The drop (temperature at which weight loss reaches 5%) from 394.8 to 385.6, typically the spinning temperature of PET will not exceed 300℃, and therefore the MPTT to PET mass ratio of not greater than 1:3 will not have a significant effect on melt processing of the blend composition, indicating that the blend composition made according to the present invention has good melt processability.
Experimental example 4 spinnability test
The blend composition prepared in example 7 was subjected to a test spinning, in which the temperature of each zone in the screw extruder was 265℃to 270℃to 270℃and the melt pipe temperature was 270℃and the spinning temperature was 280℃and the fibers were subjected to a thermal performance test at a temperature ranging from 20℃to 300℃and a heating rate of 10℃per minute under nitrogen atmosphere. The temperature rise process test result is shown in fig. 9, and the temperature reduction process test result is shown in fig. 10.
As can be seen from fig. 9 and 10, the glass transition temperature Tg of the spinneret extrudate blend fiber is not greatly changed compared to PET; the start and end positions of the cold crystallization peak Tcc are basically the same, and the peak top temperature moves towards the low temperature direction, which shows that the crystallization property is slightly increased, thus indicating that the prepared blend composition can be spun, and the thermal property of the prepared blend polyester fiber is basically the same as that of PET, and the blend composition has good spinnability.
The invention has been described in detail in connection with the specific embodiments and exemplary examples thereof, but such description is not to be construed as limiting the invention. It will be understood by those skilled in the art that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, and these fall within the scope of the present invention. The scope of the invention is defined by the appended claims.

Claims (6)

1. A blend composition comprising poly-2-methylpropanediol terephthalate and polyethylene terephthalate, wherein the mass ratio of poly-2-methylpropanediol terephthalate to polyethylene terephthalate is 1: (0.5-1000);
the blending composition is prepared by blending raw materials comprising poly-2-methyl propylene glycol terephthalate and polyethylene terephthalate;
the blend composition is prepared by a process comprising the steps of:
step 1, drying polyethylene terephthalate 2-methyl propylene glycol ester, and pre-crystallizing and drying polyethylene terephthalate slices, wherein the intrinsic viscosity of the polyethylene terephthalate 2-methyl propylene glycol ester is 0.5-1.0, and the relative molecular mass of the polyethylene terephthalate 2-methyl propylene glycol ester is 14000-28000;
and 2, slicing and blending the treated poly (2-methylpropanediol) terephthalate and the treated polyethylene terephthalate, wherein the blending temperature is 255-300 ℃.
2. The blend composition of claim 1, wherein,
the glass transition temperature of the blending composition is 70-80 ℃;
the melting point of the blending composition is 240-260 ℃, the cold crystallization temperature is 120-140 ℃, the hot crystallization temperature is 210-220 ℃, and the crystallinity is 20-40%.
3. A method of preparing the blend composition of claim 1 or 2, wherein the blend composition is prepared by a process comprising the steps of:
step 1, drying polyethylene terephthalate-2-methyl propylene glycol ester, and pre-crystallizing and drying polyethylene terephthalate slices;
step 2, slicing and blending the treated poly-2-methylpropanediol terephthalate and polyethylene terephthalate;
in the step 2 of the process, the process is carried out,
the blending temperature is 255-300 ℃.
4. A process according to claim 3, wherein in step 2,
the mass ratio of the poly-2-methyl propylene glycol terephthalate to the polyethylene terephthalate is 1: (0.5-1000).
5. A process according to claim 3, wherein in step 2,
the blending is carried out in a double-screw extruder, and the temperatures of all the areas in the double-screw extruder are respectively (260-280 ℃) - (250-270 ℃) - (245-265 ℃) - (240-260 ℃) - (230-260 ℃);
the temperature of the die head is 200-260 ℃.
6. A blended polyester fiber, characterized in that the blended polyester fiber is produced by spinning the blend composition of claim 1 or 2;
the fineness of the blended polyester fiber is 24-80 dtex/48f, the strength is 2-5 cN/dtex, and the elongation at break is 7-160%.
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JP2003138030A (en) * 2001-11-06 2003-05-14 Polyplastics Co Polyester resin molding
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CN103772670A (en) * 2012-10-19 2014-05-07 东丽纤维研究所（中国）有限公司 Copolyester, and production method and application thereof
CN104987498A (en) * 2015-04-02 2015-10-21 沈阳工业大学 Low-melting point copolyester preparation method
CN105121501A (en) * 2013-04-09 2015-12-02 佳能株式会社 Resin for toner and toner

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003138030A (en) * 2001-11-06 2003-05-14 Polyplastics Co Polyester resin molding
JP2008069225A (en) * 2006-09-13 2008-03-27 Dainippon Ink & Chem Inc Modifier for cellulose ester resin, and cellulose ester film containing the same
CN103772670A (en) * 2012-10-19 2014-05-07 东丽纤维研究所（中国）有限公司 Copolyester, and production method and application thereof
CN105121501A (en) * 2013-04-09 2015-12-02 佳能株式会社 Resin for toner and toner
CN104987498A (en) * 2015-04-02 2015-10-21 沈阳工业大学 Low-melting point copolyester preparation method

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