CN109929115A - Polyester block copolymer, the production method of polyester block copolymer and polyester fiber - Google Patents
Polyester block copolymer, the production method of polyester block copolymer and polyester fiber Download PDFInfo
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- CN109929115A CN109929115A CN201711370238.3A CN201711370238A CN109929115A CN 109929115 A CN109929115 A CN 109929115A CN 201711370238 A CN201711370238 A CN 201711370238A CN 109929115 A CN109929115 A CN 109929115A
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- block copolymer
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- polyethylene naphthalate
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Abstract
The present invention relates to polyester block copolymer, the production method of polyester block copolymer and polyester fibers.The present invention provides a kind of production method of polyester block copolymer comprising makes polyethylene terephthalate and polyethylene naphthalate combined polymerization to form polyester block copolymer in the presence of a catalyst.Catalyst is the compound as composed by cobalt, chromium, manganese and antimony.The molecular weight of poly- polyethylene terephthalate is 19000g/mol~21000g/mol.The molecular weight of polyethylene naphthalate is 18000g/mol~24000g/mol.Thus polyester fiber manufactured by polyester block copolymer has tensile elasticity and recovery characteristic, and tensile elasticity and recovery characteristic can regulate and control easily by the molar ratio for adjusting poly- polyethylene terephthalate and polyethylene naphthalate, therefore the application of polyester fiber can extensively meet needed for miscellaneous product.
Description
Technical field
The present invention relates to polyester block copolymer, the production method of polyester block copolymer and polyester fibers.The present invention
Polyester block copolymer is formed by especially with regard to by polyethylene terephthalate and polyethylene naphthalate combined polymerization
And preparation method thereof, and the polyester fiber containing this polyester block copolymer.
Background technique
Since autohemagglutination ester fiber comes out, due to it is high with intensity, elasticity is good, wrinkle resistance is strong, easy to dye and cost compared with
Low advantage, and can be widely used on various fabrics.However, only including the polyester for being formed by polyester by single kind of monomer
Fibre property is fixed and is not easy to adjust, and can not meet needed for miscellaneous product.
In view of above-mentioned, in order to further expand the application of polyester fiber, need to develop other kinds of polyester at present
To make polyester fiber to meet needed for various products.
Summary of the invention
The purpose of the present invention is to provide a kind of polyester block copolymer, with produce meet various products needed for polyester
Fiber.
This disclosure provides a kind of production method of polyester block copolymer comprising makes poly- pair in the presence of a catalyst
Polyethylene terephthalate (polyethylene terephthalate；PET) with polyethylene naphthalate (polyethylene
naphthalate；PEN) combined polymerization is to form polyester block copolymer, and wherein catalyst is as composed by cobalt, chromium, manganese and antimony
Compound, and the molecular weight of poly- polyethylene terephthalate is 19000g/mol~21000g/mol, polyethylene naphthalate
Molecular weight is 18000g/mol~24000g/mol.
In some embodiments, the concentration of catalyst is in the range of between 200ppm~1000ppm.
In some embodiments, polyethylene naphthalate is 2~10 molar parts, polyethylene terephthalate 90
~98 molar parts.
In some embodiments, the essential viscosity of polyethylene naphthalate is in the model between 0.6g/dL~0.7g/dL
In enclosing, the essential viscosity of polyethylene terephthalate is in the range of between 0.6g/dL~0.7g/dL.
This disclosure provides a kind of polyester block copolymer, is by polyethylene terephthalate and poly- naphthalenedicarboxylic acid
Second diester combined polymerization forms, wherein polyethylene terephthalate be 90~98 molar parts and have 19000g/mol~
The molecular weight of 21000g/mol, polyethylene naphthalate are 2~10 molar parts and have 18000g/mol~24000g/mol
Molecular weight.
In some embodiments, the essential viscosity of polyester block copolymer is in the range between 0.5g/dL~0.7g/dL
It is interior.
In some embodiments, the fusing point of polyester block copolymer is in the range of between 220 DEG C~260 DEG C.
This disclosure provides a kind of polyester fiber comprising polyester block copolymer, polyester block copolymer are by gathering
Ethylene terephthalate and polyethylene naphthalate combined polymerization form, and wherein polyethylene terephthalate is rubbed for 90~98
That part and the molecular weight with 19000g/mol~21000g/mol, polyethylene naphthalate are 2~10 molar parts and have
The molecular weight of 18000g/mol~24000g/mol.
In some embodiments, the recovery stretch of polyester fiber is in the range of between 50%~100%.
In some embodiments, the fibre fineness of polyester fiber is in the range of between 3.17~3.73dtex.
Compared with the prior art, the advantages of the present invention are as follows: the present invention is by that substantially can't destroy or recombinate poly- pair
The copolymerization of polyethylene terephthalate or the respective molecular conformation of polyethylene naphthalate, by the two direct copolymerization with
Form polyester block copolymer；Also, can by adjustment for synthesize polyester block copolymer poly- polyethylene terephthalate and
The molar ratio of polyethylene naphthalate regulates and controls the characteristic of obtained polyester fiber such as tensile elasticity and recovery characteristic etc, therefore
The application of the polyester fiber is wide and can meet needed for miscellaneous product.
It should be understood that general description above-mentioned and it is following illustrate it is only exemplary and explanatory, and
It is intended to provide required further explanation of the invention.
Detailed description of the invention
Above and other aspect, feature and other advantages of the present invention referring to description and cooperate attached drawing to be become apparent from
Understanding, in which:
Fig. 1 is painted the test result of the recovery stretch of the polyester fiber of comparative example and some embodiments of this disclosure；
Wherein, symbol description:
110,120,130,140,150,160: curve.
Specific embodiment
Disclosure below provides many different embodiments or example, to realize different characteristic of the invention.It is specific
The composition and layout of example are described below, to simplify the present invention.Certainly these are only examples, not to limit.
In order to solve the problems, such as described in prior art, this disclosure provides a kind of polyester block copolymer and its production
Method.Polyester block copolymer is formed by polyethylene terephthalate and polyethylene naphthalate combined polymerization.Polyester is embedding
The production method of section copolymer includes following operation: in the presence of a catalyst, with polyethylene terephthalate and poly- naphthalene diformazan
Sour second diester forms polyester block copolymer as reactant, with combined polymerization.Specifically, after combined polymerization, gather to benzene two
Formic acid second diester segment and polyethylene naphthalate segment meeting random alignment are simultaneously mutually bonded with ester bond to form polyester block
Copolymer, and this polyester block copolymer is random block copolymer (random block copolymer).It need to pay special attention to
, above-mentioned copolymerization substantially can't destroy or recombinate polyethylene terephthalate or poly- naphthalenedicarboxylic acid second two
The respective molecular conformation of ester, but make the two direct copolymerization to form polyester block copolymer.In other words, gather in above-mentioned
In ester block copolymer, the molecular weight of polyethylene terephthalate block and the poly terephthalic acid second two before copolymerization
The molecular weight of ester is substantially the same, and the molecular weight of polyethylene naphthalate block and the poly- naphthalenedicarboxylic acid before copolymerization
The molecular weight of second diester is substantially the same.
The molecular weight of polyethylene naphthalate is 18000g/mol~24000g/mol.In some embodiments, gather
The essential viscosity of polyethylene naphthalate is in the range of between 0.6g/dL~0.7g/dL.Polyethylene naphthalate is by right
Naphthalenedicarboxylic acid and ethylene glycol combined polymerization form, by the molar ratio of both adjustment, point of controllable polyethylene naphthalate
Son amount and essential viscosity.
The molecular weight of poly- polyethylene terephthalate is 19000g/mol~21000g/mol.In some embodiments, gather
The essential viscosity of ethylene terephthalate is in the range of between 0.6g/dL~0.7g/dL.Poly- polyethylene terephthalate be by
Terephthalic acid (TPA) and ethylene glycol combined polymerization form, by adjustment both molar ratio, controllable poly- polyethylene terephthalate
Molecular weight and essential viscosity.
In some embodiments, polyethylene naphthalate is 2~10 molar parts, polyethylene terephthalate 90
~98 molar parts.For example, polyethylene naphthalate 3,4,5,6,7,8 or 9 molar parts, polyethylene terephthalate
For 91,92,93,94,95,96 or 97 molar parts.
In some embodiments, the essential viscosity of polyester block copolymer is in the range between 0.5g/dL~0.7g/dL
It is interior.In some embodiments, the fusing point of polyester block copolymer is in the range of between 220 DEG C~260 DEG C.
Catalyst used is the compound as composed by cobalt, chromium, manganese and antimony during the reaction, and each member in catalyst
Cellulose content is, for example: the cobalt of 0.1~0.5 parts by weight；The chromium of 0.1~0.5 parts by weight；The manganese of 0.1~0.5 parts by weight；And 1 weight
The antimony for measuring part, also that is, cobalt: chromium: manganese: the weight ratio of antimony is 0.1~0.5:0.1~0.5:0.1~0.5:1.In some embodiment party
In formula, the concentration of catalyst is in the range of between 200ppm~1000ppm.For example, the concentration of catalyst be 300,
400,500,600,700,800 or 900ppm.
Polyester block copolymer above-mentioned has spinnability, and therefore, this disclosure provides a kind of polyester fiber comprising
Polyester block copolymer above-mentioned.The description of polyester block copolymer is please referred to above, details are not described herein again.
In some embodiments, the recovery stretch of polyester fiber is in the range of between 50%~100%.Some
In embodiment, the fibre fineness of polyester fiber is in the range of between 3.17~3.73dtex.In some embodiments, gather
The intensity of ester fiber is in the range of between 1.6g/den~1.9g/den.In some embodiments, the elongation of polyester fiber
In the range of between 120%~145%.
It is worth noting that, the polyester fiber containing aforementioned polyester block copolymer has tensile elasticity and recovery characteristic.This may be
Because height can occur for the segment of poly- polyethylene terephthalate and the segment of polyethylene naphthalate in polyester block copolymer
Physical entanglement.The tensile elasticity and recovery characteristic of polyester fiber can be by the polyphenyl dioctyl phthalate adjusted for synthesizing polyester block copolymer
Second diester and the molar ratio of polyethylene naphthalate regulate and control.
Embodiment below is and to make to have in the technical field of the invention logical particular aspect of the invention is described in detail
Normal skill is carried out the present invention.However, embodiment below should not be taken to be limiting the present invention.
Experimental example 1: synthesis polyester block copolymer simultaneously carries out property test
In this experimental example, make polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) combined polymerization with
Form polyester block copolymer.Embodiment one~five is utilized respectively the polyethylene terephthalate and poly- naphthalene two of different molar parts
Formic acid second diester is as reactant.The molecular weight of polyethylene terephthalate is 19000g/mol~21000g/mol.Poly- naphthalene
The molecular weight of dioctyl phthalate second diester is 18000g/mol~24000g/mol.Reactant used in each embodiment and generated poly-
The essential viscosity and fusing point of ester block copolymer please join following table one.
Table one
Experimental example 2: Spinning
In this experimental example, the polyester block copolymer of embodiment one~five is prepared as polyester by spinning processing procedure respectively
After fiber, then measure polyester fiber physical property.The polyester fiber of this experimental example is preoriented yarn (pre-oriented yarn；
POY), fiber dimensious 120d/36f.The winding rate of spinning processing procedure is 2400 ms/min.Polyester fiber physical property refer to
Following table two.
Table two
As shown in Table 2, all had well by polyester fiber prepared by the polyester block copolymer of embodiment one~five respectively
Intensity.
Next, the stretching further to the polyester fiber of the polyester block copolymer preparation by embodiment one~five is returned
The multiple physical property such as rate and elongation are tested.Test result refers to following table three.
Recovery stretch is to utilize Dynamic Mechanical Analyzer (dynamic mechanical analyzer；DMA it) is surveyed
Amount.The model Q800 of DMA, the manufacturer for providing DMA is that US business's Butterworth is special (TA).
The measurement method of the recovery stretch of polyester fiber is as follows: the test piece of fiber to be measured being first warming up to 150 DEG C, and is held
Temperature 5 minutes.Next, being decontroled again after being stretched with the pulling force of 50mN test piece 15 minutes of fiber to be measured.The calculating of recovery stretch
Mode is as follows: deformation length × 100% after (replying deformation length after stretching after deformation length-stretching)/stretching.
The test result of the recovery stretch of the polyester fiber of embodiment one~five is referring to Figure 1.In addition, providing herein only
It is compared by the polyester fiber that polyethylene terephthalate is spun into as comparative example, is preoriented yarn, fiber dimensious is
120d/36f.The winding rate of spinning processing procedure is 2400 ms/min.Fig. 1 is painted comparative example and the polyester of embodiment one~five is fine
The test result of the recovery stretch of dimension.The longitudinal axis is recovery stretch, and horizontal axis is the time decontroled after the test piece of fiber to be measured.It is bent
Line 110 is the test result of the polyester fiber of comparative example；Curve 120 is the test result of the polyester fiber of embodiment one；Curve
130 be the test result of the polyester fiber of embodiment two；Curve 140 is the test result of the polyester fiber of embodiment three；Curve
150 be the test result of the polyester fiber of example IV；Curve 160 is the test result of the polyester fiber of embodiment five.From Fig. 1
It can be seen that, in different time, the recovery stretch of the polyester fiber of embodiment one~five is all higher than the polyester fiber of comparative example
Recovery stretch, that is, embodiment one~five compared to for comparative example have preferable extension recovery rate.Following table three is only
After listing test piece 3 minutes of fiber to be measured that decontrol embodiment one~five and the recovery stretch after 15 minutes.
Table three
According to aforementioned table one it is found that in example 1, for synthesizing the poly- naphthalenedicarboxylic acid second two of polyester block copolymer
Ester content is minimum；In embodiment five, the polyethylene naphthalate content for synthesizing polyester block copolymer is most.It asks again
It is the thus polyester it is found that when the polyethylene naphthalate content that be used to form in polyester block copolymer is more referring to table three
Block copolymer is formed by the recovery stretch of polyester fiber and extension recovery rate and can also increase accordingly, and also implies that this is poly-
Ester fiber is less likely to occur deformation and rigidity with higher.Also, table three illustrates the drawing of the polyester fiber of this disclosure
Stretching response rate and elongation can all adjust by the molar ratio for changing polyethylene terephthalate and polyethylene naphthalate
Control.
In conclusion the poly terephthalic acid second that this disclosure is 19000g/mol~21000g/mol by molecular weight
The polyethylene naphthalate segment combined polymerization that diester segment and molecular weight are 18000g/mol~24000g/mol is poly- to be formed
Ester block copolymer, and thus polyester fiber manufactured by polyester block copolymer has tensile elasticity and recovery characteristic.Further, since stretching
Recovery can regulate and control easily by the molar ratio for adjusting poly- polyethylene terephthalate and polyethylene naphthalate, therefore,
The application of the polyester fiber of this disclosure is wide, so as to meet needed for miscellaneous product.For example, in this announcement
The polyester fiber of appearance can be used for manufacturing impact-resistant protective textiles and improve the comfort of textile.
Although the present invention is disclosed above with embodiment, the foregoing is merely presently preferred embodiments of the present invention, not uses
It is any to be familiar with this those skilled in the art to limit the present invention, without departing from the spirit and scope of the present invention, when the equalization that can make various becomes
Change and modify, be all covered by the present invention, therefore protection scope of the present invention is when view appended claims institute
Subject to defender.
Claims (10)
1. a kind of production method of polyester block copolymer characterized by comprising
Make polyethylene terephthalate and polyethylene naphthalate combined polymerization to form the polyester in the presence of a catalyst
Block copolymer, wherein the catalyst is the compound as composed by cobalt, chromium, manganese and antimony, and the poly- ethylene two
The molecular weight of ester is 19000g/mol~21000g/mol, the molecular weight of the polyethylene naphthalate be 18000g/mol~
24000g/mol。
2. production method as described in claim 1, wherein the concentration of the catalyst is in the model between 200ppm~1000ppm
In enclosing.
3. production method as described in claim 1, wherein the polyethylene naphthalate is 2~10 molar parts, it is described poly-
Ethylene terephthalate is 90~98 molar parts.
4. production method as described in claim 1, wherein the essential viscosity of the polyethylene naphthalate is between 0.6g/
In the range of dL~0.7g/dL, the essential viscosity of the polyethylene terephthalate is between 0.6g/dL~0.7g/dL's
In range.
5. a kind of polyester block copolymer, which is characterized in that the polyester block copolymer is by polyethylene terephthalate
And polyethylene naphthalate combined polymerization forms, wherein the polyethylene terephthalate is 90~98 molar parts and has
The molecular weight of 19000g/mol~21000g/mol, the polyethylene naphthalate are 2~10 molar parts and have 18000g/
The molecular weight of mol~24000g/mol.
6. polyester block copolymer as claimed in claim 5, wherein the essential viscosity of the polyester block copolymer between
In the range of 0.5g/dL~0.7g/dL.
7. polyester block copolymer as claimed in claim 5, wherein the fusing point of the polyester block copolymer is between 220 DEG C
In the range of~260 DEG C.
8. a kind of polyester fiber, which is characterized in that including polyester block copolymer, the polyester block copolymer is by poly- to benzene
Dioctyl phthalate second diester and polyethylene naphthalate combined polymerization form, wherein the polyethylene terephthalate is rubbed for 90~98
Your part and molecular weight with 19000g/mol~21000g/mol, the polyethylene naphthalate be 2~10 molar parts and
Molecular weight with 18000g/mol~24000g/mol.
9. polyester fiber as claimed in claim 8, wherein the recovery stretch of the polyester fiber is between 50%~100%
In the range of.
10. polyester fiber as claimed in claim 8, wherein the fibre fineness of the polyester fiber between 3.17~
In the range of 3.73dtex.
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| CN201711370238.3A CN109929115A (en) | 2017-12-19 | 2017-12-19 | Polyester block copolymer, the production method of polyester block copolymer and polyester fiber |
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