CN107011516A - Poly- pentanediamine binary acid block copolymer of polyester and preparation method thereof and fiber - Google Patents
Poly- pentanediamine binary acid block copolymer of polyester and preparation method thereof and fiber Download PDFInfo
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- CN107011516A CN107011516A CN201710222493.7A CN201710222493A CN107011516A CN 107011516 A CN107011516 A CN 107011516A CN 201710222493 A CN201710222493 A CN 201710222493A CN 107011516 A CN107011516 A CN 107011516A
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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- D—TEXTILES; PAPER
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- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- D01F6/82—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from polyester amides or polyether amides
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Abstract
The present invention relates to poly- pentanediamine binary acid block copolymer of a kind of polyester and preparation method thereof and fiber, ethylene glycol terephthalate is prepared first, ethylene glycol terephthalate obtains the oligomer for the ethylene glycol terephthalate that the degree of polymerization is 5~20 through polycondensation reaction, then the aqueous solution of pentanediamine dicarboxylate is subjected to the oligomer that polycondensation reaction obtains the pentanediamine binary acid that the degree of polymerization is 2~10, polycondensation reaction is carried out after finally two kinds of oligomers are mixed and obtains the poly- pentanediamine binary acid block copolymer of polyester, the mass ratio of polyethylene terephthalate block and poly- pentanediamine binary acid block is 90~10 in copolymer:10~90.Fiber is made in the poly- pentanediamine binary acid block copolymer of polyester after pre-crystallized, dry, spinning and drawing-off, the elasticity and moisture pick-up properties of fiber are excellent, determines elastic recovery rate >=85% that elongation is 10%, regain is 0.6~5.0%.
Description
Technical field
The invention belongs to polymeric material field, it is related to a kind of polyester-poly- pentanediamine binary acid block copolymer and its system
Preparation Method and fiber.
Background technology
The molecular structure of polyethylene terephthalate (PET) fiber has stereospecificity height, strand arrangement tight
The features such as containing rigid phenyl ring in close, symmetrical configuration and strand, thus PET has good physics and mechanicalness
Can, and resistant to chemical etching and antimicrobial erosion.Simultaneously as PET have crystallinity it is high, into degree of orientation height during fibre etc.
Characteristic so that the fabric as made from PET has the features such as conformality is good, stiffness is high and quick-drying washable, thus is disappeared deeply
The person of expense welcomes.However, because PET itself characteristic make it that the elasticity and hydrophily of PET are poor, hindering to a certain extent
It is further applied and development.Therefore, while PET comes out, people have begun to the research work being modified to PET,
It is intended to overcome PET shortcoming and deficiency.
PET method of modifying can be divided into chemical modification method and physical modification method, and wherein chemical modification method is to compare
Stable, lasting and effective method.Chemical modification has the methods such as copolymerization, grafting and surface chemical reaction, and wherein modification by copolymerization is
A kind of very important method in chemical modification, it be with p-phthalic acid (PTA) and ethylene glycol (EG) for primary raw material,
Synthesis phase adds a certain amount of other component progress copolyreaction and prepares modified poly ester.
In the 1950s, du pont company adds monomer SIP in polymerization, cation dyeable polyester has been invented
Fiber, abbreviation CDP.CDP improves the dyeability of polyester fiber, but the elasticity, hydrophilicity to PET are without obvious
Improve.
The patent application of Application No. 201410077464.2 discloses polyesteramide and preparation method thereof and fibre,
By raw material dihydric alcohol, terephthalic acid (TPA) and nylon salt synthesis of polyester amide in patent, polyesteramide is recycled to prepare fiber.By
Added simultaneously in three kinds of monomers, form random copolymer, improve the dyeability of fiber, but final obtained fiber is still
So there is the problem of elastic recovery rate is relatively low, it is 60~70% to determine the elastic recovery rate that elongation is 10%.
The patent application of Application No. 201410077480.1 discloses polyamide modified polyester and changed by the polyamide
Property fiber made from polyester, pass through in patent and add aliphatic Buddhist nun after esterification occurs for raw material dihydric alcohol and terephthalic acid (TPA)
Polyamide modified polyester is made in dragon, further, and fiber is made using the polyamide modified polyester.This fiber has preferable
Dyeability and hydrophily, but final obtained fiber still has the problem of elastic recovery rate is relatively low, it is 10% to determine elongation
Elastic recovery rate be 60~70%.
The patent application of Application No. 201410077537.8 discloses polyesteramide and preparation method thereof and gathered by this
Using anti-between raw material dihydric alcohol, terephthalic acid (TPA), diamine and/or its derivative in fiber made from esteramides, patent
Polyesteramide should be made, recycles polyesteramide to prepare fiber.This polyesteramide due to terephthalic acid (TPA) and diamine and/or
Reactivity between its derivative be significantly larger than and dihydric alcohol reactivity, the fiber quality uniformity thus prepared compared with
Difference.
The content of the invention
The purpose of the present invention is that there is provided one the problem of overcoming the elasticity of PET in the prior art and poor moisture pick-up properties
Polyester-poly- pentanediamine binary acid block copolymer and preparation method thereof is planted, and is total to using the polyester-poly- pentanediamine binary acid block
Polymers prepares elasticity and the preferable fiber of moisture pick-up properties.
To reach above-mentioned purpose, the technical solution adopted by the present invention is：
A kind of polyester-poly- pentanediamine binary acid block copolymer, polyester-poly- pentanediamine binary acid block copolymer is by poly- pair
PET block and poly- pentanediamine binary acid block are constituted, polyethylene terephthalate block and poly- penta 2
The mass ratio of amine binary acid block is 90~10:10~90；
The structural formula of the polyethylene terephthalate block is as follows：
Wherein, m1For the degree of polymerization of polyethylene terephthalate block, m1=5~20；
The structural formula of the poly- pentanediamine binary acid block is as follows：
Wherein, m2For the degree of polymerization of poly- pentanediamine binary acid block, m2=2~10, n are the number of methylene, and n is even number,
Span is 4~20.
It is used as preferred technical scheme：
A kind of polyester-poly- pentanediamine binary acid block copolymer as described above, the poly- pentanediamine binary acid block
Glass transition temperature is 20~65 DEG C.
A kind of polyester-poly- pentanediamine binary acid block copolymer as described above, the polyester-poly- pentanediamine binary acid is embedding
The number-average molecular weight of section copolymer is 15000~30000；The characteristic of the polyester-poly- pentanediamine binary acid block copolymer is glued
Spend for 0.50~1.1dL/g, fusing point is 210~255 DEG C.
Present invention also offers a kind of preparation method of polyester-poly- pentanediamine binary acid block copolymer, step is as follows：
(1) carry out esterification after mixing terephthalic acid (TPA) and ethylene glycol and obtain ethylene glycol terephthalate, add
Change reaction condition after catalyst and carry out the oligomer that polycondensation reaction obtains ethylene glycol terephthalate, the terephthalic acid (TPA)
The degree of polymerization of the oligomer of glycol ester is 5~20；
(2) aqueous solution of pentanediamine dicarboxylate is subjected to the oligomer that polycondensation reaction obtains pentanediamine binary acid, it is described
Binary acid in pentanediamine dicarboxylate is the Straight chain diatomic acid that carbon atom number is even number and span is 4~20, described
The degree of polymerization of the oligomer of pentanediamine binary acid is 2~10；
(3) polycondensation is carried out after the oligomer of the oligomer of ethylene glycol terephthalate and pentanediamine binary acid is mixed anti-
Polyester-poly- pentanediamine binary acid block copolymer should be obtained.
A kind of preparation method of polyester-poly- pentanediamine binary acid block copolymer as described above, is comprised the following steps that：
(1) terephthalic acid (TPA) and ethylene glycol are added into progress esterification in esterifying kettle and obtains terephthalate
Ester, the temperature of esterification is 220~260 DEG C, and the time is 1~3 hour, and reaction enters the first polymeric kettle after terminating, and addition is urged
The oligomer that polycondensation reaction obtains ethylene glycol terephthalate is carried out after agent, the temperature of polycondensation reaction is 260~285 DEG C,
Time is 0.1~0.5 hour, and the vacuum of polycondensation reaction system is 100~1000Pa；
(2) aqueous solution of pentanediamine dicarboxylate is added into progress polycondensation reaction in the second polymeric kettle and obtains pentanediamine binary
The oligomer of acid, the temperature of polycondensation reaction is 250~280 DEG C, and the time is 0.5~1 hour, and the vacuum of polycondensation reaction system is
1000~5000Pa；
(3) oligomer of the oligomer of ethylene glycol terephthalate and pentanediamine binary acid is added into third polymerization kettle
In, add progress polycondensation reaction after catalyst and obtain polyester-poly- pentanediamine binary acid block copolymer, the temperature of polycondensation reaction is
260~280 DEG C, the time is 2~3 hours, and the vacuum of polycondensation reaction system is 10~100Pa.
It is described in a kind of preparation method of polyester-poly- pentanediamine binary acid block copolymer as described above, step (1)
The mol ratio of terephthalic acid (TPA) and ethylene glycol is 1:1.1~1.6, the catalyst is antimony acetate or antimony glycol, with to benzene two
On the basis of the quality of formic acid glycol ester, the addition of catalyst is 0.02~0.05wt%, the terephthalate
The inherent viscosity of the oligomer of ester is 0.05~0.2dL/g.
It is described in a kind of preparation method of polyester-poly- pentanediamine binary acid block copolymer as described above, step (2)
The concentration of the aqueous solution of pentanediamine dicarboxylate is 50~80wt%, and the inherent viscosity of the oligomer of the pentanediamine binary acid is
0.1~0.5dL/g.
It is described in a kind of preparation method of polyester-poly- pentanediamine binary acid block copolymer as described above, step (3)
Catalyst is antimony acetate or antimony glycol, with the oligomer of the oligomer of ethylene glycol terephthalate and pentanediamine binary acid
On the basis of gross mass, the addition of catalyst is 0.02~0.05wt%.
Present invention also offers one kind fiber as made from polyester-poly- pentanediamine binary acid block copolymer, fiber is by gathering
Ester-poly- pentanediamine binary acid block copolymer is made after pre-crystallized, dry, spinning and drawing-off, the filament number of the fiber
For 0.3~10dtex, fracture strength is 2.0~7.0cN/dtex, determines elastic recovery rate >=85% that elongation is 10%, moisture regain
Rate is 0.6~5.0%.
Inventive principle：
The arrangement of polyethylene terephthalate (PET) strand is close, symmetrical configuration, containing rigid phenyl ring on main chain,
Its fiber has good heat endurance and mechanical property, thus is widely used.But PET is because with higher crystallization
Lack hydrophilic radical on degree and strand, cause that its elasticity is relatively low, moisture pick-up properties is poor.The present invention is by PET macromolecular chains
The middle poly- pentanediamine binary acid segment of insertion improves the elasticity and hygroscopicity of polyester-poly- pentanediamine binary acid block copolymer fiber
Can, elastic raising is odd number, polyamide molecule mainly due to carbon atom number in the poly- pentanediamine binary acid segment being introduced into
Carbonyl and amino in interchain can form hydrogen bond, and hydrogen bond is the predominant intermolecular forces for maintaining polyamide secondary structure, traditional idol
Hydrogen bond structure can be formed in theory between number strand carbonyl and amino, i.e., intermolecular carbonyl and amino formation hydrogen bond is most
Vast scale is 100%, and poly- pentanediamine binary acid segment at least 50% carbonyl and the amino containing odd number carbon does not form hydrogen
Active force between key, therefore molecule is reduced, and is easy to the recovery of stretching, while poly- pentanediamine binary acid segment is linear chain structure,
The locomitivity of poly- pentanediamine binary acid segment is stronger under stress, easy crimp shrinkage or elongation so that fiber has
Telescopic resilience；The raising of PET moisture pick-up properties mainly due in the poly- pentanediamine binary acid segment being introduced into contain hydrophilic radical (amine
Base group), amine groups have affinity interaction with the hydrone in air, are carried the hydrophilicity of block copolymer fiber
It is high.
Beneficial effect：
1) preparation method of polyester-poly- pentanediamine binary acid block copolymer is simple in the present invention, easily operation；
2) polyester-poly- pentanediamine binary acid block copolymer of the invention make use of the bullet of poly- pentanediamine binary acid block
Property, the rigidity of the hydrophily of amine groups and polyester aromatic ring so that copolymer fibre be provided simultaneously with elastic good, hygroscopicity it is high and
The characteristics of good mechanical performance；
3) fiber of the invention as made from polyester-poly- pentanediamine binary acid block copolymer has higher elasticity, fiber
Determining elastic recovery rate >=85% that elongation is 10%, the elasticity time that elongation is 10% is being determined much larger than common PET fiber
Multiple rate 60~70%, the elasticity of fiber produced by the present invention is significantly improved for prior art；
4) fiber of the invention as made from polyester-poly- pentanediamine binary acid block copolymer has excellent moisture pick-up properties,
The regain of fiber is 0.6~5.0%, higher than the regain 0.4% of common PET fiber, the moisture absorption of fiber produced by the present invention
Performance is significantly improved relative to prior art.
Embodiment
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair
Bright rather than limitation the scope of the present invention.In addition, it is to be understood that after the content of the invention lectured has been read, art technology
Personnel can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Fixed scope.
Embodiment 1
A kind of preparation method of polyester-poly- pentanediamine binary acid block copolymer, step is as follows：
(1) terephthalic acid (TPA) and ethylene glycol are added into progress esterification in esterifying kettle and obtains terephthalate
The mol ratio of ester, terephthalic acid (TPA) and glycol ester is 1:1.1, the temperature of esterification is 220 DEG C, and the time is 1 hour, reaction
Enter the first polymeric kettle after end, it is 5~10, inherent viscosity to add progress polycondensation reaction after catalyst acetic acid antimony and obtain the degree of polymerization
For the oligomer of 0.05~0.1dL/g ethylene glycol terephthalate, on the basis of the quality of ethylene glycol terephthalate,
The addition of catalyst is 0.02wt%, and the temperature of polycondensation reaction is 260 DEG C, and the time is 0.1 hour, polycondensation reaction system it is true
Reciprocal of duty cycle is 1000Pa；
(2) concentration is added in the second polymeric kettle for the aqueous solution of 50wt% pentanediamine dicarboxylate and carries out polycondensation reaction
Obtain the oligomer that the degree of polymerization is the pentanediamine binary acid that 2~6, inherent viscosity is 0.1~0.15dL/g, the temperature of polycondensation reaction
For 250 DEG C, the time is 0.5 hour, and the vacuum of polycondensation reaction system is that the binary acid in 5000Pa, pentanediamine dicarboxylate is
Carbon atom number is 4 Straight chain diatomic acid；
(3) by the oligomer of the oligomer of ethylene glycol terephthalate and pentanediamine binary acid with 90:10 mass ratio
Add third polymerization kettle in, add catalyst acetic acid antimony after carry out polycondensation reaction obtain polyester-poly- pentanediamine binary acid block be total to
Polymers, on the basis of the gross mass of the oligomer of ethylene glycol terephthalate and the oligomer of pentanediamine binary acid, catalyst
Addition be 0.02wt%, the temperature of polycondensation reaction is 260 DEG C, and the time is 2 hours, and the vacuum of polycondensation reaction system is
30Pa。
Final obtained polyester-poly- pentanediamine binary acid block copolymer is by polyethylene terephthalate block and gathers
Pentanediamine binary acid block is constituted, and the glass transition temperature of poly- pentanediamine binary acid block is 65 DEG C；Poly terephthalic acid second
The structural formula of diol ester block is as follows：
Wherein, m1For the degree of polymerization of polyethylene terephthalate block；
The structural formula of poly- pentanediamine binary acid block is as follows：
Wherein, m2For the degree of polymerization of poly- pentanediamine binary acid block, n is 4；
The number-average molecular weight of polyester-poly- pentanediamine binary acid block copolymer is 15000, polyester-poly- pentanediamine binary acid
The inherent viscosity of block copolymer is 0.55dL/g, and fusing point is 255 DEG C.
Fiber is made in polyester-poly- pentanediamine binary acid block copolymer after pre-crystallized, dry, spinning and drawing-off, it is fine
The filament number 0.3dtex of dimension, fracture strength is 2.0cN/dtex, and it is 90% to determine the elastic recovery rate that elongation is 10%, is returned
Damp rate is 2.0%.
The method of testing of inherent viscosity is with reference to ASTM D4603-2003；
The method of testing of fibrous fracture intensity is with reference to GB/T3916-1997；
The method of testing of fiber regain is with reference to GB/T 6503-2008；
The method of testing of fibrous elasticity response rate：Using Yarn Strength instrument, clamping gauge is 500mm, constant speed stretching
500mm/min, elastic recovery extends for the 10% of gauge surely, stretching and replys holding time 20s, and stretching circulation 3 times is specific to survey
Method for testing reference《GB/T14344-2008 chemical fiber filament Erichsen test methods》Carry out；Elastic recovery rate calculation formula
It is as follows：
Elastic recovery rate (%)=(L-L1)/(L-L0) × 100%；
In formula：L0 is sample original length, and L is that sample is stretched to the length determined after elongation, and L1 is the length after sample resets
Degree.
Comparative example 1
The oligomer of ethylene glycol terephthalate is made in the step of using with embodiment 1 (1) identical reaction condition, so
The oligomer of ethylene glycol terephthalate is added in third polymerization kettle afterwards, polycondensation reaction is carried out after adding catalyst acetic acid antimony
Polyethylene terephthalate is obtained, on the basis of the gross mass of the oligomer of ethylene glycol terephthalate, catalyst
Addition is 0.02wt%, and the temperature of polycondensation reaction is 260 DEG C, and the time is 2 hours, and the vacuum of polycondensation reaction system is
30Pa.Fiber, the list of fiber is made in obtained polyethylene terephthalate after pre-crystallized, dry, spinning and drawing-off
Silk size 0.3dtex, fracture strength is 4.0cN/dtex, and it is 70% to determine the elastic recovery rate that elongation is 10%, and regain is
0.4%.Comparative example 1 and embodiment 1 are contrasted as can be seen that introducing elastic after poly- pentanediamine binary acid segment in PET strands
It is obvious with moisture pick-up properties lifting, determine the elastic recovery rate that elongation is 10% and increase 29%, regain increases 400%.
Embodiment 2
A kind of preparation method of polyester-poly- pentanediamine binary acid block copolymer, step is as follows：
(1) terephthalic acid (TPA) and ethylene glycol are added into progress esterification in esterifying kettle and obtains terephthalate
The mol ratio of ester, terephthalic acid (TPA) and glycol ester is 1:1.2, the temperature of esterification is 224 DEG C, and the time is 1 hour, reaction
Enter the first polymeric kettle after end, it is 10~15, characteristic to add progress polycondensation reaction after catalyst glycol antimony and obtain the degree of polymerization
Viscosity for 0.1~0.15dL/g ethylene glycol terephthalate oligomer, using the quality of ethylene glycol terephthalate as
Benchmark, the addition of catalyst is 0.024wt%, and the temperature of polycondensation reaction is 270 DEG C, and the time is 0.3 hour, polycondensation reaction body
The vacuum of system is 200Pa；
(2) concentration is added in the second polymeric kettle for the aqueous solution of 60wt% pentanediamine dicarboxylate and carries out polycondensation reaction
Obtain the oligomer that the degree of polymerization is the pentanediamine binary acid that 3~6, inherent viscosity is 0.15~0.3dL/g, the temperature of polycondensation reaction
For 260 DEG C, the time is 0.7 hour, and the vacuum of polycondensation reaction system is that the binary acid in 1500Pa, pentanediamine dicarboxylate is
Carbon atom number is 6 Straight chain diatomic acid；
(3) by the oligomer of the oligomer of ethylene glycol terephthalate and pentanediamine binary acid with 50:50 mass ratio
Add in third polymerization kettle, add progress polycondensation reaction after catalyst glycol antimony and obtain polyester-poly- pentanediamine binary acid block
Copolymer, on the basis of the gross mass of the oligomer of ethylene glycol terephthalate and the oligomer of pentanediamine binary acid, catalysis
The addition of agent is 0.025wt%, and the temperature of polycondensation reaction is 270 DEG C, and the time is 2 hours, the vacuum of polycondensation reaction system
For 20Pa.
Final obtained polyester-poly- pentanediamine binary acid block copolymer is by polyethylene terephthalate block and gathers
Pentanediamine binary acid block is constituted, and the glass transition temperature of poly- pentanediamine binary acid block is 55 DEG C；Poly terephthalic acid second
The structural formula of diol ester block is as follows：
Wherein, m1For the degree of polymerization of polyethylene terephthalate block；
The structural formula of poly- pentanediamine binary acid block is as follows：
Wherein, m2For the degree of polymerization of poly- pentanediamine binary acid block, n is 6；
The number-average molecular weight of polyester-poly- pentanediamine binary acid block copolymer is 20000, polyester-poly- pentanediamine binary acid
The inherent viscosity of block copolymer is 0.65dL/g, and fusing point is 250 DEG C.
Fiber is made in polyester-poly- pentanediamine binary acid block copolymer after pre-crystallized, dry, spinning and drawing-off, it is fine
The filament number 2.0dtex of dimension, fracture strength is 4.0cN/dtex, and it is 90% to determine the elastic recovery rate that elongation is 10%, is returned
Damp rate is 2.5%.
Comparative example 2
The oligomer of ethylene glycol terephthalate is made in the step of using with embodiment 2 (1) identical reaction condition, so
The oligomer of ethylene glycol terephthalate is added in third polymerization kettle afterwards, progress polycondensation after catalyst glycol antimony is added anti-
Polyethylene terephthalate should be obtained, on the basis of the gross mass of the oligomer of ethylene glycol terephthalate, catalyst
Addition be 0.025wt%, the temperature of polycondensation reaction is 270 DEG C, and the time is 2 hours, and the vacuum of polycondensation reaction system is
20Pa.Fiber, the list of fiber is made in obtained polyethylene terephthalate after pre-crystallized, dry, spinning and drawing-off
Silk size 2.0dtex, fracture strength is 5.0cN/dtex, and it is 60% to determine the elastic recovery rate that elongation is 10%, and regain is
0.4%.Comparative example 2 and embodiment 2 are contrasted as can be seen that introducing elastic after poly- pentanediamine binary acid segment in PET strands
It is obvious with moisture pick-up properties lifting, determine the elastic recovery rate that elongation is 10% and increase 50%, regain increases 525%.
Embodiment 3
A kind of preparation method of polyester-poly- pentanediamine binary acid block copolymer, step is as follows：
(1) terephthalic acid (TPA) and ethylene glycol are added into progress esterification in esterifying kettle and obtains terephthalate
The mol ratio of ester, terephthalic acid (TPA) and glycol ester is 1:1.2, the temperature of esterification is 220 DEG C, and the time is 1 hour, reaction
Enter the first polymeric kettle after end, it is 10~15, characteristic to add progress polycondensation reaction after catalyst glycol antimony and obtain the degree of polymerization
Viscosity for 0.1~0.15dL/g ethylene glycol terephthalate oligomer, using the quality of ethylene glycol terephthalate as
Benchmark, the addition of catalyst is 0.024wt%, and the temperature of polycondensation reaction is 270 DEG C, and the time is 0.3 hour, polycondensation reaction body
The vacuum of system is 200Pa；
(2) concentration is added in the second polymeric kettle for the aqueous solution of 60wt% pentanediamine dicarboxylate and carries out polycondensation reaction
Obtain the oligomer that the degree of polymerization is the pentanediamine binary acid that 3~6, inherent viscosity is 0.15~0.3dL/g, the temperature of polycondensation reaction
For 260 DEG C, the time is 0.7 hour, and the vacuum of polycondensation reaction system is that the binary acid in 1500Pa, pentanediamine dicarboxylate is
Carbon atom number is 6 Straight chain diatomic acid；
(3) by the oligomer of the oligomer of ethylene glycol terephthalate and pentanediamine binary acid with 90:10 mass ratio
Add in third polymerization kettle, add progress polycondensation reaction after catalyst glycol antimony and obtain polyester-poly- pentanediamine binary acid block
Copolymer, on the basis of the gross mass of the oligomer of ethylene glycol terephthalate and the oligomer of pentanediamine binary acid, catalysis
The addition of agent is 0.025wt%, and the temperature of polycondensation reaction is 270 DEG C, and the time is 2 hours, the vacuum of polycondensation reaction system
For 10Pa.
Final obtained polyester-poly- pentanediamine binary acid block copolymer is by polyethylene terephthalate block and gathers
Pentanediamine binary acid block is constituted, and the glass transition temperature of poly- pentanediamine binary acid block is 65 DEG C；Poly terephthalic acid second
The structural formula of diol ester block is as follows：
Wherein, m1For the degree of polymerization of polyethylene terephthalate block；
The structural formula of poly- pentanediamine binary acid block is as follows：
Wherein, m2For the degree of polymerization of poly- pentanediamine binary acid block, n is 6；
The number-average molecular weight of polyester-poly- pentanediamine binary acid block copolymer is 20000, polyester-poly- pentanediamine binary acid
The inherent viscosity of block copolymer is 0.65dL/g, and fusing point is 255 DEG C.
Fiber is made in polyester-poly- pentanediamine binary acid block copolymer after pre-crystallized, dry, spinning and drawing-off, it is fine
The filament number 2.0dtex of dimension, fracture strength is 4.5cN/dtex, and it is 85% to determine the elastic recovery rate that elongation is 10%, is returned
Damp rate is 0.6%.
Embodiment 4
A kind of preparation method of polyester-poly- pentanediamine binary acid block copolymer, step is as follows：
(1) terephthalic acid (TPA) and ethylene glycol are added into progress esterification in esterifying kettle and obtains terephthalate
The mol ratio of ester, terephthalic acid (TPA) and glycol ester is 1:1.2, the temperature of esterification is 224 DEG C, and the time is 1 hour, reaction
Enter the first polymeric kettle after end, it is 10~15, characteristic to add progress polycondensation reaction after catalyst glycol antimony and obtain the degree of polymerization
Viscosity for 0.1~0.15dL/g ethylene glycol terephthalate oligomer, using the quality of ethylene glycol terephthalate as
Benchmark, the addition of catalyst is 0.024wt%, and the temperature of polycondensation reaction is 270 DEG C, and the time is 0.3 hour, polycondensation reaction body
The vacuum of system is 200Pa；
(2) concentration is added in the second polymeric kettle for the aqueous solution of 60wt% pentanediamine dicarboxylate and carries out polycondensation reaction
Obtain the oligomer that the degree of polymerization is the pentanediamine binary acid that 3~6, inherent viscosity is 0.15~0.3dL/g, the temperature of polycondensation reaction
For 260 DEG C, the time is 0.7 hour, and the vacuum of polycondensation reaction system is that the binary acid in 1500Pa, pentanediamine dicarboxylate is
Carbon atom number is 6 Straight chain diatomic acid；
(3) by the oligomer of the oligomer of ethylene glycol terephthalate and pentanediamine binary acid with 10:90 mass ratio
Add in third polymerization kettle, add progress polycondensation reaction after catalyst glycol antimony and obtain polyester-poly- pentanediamine binary acid block
Copolymer, on the basis of the gross mass of the oligomer of ethylene glycol terephthalate and the oligomer of pentanediamine binary acid, catalysis
The addition of agent is 0.025wt%, and the temperature of polycondensation reaction is 270 DEG C, and the time is 2 hours, the vacuum of polycondensation reaction system
For 20Pa.
Final obtained polyester-poly- pentanediamine binary acid block copolymer is by polyethylene terephthalate block and gathers
Pentanediamine binary acid block is constituted, and the glass transition temperature of poly- pentanediamine binary acid block is 45 DEG C；Poly terephthalic acid second
The structural formula of diol ester block is as follows：
Wherein, m1For the degree of polymerization of polyethylene terephthalate block；
The structural formula of poly- pentanediamine binary acid block is as follows：
Wherein, m2For the degree of polymerization of poly- pentanediamine binary acid block, n is 6；
The number-average molecular weight of polyester-poly- pentanediamine binary acid block copolymer is 20000, polyester-poly- pentanediamine binary acid
The inherent viscosity of block copolymer is 0.65dL/g, and fusing point is 250 DEG C.
Fiber is made in polyester-poly- pentanediamine binary acid block copolymer after pre-crystallized, dry, spinning and drawing-off, it is fine
The filament number 2.0dtex of dimension, fracture strength is 3.5cN/dtex, and it is 95% to determine the elastic recovery rate that elongation is 10%, is returned
Damp rate is 5.0%.
Embodiment 5
A kind of preparation method of polyester-poly- pentanediamine binary acid block copolymer, step is as follows：
(1) terephthalic acid (TPA) and ethylene glycol are added into progress esterification in esterifying kettle and obtains terephthalate
The mol ratio of ester, terephthalic acid (TPA) and glycol ester is 1:1.3, the temperature of esterification is 235 DEG C, and the time is 1.5 hours, instead
Enter the first polymeric kettle after should terminating, it is 10~13, characteristic to add progress polycondensation reaction after catalyst acetic acid antimony and obtain the degree of polymerization
Viscosity for 0.1~0.12dL/g ethylene glycol terephthalate oligomer, using the quality of ethylene glycol terephthalate as
Benchmark, the addition of catalyst is 0.031wt%, and the temperature of polycondensation reaction is 267 DEG C, and the time is 0.26 hour, polycondensation reaction
The vacuum of system is 400Pa；
(2) concentration is added in the second polymeric kettle for the aqueous solution of 60wt% pentanediamine dicarboxylate and carries out polycondensation reaction
Obtain the oligomer that the degree of polymerization is the pentanediamine binary acid that 4~7, inherent viscosity is 0.28~0.31dL/g, the temperature of polycondensation reaction
Spend for 260 DEG C, the time is 0.7 hour, the vacuum of polycondensation reaction system is the binary acid in 2200Pa, pentanediamine dicarboxylate
It is the Straight chain diatomic acid that carbon atom number is 8；
(3) by the oligomer of the oligomer of ethylene glycol terephthalate and pentanediamine binary acid with 70:30 mol ratio
Add third polymerization kettle in, add catalyst acetic acid antimony after carry out polycondensation reaction obtain polyester-poly- pentanediamine binary acid block be total to
Polymers, on the basis of the gross mass of the oligomer of ethylene glycol terephthalate and the oligomer of pentanediamine binary acid, catalyst
Addition be 0.032wt%, the temperature of polycondensation reaction is 266 DEG C, and the time is 2.3 hours, the vacuum of polycondensation reaction system
For 32Pa.
Final obtained polyester-poly- pentanediamine binary acid block copolymer is by polyethylene terephthalate block and gathers
Pentanediamine binary acid block is constituted, and the glass transition temperature of poly- pentanediamine binary acid block is 45 DEG C；Poly terephthalic acid second
The structural formula of diol ester block is as follows：
Wherein, m1For the degree of polymerization of polyethylene terephthalate block；
The structural formula of poly- pentanediamine binary acid block is as follows：
Wherein, m2For the degree of polymerization of poly- pentanediamine binary acid block, n is 8；
The number-average molecular weight of polyester-poly- pentanediamine binary acid block copolymer is 20000, polyester-poly- pentanediamine binary acid
The inherent viscosity of block copolymer is 0.65dL/g, and fusing point is 225 DEG C.
Fiber is made in polyester-poly- pentanediamine binary acid block copolymer after pre-crystallized, dry, spinning and drawing-off, it is fine
The filament number 2.3dtex of dimension, fracture strength is 3.8cN/dtex, and it is 87.2% to determine the elastic recovery rate that elongation is 10%,
Regain is 1%.
Embodiment 6
A kind of preparation method of polyester-poly- pentanediamine binary acid block copolymer, step is as follows：
(1) terephthalic acid (TPA) and glycol ester are added into progress esterification in esterifying kettle and obtains terephthalate
The mol ratio of ester, terephthalic acid (TPA) and glycol ester is 1:1.32, the temperature of esterification is 240 DEG C, and the time is 1.8 hours,
Reaction enters the first polymeric kettle after terminating, add after catalyst glycol antimony carry out polycondensation reaction obtain the degree of polymerization for 11~14,
Inherent viscosity is the oligomer of 0.12~0.15dL/g ethylene glycol terephthalate, with the matter of ethylene glycol terephthalate
On the basis of amount, the addition of catalyst is 0.036wt%, and the temperature of polycondensation reaction is 270 DEG C, and the time is 0.3 hour, and polycondensation is anti-
The vacuum for answering system is 500Pa；
(2) concentration is added in the second polymeric kettle for the aqueous solution of 63wt% pentanediamine dicarboxylate and carries out polycondensation reaction
Obtain the oligomer that the degree of polymerization is the pentanediamine binary acid that 5~7, inherent viscosity is 0.31~0.35dL/g, the temperature of polycondensation reaction
Spend for 263 DEG C, the time is 0.75 hour, the vacuum of polycondensation reaction system is the binary in 3100Pa, pentanediamine dicarboxylate
Acid is the Straight chain diatomic acid that carbon atom number is 10；
(3) by the oligomer of the oligomer of ethylene glycol terephthalate and pentanediamine binary acid with 50:50 mol ratio
Add in third polymerization kettle, add progress polycondensation reaction after catalyst glycol antimony and obtain polyester-poly- pentanediamine binary acid block
Copolymer, on the basis of the gross mass of the oligomer of ethylene glycol terephthalate and the oligomer of pentanediamine binary acid, catalysis
The addition of agent is 0.038wt%, and the temperature of polycondensation reaction is 268 DEG C, and the time is 2.4 hours, the vacuum of polycondensation reaction system
Spend for 45Pa.
Final obtained polyester-poly- pentanediamine binary acid block copolymer is by polyethylene terephthalate block and gathers
Pentanediamine binary acid block is constituted, and the glass transition temperature of poly- pentanediamine binary acid block is 30 DEG C；Poly terephthalic acid second
The structural formula of diol ester block is as follows：
Wherein, m1For the degree of polymerization of polyethylene terephthalate block；
The structural formula of poly- pentanediamine binary acid block is as follows：
Wherein, m2For the degree of polymerization of poly- pentanediamine binary acid block, n is 10；
The number-average molecular weight of polyester-poly- pentanediamine binary acid block copolymer is 20000, polyester-poly- pentanediamine binary acid
The inherent viscosity of block copolymer is 0.70dL/g, and fusing point is 223 DEG C.
Fiber is made in polyester-poly- pentanediamine binary acid block copolymer after pre-crystallized, dry, spinning and drawing-off, it is fine
The filament number 5.0dtex of dimension, fracture strength is 4.0cN/dtex, and it is 87.8% to determine the elastic recovery rate that elongation is 10%,
Regain is 2.0%.
Embodiment 7
A kind of preparation method of polyester-poly- pentanediamine binary acid block copolymer, step is as follows：
(1) terephthalic acid (TPA) and glycol ester are added into progress esterification in esterifying kettle and obtains terephthalate
The mol ratio of ester, terephthalic acid (TPA) and glycol ester is 1:1.32, the temperature of esterification is 244 DEG C, and the time is 2 hours, instead
Enter the first polymeric kettle after should terminating, it is 12~16, spy to add progress polycondensation reaction after catalyst glycol antimony and obtain the degree of polymerization
Property viscosity for 0.13~0.16dL/g ethylene glycol terephthalate oligomer, with the quality of ethylene glycol terephthalate
On the basis of, the addition of catalyst is 0.04wt%, and the temperature of polycondensation reaction is 272 DEG C, and the time is 0.36 hour, polycondensation reaction
The vacuum of system is 600Pa；
(2) concentration is added in the second polymeric kettle for the aqueous solution of 66wt% pentanediamine dicarboxylate and carries out polycondensation reaction
Obtain the oligomer that the degree of polymerization is the pentanediamine binary acid that 5~8, inherent viscosity is 0.38~0.40dL/g, the temperature of polycondensation reaction
Spend for 267 DEG C, the time is 0.8 hour, the vacuum of polycondensation reaction system is the binary acid in 3200Pa, pentanediamine dicarboxylate
It is the Straight chain diatomic acid that carbon atom number is 12；
(3) by the oligomer of the oligomer of ethylene glycol terephthalate and pentanediamine binary acid with 45:55 mol ratio
Add in third polymerization kettle, add progress polycondensation reaction after catalyst glycol antimony and obtain polyester-poly- pentanediamine binary acid block
Copolymer, on the basis of the gross mass of the oligomer of ethylene glycol terephthalate and the oligomer of pentanediamine binary acid, catalysis
The addition of agent is 0.041wt%, and the temperature of polycondensation reaction is 270 DEG C, and the time is 2.5 hours, the vacuum of polycondensation reaction system
Spend for 53Pa.
Final obtained polyester-poly- pentanediamine binary acid block copolymer is by polyethylene terephthalate block and gathers
Pentanediamine binary acid block is constituted, and the glass transition temperature of poly- pentanediamine binary acid block is 27 DEG C；Poly terephthalic acid second
The structural formula of diol ester block is as follows：
Wherein, m1For the degree of polymerization of polyethylene terephthalate block；
The structural formula of poly- pentanediamine binary acid block is as follows：
Wherein, m2For the degree of polymerization of poly- pentanediamine binary acid block, n is 12；
The number-average molecular weight of polyester-poly- pentanediamine binary acid block copolymer is 23000, polyester-poly- pentanediamine binary acid
The inherent viscosity of block copolymer is 0.78dL/g, and fusing point is 220 DEG C.
Fiber is made in polyester-poly- pentanediamine binary acid block copolymer after pre-crystallized, dry, spinning and drawing-off, it is fine
The filament number 5.0dtex of dimension, fracture strength is 4.0cN/dtex, and it is 88.5% to determine the elastic recovery rate that elongation is 10%,
Regain is 1.7%.
Embodiment 8
A kind of preparation method of polyester-poly- pentanediamine binary acid block copolymer, step is as follows：
(1) terephthalic acid (TPA) and glycol ester are added into progress esterification in esterifying kettle and obtains terephthalate
The mol ratio of ester, terephthalic acid (TPA) and glycol ester is 1:1.37, the temperature of esterification is 250 DEG C, and the time is 2.2 hours,
Reaction enters the first polymeric kettle after terminating, add after catalyst glycol antimony carry out polycondensation reaction obtain the degree of polymerization for 14~16,
Inherent viscosity is the oligomer of 0.15~0.17dL/g ethylene glycol terephthalate, with the matter of ethylene glycol terephthalate
On the basis of amount, the addition of catalyst is 0.044wt%, and the temperature of polycondensation reaction is 275 DEG C, and the time is 0.4 hour, and polycondensation is anti-
The vacuum for answering system is 700Pa；
(2) concentration is added in the second polymeric kettle for the aqueous solution of 70wt% pentanediamine dicarboxylate and carries out polycondensation reaction
Obtain the oligomer that the degree of polymerization is the pentanediamine binary acid that 6~9, inherent viscosity is 0.41~0.43dL/g, the temperature of polycondensation reaction
Spend for 270 DEG C, the time is 0.9 hour, the vacuum of polycondensation reaction system is the binary acid in 3500Pa, pentanediamine dicarboxylate
It is the Straight chain diatomic acid that carbon atom number is 14；
(3) by the oligomer of the oligomer of ethylene glycol terephthalate and pentanediamine binary acid with 40:60 mol ratio
Add in third polymerization kettle, add progress polycondensation reaction after catalyst glycol antimony and obtain polyester-poly- pentanediamine binary acid block
Copolymer, on the basis of the gross mass of the oligomer of ethylene glycol terephthalate and the oligomer of pentanediamine binary acid, catalysis
The addition of agent is 0.048wt%, and the temperature of polycondensation reaction is 272 DEG C, and the time is 2.6 hours, the vacuum of polycondensation reaction system
Spend for 60Pa.
Final obtained polyester-poly- pentanediamine binary acid block copolymer is by polyethylene terephthalate block and gathers
Pentanediamine binary acid block is constituted, and the glass transition temperature of poly- pentanediamine binary acid block is 25 DEG C；Poly terephthalic acid second
The structural formula of diol ester block is as follows：
Wherein, m1For the degree of polymerization of polyethylene terephthalate block；
The structural formula of poly- pentanediamine binary acid block is as follows：
Wherein, m2For the degree of polymerization of poly- pentanediamine binary acid block, n is 14；
The number-average molecular weight of polyester-poly- pentanediamine binary acid block copolymer is 25000, polyester-poly- pentanediamine binary acid
The inherent viscosity of block copolymer is 0.83dL/g, and fusing point is 218 DEG C.
Fiber is made in polyester-poly- pentanediamine binary acid block copolymer after pre-crystallized, dry, spinning and drawing-off, it is fine
The filament number 6.5dtex of dimension, fracture strength is 3.5cN/dtex, and it is 89.2% to determine the elastic recovery rate that elongation is 10%,
Regain is 1.5%.
Embodiment 9
A kind of preparation method of polyester-poly- pentanediamine binary acid block copolymer, step is as follows：
(1) terephthalic acid (TPA) and glycol ester are added into progress esterification in esterifying kettle and obtains terephthalate
The mol ratio of ester, terephthalic acid (TPA) and glycol ester is 1:1.44, the temperature of esterification is 252 DEG C, and the time is 2.4 hours,
React and enter the first polymeric kettle after terminating, it is 15~18, spy to add progress polycondensation reaction after catalyst acetic acid antimony and obtain the degree of polymerization
Property viscosity for 0.16~0.17dL/g ethylene glycol terephthalate oligomer, with the quality of ethylene glycol terephthalate
On the basis of, the addition of catalyst is 0.047wt%, and the temperature of polycondensation reaction is 277 DEG C, and the time is 0.46 hour, and polycondensation is anti-
The vacuum for answering system is 800Pa；
(2) concentration is added in the second polymeric kettle for the aqueous solution of 73wt% pentanediamine dicarboxylate and carries out polycondensation reaction
Obtain the oligomer that the degree of polymerization is the pentanediamine binary acid that 7~9, inherent viscosity is 0.48~0.50dL/g, the temperature of polycondensation reaction
Spend for 273 DEG C, the time is 0.95 hour, the vacuum of polycondensation reaction system is the binary in 4000Pa, pentanediamine dicarboxylate
Acid is the Straight chain diatomic acid that carbon atom number is 16；
(3) by the oligomer of the oligomer of ethylene glycol terephthalate and pentanediamine binary acid with 35:65 mol ratio
Add third polymerization kettle in, add catalyst acetic acid antimony after carry out polycondensation reaction obtain polyester-poly- pentanediamine binary acid block be total to
Polymers, on the basis of the gross mass of the oligomer of ethylene glycol terephthalate and the oligomer of pentanediamine binary acid, catalyst
Addition be 0.046wt%, the temperature of polycondensation reaction is 274 DEG C, and the time is 2.7 hours, the vacuum of polycondensation reaction system
For 70Pa.
Final obtained polyester-poly- pentanediamine binary acid block copolymer is by polyethylene terephthalate block and gathers
Pentanediamine binary acid block is constituted, and the glass transition temperature of poly- pentanediamine binary acid block is 23 DEG C；Poly terephthalic acid second
The structural formula of diol ester block is as follows：
Wherein, m1For the degree of polymerization of polyethylene terephthalate block；
The structural formula of poly- pentanediamine binary acid block is as follows：
Wherein, m2For the degree of polymerization of poly- pentanediamine binary acid block, n is 16；
The number-average molecular weight of polyester-poly- pentanediamine binary acid block copolymer is 27000, polyester-poly- pentanediamine binary acid
The inherent viscosity of block copolymer is 0.88dL/g, and fusing point is 215 DEG C.
Fiber is made in polyester-poly- pentanediamine binary acid block copolymer after pre-crystallized, dry, spinning and drawing-off, it is fine
The filament number 7.8dtex of dimension, fracture strength is 3.0cN/dtex, and it is 90.4% to determine the elastic recovery rate that elongation is 10%,
Regain is 1.4%.
Embodiment 10
A kind of preparation method of polyester-poly- pentanediamine binary acid block copolymer, step is as follows：
(1) terephthalic acid (TPA) and glycol ester are added into progress esterification in esterifying kettle and obtains terephthalate
The mol ratio of ester, terephthalic acid (TPA) and glycol ester is 1:1.51, the temperature of esterification is 256 DEG C, and the time is 2.6 hours,
React and enter the first polymeric kettle after terminating, it is 17~19, spy to add progress polycondensation reaction after catalyst acetic acid antimony and obtain the degree of polymerization
Property viscosity for 0.17~0.2dL/g ethylene glycol terephthalate oligomer, with the quality of ethylene glycol terephthalate
On the basis of, the addition of catalyst is 0.043wt%, and the temperature of polycondensation reaction is 280 DEG C, and the time is 0.47 hour, and polycondensation is anti-
The vacuum for answering system is 900Pa；
(2) concentration is added in the second polymeric kettle for the aqueous solution of 77wt% pentanediamine dicarboxylate and carries out polycondensation reaction
Obtain the oligomer that the degree of polymerization is the pentanediamine binary acid that 7~10, inherent viscosity is 0.48~0.49dL/g, the temperature of polycondensation reaction
Spend for 277 DEG C, the time is 1 hour, the vacuum of polycondensation reaction system is that the binary acid in 4500Pa, pentanediamine dicarboxylate is
Carbon atom number is 18 Straight chain diatomic acid；
(3) by the oligomer of the oligomer of ethylene glycol terephthalate and pentanediamine binary acid with 32:68 mol ratio
Add third polymerization kettle in, add catalyst acetic acid antimony after carry out polycondensation reaction obtain polyester-poly- pentanediamine binary acid block be total to
Polymers, on the basis of the gross mass of the oligomer of ethylene glycol terephthalate and the oligomer of pentanediamine binary acid, catalyst
Addition be 0.046wt%, the temperature of polycondensation reaction is 276 DEG C, and the time is 2.8 hours, the vacuum of polycondensation reaction system
For 85Pa.
Final obtained polyester-poly- pentanediamine binary acid block copolymer is by polyethylene terephthalate block and gathers
Pentanediamine binary acid block is constituted, and the glass transition temperature of poly- pentanediamine binary acid block is 21 DEG C；Poly terephthalic acid second
The structural formula of diol ester block is as follows：
Wherein, m1For the degree of polymerization of polyethylene terephthalate block；
The structural formula of poly- pentanediamine binary acid block is as follows：
Wherein, m2For the degree of polymerization of poly- pentanediamine binary acid block, n is 18；
The number-average molecular weight of polyester-poly- pentanediamine binary acid block copolymer is 28000, polyester-poly- pentanediamine binary acid
The inherent viscosity of block copolymer is 0.90dL/g, and fusing point is 212 DEG C.
Fiber is made in polyester-poly- pentanediamine binary acid block copolymer after pre-crystallized, dry, spinning and drawing-off, it is fine
The filament number 8.5dtex of dimension, fracture strength is 2.5cN/dtex, and it is 91.8% to determine the elastic recovery rate that elongation is 10%,
Regain is 1.2%.
Embodiment 11
A kind of preparation method of polyester-poly- pentanediamine binary acid block copolymer, step is as follows：
(1) terephthalic acid (TPA) and glycol ester are added into progress esterification in esterifying kettle and obtains terephthalate
The mol ratio of ester, terephthalic acid (TPA) and glycol ester is 1:1.6, the temperature of esterification is 260 DEG C, and the time is 3 hours, reaction
Enter the first polymeric kettle after end, it is 18~20, characteristic to add progress polycondensation reaction after catalyst glycol antimony and obtain the degree of polymerization
Viscosity for 0.18~0.2dL/g ethylene glycol terephthalate oligomer, using the quality of ethylene glycol terephthalate as
Benchmark, the addition of catalyst is 0.05wt%, and the temperature of polycondensation reaction is 285 DEG C, and the time is 0.5 hour, polycondensation reaction body
The vacuum of system is 1000Pa；
(2) concentration is added in the second polymeric kettle for the aqueous solution of 80wt% pentanediamine dicarboxylate and carries out polycondensation reaction
Obtain the oligomer that the degree of polymerization is the pentanediamine binary acid that 8~10, inherent viscosity is 0.49~0.50dL/g, the temperature of polycondensation reaction
Spend for 280 DEG C, the time is 1 hour, the vacuum of polycondensation reaction system is that the binary acid in 5000Pa, pentanediamine dicarboxylate is
Carbon atom number is 20 Straight chain diatomic acid；
(3) by the oligomer of the oligomer of ethylene glycol terephthalate and pentanediamine binary acid with 30:70 mol ratio
Add in third polymerization kettle, add progress polycondensation reaction after catalyst glycol antimony and obtain polyester-poly- pentanediamine binary acid block
Copolymer, on the basis of the gross mass of the oligomer of ethylene glycol terephthalate and the oligomer of pentanediamine binary acid, catalysis
The addition of agent is 0.05wt%, and the temperature of polycondensation reaction is 280 DEG C, and the time is 3 hours, and the vacuum of polycondensation reaction system is
100Pa。
Final obtained polyester-poly- pentanediamine binary acid block copolymer is by polyethylene terephthalate block and gathers
Pentanediamine binary acid block is constituted, and the glass transition temperature of poly- pentanediamine binary acid block is 20 DEG C；Poly terephthalic acid second
The structural formula of diol ester block is as follows：
Wherein, m1For the degree of polymerization of polyethylene terephthalate block；
The structural formula of poly- pentanediamine binary acid block is as follows：
Wherein, m2For the degree of polymerization of poly- pentanediamine binary acid block, n is 20；
The number-average molecular weight of polyester-poly- pentanediamine binary acid block copolymer is 30000, polyester-poly- pentanediamine binary acid
The inherent viscosity of block copolymer is 1.1dL/g, and fusing point is 210 DEG C.
Fiber is made in polyester-poly- pentanediamine binary acid block copolymer after pre-crystallized, dry, spinning and drawing-off, it is fine
The filament number 10dtex of dimension, fracture strength is 2.0cN/dtex, and it is 92.5% to determine the elastic recovery rate that elongation is 10%, is returned
Damp rate is 1.1%.
Claims (9)
1. a kind of polyester-poly- pentanediamine binary acid block copolymer, it is characterized in that：Polyester-poly- pentanediamine binary acid block copolymerization
Thing is made up of polyethylene terephthalate block and poly- pentanediamine binary acid block, polyethylene terephthalate block
Mass ratio with poly- pentanediamine binary acid block is 90~10:10~90；
The structural formula of the polyethylene terephthalate block is as follows：
Wherein, m1For the degree of polymerization of polyethylene terephthalate block, m1=5~20；
The structural formula of the poly- pentanediamine binary acid block is as follows：
Wherein, m2For the degree of polymerization of poly- pentanediamine binary acid block, m2=2~10, n are the number of methylene, and n is even number, value
Scope is 4~20.
2. a kind of polyester according to claim 1-poly- pentanediamine binary acid block copolymer, it is characterised in that described poly-
The glass transition temperature of pentanediamine binary acid block is 20~65 DEG C.
3. a kind of polyester according to claim 1-poly- pentanediamine binary acid block copolymer, it is characterised in that described poly-
The number-average molecular weight of ester-poly- pentanediamine binary acid block copolymer is 15000~30000；The polyester-poly- pentanediamine binary acid
The inherent viscosity of block copolymer is 0.50~1.1dL/g, and fusing point is 210~255 DEG C.
4. a kind of preparation method of polyester-poly- pentanediamine binary acid block copolymer as described in any one of claims 1 to 3,
It is characterized in that, step is as follows：
(1) carry out esterification after mixing terephthalic acid (TPA) and ethylene glycol and obtain ethylene glycol terephthalate, add catalysis
Change reaction condition after agent and carry out the oligomer that polycondensation reaction obtains ethylene glycol terephthalate, the terephthalic acid (TPA) second two
The degree of polymerization of the oligomer of alcohol ester is 5~20；
(2) aqueous solution of pentanediamine dicarboxylate is subjected to the oligomer that polycondensation reaction obtains pentanediamine binary acid, described penta 2
Binary acid in amine dicarboxylate is the Straight chain diatomic acid that carbon atom number is even number and span is 4~20, described penta 2
The degree of polymerization of the oligomer of amine binary acid is 2~10；
(3) polycondensation reaction is carried out after the oligomer of the oligomer of ethylene glycol terephthalate and pentanediamine binary acid is mixed to obtain
To polyester-poly- pentanediamine binary acid block copolymer.
5. a kind of preparation method of polyester according to claim 4-poly- pentanediamine binary acid block copolymer, its feature exists
In comprising the following steps that：
(1) terephthalic acid (TPA) and ethylene glycol are added into progress esterification in esterifying kettle and obtains ethylene glycol terephthalate, ester
The temperature for changing reaction is 220~260 DEG C, and the time is 1~3 hour, and reaction enters the first polymeric kettle after terminating, and adds after catalyst
Carry out polycondensation reaction and obtain the oligomer of ethylene glycol terephthalate, the temperature of polycondensation reaction is 260~285 DEG C, the time is
0.1~0.5 hour, the vacuum of polycondensation reaction system was 100~1000Pa；
(2) aqueous solution of pentanediamine dicarboxylate is added into progress polycondensation reaction in the second polymeric kettle and obtains pentanediamine binary acid
Oligomer, the temperature of polycondensation reaction is 250~280 DEG C, and the time is 0.5~1 hour, and the vacuum of polycondensation reaction system is 1000
~5000Pa；
(3) oligomer of the oligomer of ethylene glycol terephthalate and pentanediamine binary acid is added in third polymerization kettle, plus
Enter to carry out polycondensation reaction after catalyst to obtain polyester-poly- pentanediamine binary acid block copolymer, the temperature of polycondensation reaction for 260~
280 DEG C, the time is 2~3 hours, and the vacuum of polycondensation reaction system is 10~100Pa.
6. a kind of preparation method of polyester according to claim 5-poly- pentanediamine binary acid block copolymer, its feature exists
In in step (1), the mol ratio of the terephthalic acid (TPA) and ethylene glycol is 1:1.1~1.6, the catalyst be antimony acetate or
Antimony glycol, on the basis of the quality of ethylene glycol terephthalate, the addition of catalyst is 0.02~0.05wt%, described
The inherent viscosity of the oligomer of ethylene glycol terephthalate is 0.05~0.2dL/g.
7. a kind of preparation method of polyester according to claim 5-poly- pentanediamine binary acid block copolymer, its feature exists
In in step (2), the concentration of the aqueous solution of the pentanediamine dicarboxylate is 50~80wt%, the pentanediamine binary acid
The inherent viscosity of oligomer is 0.1~0.5dL/g.
8. a kind of preparation method of polyester according to claim 5-poly- pentanediamine binary acid block copolymer, its feature exists
In in step (3), the catalyst is antimony acetate or antimony glycol, with the oligomer of ethylene glycol terephthalate and penta 2
On the basis of the gross mass of the oligomer of amine binary acid, the addition of catalyst is 0.02~0.05wt%.
9. made from a kind of a kind of polyester-poly- pentanediamine binary acid block copolymer as described in any one of claims 1 to 3
Fiber, it is characterized in that：Fiber is made by polyester-poly- pentanediamine binary acid block copolymer after pre-crystallized, dry, spinning and drawing-off
, the filament number of the fiber is 0.3~10dtex, and fracture strength is 2.0~7.0cN/dtex, and it is 10% to determine elongation
Elastic recovery rate >=85%, regain is 0.6~5.0%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109265355A (en) * | 2018-10-16 | 2019-01-25 | 南京工业大学 | Pentanediamine suberate and its crystal |
| CN111825838A (en) * | 2019-04-16 | 2020-10-27 | 上海凯赛生物技术股份有限公司 | Polyester amide and preparation method thereof and fiber |
| CN115716913A (en) * | 2021-08-27 | 2023-02-28 | 上海凯赛生物技术股份有限公司 | Odd-carbon polyamide elastomer and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104846507A (en) * | 2015-05-20 | 2015-08-19 | 浙江蓝天海纺织服饰科技有限公司 | Polyesteramide short fiber and cotton fiber blended workwear fabric |
| CN104846500A (en) * | 2015-05-20 | 2015-08-19 | 浙江蓝天海纺织服饰科技有限公司 | Polyesteramide short fiber and cotton fiber blended yarn |
| CN104892933A (en) * | 2014-03-04 | 2015-09-09 | 上海凯赛生物技术研发中心有限公司 | Polyamide-modified polyester and preparation method thereof, and fibers prepared from polyamide-modified polyester |
| CN105885038A (en) * | 2015-05-12 | 2016-08-24 | 上海凯赛生物技术研发中心有限公司 | Method for preparing polyamide |
-
2017
- 2017-04-07 CN CN201710222493.7A patent/CN107011516B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104892933A (en) * | 2014-03-04 | 2015-09-09 | 上海凯赛生物技术研发中心有限公司 | Polyamide-modified polyester and preparation method thereof, and fibers prepared from polyamide-modified polyester |
| CN105885038A (en) * | 2015-05-12 | 2016-08-24 | 上海凯赛生物技术研发中心有限公司 | Method for preparing polyamide |
| CN104846507A (en) * | 2015-05-20 | 2015-08-19 | 浙江蓝天海纺织服饰科技有限公司 | Polyesteramide short fiber and cotton fiber blended workwear fabric |
| CN104846500A (en) * | 2015-05-20 | 2015-08-19 | 浙江蓝天海纺织服饰科技有限公司 | Polyesteramide short fiber and cotton fiber blended yarn |
Non-Patent Citations (1)
| Title |
|---|
| 徐卫海等: ""生物基戊二胺己二酸盐改性聚酯的合成及结构分析"", 《东华大学学报（自然科学版）》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109265355A (en) * | 2018-10-16 | 2019-01-25 | 南京工业大学 | Pentanediamine suberate and its crystal |
| CN109265355B (en) * | 2018-10-16 | 2021-06-25 | 南京工业大学 | Pentanediamine suberate salt and crystal thereof |
| CN111825838A (en) * | 2019-04-16 | 2020-10-27 | 上海凯赛生物技术股份有限公司 | Polyester amide and preparation method thereof and fiber |
| CN111825838B (en) * | 2019-04-16 | 2022-10-11 | 上海凯赛生物技术股份有限公司 | Polyester amide and preparation method thereof and fiber |
| CN115716913A (en) * | 2021-08-27 | 2023-02-28 | 上海凯赛生物技术股份有限公司 | Odd-carbon polyamide elastomer and preparation method thereof |
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| CN107011516B (en) | 2020-05-12 |
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