CN111607843A - Preparation method of anhydride modified sheath-core composite fiber - Google Patents
Preparation method of anhydride modified sheath-core composite fiber Download PDFInfo
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- CN111607843A CN111607843A CN202010591513.XA CN202010591513A CN111607843A CN 111607843 A CN111607843 A CN 111607843A CN 202010591513 A CN202010591513 A CN 202010591513A CN 111607843 A CN111607843 A CN 111607843A
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- composite fiber
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- polybutylene terephthalate
- anhydride
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- 239000000835 fiber Substances 0.000 title claims abstract description 111
- 239000002131 composite material Substances 0.000 title claims abstract description 97
- 150000008064 anhydrides Chemical class 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 52
- -1 polybutylene Polymers 0.000 claims abstract description 42
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 29
- 229920000570 polyether Polymers 0.000 claims abstract description 29
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 28
- 229920001748 polybutylene Polymers 0.000 claims abstract description 26
- 229920005862 polyol Polymers 0.000 claims abstract description 26
- 238000005886 esterification reaction Methods 0.000 claims abstract description 25
- 239000012792 core layer Substances 0.000 claims abstract description 23
- 238000009987 spinning Methods 0.000 claims abstract description 23
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 229920001577 copolymer Polymers 0.000 claims abstract description 15
- 150000003077 polyols Chemical class 0.000 claims abstract description 12
- 239000003381 stabilizer Substances 0.000 claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 11
- 150000002148 esters Chemical class 0.000 claims abstract description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 239000003999 initiator Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000012974 tin catalyst Substances 0.000 claims abstract description 6
- 238000001291 vacuum drying Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 25
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 19
- 239000002202 Polyethylene glycol Substances 0.000 claims description 19
- 239000003963 antioxidant agent Substances 0.000 claims description 17
- 230000003078 antioxidant effect Effects 0.000 claims description 16
- 239000010410 layer Substances 0.000 claims description 13
- 229920001223 polyethylene glycol Polymers 0.000 claims description 13
- 229920001400 block copolymer Polymers 0.000 claims description 12
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 10
- 229940035437 1,3-propanediol Drugs 0.000 claims description 10
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 10
- QPGQPZQYAMNOPE-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate;sodium Chemical group [Na].COC(=O)C1=CC=CC(C(=O)OC)=C1 QPGQPZQYAMNOPE-UHFFFAOYSA-N 0.000 claims description 9
- 239000012760 heat stabilizer Substances 0.000 claims description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 8
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 7
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 7
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000003242 anti bacterial agent Substances 0.000 claims description 6
- 238000000354 decomposition reaction Methods 0.000 claims description 6
- 150000002978 peroxides Chemical class 0.000 claims description 6
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 6
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 5
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 5
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 7
- 229920000728 polyester Polymers 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 8
- 238000004043 dyeing Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 229920001634 Copolyester Polymers 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 239000002657 fibrous material Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 210000004243 sweat Anatomy 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920006052 Chinlon® Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 229920002334 Spandex Polymers 0.000 description 1
- 229920004933 Terylene® Polymers 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- HGINCPLSRVDWNT-UHFFFAOYSA-N acrylaldehyde Natural products C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000004759 spandex Substances 0.000 description 1
- 230000009182 swimming Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
-
- 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
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
- D01D5/34—Core-skin structure; Spinnerette packs therefor
-
- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Multicomponent Fibers (AREA)
Abstract
The invention relates to a preparation method of anhydride modified sheath-core composite fiber, which comprises the steps of taking polybutylene terephthalate-polyalcohol segmented copolymer (the molecular weight of a segmented polyether chain segment is 1000-5000) as a sheath raw material, taking segmented copolyether ester high polymer (the molecular weight of the polyether chain segment is 1000-5000) as a core layer raw material, and spinning by adopting a sheath-core composite spinning process to prepare the composite fiber; the preparation process of the polybutylene terephthalate-polyalcohol segmented copolymer comprises the following steps: (1) stirring and uniformly mixing the polyol and the terephthalic acid after vacuum drying to obtain the product; (2) adding an organic tin catalyst, an initiator, a modified monomer, maleic anhydride and a stabilizer into the molten mixture to perform esterification reaction to obtain a polybutylene terephthalate-polyol segmented copolymer; the prepared polybutylene terephthalate-polyalcohol segmented copolymer has good moisture absorption performance, and the hydrophilic performance and the spinnability of the composite fiber are optimal.
Description
Technical Field
The invention belongs to the technical field of sheath-core composite fibers, and particularly relates to a preparation method of an anhydride modified sheath-core composite fiber.
Background
In recent years, people pay more attention to healthy and comfortable life style, and the pursuit of clothes pay more attention to comfort in addition to style and color, especially in hot summer. Most of the fabrics in the current market are polyester fibers, acrylon, chinlon, spandex, cotton and the like, and the polyester fibers occupy the vast majority of the market by the characteristics of price advantage, washability, stiffness, smoothness and the like. However, the common terylene has the characteristics of poor moisture absorption, stuffy and hot wearing, general dyeing performance and permeability resistance, and the like, and particularly in summer, people are very easy to sweat and love swimming, and the moisture absorption, sweat release and permeability resistance are particularly important. At present, a plurality of differentiated polyester fibers exist in the market, such as moisture absorption and sweat releasing polyester fibers, cationic dyeable polyester fibers, cool polyester fibers and the like, but the functions of the sold differentiated polyester fibers are more and single, and the multifunctional requirement of a client on one fabric cannot be met.
Polyester is one of the most widely used high molecular materials in the world, and has been widely used in the fields of textile fibers, packaging materials, film media and the like due to its excellent properties. Polyester fibers were originally developed based on cotton-like fibers, but polyester fibers still have poor moisture absorption and breathability and poor dyeing properties compared to cotton. Generally, polyester can only be dyed by disperse dyes under high temperature and high pressure, and a two-step dyeing method is often adopted when polyester and cotton fibers are blended, so that the dyeing process is complicated, and the cost is correspondingly increased.
Disclosure of Invention
The invention aims to provide a preparation method of an anhydride modified sheath-core composite fiber,
in order to achieve the purpose, the invention adopts the following scheme:
a preparation method of anhydride modified sheath-core composite fiber takes polybutylene terephthalate-polyalcohol segmented copolymer (dyeable polyester) as a sheath raw material and takes segmented copolyether ester high polymer (polyterephthalate) as a core layer raw material, and adopts a sheath-core composite spinning process to spin (stretch and spin through a spinning component) to prepare the sheath-core composite fiber;
the block copolyether ester high polymer is more than one of polybutylene terephthalate-polybutylene glycol, polyethylene terephthalate-polyethylene glycol and polybutylene terephthalate-polyethylene glycol;
the preparation process of the polybutylene terephthalate-polyalcohol segmented copolymer comprises the following steps:
(1) stirring and uniformly mixing the polyol and the terephthalic acid which are subjected to vacuum drying (the drying temperature is 60-120 ℃ and the drying time is 8-12 h) to obtain the mixture;
(2) adding an organic tin catalyst, an initiator, a modified monomer, maleic anhydride and a stabilizer into the molten mixture to carry out esterification reaction to obtain the polybutylene terephthalate-polyol segmented copolymer.
Maleic anhydride is grafted on the polyhydric alcohol to generate a branched chain, so that the molecular structure of the polyhydric alcohol is changed, the polyhydric alcohol is degraded in the grafting process, the entanglement among molecules is reduced, the regularity of the polyhydric alcohol is increased, the polyhydric alcohol is easy to crystallize, and the melting point is reduced; the prepared polyester has the characteristic of low melting point, and the fiber spun by the polyester has good fluffiness, high strength and high elastic recovery rate; the produced non-woven fabric has the characteristics of soft hand feeling, high elasticity and the like, is wide in application range, and the skin layer of the skin-core type low-melting-point polyester composite fiber reserves the characteristic part of the conventional polyester and has good compatibility with the conventional polyester. The melting point difference between the skin layer and the core layer in the skin-core structure fiber is large, and the processing window of the composite material is wide.
Maleic anhydride is grafted to polyhydric alcohol, so that polar monomers are connected to a polyhydric alcohol chain to endow the polyhydric alcohol with polarity, and the polyhydric alcohol is modified to be a weak polar copolymer, so that the biocompatibility of the sheath-core composite fiber is improved.
As a preferred technical scheme:
according to the preparation method of the anhydride modified sheath-core composite fiber, the volume ratio of the core layer to the sheath layer is 4-6: 6-4.
In the preparation method of the anhydride modified sheath-core composite fiber, in the polybutylene terephthalate-polyol block copolymer, the molecular weight of the block polyether chain segment is 1000-5000, preferably the molecular weight of the polyether chain segment is 2000-4000; in the block copolyether ester high polymer, the molecular weight of a polyether chain segment is 1000-5000, and preferably, the molecular weight of the polyether chain segment is 2000-4000.
The higher the molecular weight, the better the hydrophilic copolyester corresponding to the polyether, i.e. the better the hydrophilic performance of the prepared polybutylene terephthalate-polyol block copolymer, but the addition of the polyether with large molecular weight also causes the activity of the polyester to be lower, the polyester cannot be grafted into the polyester molecular chain in a copolymerization form, and most of the polyether is in a blending form, thus causing the spinnability of the composite fiber to be poor and the fiber quality to be uneven. When the molecular weight of the block polyether chain segment of the skin layer and the core layer is in the range of 2000-4000, the prepared copolyester has the best hydrophilic property.
The preparation method of the anhydride modified sheath-core composite fiber is characterized in that the polyalcohol is a mixture of polyethylene glycol and 1, 3-propylene glycol; the initiator is benzoyl peroxide or di-tert-butyl peroxide; the modified monomer is dimethyl isophthalate sodium sulfonate; the stabilizer is a mixture of an antioxidant and a heat stabilizer.
In the preparation method of the anhydride modified core-sheath composite fiber, the 1, 3-propanediol is synthesized biologically. The hydrophilic chemical modification method is mainly to copolymerize polyethylene glycol (PEG) with certain relative molecular mass, so that the fiber surface has permanent hydrophilicity and antistatic property to a certain extent. The biological synthesis of polyhydric alcohol is adopted to replace the traditional petroleum processing product ethylene glycol Monomer (MEG) to synthesize the poly terephthalic acid. The polyester fiber produced by the polyol ester is superior to the common polyester fiber in the aspects of dyeing performance, hand feeling and the like, and can reduce the dye and the dyeing and finishing energy consumption by 10 percent. Also, the dyeing property of the novel polyester polytrimethylene terephthalate (PTT) fiber produced by biologically synthesized 1, 3-Propanediol (PDO) is greatly broken through.
According to the preparation method of the anhydride modified sheath-core composite fiber, in the polyhydric alcohol, the mixing ratio of polyethylene glycol and 1, 3-propylene glycol is 1-9: 9-1; the antioxidant is a hydrogen donating phenol antioxidant or a peroxide decomposition type phosphorous antioxidant; the heat stabilizer may be any one of phosphoric acid, polyphosphoric acid, and derivatives thereof; the mixing ratio of the antioxidant to the heat stabilizer is 1: 1-4.5.
According to the preparation method of the anhydride modified core-sheath composite fiber, the organic antibacterial agent master batch is added in the esterification reaction. The polyester fiber has more accurate, rapid and efficient inhibition effect on fungi and virus strains by adopting the macromolecular organic antibacterial agent, and is different from broad-spectrum antibacterial.
In the preparation method of the anhydride modified sheath-core composite fiber, the organic antibacterial agent is polyguanidine salts.
According to the preparation method of the anhydride modified sheath-core composite fiber, the molar ratio of the polyalcohol to the terephthalic acid is 1: 1.55-1.65; the content of the initiator is 0.005-0.007 wt% of the addition amount of the terephthalic acid, the molar ratio of the modified monomer to the terephthalic acid is 1: 0.02-0.1, the content of the maleic anhydride is 1.6-2.1 wt% of the polyol, and the content of the stabilizer is 0.1-0.2 wt%;
the esterification reaction is carried out at the temperature of 240-250 ℃ and under the pressure of 0.3-0.6 Mpa for 2-4 hours.
According to the preparation method of the anhydride modified sheath-core composite fiber, in the sheath-core composite spinning process, the stretching temperature is 150-250 ℃, and the spinning speed is 1000-2000 m/min.
Has the advantages that:
(1) according to the preparation method of the anhydride modified sheath-core composite fiber, sodium sulfonate groups are introduced to a molecular chain, so that the fiber is easier to dye; maleic anhydride is grafted on a molecular chain by a melt grafting method, so that the molecular chain contains a hydrophilic group-COOH, and the prepared modified low-melting-point polyester (namely the polybutylene terephthalate-polyalcohol segmented copolymer) has good permanent moisture absorption performance;
(2) according to the preparation method of the anhydride modified sheath-core composite fiber, the molecular weight of polyether chain segments of the sheath layer and the core layer is 2000-4000, the hydrophilic property and the spinnability of the prepared polyester are optimal, and the fiber quality is highest;
(3) the preparation method of the anhydride modified sheath-core composite fiber is simple, the obtained sheath-core composite fiber has good compatibility and long service life, and the physical properties of the sheath-core composite fiber, such as mechanical strength, osmotic pressure, thermal stability and the like, are further improved, so that the sheath-core composite fiber has great practical application prospect.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
A preparation method of anhydride modified sheath-core composite fiber is characterized by taking polybutylene terephthalate-polyol block copolymer (the molecular weight of a block polyether chain segment is 1000-5000) as a sheath raw material, taking block copolyether ester high polymer (the molecular weight of the polyether chain segment is 1000-5000) as a core layer raw material, and spinning by adopting a sheath-core composite spinning process (the volume ratio of the core layer to the sheath layer is 4-6: 6-4) to prepare the sheath-core composite fiber;
the preparation process of the polybutylene terephthalate-polyalcohol segmented copolymer comprises the following steps:
(1) stirring and uniformly mixing the polyol (a mixture of polyethylene glycol and 1, 3-propylene glycol with a mixing ratio of 1-9: 9-1) and terephthalic acid after vacuum drying to obtain the polyatomic alcohol;
(2) adding an organotin catalyst, an initiator (benzoyl peroxide or di-tert-butyl peroxide), a modified monomer (sodium dimethyl isophthalate), maleic anhydride and a stabilizer (a mixture of an antioxidant and a heat stabilizer in a mixing ratio of 1: 1-4.5) into the molten mixture for esterification reaction to obtain the polybutylene terephthalate-polyol block copolymer.
The block copolyether ester high polymer is more than one of polybutylene terephthalate-polytetramethylene glycol, polyethylene terephthalate-polyethylene glycol and polybutylene terephthalate-polyethylene glycol.
The 1, 3-propanediol is synthesized biologically.
The antioxidant is a hydrogen donating phenol antioxidant or a peroxide decomposition type phosphorous antioxidant; the heat stabilizer may be any one of phosphoric acid, polyphosphoric acid, and derivatives thereof;
and organic antibacterial agent (polyguanidine salt) master batch is also added in the esterification reaction.
The molar ratio of the polyhydric alcohol to the terephthalic acid is 1: 1.55-1.65; the content of the initiator is 0.005-0.007 wt% of the addition amount of the terephthalic acid, the molar ratio of the modified monomer to the terephthalic acid is 1: 0.02-0.1, the content of the maleic anhydride is 1.6-2.1 wt% of the polyol, and the content of the stabilizer is 0.1-0.2 wt%;
the esterification reaction is carried out at the temperature of 240-250 ℃ and under the pressure of 0.3-0.6 Mpa for 2-4 hours.
In the skin-core composite spinning process, the stretching temperature is 150-250 ℃, and the spinning speed is 1000-2000 m/min.
Example 1
A preparation method of an anhydride modified sheath-core composite fiber comprises the following steps:
(1) mixing polyethylene glycol and 1, 3-propanediol in a mixing ratio of 2:5, adding terephthalic acid, drying for 8.5 hours at 100 ℃, stirring and uniformly mixing to perform esterification reaction, wherein the molar ratio of the total amount of the polyethylene glycol and the 1, 3-propanediol to the terephthalic acid is 1:1.6 to obtain a molten mixture, adding an organic tin catalyst in the reaction process, and stirring to react to obtain a polybutylene terephthalate-polyol block copolymer, wherein the molecular weight of a block polyether chain segment is 2000; the temperature of the esterification reaction is 240 ℃, the pressure of the esterification reaction is 0.3Mpa, and the esterification reaction time is 3 hours;
(2) in the esterification reaction process, a mixture of benzoyl peroxide, dimethyl isophthalate sodium sulfonate, maleic anhydride, a peroxide decomposition type phosphorous antioxidant and polyphosphoric acid is sequentially added, wherein the content of benzoyl peroxide is 0.005 wt% of the total amount of terephthalic acid, the molar ratio of dimethyl isophthalate sodium sulfonate to terephthalic acid is 1:0.06, the content of maleic anhydride is 1.8 wt% of polyol, and the content of a stabilizer is 0.1 wt%;
(3) the core layer is polybutylene terephthalate-polybutylene glycol, the molecular weight of the polyether chain segment is 2000, and the ratio of the core layer to the polybutylene terephthalate-polyalcohol segmented copolymer is 4: 6;
(4) stretching and spinning through a spinning assembly to obtain a composite fiber material with dyeable polyester fiber as a skin layer and poly-p-phenyl alcohol as a core layer; wherein the drawing temperature is 200 ℃, and the spinning speed is 1500 m/min.
The linear density of the composite fiber is 10.4dtex, the breaking strength is 1.28cN/dtex, the linear density is low, and the mechanical property is integrally improved; the moisture regain of the composite fiber is 2.7%, and the composite fiber can be dyed in any color. The skin-core composite fiber has no cracks between the skin and the core and has good skin-core compatibility.
Example 2
A preparation method of an anhydride modified sheath-core composite fiber comprises the following steps:
(1) mixing polyethylene glycol and 1, 3-propanediol in a mixing ratio of 2:8, adding terephthalic acid, drying at 100 ℃ for 10h in vacuum, stirring and mixing uniformly to perform esterification reaction, wherein the molar ratio of the total amount of the polyethylene glycol and the 1, 3-propanediol to the terephthalic acid is 1:1.65 to obtain a molten mixture, adding an organic tin catalyst in the reaction process, and performing stirring reaction to obtain a polybutylene terephthalate-polyol block copolymer, wherein the molecular weight of a block polyether chain segment is 3000, the temperature of the esterification reaction is 240 ℃, the pressure of the esterification reaction is 0.5Mpa, and the esterification reaction time is 3 hours;
(2) in the esterification reaction process, a mixture of di-tert-butyl peroxide, dimethyl isophthalate sodium sulfonate, maleic anhydride, peroxide decomposition type phosphorous acid antioxidant and polyphosphoric acid is sequentially added, wherein the content of the di-tert-butyl peroxide is 0.005 wt% of the total amount of terephthalic acid, the molar ratio of the dimethyl isophthalate sodium sulfonate to the terephthalic acid is 1:0.06, the content of the maleic anhydride is 1.6 wt% of polyol, and the content of the stabilizer is 0.1 wt%;
(3) the core layer is polybutylene terephthalate-polybutylene glycol, the molecular weight of the polyether chain segment is 3000, and the ratio of the core layer to the polybutylene terephthalate-polyalcohol segmented copolymer is 4: 6;
(4) stretching and spinning through a spinning assembly to obtain a composite fiber material with dyeable polyester fiber as a skin layer and poly-p-phenyl alcohol as a core layer; wherein the drawing temperature is 200 ℃, and the spinning speed is 1500 m/min.
The linear density of the composite fiber is 10.5dtex, the breaking strength is 1.25cN/dtex, the linear density is low, and the mechanical property is integrally improved; the moisture regain of the composite fiber is 2.9%, and the composite fiber can be dyed in any color. The skin-core composite fiber has no cracks between the skin and the core and has good skin-core compatibility.
Example 3
A preparation method of an anhydride modified sheath-core composite fiber comprises the following steps:
(1) mixing polyethylene glycol and 1, 3-propanediol in a mixing ratio of 2:5, adding terephthalic acid, drying at 100 ℃ for 8.5h in vacuum, stirring and uniformly mixing to perform esterification reaction, wherein the molar ratio of the total amount of the polyethylene glycol and the 1, 3-propanediol to the terephthalic acid is 1:1.6 to obtain a molten mixture, adding an organic tin catalyst in the reaction process, and stirring to perform reaction to obtain a polybutylene terephthalate-polyol block copolymer, wherein the molecular weight of a block polyether chain segment is 4000, the temperature of the esterification reaction is 240 ℃, the pressure of the esterification reaction is 0.3Mpa, and the esterification reaction time is 3 hours;
(2) in the esterification process, benzoyl peroxide, sodium dimethyl isophthalate sulfonate, maleic anhydride and a mixture of peroxide decomposition type phosphorous antioxidants and polyphosphoric acid are sequentially added, wherein the content of the benzoyl peroxide is 0.005 wt% of the total amount of the terephthalic acid, the molar ratio of the sodium dimethyl isophthalate sulfonate to the terephthalic acid is 1:0.06, the content of the maleic anhydride is 2.1 wt% of the polyhydric alcohol, and the content of the stabilizing agent is 0.1 wt%;
(3) the core layer is polybutylene terephthalate-polybutylene glycol, the molecular weight of the polyether chain segment is 4000, and the ratio of the core layer to the polybutylene terephthalate-polyalcohol segmented copolymer is 4: 6;
(4) stretching and spinning the prepared skin layer and the core layer through a spinning assembly to obtain a composite fiber material taking dyeable polyester fiber as the skin layer and poly-p-phenyl alcohol as the core layer; wherein the drawing temperature is 200 ℃, and the spinning speed is 1500 m/min.
The linear density of the composite fiber is 10.8dtex, the breaking strength is 1.28cN/dtex, the linear density is low, and the mechanical property is integrally improved; the moisture regain of the composite fiber is 2.9%, and the composite fiber can be dyed in any color. The skin-core composite fiber has no cracks between the skin and the core and has good skin-core compatibility.
In order to further illustrate that when the molecular weight of the polyether chain segments of the skin layer and the core layer is between 2000 and 4000, the performance of the prepared skin-core composite fiber is optimal, and comparative examples 1 to 3 are added; in addition, in order to highlight the influence of the anhydride modification on the performance of the sheath-core composite fiber, comparative examples 4-6 are added.
Comparative example 1
A method for preparing an anhydride modified sheath-core composite fiber, which comprises the same steps as example 1, except that in the step (1), the molecular weight of the block polyether segment of the polybutylene terephthalate-polyol block copolymer is 1000; the composite fiber prepared by the method has the advantages of linear density of 10.3dtex, breaking strength of 1.29cN/dtex, low linear density and overall improved mechanical properties. The moisture regain of the composite fiber is 1.4%, and the composite fiber can be dyed in any color. The skin-core composite fiber has no cracks between the skin and the core and has good skin-core compatibility.
Comparative example 2
The preparation method of the anhydride modified sheath-core composite fiber is the same as that in the example 2, and is characterized in that in the step (3), the core layer is polybutylene terephthalate-polybutylene glycol, the molecular weight of the polyether chain segment is 1000, and the composite fiber prepared by the method has the advantages of linear density of 10.6dtex, breaking strength of 1.28cN/dtex, low linear density and overall improved mechanical property. The moisture regain of the composite fiber is 1.5%, and the composite fiber can be dyed in any color. The skin-core composite fiber has no cracks between the skin and the core and has good skin-core compatibility.
Comparative example 3
The preparation method of the anhydride modified sheath-core composite fiber comprises the same steps as the example 3, except that in the step (1), the molecular weight of a polybutylene terephthalate-polyol block copolymer and a block polyether chain segment is 1500; in the step (3), the core layer is polybutylene terephthalate-polybutylene glycol, the molecular weight of the polyether chain segment is 1500, the moisture regain of the composite fiber prepared by the method is 1.9%, and the composite fiber can be dyed in any color.
Comparative example 4
The preparation method of the sheath-core composite fiber is the same as that in the example 1, except that no maleic anhydride is added in the step (2), and the composite fiber prepared by the method has the linear density of 10.2dtex, the breaking strength of 1.27cN/dtex, low linear density and integrally improved mechanical properties. The moisture regain of the composite fiber is 1.2%, and the composite fiber can be dyed in any color. The skin-core composite fiber has no cracks between the skin and the core and has good skin-core compatibility.
Comparative example 5
The preparation method of the sheath-core composite fiber is the same as that in the example 2, except that no maleic anhydride is added in the step (2), and the composite fiber prepared by the method has the linear density of 10.7dtex, the breaking strength of 1.29cN/dtex, low linear density and integrally improved mechanical properties. The moisture regain of the composite fiber was 1.5%. The skin-core composite fiber has no cracks between the skin and the core and has good skin-core compatibility.
Comparative example 6
The preparation method of the sheath-core composite fiber is the same as that in the example 3, except that no maleic anhydride is added in the step (2), and the composite fiber prepared by the method has the linear density of 10.6dtex, the breaking strength of 1.28cN/dtex, low linear density and integrally improved mechanical properties. The moisture regain of the composite fiber was 1.4%. Any color can be dyed. The skin-core composite fiber has no cracks between the skin and the core and has good skin-core compatibility.
In conclusion, the composite fiber prepared by the preparation method of the anhydride modified sheath-core composite fiber provided by the invention is easier to dye by introducing sodium sulfonate groups on a molecular chain; and maleic anhydride is grafted on a molecular chain by a melt grafting method, so that the molecular chain contains a hydrophilic group-COOH, the prepared modified low-melting-point polyester has good permanent moisture absorption performance, the molecular weight of a polyether chain segment is 2000-4000, the prepared copolyester has optimal hydrophilic performance and spinnability, and the fiber quality is highest.
Claims (10)
1. A preparation method of anhydride modified sheath-core composite fiber is characterized by comprising the following steps: the preparation method comprises the following steps of (1) spinning by using a polybutylene terephthalate-polyol block copolymer as a skin layer raw material and a block copolyether ester high polymer as a core layer raw material by adopting a skin-core composite spinning process to prepare a skin-core composite fiber;
the molecular weight of a block polyether chain segment in the polybutylene terephthalate-polyalcohol block copolymer is 1000-5000; the molecular weight of a polyether chain segment in the block copolyether ester high polymer is 1000-5000;
the preparation process of the polybutylene terephthalate-polyalcohol segmented copolymer comprises the following steps:
(1) stirring and uniformly mixing the polyol and the terephthalic acid after vacuum drying to obtain the product;
(2) adding an organic tin catalyst, an initiator, a modified monomer, maleic anhydride and a stabilizer into the molten mixture to carry out esterification reaction to obtain the polybutylene terephthalate-polyol segmented copolymer.
2. The method for preparing the anhydride modified sheath-core composite fiber according to claim 1, wherein the ratio of the core layer to the sheath layer is 4-6: 6-4; the molecular weight of a block polyether chain segment in the polybutylene terephthalate-polyalcohol block copolymer is 2000-4000; the molecular weight of a polyether chain segment in the block copolyether ester high polymer is 2000-4000.
3. The method for preparing the anhydride modified sheath-core composite fiber according to claim 2, wherein the block copolyether ester high polymer is one or more of polybutylene terephthalate-polybutylene glycol, polyethylene terephthalate-polyethylene glycol and polybutylene terephthalate-polyethylene glycol.
4. The method for preparing the anhydride-modified core-sheath composite fiber according to claim 3, wherein the polyol is a mixture of polyethylene glycol and 1, 3-propylene glycol; the initiator is benzoyl peroxide or di-tert-butyl peroxide; the modified monomer is dimethyl isophthalate sodium sulfonate; the stabilizer is a mixture of an antioxidant and a heat stabilizer.
5. The method for preparing the anhydride-modified core-sheath composite fiber according to claim 4, wherein the 1, 3-propanediol is synthesized biologically.
6. The method for preparing the anhydride modified sheath-core composite fiber according to claim 4, wherein in the polyol, the mixing ratio of polyethylene glycol and 1, 3-propylene glycol is 1-9: 9-1; the antioxidant is a hydrogen donating phenol antioxidant or a peroxide decomposition type phosphorous antioxidant; the heat stabilizer may be any one of phosphoric acid, polyphosphoric acid, and derivatives thereof; the mixing ratio of the antioxidant to the heat stabilizer is 1: 1-4.5.
7. The method for preparing the anhydride modified core-sheath composite fiber according to claim 1, wherein an organic antibacterial agent masterbatch is further added in the esterification reaction.
8. The method for preparing the anhydride-modified core-sheath composite fiber according to claim 7, wherein the organic antibacterial agent is polyguanidine.
9. The method for preparing the anhydride modified sheath-core composite fiber according to claim 6, wherein the molar ratio of the polyol to the terephthalic acid is 1: 1.55-1.65; the content of the initiator is 0.005-0.007 wt% of the addition amount of the terephthalic acid, the molar ratio of the modified monomer to the terephthalic acid is 1: 0.02-0.1, the content of the maleic anhydride is 1.6-2.1 wt% of the polyol, and the content of the stabilizer is 0.1-0.2 wt%;
the esterification reaction is carried out at the temperature of 240-250 ℃ and under the pressure of 0.3-0.6 Mpa for 2-4 hours.
10. The method for preparing the anhydride modified sheath-core composite fiber according to claim 9, wherein in the sheath-core composite spinning process, the drawing temperature is 150-250 ℃, and the spinning speed is 1000-2000 m/min.
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