CN112359439A - Preparation method of high-elongation low-modulus polyurethane elastic fiber - Google Patents
Preparation method of high-elongation low-modulus polyurethane elastic fiber Download PDFInfo
- Publication number
- CN112359439A CN112359439A CN202011346750.6A CN202011346750A CN112359439A CN 112359439 A CN112359439 A CN 112359439A CN 202011346750 A CN202011346750 A CN 202011346750A CN 112359439 A CN112359439 A CN 112359439A
- Authority
- CN
- China
- Prior art keywords
- isocyanate
- solution
- elastic fiber
- polyurethane elastic
- terminated prepolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 62
- 239000004814 polyurethane Substances 0.000 title claims abstract description 62
- 210000004177 elastic tissue Anatomy 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000009987 spinning Methods 0.000 claims abstract description 56
- 229920000728 polyester Polymers 0.000 claims abstract description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 31
- 229920002396 Polyurea Polymers 0.000 claims abstract description 24
- 239000002808 molecular sieve Substances 0.000 claims abstract description 24
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000001412 amines Chemical class 0.000 claims abstract description 23
- 229920000909 polytetrahydrofuran Polymers 0.000 claims abstract description 20
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 18
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000578 dry spinning Methods 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 150000002009 diols Chemical class 0.000 claims description 60
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 239000003513 alkali Substances 0.000 claims description 16
- 238000004043 dyeing Methods 0.000 claims description 13
- 239000000314 lubricant Substances 0.000 claims description 13
- 239000001361 adipic acid Substances 0.000 claims description 12
- 235000011037 adipic acid Nutrition 0.000 claims description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims description 11
- 230000002745 absorbent Effects 0.000 claims description 11
- 239000002250 absorbent Substances 0.000 claims description 11
- 239000003963 antioxidant agent Substances 0.000 claims description 11
- 230000003078 antioxidant effect Effects 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims description 11
- 238000004804 winding Methods 0.000 claims description 11
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 10
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 10
- XPFCZYUVICHKDS-UHFFFAOYSA-N 3-methylbutane-1,3-diol Chemical compound CC(C)(O)CCO XPFCZYUVICHKDS-UHFFFAOYSA-N 0.000 claims description 9
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 8
- 150000004985 diamines Chemical class 0.000 claims description 6
- 229940035437 1,3-propanediol Drugs 0.000 claims description 4
- ZWNMRZQYWRLGMM-UHFFFAOYSA-N 2,5-dimethylhexane-2,5-diol Chemical compound CC(C)(O)CCC(C)(C)O ZWNMRZQYWRLGMM-UHFFFAOYSA-N 0.000 claims description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- 239000004970 Chain extender Substances 0.000 claims description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- 239000002981 blocking agent Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 4
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 4
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 3
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000006068 polycondensation reaction Methods 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 description 79
- 230000000052 comparative effect Effects 0.000 description 11
- 239000005543 nano-size silicon particle Substances 0.000 description 9
- 235000012239 silicon dioxide Nutrition 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 230000007062 hydrolysis Effects 0.000 description 8
- 238000006460 hydrolysis reaction Methods 0.000 description 8
- 239000012948 isocyanate Substances 0.000 description 8
- 150000002513 isocyanates Chemical class 0.000 description 8
- 239000011550 stock solution Substances 0.000 description 8
- 239000000835 fiber Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000009941 weaving Methods 0.000 description 5
- 125000004185 ester group Chemical group 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000008186 active pharmaceutical agent Substances 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 238000004260 weight control Methods 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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Artificial Filaments (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a preparation method of high-elongation low-modulus polyurethane elastic fiber, which comprises the following steps: mixing polytetramethylene ether glycol, polyester dihydric alcohol and a molecular sieve to form a dihydric alcohol mixture; simultaneously adding a mixture of 4, 4' -diphenylmethane diisocyanate and dihydric alcohol into a first reactor, reacting at 70-80 ℃ to obtain an isocyanate-terminated prepolymer, and fully dissolving the isocyanate-terminated prepolymer in a high-speed dissolving machine by using N, N-dimethylacetamide as a solvent to obtain an isocyanate-terminated prepolymer N, N-dimethylacetamide solution; in a second reactor, chain extension is carried out on the isocyanate-terminated prepolymer N, N-dimethylacetamide solution by adopting a mixed amine N, N-dimethylacetamide solution to obtain a polyurethane-polyurea solution; adding an auxiliary agent into the polyurethane-polyurea solution, and carrying out spinning and stretching on the spinning solution by a dry spinning system to obtain the high-elongation low-modulus polyurethane elastic fiber.
Description
Technical Field
The invention belongs to a preparation method of dry-process polyurethane elastic fiber, and particularly relates to a preparation method of high-elongation low-modulus polyurethane elastic fiber.
Background
In recent years, the polyurethane elastic fiber industry in China enters a rapid development period, and along with the expansion of the capacity of the eliminated advanced capacity and the change of the pattern of leading competition of high-quality enterprises, the yield of the polyurethane elastic fiber is greatly improved, and the industrial concentration is continuously improved. However, the sudden increase of the production capacity brings the excess of the staged and structural production capacity, so that the price of the polyurethane elastic fiber is greatly lowered, and the downstream customer demand is more and more demanding. In particular, some customers have put high stretch and low modulus demands on polyurethane elastic fibers in order to reduce costs. The high-elongation low-modulus polyurethane elastic fiber has higher elongation at break and can be woven under higher draft multiple, so that under the same spinning cake weight, the obtained yarn is longer and more economical in material; but the corresponding modulus is improved along with the increase of the drafting multiple, so that the fabric has larger stress and is tense when being worn, and therefore, the modulus needs to be reduced, the modulus is proper under higher drafting, and the wearing comfort is ensured.
The polyurethane elastic fiber adopts polytetramethylene ether glycol as a soft segment, and because the regularity is good and the micro-phase separation degree of the soft segment and the hard segment is higher, the polyurethane elastic fiber can be endowed with the low-elongation high-modulus property. The polyester diol and polytetramethylene ether glycol belong to the soft polyurethane segment, and have the characteristics of low price, various varieties, easy molecular weight control and the like. Due to poor regularity, the micro-phase separation degree of soft and hard chain segments is weakened, the tensile strength and the breaking strength are increased, and the rebound resilience is reduced, so that the weaving of the polyurethane elastic fiber under high-power drafting is facilitated.
Patent 201811172376.5 adopts alicyclic polyester diol, improves the stability of polyurethane elastic fiber, and effectively solves the influence of environmental temperature and humidity change on the product performance. Patent 201210448865.5 uses a small amount of aliphatic polyester diol to reduce the setting temperature of polyurethane elastic fiber, thereby ensuring that the tissue structure of other fibers is not damaged when the polyurethane elastic fiber is set with other fibers with poor heat resistance. Patent 201510170468.X adopts aromatic polyester diol to enhance crystallinity of polyurethane elastic fiber, thereby improving strength and toughness of the product. Therefore, the introduction of the polyester diol can improve the quality of the polyurethane elastic fiber to a certain extent and endow the fiber with differentiated characteristics; however, no report on the preparation of high-elongation and low-modulus products is found.
The large amount of polyester diol is adopted to realize the large-scale production of the polyurethane elastic fiber under a large addition amount, so that the cost can be obviously reduced, the high-elongation low-modulus characteristic can be endowed, and the wide market prospect is realized. However, polyester diol is prepared by polycondensation, the water content of the product is difficult to remove, and the product is easy to react with diisocyanate to generate gel to block a spinneret plate; meanwhile, the reduction of the modulus can cause insufficient fiber tension in the channel, and doubling and hanging are caused under the condition of strong wind volume of the channel. In addition, polyester diols contain ester groups and are decomposed into acids and alcohols after hydrolysis, and the acids play a catalytic role to further promote the hydrolysis, so that the polyester diols are decomposed into small molecules, and the alkali resistance of the polyurethane elastic fibers is insufficient. Furthermore, polyester diols have a strong adhesive character and adversely affect the unwinding properties of the spinning cake. The above problems need to be overcome in the development of polyurethane elastic fibers.
In conclusion, in the production process of the polyurethane elastic fiber, a large amount of polyester diol is adopted to replace polyether diol in a high proportion, so that the production cost can be greatly reduced, the weaving of the fiber under high-power drafting can be realized, and the market share of the corresponding field can be improved. However, how to overcome the adverse effects of polyester diol on spinnability, unwinding property and hydrolysis resistance and make the polyurethane elastic fiber meet the requirements of production, weaving and dyeing and finishing needs to be further researched and developed.
Disclosure of Invention
The technical problem is as follows: the invention aims to provide a preparation method of high-elongation low-modulus polyurethane elastic fiber, which adopts a large amount of polyester diol to replace polyether diol at a high proportion, can greatly reduce the production cost and is beneficial to realizing the weaving of the fiber under high-power drafting. But the adverse effects of polyester diol on the spinnability, unwinding property and hydrolysis resistance of the polyurethane elastic fiber need to be overcome, so that the requirements of production, weaving and dyeing and finishing are met.
The technical scheme is as follows: the invention relates to a preparation method of high-elongation low-modulus polyurethane elastic fiber, which comprises the following steps:
step 1, mixing polytetramethylene ether glycol, polyester dihydric alcohol and a molecular sieve to form a dihydric alcohol mixture;
step 2, adding a mixture of 4, 4' -diphenylmethane diisocyanate and dihydric alcohol into the first reactor at the same time, placing the mixture at the temperature of 70-80 ℃, fully performing prepolymerization reaction to obtain an isocyanate-terminated prepolymer,
step 3, in a high-speed dissolving machine, adopting N, N-dimethylacetamide as a solvent to fully dissolve the isocyanate-terminated prepolymer to obtain an isocyanate-terminated prepolymer N, N-dimethylacetamide solution;
step 4, adopting a mixed amine N, N-dimethylacetamide solution to carry out chain extension on the isocyanate-terminated prepolymer N, N-dimethylacetamide solution in a second reactor to obtain a polyurethane-polyurea solution;
step 5, adding an alkali-resistant auxiliary agent and an anti-adhesion agent into the polyurethane-polyurea solution, and simultaneously optionally adding an antioxidant, an ultraviolet absorbent, a lubricant, a delustering agent and a dyeing auxiliary agent, and fully stirring, dispersing and curing to obtain a spinning solution;
and 6, feeding the spinning solution into a dry spinning system through a metering pump, carrying out spinning and stretching on the spinning solution by means of a spinneret plate, and carrying out high-temperature drying, oiling and winding forming on a channel to obtain the high-elongation low-modulus polyurethane elastic fiber.
Wherein:
the molecular weight of the polytetramethylene ether glycol is 1500-2500.
The polyester dihydric alcohol is obtained by carrying out polycondensation on branched chain dihydric alcohol, straight chain dihydric alcohol and adipic acid; the molecular weight of the polyester dihydric alcohol is 1000-2000; the molar ratio of the polytetramethylene ether glycol to the polyester glycol is 0.4: 0.6-0.6: 0.4;
the branched diol is one or more of 2, 5-dimethyl-2, 5-hexanediol, 3-methyl-1, 3-butanediol, 2-dimethyl-1, 3-propanediol, or 2-methyl-1, 3-propanediol; the straight-chain dihydric alcohol is one or more of 1, 3-propylene glycol, 1, 4-butanediol and 1, 6-hexanediol; the molar ratio of the branched chain dihydric alcohol to the straight chain dihydric alcohol is 0.4: 0.6-0.6: 0.4.
The molar ratio of the branched chain dihydric alcohol to the straight chain dihydric alcohol to the adipic acid is 0.5: 0.5-0.6: 0.4.
The molar ratio of the polytetramethylene ether glycol to the polyester diol is more than 0.4: 0.6.
The molecular sieve is one or a combination of more of a 3A molecular sieve, a 5A molecular sieve and a ZSM-5 molecular sieve; the average particle size of the molecular sieve is 300-500 nm, preferably 350 nm. The content of the molecular sieve is 0.5 to 1.0 weight percent of the dihydric alcohol mixture,
the molar ratio of the 4, 4' -diphenylmethane diisocyanate to the dihydric alcohol mixture is 1.42: 1-2.60: 1; the isocyanate-terminated prepolymer contains 1.8 to 3.5 weight percent of isocyanate group; the content of the isocyanate-terminated prepolymer in the isocyanate-terminated prepolymer N, N-dimethylacetamide solution is 35-70 wt% of the isocyanate-terminated prepolymer N, N-dimethylacetamide solution.
The content of the mixed amine in the mixed amine N, N-dimethylacetamide solution is 4-6 wt% of the mixed amine N, N-dimethylacetamide solution; the molar ratio of the amino group to the isocyanate group of the mixed amine N, N-dimethylacetamide solution to the isocyanate-terminated prepolymer is 1.00: 1-1.05: 1.
The mixed amine N, N-dimethylacetamide solution is characterized in that the mixed amine comprises diamine as a chain extender and monoamine as a chain terminator, and the diamine as the chain extender is one or more of ethylene diamine, 1, 2-propylene diamine and 2-methyl-1, 5-pentanediamine; the monoamine serving as the chain terminator is one or more of dimethylamine, diethylamine, dipropylamine, ethanolamine and diethanolamine; the molar ratio of the diamine to the amine group of the monoamine is 10: 1-20: 1.
The alkali-resistant auxiliary agent is one or a combination of nano silicon dioxide and nano titanium dioxide, and the addition amount of the alkali-resistant auxiliary agent is 0.5-1.5 wt% of the polyurethane elastic fiber; the anti-blocking agent is one or a combination of polyethylene glycol with the molecular weight of 2000 and polyvinyl alcohol with the molecular weight of 2000, and the addition amount of the anti-blocking agent is 0.1-0.2 wt% of the polyurethane elastic fiber.
Has the advantages that: compared with the prior art, the invention has the following advantages:
1. the molecular sieve can selectively absorb water molecules in the polyester dihydric alcohol, and the effect is durable and efficient, so that the water content in the polyester dihydric alcohol is effectively reduced and kept below 100ppm, thereby avoiding side reactions of gel and ensuring the spinnability; on the other hand, the molecular sieve belongs to inorganic nano powder, can play a role in reinforcement, and effectively improves the fiber rigidity, thereby avoiding doubling and hanging under the condition of strong air volume of a corridor.
2. By adding alkali-resistant auxiliaries which are easy to react with alkali such as nano silicon dioxide and nano titanium dioxide, the alkali-resistant auxiliaries can preferentially react with alkali in the subsequent alkali washing process, so that the concentration of alkali liquor around an ester group on a polyurethane main chain is greatly reduced, an ester group is protected, the polyurethane main chain is prevented from being hydrolyzed, and the polyurethane elastic fiber is ensured to have excellent mechanical properties after the subsequent alkali washing; the polyester diol is prepared from 2, 5-dimethyl-2, 5-hexanediol, 3-methyl-1, 3-butanediol, 2-dimethyl-1, 3-propanediol or 2-methyl-1, 3-propanediol and other branched chain diols, and the contained branched chain can form isolation between an ester group and water molecules and inhibit hydrolysis, so that the hydrolysis resistance of the polyurethane elastic fiber in the using process is improved.
3. In the polyester diol, the presence of a pendant methyl group suppresses hydrolysis, but also further reduces the regularity of the polyester diol, resulting in a decrease in the degree of microphase separation of soft and hard segments, and a significant decrease in modulus. In order to ensure the regularity of the polyester diol, the polyester diol is prepared by blending a straight-chain diol such as 1, 3-propanediol, 1, 4-butanediol, or 1, 6-hexanediol. The method is a key point for preparing the polyurethane elastic fiber with excellent hydrolysis resistance and proper modulus by regulating the proportion of the branched chain diol to the straight chain diol in the polyester diol, for example, the molar ratio of the branched chain diol to the straight chain diol is 0.4: 0.6-0.6: 0.4.
4. The polyethylene glycol with the molecular weight of 2000, the polyvinyl alcohol with the molecular weight of 2000 and other organic anti-adhesion agents are matched with conventional inorganic lubricants, so that the polyurethane elastic fiber is endowed with lasting unwinding performance while good molding is ensured. Compared with inorganic lubricants, the organic anti-adhesion agent has good compatibility with polyurethane elastic fibers, is not easy to enrich on the surface of the polyurethane elastic fibers, is reasonably compounded, can ensure that the monofilament is not influenced by over-slip to form, and meanwhile, the organic anti-adhesion agent can slowly enrich on the surface, thereby solving the problem of the reduction of unwinding performance caused by the volatilization of oil.
Detailed Description
The preparation method of the high-elongation low-modulus polyurethane elastic fiber comprises the following steps:
step 1, mixing polytetramethylene ether glycol, polyester dihydric alcohol and a molecular sieve to form a dihydric alcohol mixture;
step 2, adding a mixture of 4, 4' -diphenylmethane diisocyanate and dihydric alcohol into the first reactor at the same time, placing the mixture at the temperature of 70-80 ℃, fully performing prepolymerization reaction to obtain an isocyanate-terminated prepolymer,
step 3, in a high-speed dissolving machine, adopting N, N-dimethylacetamide as a solvent to fully dissolve the isocyanate-terminated prepolymer to obtain an isocyanate-terminated prepolymer N, N-dimethylacetamide solution;
step 4, adopting a mixed amine N, N-dimethylacetamide solution to carry out chain extension on the isocyanate-terminated prepolymer N, N-dimethylacetamide solution in a second reactor to obtain a polyurethane-polyurea solution;
step 5, adding an alkali-resistant auxiliary agent and an anti-adhesion agent into the polyurethane-polyurea solution, and simultaneously optionally adding an antioxidant, an ultraviolet absorbent, a lubricant, a delustering agent and a dyeing auxiliary agent, and fully stirring, dispersing and curing to obtain a spinning solution;
and 6, feeding the spinning solution into a dry spinning system through a metering pump, carrying out spinning and stretching on the spinning solution by means of a spinneret plate, and carrying out high-temperature drying, oiling and winding forming on a channel to obtain the high-elongation low-modulus polyurethane elastic fiber.
Example 1
1. 50.00kg of polyester diol (3-methyl-1, 3-butanediol, 1, 4-butanediol, adipic acid polycondensed according to a molar ratio of 0.27:0.28:0.45, molecular weight 1800), 50.00kg of polytetramethylene ether glycol (molecular weight 1800) and 0.80kg of 5A molecular sieve are mixed to form a diol mixture;
2. simultaneously feeding 23.46kg of 4, 4' -diphenylmethane diisocyanate and 100.80kg of a diol mixture into a first reactor, reacting for 2.2h at 70 ℃ to obtain an isocyanate-terminated prepolymer, and fully dissolving the isocyanate-terminated prepolymer in a high-speed dissolving machine by using 195.53kg of N, N-dimethylacetamide as a solvent to obtain an isocyanate-terminated prepolymer N, N-dimethylacetamide solution;
3. 319.79kg of isocyanate terminated prepolymer N, N-dimethylacetamide solution and 50.40kg of mixed amine N, N-dimethylacetamide solution (including 2.18kg of ethylenediamine and 0.34kg of diethylamine) were mixed in a second reactor, and rapid stirring was performed to allow simultaneous chain growth and chain termination to occur, to prepare polyurethane-polyurea solution;
5. adding 1.29kg of nano silicon dioxide and 0.19kg of polyethylene glycol with the molecular weight of 2000 into the polyurethane-polyurea solution, simultaneously adding an antioxidant, an ultraviolet absorbent, a lubricant, a delustering agent and a dyeing auxiliary agent, and fully stirring, dispersing and curing to obtain a spinning stock solution;
6. feeding the spinning solution into a dry spinning system through a metering pump, and carrying out spinning and stretching on the spinning solution by means of a spinneret plate, wherein the specification is 30D, the spinneret plate is 3 holes with 36 heads, the upper stack temperature is 260 ℃, the lower stack temperature is 190 ℃, and the spinning speed is 800 m/min;
7. oiling according to the oiling rate of 5 wt%, and winding to form the high-elongation low-modulus polyurethane elastic fiber.
Example 2
1. 10.00kg of polyester diol (3-methyl-1, 3-butanediol, 1, 4-butanediol, adipic acid polycondensed according to a molar ratio of 0.27:0.28:0.45, molecular weight 1800), 90.00kg of polytetramethylene ether glycol (molecular weight 1800) and 0.80kg of 5A molecular sieve are mixed to form a diol mixture;
2. simultaneously feeding 23.46kg of 4, 4' -diphenylmethane diisocyanate and 100.80kg of a diol mixture into a first reactor, reacting for 2.2h at 70 ℃ to obtain an isocyanate-terminated prepolymer, and fully dissolving the isocyanate-terminated prepolymer in a high-speed dissolving machine by using 195.53kg of N, N-dimethylacetamide as a solvent to obtain an isocyanate-terminated prepolymer N, N-dimethylacetamide solution;
3. 319.79kg of isocyanate terminated prepolymer N, N-dimethylacetamide solution and 50.40kg of mixed amine N, N-dimethylacetamide solution (including 2.18kg of ethylenediamine and 0.34kg of diethylamine) were mixed in a second reactor, and rapid stirring was performed to allow simultaneous chain growth and chain termination to occur, to prepare polyurethane-polyurea solution;
5. adding 1.29kg of nano silicon dioxide and 0.19kg of polyethylene glycol with the molecular weight of 2000 into the polyurethane-polyurea solution, simultaneously adding an antioxidant, an ultraviolet absorbent, a lubricant, a delustering agent and a dyeing auxiliary agent, and fully stirring, dispersing and curing to obtain a spinning stock solution;
6. feeding the spinning solution into a dry spinning system through a metering pump, and carrying out spinning and stretching on the spinning solution by means of a spinneret plate, wherein the specification is 30D, the spinneret plate is 3 holes with 36 heads, the upper stack temperature is 260 ℃, the lower stack temperature is 190 ℃, and the spinning speed is 800 m/min;
7. oiling according to the oiling rate of 5 wt%, and winding to form the high-elongation low-modulus polyurethane elastic fiber.
Example 3
1. 60.00kg of polyester diol (2, 5-dimethyl-2, 5-hexanediol, 1, 4-butanediol, adipic acid polycondensed according to a molar ratio of 0.27:0.27:0.45, molecular weight 1800), 40.00kg of polytetramethylene ether glycol (molecular weight 1800) and 0.50kg of ZSM-5 molecular sieve are mixed to form a diol mixture;
2. simultaneously feeding 23.46kg of 4, 4' -diphenylmethane diisocyanate and 100.80kg of a diol mixture into a first reactor, reacting for 2.2h at 70 ℃ to obtain an isocyanate-terminated prepolymer, and fully dissolving the isocyanate-terminated prepolymer in a high-speed dissolving machine by using 195.53kg of N, N-dimethylacetamide as a solvent to obtain an isocyanate-terminated prepolymer N, N-dimethylacetamide solution;
3. 319.79kg of isocyanate terminated prepolymer N, N-dimethylacetamide solution and 50.40kg of mixed amine N, N-dimethylacetamide solution (including 2.18kg of ethylenediamine and 0.34kg of diethylamine) were mixed in a second reactor, and rapid stirring was performed to allow simultaneous chain growth and chain termination to occur, to prepare polyurethane-polyurea solution;
5. adding 1.29kg of nano silicon dioxide and 0.19kg of polyethylene glycol with the molecular weight of 2000 into the polyurethane-polyurea solution, simultaneously adding an antioxidant, an ultraviolet absorbent, a lubricant, a delustering agent and a dyeing auxiliary agent, and fully stirring, dispersing and curing to obtain a spinning stock solution;
6. feeding the spinning solution into a dry spinning system through a metering pump, and carrying out spinning and stretching on the spinning solution by means of a spinneret plate, wherein the specification is 30D, the spinneret plate is 3 holes with 36 heads, the upper stack temperature is 260 ℃, the lower stack temperature is 190 ℃, and the spinning speed is 800 m/min;
7. oiling according to the oiling rate of 5 wt%, and winding to form the high-elongation low-modulus polyurethane elastic fiber.
Comparative example 1
1. 50.00kg of polyester diol (3-methyl-1, 3-butanediol, 1, 4-butanediol, adipic acid polycondensed in a molar ratio of 0.27:0.28:0.45, molecular weight 1800) was mixed with 50.00kg of polytetramethylene ether glycol (molecular weight 1800) to form a diol mixture;
2. simultaneously feeding 23.46kg of 4, 4' -diphenylmethane diisocyanate and 100.80kg of a diol mixture into a first reactor, reacting for 2.2h at 70 ℃ to obtain an isocyanate-terminated prepolymer, and fully dissolving the isocyanate-terminated prepolymer in a high-speed dissolving machine by using 195.53kg of N, N-dimethylacetamide as a solvent to obtain an isocyanate-terminated prepolymer N, N-dimethylacetamide solution;
3. 319.79kg of isocyanate terminated prepolymer N, N-dimethylacetamide solution and 50.40kg of mixed amine N, N-dimethylacetamide solution (including 2.18kg of ethylenediamine and 0.34kg of diethylamine) were mixed in a second reactor, and rapid stirring was performed to allow simultaneous chain growth and chain termination to occur, to prepare polyurethane-polyurea solution;
5. adding 1.29kg of nano silicon dioxide, 0.19kg of polyethylene glycol with the molecular weight of 2000 and 0.80kg of 5A molecular sieve into the polyurethane-polyurea solution, and simultaneously adding an antioxidant, an ultraviolet absorbent, a lubricant, a delustering agent and a dyeing auxiliary agent, and fully stirring, dispersing and curing to obtain a spinning stock solution;
5. feeding the spinning solution into a dry spinning system through a metering pump, and carrying out spinning and stretching on the spinning solution by means of a spinneret plate, wherein the specification is 30D, the spinneret plate is 3 holes with 36 heads, the upper stack temperature is 260 ℃, the lower stack temperature is 190 ℃, and the spinning speed is 800 m/min;
7. oiling according to the oiling rate of 5 wt%, and winding to form the high-elongation low-modulus polyurethane elastic fiber.
Comparative example 2
1. 50.00kg of polyester diol (3-methyl-1, 3-butanediol, 1, 4-butanediol, adipic acid polycondensed according to a molar ratio of 0.27:0.28:0.45, molecular weight 1800), 50.00kg of polytetramethylene ether glycol (molecular weight 1800) and 0.80kg of 5A molecular sieve are mixed to form a diol mixture;
2. simultaneously feeding 23.46kg of 4, 4' -diphenylmethane diisocyanate and 100.80kg of a diol mixture into a first reactor, reacting for 2.2h at 70 ℃ to obtain an isocyanate-terminated prepolymer, and fully dissolving the isocyanate-terminated prepolymer in a high-speed dissolving machine by using 195.53kg of N, N-dimethylacetamide as a solvent to obtain an isocyanate-terminated prepolymer N, N-dimethylacetamide solution;
3. 319.79kg of isocyanate terminated prepolymer N, N-dimethylacetamide solution and 50.40kg of mixed amine N, N-dimethylacetamide solution (including 2.18kg of ethylenediamine and 0.34kg of diethylamine) were mixed in a second reactor, and rapid stirring was performed to allow simultaneous chain growth and chain termination to occur, to prepare polyurethane-polyurea solution;
5. adding 0.19kg of 2000-molecular-weight polyethylene glycol into the polyurethane-polyurea solution, and simultaneously adding an antioxidant, an ultraviolet absorbent, a lubricant, a delustering agent and a dyeing auxiliary agent, and fully stirring, dispersing and curing to obtain a spinning stock solution;
6. feeding the spinning solution into a dry spinning system through a metering pump, and carrying out spinning and stretching on the spinning solution by means of a spinneret plate, wherein the specification is 30D, the spinneret plate is 3 holes with 36 heads, the upper stack temperature is 260 ℃, the lower stack temperature is 190 ℃, and the spinning speed is 800 m/min;
7. oiling according to the oiling rate of 5 wt%, and winding to form the high-elongation low-modulus polyurethane elastic fiber.
Comparative example 3
1. 50.00kg of polyester diol (1, 4-butanediol, adipic acid polycondensed in a molar ratio of 0.55:0.45, molecular weight 1800), 50.00kg of polytetramethylene ether glycol (molecular weight 1800) and 0.80kg of 5A molecular sieve were mixed to form a diol mixture;
2. simultaneously feeding 23.46kg of 4, 4' -diphenylmethane diisocyanate and 100.80kg of a diol mixture into a first reactor, reacting for 2.2h at 70 ℃ to obtain an isocyanate-terminated prepolymer, and fully dissolving the isocyanate-terminated prepolymer in a high-speed dissolving machine by using 195.53kg of N, N-dimethylacetamide as a solvent to obtain an isocyanate-terminated prepolymer N, N-dimethylacetamide solution;
3. 319.79kg of isocyanate terminated prepolymer N, N-dimethylacetamide solution and 50.40kg of mixed amine N, N-dimethylacetamide solution (including 2.18kg of ethylenediamine and 0.34kg of diethylamine) were mixed in a second reactor, and rapid stirring was performed to allow simultaneous chain growth and chain termination to occur, to prepare polyurethane-polyurea solution;
5. adding 1.29kg of nano silicon dioxide and 0.19kg of polyethylene glycol with the molecular weight of 2000 into the polyurethane-polyurea solution, simultaneously adding an antioxidant, an ultraviolet absorbent, a lubricant, a delustering agent and a dyeing auxiliary agent, and fully stirring, dispersing and curing to obtain a spinning stock solution;
6. feeding the spinning solution into a dry spinning system through a metering pump, and carrying out spinning and stretching on the spinning solution by means of a spinneret plate, wherein the specification is 30D, the spinneret plate is 3 holes with 36 heads, the upper stack temperature is 260 ℃, the lower stack temperature is 190 ℃, and the spinning speed is 800 m/min;
7. oiling according to the oiling rate of 5 wt%, and winding to form the high-elongation low-modulus polyurethane elastic fiber.
Comparative example 4
1. 50.00kg of polyester diol (3-methyl-1, 3-butanediol, adipic acid polycondensed at a molar ratio of 0.55:0.45, molecular weight 1800), 50.00kg of polytetramethylene ether glycol (molecular weight 1800) and 0.80kg of 5A molecular sieve were mixed to form a diol mixture;
2. simultaneously feeding 23.46kg of 4, 4' -diphenylmethane diisocyanate and 100.80kg of a diol mixture into a first reactor, reacting for 2.2h at 70 ℃ to obtain an isocyanate-terminated prepolymer, and fully dissolving the isocyanate-terminated prepolymer in a high-speed dissolving machine by using 195.53kg of N, N-dimethylacetamide as a solvent to obtain an isocyanate-terminated prepolymer N, N-dimethylacetamide solution;
3. 319.79kg of isocyanate terminated prepolymer N, N-dimethylacetamide solution and 50.40kg of mixed amine N, N-dimethylacetamide solution (including 2.18kg of ethylenediamine and 0.34kg of diethylamine) were mixed in a second reactor, and rapid stirring was performed to allow simultaneous chain growth and chain termination to occur, to prepare polyurethane-polyurea solution;
5. adding 1.29kg of nano silicon dioxide and 0.19kg of polyethylene glycol with the molecular weight of 2000 into the polyurethane-polyurea solution, simultaneously adding an antioxidant, an ultraviolet absorbent, a lubricant, a delustering agent and a dyeing auxiliary agent, and fully stirring, dispersing and curing to obtain a spinning stock solution;
6. feeding the spinning solution into a dry spinning system through a metering pump, and carrying out spinning and stretching on the spinning solution by means of a spinneret plate, wherein the specification is 30D, the spinneret plate is 3 holes with 36 heads, the upper stack temperature is 260 ℃, the lower stack temperature is 190 ℃, and the spinning speed is 800 m/min;
7. oiling according to the oiling rate of 5 wt%, and winding to form the high-elongation low-modulus polyurethane elastic fiber.
Comparative example 5
1. 90.00kg of polyester diol (3-methyl-1, 3-butanediol, 1, 4-butanediol, adipic acid polycondensed according to a molar ratio of 0.27:0.28:0.45, molecular weight 1800), 10.00kg of polytetramethylene ether glycol (molecular weight 1800) and 0.80kg of 5A molecular sieve are mixed to form a diol mixture;
2. simultaneously feeding 23.46kg of 4, 4' -diphenylmethane diisocyanate and 100.80kg of a diol mixture into a first reactor, reacting for 2.2h at 70 ℃ to obtain an isocyanate-terminated prepolymer, and fully dissolving the isocyanate-terminated prepolymer in a high-speed dissolving machine by using 195.53kg of N, N-dimethylacetamide as a solvent to obtain an isocyanate-terminated prepolymer N, N-dimethylacetamide solution;
3. 319.79kg of isocyanate terminated prepolymer N, N-dimethylacetamide solution and 50.40kg of mixed amine N, N-dimethylacetamide solution (including 2.18kg of ethylenediamine and 0.34kg of diethylamine) were mixed in a second reactor, and rapid stirring was performed to allow simultaneous chain growth and chain termination to occur, to prepare polyurethane-polyurea solution;
5. adding 1.29kg of nano silicon dioxide and 0.19kg of polyethylene glycol with the molecular weight of 2000 into the polyurethane-polyurea solution, simultaneously adding an antioxidant, an ultraviolet absorbent, a lubricant, a delustering agent and a dyeing auxiliary agent, and fully stirring, dispersing and curing to obtain a spinning stock solution;
6. feeding the spinning solution into a dry spinning system through a metering pump, and carrying out spinning and stretching on the spinning solution by means of a spinneret plate, wherein the specification is 30D, the spinneret plate is 3 holes with 36 heads, the upper stack temperature is 260 ℃, the lower stack temperature is 190 ℃, and the spinning speed is 800 m/min;
7. oiling according to the oiling rate of 5 wt%, and winding to form the high-elongation low-modulus polyurethane elastic fiber.
The following is a comparative table of the performance results of the examples of the invention:
| spinnability | SS300/MPa | DS/MPa | DE/％ | Alkali resistance performance/%) | |
| Example 1 | Good effect | 5.38 | 8.76 | 580.37 | 67.88 |
| Example 2 | Good effect | 6.22 | 9.20 | 483.52 | 70.15 |
| Example 3 | Good effect | 5.27 | 8.58 | 585.48 | 72.13 |
| Comparative example 1 | Non-spinnable | - | - | - | - |
| Comparative example 2 | Good effect | 5.49 | 8.87 | 573.55 | 37.22 |
| Comparative example 3 | Good effect | 5.84 | 9.01 | 553.55 | 31.13 |
| Comparative example 4 | Non-spinnable | - | - | - | - |
| Comparative example 5 | Non-spinnable | - | - | - | - |
Wherein SS300 is the corresponding modulus at 300% stretching, DS is the corresponding modulus at break, DE is the corresponding elongation at break, and alkali resistance is the retention rate of the polyurethane elastic fiber DS after being soaked in 3 wt% sodium hydroxide solution for 15min at 190 ℃.
Claims (10)
1. A preparation method of high-elongation low-modulus polyurethane elastic fiber is characterized by comprising the following steps:
step 1, mixing polytetramethylene ether glycol, polyester dihydric alcohol and a molecular sieve to form a dihydric alcohol mixture;
step 2, adding a mixture of 4, 4' -diphenylmethane diisocyanate and dihydric alcohol into the first reactor at the same time, placing the mixture at the temperature of 70-80 ℃, fully performing prepolymerization reaction to obtain an isocyanate-terminated prepolymer,
step 3, in a high-speed dissolving machine, adopting N, N-dimethylacetamide as a solvent to fully dissolve the isocyanate-terminated prepolymer to obtain an isocyanate-terminated prepolymer N, N-dimethylacetamide solution;
step 4, adopting a mixed amine N, N-dimethylacetamide solution to carry out chain extension on the isocyanate-terminated prepolymer N, N-dimethylacetamide solution in a second reactor to obtain a polyurethane-polyurea solution;
step 5, adding an alkali-resistant auxiliary agent and an anti-adhesion agent into the polyurethane-polyurea solution, and simultaneously optionally adding an antioxidant, an ultraviolet absorbent, a lubricant, a delustering agent and a dyeing auxiliary agent, and fully stirring, dispersing and curing to obtain a spinning solution;
and 6, feeding the spinning solution into a dry spinning system through a metering pump, carrying out spinning and stretching on the spinning solution by means of a spinneret plate, and carrying out high-temperature drying, oiling and winding forming on a channel to obtain the high-elongation low-modulus polyurethane elastic fiber.
2. The method for preparing high-elongation low-modulus polyurethane elastic fiber according to claim 1, wherein the polytetramethylene ether glycol has a molecular weight of 1500 to 2500; the polyester dihydric alcohol is obtained by carrying out polycondensation on branched chain dihydric alcohol, straight chain dihydric alcohol and adipic acid; the molecular weight of the polyester dihydric alcohol is 1000-2000;
the molar ratio of the polytetramethylene ether glycol to the polyester diol is more than 0.4: 0.6.
3. The method of preparing high-elongation low-modulus polyurethane elastic fiber according to claim 2, wherein the branched diol is one or more of 2, 5-dimethyl-2, 5-hexanediol, 3-methyl-1, 3-butanediol, 2-dimethyl-1, 3-propanediol, or 2-methyl-1, 3-propanediol; the straight-chain dihydric alcohol is one or more of 1, 3-propylene glycol, 1, 4-butanediol and 1, 6-hexanediol; the molar ratio of the branched chain dihydric alcohol to the straight chain dihydric alcohol is 0.4: 0.6-0.6: 0.4.
4. The method for preparing the high-elongation low-modulus polyurethane elastic fiber according to claim 2, wherein the molar ratio of the branched diol to the linear diol to the adipic acid is 0.5: 0.5-0.6: 0.4.
5. The method for preparing high-elongation low-modulus polyurethane elastic fiber according to claim 2, wherein the molar ratio of polytetramethylene ether glycol to polyester diol is 0.4: 0.6-0.6: 0.4.
6. The method for preparing high-elongation low-modulus polyurethane elastic fiber according to claim 1, wherein the molecular sieve is one or more of 3A molecular sieve, 5A molecular sieve and ZSM-5 molecular sieve; the average particle size of the molecular sieve is 300-500 nm, and the content of the molecular sieve is 0.5-1.0 wt% of that of the dihydric alcohol mixture.
7. The method for preparing high-elongation low-modulus polyurethane elastic fiber according to claim 1, wherein the molar ratio of 4, 4' -diphenylmethane diisocyanate to the diol mixture is 1.42: 1-2.60: 1; the isocyanate-terminated prepolymer contains 1.8 to 3.5 weight percent of isocyanate group; the content of the isocyanate-terminated prepolymer in the isocyanate-terminated prepolymer N, N-dimethylacetamide solution is 35-70 wt% of the isocyanate-terminated prepolymer N, N-dimethylacetamide solution.
8. The method for preparing high-elongation low-modulus polyurethane elastic fiber according to claim 1, wherein the mixed amine N, N-dimethylacetamide solution has a mixed amine content of 4-6 wt% based on the mixed amine N, N-dimethylacetamide solution; the molar ratio of the amino group to the isocyanate group of the mixed amine N, N-dimethylacetamide solution to the isocyanate-terminated prepolymer is 1.00: 1-1.05: 1.
9. The method of claim 8, wherein the mixed amine solution of N, N-dimethylacetamide comprises a diamine as a chain extender in combination with a monoamine as a chain terminator, and the diamine as a chain extender is one or more selected from the group consisting of ethylenediamine, 1, 2-propylenediamine, and 2-methyl-1, 5-pentylenediamine; the monoamine serving as the chain terminator is one or more of dimethylamine, diethylamine, dipropylamine, ethanolamine and diethanolamine; the molar ratio of the diamine to the amine group of the monoamine is 10: 1-20: 1.
10. The method for preparing high-elongation low-modulus polyurethane elastic fiber according to claim 8, wherein the alkali-resistant auxiliary agent is one or more of nano silica and nano titanium dioxide, and the addition amount is 0.5-1.5 wt% of the polyurethane elastic fiber; the anti-blocking agent is one or a combination of polyethylene glycol with the molecular weight of 2000 and polyvinyl alcohol with the molecular weight of 2000, and the addition amount of the anti-blocking agent is 0.1-0.2 wt% of the polyurethane elastic fiber.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011346750.6A CN112359439A (en) | 2020-11-26 | 2020-11-26 | Preparation method of high-elongation low-modulus polyurethane elastic fiber |
| CN202111357924.3A CN114540975B (en) | 2020-11-26 | 2021-11-16 | High-elongation low-modulus polyurethane elastic fiber and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011346750.6A CN112359439A (en) | 2020-11-26 | 2020-11-26 | Preparation method of high-elongation low-modulus polyurethane elastic fiber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112359439A true CN112359439A (en) | 2021-02-12 |
Family
ID=74532945
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011346750.6A Pending CN112359439A (en) | 2020-11-26 | 2020-11-26 | Preparation method of high-elongation low-modulus polyurethane elastic fiber |
| CN202111357924.3A Active CN114540975B (en) | 2020-11-26 | 2021-11-16 | High-elongation low-modulus polyurethane elastic fiber and preparation method thereof |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111357924.3A Active CN114540975B (en) | 2020-11-26 | 2021-11-16 | High-elongation low-modulus polyurethane elastic fiber and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN112359439A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113005559A (en) * | 2021-03-05 | 2021-06-22 | 华峰重庆氨纶有限公司 | Preparation method of nano-modified spandex easy to unwind |
| CN114540975A (en) * | 2020-11-26 | 2022-05-27 | 华峰化学股份有限公司 | High-elongation low-modulus polyurethane elastic fiber and preparation method thereof |
| CN116356449A (en) * | 2021-12-28 | 2023-06-30 | 华峰化学股份有限公司 | A kind of spandex and its preparation method and application |
| CN116356450A (en) * | 2021-12-28 | 2023-06-30 | 华峰化学股份有限公司 | Polyurethane elastic fiber and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN119932761B (en) * | 2025-03-04 | 2026-01-09 | 华峰化学股份有限公司 | A low-temperature easily set composite spandex and its preparation method |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RO90210A2 (en) * | 1984-07-23 | 1986-10-30 | Combinatul De Fibre Sintetice,Ro | PROCESS FOR OBTAINING POROUS POLYACRYLONITRYLIC FIBERS |
| KR930005099B1 (en) * | 1991-07-04 | 1993-06-15 | 제일합섬 주식회사 | Manufacturing method of polyurethane elastic yarn excellent in antibacterial deodorization |
| KR19980068298A (en) * | 1997-02-17 | 1998-10-15 | 한형수 | Manufacturing method of polyurethane elastic fiber |
| KR100598870B1 (en) * | 2003-11-25 | 2006-07-10 | 태광산업주식회사 | Polyurethane urea elastic fiber with excellent heat resistance and setability and its manufacturing method |
| KR20060036972A (en) * | 2004-10-27 | 2006-05-03 | 주식회사 코오롱 | Manufacturing method of polyurethane urea elastic yarn with excellent antibacterial and deodorizing property |
| KR20070071157A (en) * | 2005-12-29 | 2007-07-04 | 주식회사 효성 | Elastic fiber having antibiotic property |
| CN101432326A (en) * | 2006-04-25 | 2009-05-13 | 巴斯夫欧洲公司 | Segmented polyurethane elastomers with high elongation at tear |
| CN100547131C (en) * | 2007-11-28 | 2009-10-07 | 吉林大学 | Method for preparing hollow molecular sieve fibers with hierarchical structure by coaxial spinning technology |
| WO2011052185A1 (en) * | 2009-10-26 | 2011-05-05 | Toray Opelontex Co., Ltd. | Polyurethane elastic yarn and production method thereof |
| CN102899740B (en) * | 2012-11-09 | 2014-05-21 | 浙江华峰氨纶股份有限公司 | Method for preparing low-temperature finalizing polyurethane elastic fiber |
| CN104178842B (en) * | 2014-08-19 | 2017-02-15 | 浙江华峰氨纶股份有限公司 | Silk-like spandex fiber and preparation method thereof |
| CN105019052B (en) * | 2015-06-29 | 2018-02-02 | 浙江华峰氨纶股份有限公司 | A kind of preparation method of high performance polyurethane elastomer |
| KR101956332B1 (en) * | 2017-07-27 | 2019-03-08 | 주식회사 나노텍세라믹스 | An additive slurry for the production of polyurethane-urea elastic fibers |
| CN112359439A (en) * | 2020-11-26 | 2021-02-12 | 华峰化学股份有限公司 | Preparation method of high-elongation low-modulus polyurethane elastic fiber |
-
2020
- 2020-11-26 CN CN202011346750.6A patent/CN112359439A/en active Pending
-
2021
- 2021-11-16 CN CN202111357924.3A patent/CN114540975B/en active Active
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114540975A (en) * | 2020-11-26 | 2022-05-27 | 华峰化学股份有限公司 | High-elongation low-modulus polyurethane elastic fiber and preparation method thereof |
| CN114540975B (en) * | 2020-11-26 | 2024-04-26 | 华峰化学股份有限公司 | High-elongation low-modulus polyurethane elastic fiber and preparation method thereof |
| CN113005559A (en) * | 2021-03-05 | 2021-06-22 | 华峰重庆氨纶有限公司 | Preparation method of nano-modified spandex easy to unwind |
| CN116356449A (en) * | 2021-12-28 | 2023-06-30 | 华峰化学股份有限公司 | A kind of spandex and its preparation method and application |
| CN116356450A (en) * | 2021-12-28 | 2023-06-30 | 华峰化学股份有限公司 | Polyurethane elastic fiber and preparation method thereof |
| CN116356450B (en) * | 2021-12-28 | 2025-03-18 | 华峰化学股份有限公司 | Polyurethane elastic fiber and preparation method thereof |
| CN116356449B (en) * | 2021-12-28 | 2025-08-12 | 华峰化学股份有限公司 | Spandex and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114540975A (en) | 2022-05-27 |
| CN114540975B (en) | 2024-04-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112359439A (en) | Preparation method of high-elongation low-modulus polyurethane elastic fiber | |
| CN103710786B (en) | A kind of preparation method of the polyurethane stock solution for high speed spinning | |
| CN104153033B (en) | A kind of preparation method of porous easy dyeing spandex | |
| CN111691000A (en) | Method for preparing polyamide 56 industrial yarn by plasticizing and melting | |
| US20060135724A1 (en) | Spandex having low heat-set temperature and materials for their production | |
| CN1301280C (en) | Polyurethane urea elastic fiber having high heat resistance and fine shape-setting and process for preparing same | |
| CN102154729B (en) | Preparation method of high-elongation and high-draft polyurethane fibers | |
| CN106592010A (en) | Preparation method and application of polyurethane elastic fiber | |
| US6637181B1 (en) | Elastane threads and method for the production thereof | |
| CN110331467A (en) | A kind of super fine denier spandex and preparation method thereof to interweave with terylene | |
| CN110318106A (en) | Thick denier spandex of a kind of high rebound and preparation method thereof | |
| CN110923844B (en) | Preparation method of spandex easy to unwind | |
| CN116356450B (en) | Polyurethane elastic fiber and preparation method thereof | |
| JP5647548B2 (en) | Polyurethane composition | |
| CN112410930A (en) | Polyurethane elastic fiber with excellent dyeing property and preparation thereof | |
| CN109868524B (en) | Melt-spun spandex slice and preparation method thereof | |
| CN110644070B (en) | Method for producing polyurethaneurea elastic fiber having antibacterial and deodorizing functions, and polyurethaneurea elastic fiber produced thereby | |
| KR100780434B1 (en) | Polyurethane Urea Elastic Fiber and Manufacturing Method Thereof | |
| CN120006407A (en) | A kind of high resilience and high strength spandex fiber and preparation method thereof | |
| KR101180508B1 (en) | Polyurethane composition for high tenacity spandex fiber, and spandex fiber prepared using the polyurethane composition | |
| CN110241473A (en) | A kind of preparation method with lasting ageing-resistant performance spandex | |
| US12325771B1 (en) | Preparation method for biobased polyurethane elastic fibers | |
| CN119465438B (en) | A high melt strength regenerated polyester fiber fine denier yarn and its production process | |
| CN111472060A (en) | Preparation method of spandex with excellent spinnability | |
| CN118326552B (en) | Composite environment-friendly vamp material and production process thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20210212 |
|
| WD01 | Invention patent application deemed withdrawn after publication |