CN105544203B - A kind of preparation method of fluorescence spandex material - Google Patents
A kind of preparation method of fluorescence spandex material Download PDFInfo
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- CN105544203B CN105544203B CN201610058749.0A CN201610058749A CN105544203B CN 105544203 B CN105544203 B CN 105544203B CN 201610058749 A CN201610058749 A CN 201610058749A CN 105544203 B CN105544203 B CN 105544203B
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
- D06M14/18—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation
- D06M14/26—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of synthetic origin
- D06M14/30—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of synthetic origin of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- 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
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- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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- 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
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- 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
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- 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
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
- D06M11/64—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with nitrogen oxides; with oxyacids of nitrogen or their salts
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/38—Polyurethanes
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Abstract
The invention belongs to spandex field of material preparation, more particularly to a kind of fluorescence modified technique to spandex material.The method being grafted first by UV surface, is used for the intermediate monomer of complex rare-earth ion, then the rare earth ion (and synergy modes) with fluorescence property is directly complexed on the spandex through above-mentioned graft modification in spandex surface grafting polymerization.In the modification spandex obtained in the present invention, smaller ligand is firmly combined with stabilization with spandex matrix, effectively increases the combination degree of rare earth and spandex matrix, effectively increases fluorescence property, regeneration is also very convenient.
Description
Technical field
The invention belongs to spandex field of material preparation, more particularly to a kind of fluorescence modified technique to spandex material.
Background technology
Spandex be polyurethane elastomeric fiber referred to as, with good elastic performance and ultimate strength, therefore be typically used to
Parachute silk, rope, filter cloth etc. are made, and is widely used in textile field.As consumer is for product comfort
It is required that improving constantly, the performance such as resilience, sweat proof, sea water resistance of spandex product far can not meet requirement, and exploitation has more
Multi-functional spandex product has been trend of the times.
Fluorescence spandex product can make textile have fluorescent effect, meet the use demand in certain field.For reality
Existing above-mentioned purpose, someone is modified using inorganic nano material to spandex material, by intercalation technique, makes layered inorganic nanometer
Material reaches nano-dispersed in macromolecule matrix, can solve the above problems to a certain extent, but the deficiency of such technique
It is：Because Van der Waals force causes the reunion of inorganic nano material between nano particle.
Rare earth element not only has stronger configurational energy in China's wide, relative low price in source, rare earth metal element
Power, and with the electronic configuration that outer electronic structure is identical, internal layer 4f electron energy levels are close, thus with general element institute nothing
The spectral quality and electromagnetic performance of method analogy.
The content of the invention
Preparation technology, the side being grafted first by UV surface are modified the invention provides a kind of fluorescence to spandex material
Method, spandex surface grafting polymerization be used for complex rare-earth ion intermediate monomer, then by with fluorescence property rare earth ion (and
Synergy modes) directly it is complexed on the spandex through above-mentioned graft modification.
Above-mentioned preparation technology's concretely comprises the following steps：
(1) preparation of intermediate monomer
6-Hydroxy-2-naphthoic acid and catalyst of triethylamine are added in dichloromethane solvent, after ice bath stirs, then
Acryloyl chloride is added dropwise into solvent, is added dropwise to complete within 1-2 hours, then ice bath react 14-18 hours after, first use Solute mass fraction
After 20% watery hydrochloric acid washing, then deionized water cleaning, after anhydrous magnesium sulfate is dried, reaction product is rotated to obtain, that is, is contained
The naphthoic acid monomer of double bond, i.e. intermediate monomer required for the present invention,
Wherein, the mol ratio of the addition of 6-Hydroxy-2-naphthoic acid and catalyst of triethylamine is 1：0.8-1.2,
The mol ratio of the addition of 6-Hydroxy-2-naphthoic acid and acryloyl chloride is 1：1.4；
(2) preparation of light trigger support type spandex
A, in pre-polymerization tank, DMAC and PTMG (polytetramethylene ether diol) are firstly added, then according to NCO/OH moles
Than the ratio for 1.4~2.0,4,4-MDI (4,4- '-diphenylmethane diisocyanate) is added, prepolymerization reaction is fully carried out,
Wherein, the polytetramethylene ether diol PTMG of selection molecular weight is 1500~2500, DMAC and PTMG consumption
(quality) is than being 0.5-0.8：1,
After B, step A reaction terminate, light trigger is added into the system of pre-polymerization tank, is sufficiently stirred for obtaining light trigger point
The uniform oligomer solution of cloth, then it is transferred to chain extension tank,
Wherein, light trigger is 2- hydroxy-2-methyl -1- phenyl -1- acetone (1173) or 1- hydroxycyclohexylphenyl first
Ketone (184),
The consumption of light trigger is 4% -6% of PTMG and 4,4-MDI mass summation in step A,
C, in chain extension tank, under low temperature (0~10 DEG C), control is added dropwise containing Diamines chain extender, monoamine terminator
The DMAC solution of mixed amine carries out chain growth, chain termination, and finally giving blending has the polyurethane urea solutions of light trigger,
Wherein, the diamines in Diamines chain extender is that the monoamine in ethylenediamine, 1,2- propane diamine, monoamine terminator is two
Methylamine, diethylamine or di-n-propylamine,
D, the polyurethane urea solutions obtained by step C (can be introduced selectively into antioxidant, ultraviolet absorber, delustring
Agent and lubricant), it is sufficiently stirred for disperseing, cures, obtains polyurethane-urea spinning solution, it is right by dry spinning system and technique
Polyurethane-urea spinning solution carry out spinneret stretching, high temperature drying, finish oil, coiling and molding, obtain that light trigger is blended
Spandex；
(3) spandex surface grafting polymerization intermediate monomer
First the intermediate monomer obtained in step (1) is dissolved in organic solvent and (obtains being dissolved with the organic of intermediate monomer
Solution), then by the spandex that the blending obtained in step (2) has light trigger be infiltrated on wherein, under ultraviolet light irradiation 5-
15min, takes out the spandex after infiltration, and successively using chloroform, ethanol, deionized water washing, vacuum drying obtains surface grafting and gathered
The spandex for having intermediate monomer is closed,
Wherein, organic solvent is DMF or chloroform, during infiltration, and blending has the spandex of light trigger and is dissolved with intermediate monomer
Organic solution between ratio be 0.5-1：10g/mL；
(4) preparation of fluorescence spandex material
The spandex that the surface grafting polymerization obtained in step (3) has intermediate monomer is fully infiltrated on to the DMF of synergy modes
In solution, the ratio of spandex and solution is 0.5-1：10g/mL, then at 40-45 DEG C when, be added dropwise thereto under stirring it is dense
Spend the DMF solution of the europium nitrate for 0.4-0.5mol/L, control europium nitrate, the 6-Hydroxy-2-naphthoic acid in step (1), collaboration
Mol ratio between part three is 1.2：1：1.4, continue stirring reaction after 30-45 minutes completion of dropping 12 hours, take out leaching
Spandex after profit, is washed using ethanol, deionized water successively, and vacuum drying obtains the spandex material of fluorescence modification,
Above-mentioned synergy modes are 2,2-bipyridyl or Phen.
The beneficial effects of the present invention are：Spandex is modified using rare earth material in the present invention, is complexed by organic ligand dilute
The mode of native ion, imparts the stronger fluorescence activity of spandex material.But if be directly complexed using complete organic ligand
Rare earth ion complex carries out fluorescence modification to spandex, because molecular structure is than larger, is grafted to spandex and there is certain difficulty,
The fluorescence property that result in the spandex material that such technique is modified is difficult further to improve, therefore is adopted in the solution of the present invention
Graft modification is carried out to spandex in advance with the small molecule organic ligand of non-complex rare-earth ion, double bond is added on spandex surface
Level of graft polymerization, will be used for complex rare-earth ionic functional group and be stably fixed to spandex surface, then have to rare earth progress complexing
Effect adds the combination degree of rare earth and spandex matrix, effectively increases fluorescence property.And the modification ammonia obtained in the present invention
Synthetic fibre realizes that regeneration is very square due to the combination of smaller ligand and the firm stable of spandex matrix, then Absorptive complex wave rare earth
Just.
Embodiment
Embodiment 1
(1) preparation of intermediate monomer
The catalyst of triethylamine of 2mol 6-Hydroxy-2-naphthoic acid and 2.4mol is added to 80ml dichloromethane solvents
In, after ice bath stirs, then 2.8mol acryloyl chloride is added dropwise into solvent, is added dropwise to complete within 2 hours, then ice bath reaction is 15 small
Shi Hou, after first being washed with Solute mass fraction for 20% watery hydrochloric acid, then deionized water cleaning, after anhydrous magnesium sulfate is dried, rotation
Reaction product is steamed to obtain, that is, obtains double bond containing naphthoic acid monomer, i.e. intermediate monomer required for the present invention,
The reaction equation of above-mentioned steps (1) substantially is
(2) preparation of light trigger support type spandex
A, in pre-polymerization tank, be firstly added DMAC and PTMG (polytetramethylene ether diol, molecular weight 1500), then according to
NCO/OH mol ratios are 1.6 ratio, add 4,4-MDI (4,4- '-diphenylmethane diisocyanate), are warming up to 50 DEG C, pre-polymerization is anti-
Answer 100min,
Wherein, DMAC and PTMG consumption (quality) is than being 0.6：1,
After B, step A reaction terminate, light trigger 2- hydroxy-2-methyl -1- phenyl -1- is added into the system of pre-polymerization tank
Acetone (1173), is sufficiently stirred for obtaining the oligomer solution that light trigger is evenly distributed, then is transferred to chain extension tank,
Wherein, the consumption of light trigger is 4% of PTMG and 4,4-MDI mass summation in step A,
C, chain extension tank is cooled to 5 DEG C, control be added dropwise chain extender ethylenediamine, the mixed amine of terminator dimethylamine DMAC it is molten
Liquid carries out chain growth, chain termination, and finally giving blending has the polyurethane urea solutions of light trigger,
The quality of the ethylenediamine of dropwise addition is 3% of PTMG and 4,4-MDI mass summation in step A, the dimethylamine of dropwise addition
Quality is 0.5% of PTMG and 4,4-MDI mass summation in step A, and the DMAC solvent qualities of dissolving mixed amine are essentially identical to
The DMAC used in step A quality,
D, the polyurethane urea solutions obtained by step C are sufficiently stirred for disperseing, are cured, obtaining polyurethane-urea spinning solution,
By dry spinning system and technique, the stretching of polyurethane-urea spinning solution progress spinneret, high temperature drying, finish are oiled, wound
Shaping, obtains being blended the spandex of light trigger；
(3) spandex surface grafting polymerization intermediate monomer
First the intermediate monomer obtained in step (1) is dissolved in organic solvent, obtains being dissolved with the organic of intermediate monomer
Solution, then the spandex that the blending obtained in step (2) has light trigger is infiltrated on wherein, blending have the spandex of light trigger with
The ratio being dissolved between the organic solution of intermediate monomer is 0.6：10g/mL, in 500mj/cm215min is irradiated under ultraviolet light,
The spandex after infiltration is taken out, successively using chloroform, ethanol, deionized water washing, vacuum drying is obtained during surface grafting polymerization has
Between monomer spandex；
(4) preparation of fluorescence spandex material
The spandex that the surface grafting polymerization obtained in step (3) has intermediate monomer is fully infiltrated on the adjacent Féraud of synergy modes
In the DMF solution of quinoline, the ratio of spandex and solution is 0.6：10g/mL, then at 45 DEG C when, be added dropwise thereto under stirring it is dense
Spend the DMF solution of the europium nitrate for 0.5mol/L, control europium nitrate, the 6-Hydroxy-2-naphthoic acid in step (1), Phen
Mol ratio between three is 1.2：1：1.4, control to continue stirring reaction after 45 minutes completion of dropping 12 hours, take out after infiltration
Spandex, successively using ethanol, deionized water wash, vacuum drying, obtain fluorescence modification spandex material.
Comparative example 1
Step (1) is as identical such as step (1) in above-mentioned embodiment 1；
The preparation of step (2) spandex：
A, in pre-polymerization tank, be firstly added DMAC and PTMG (polytetramethylene ether diol, molecular weight 1500), then according to
NCO/OH mol ratios are 1.6 ratio, add 4,4-MDI (4,4- '-diphenylmethane diisocyanate), are warming up to 50 DEG C, pre-polymerization is anti-
Answer after 100min, be transferred to chain extension tank,
Wherein, DMAC and PTMG consumption (quality) is than being 0.6：1,
B, chain extension tank is cooled to 5 DEG C, control be added dropwise chain extender ethylenediamine, the mixed amine of terminator dimethylamine DMAC it is molten
Liquid carries out chain growth, chain termination, finally gives polyurethane urea solutions,
The quality of the ethylenediamine of dropwise addition is 3% of PTMG and 4,4-MDI mass summation in step A, the dimethylamine of dropwise addition
Quality is 0.5% of PTMG and 4,4-MDI mass summation in step A, and the DMAC solvent qualities of dissolving mixed amine are essentially identical to
The DMAC used in step A quality,
C, the polyurethane urea solutions obtained by step B are sufficiently stirred for disperseing, are cured, obtaining polyurethane-urea spinning solution,
By dry spinning system and technique, the stretching of polyurethane-urea spinning solution progress spinneret, high temperature drying, finish are oiled, wound
Shaping, obtains spandex (step (2) D is identical in such as above-mentioned embodiment 1)；
(3) spandex surface grafting polymerization intermediate monomer
First the intermediate monomer obtained in step (1) is dissolved in organic solvent, obtains being dissolved with the organic of intermediate monomer
Solution, then the spandex obtained in step (2) is infiltrated on wherein, the ratio between spandex and the organic solution for being dissolved with intermediate monomer
Example is 0.6：10g/mL, and light trigger 2- hydroxy-2-methyl -1- phenyl -1- acetone is added into the organic solution simultaneously
(1173), the consumption of light trigger is 4% of PTMG and 4,4-MDI mass summation in step (2) A, in 500mj/cm2Ultraviolet light
Lower irradiation 15min, takes out the spandex after infiltration, and successively using chloroform, ethanol, deionized water washing, vacuum drying is modified
Spandex；
Step (4) is as identical such as step (4) in above-mentioned embodiment 1.
Comparative example 2
(1) preparation of organic ligand complex rare-earth ionic complex
The catalyst of triethylamine of 2mol 6-Hydroxy-2-naphthoic acid and 2.4mol is added to 80ml dichloromethane solvents
In, after ice bath stirs, then 2.8mol acryloyl chloride is added dropwise into solvent, is added dropwise to complete within 2 hours, then ice bath reaction is 15 small
Shi Hou, after first being washed with Solute mass fraction for 20% watery hydrochloric acid, then deionized water cleaning, after anhydrous magnesium sulfate is dried, rotation
Reaction product is steamed to obtain, that is, obtains double bond containing naphthoic acid monomer,
Obtained double bond containing naphthoic acid monomer is dissolved in DMF again, double bond containing naphthoic acid monomer solution is obtained,
Phen will be dissolved with and containing the DMF solution that europium nitrate concentration is 0.5mol/L, when 45 DEG C, stirring
Under be added dropwise in above-mentioned double bond containing naphthoic acid monomer solution, control europium nitrate, the 6-Hydroxy-2-naphthoic acid in step (1), neighbour
Mol ratio between phenanthroline three is 1.2：1：1.4, control to continue stirring reaction after 45 minutes completion of dropping 12 hours, obtain
Organic ligand complex rare-earth ionic complex solution；
(2) preparation of light trigger support type spandex
As step (2) in above-mentioned embodiment 1 is identical；
(3) spandex that the blending obtained in step (2) has light trigger is infiltrated on to the organic ligand obtained in step (1)
In complex rare-earth ionic complex solution, adjustment blending has the spandex and organic ligand complex rare-earth ionic complex of light trigger
Ratio between solution is 0.6：10g/mL, 45 DEG C react 12 hours, take out infiltration after spandex, successively using ethanol, go from
Sub- water washing, vacuum drying obtains the spandex material of fluorescence modification.
The fluorescence intensity of spandex is determined using XRF：
The spandex that various embodiments above, comparative example are obtained is woven into fabric according to same weaving, then will be knitted
Thing folds 4 layers and is positioned on solid support, determines voltage and is set as 400V, the slit width for exciting and launching light is set to 5nm,
Detect that obtained fluorescence intensity data is as shown in table 1：
Table 1
| Embodiment 1 | Comparative example 1 | Comparative example 2 | |
| Fluorescence intensity (F) | 146 | 105 | 121 |
The fabric that the spandex that above-described embodiment 1, comparative example 1,2 are obtained is woven into, through overheating soap lye (10%) processing (bath
Than 50：1,65 DEG C of processing 45min, cold water wash is only after detection after being dried at 60 DEG C) after, then detect that its remaining fluorescence is strong
Degree, as a result as shown in table 2：
Table 2
| Embodiment 1 | Comparative example 1 | Comparative example 2 | |
| Fluorescence intensity (F) | 138 | 89 | 106 |
Claims (9)
1. a kind of preparation method of fluorescence spandex material, it is characterised in that：The preparation method is concretely comprised the following steps
(1) preparation of intermediate monomer
6-Hydroxy-2-naphthoic acid and catalyst of triethylamine are added in dichloromethane solvent, after ice bath stirs, then to molten
Acryloyl chloride is added dropwise in agent, is added dropwise to complete within 1-2 hours, then ice bath react 14-18 hours after, be with Solute mass fraction first
After 20% watery hydrochloric acid washing, then deionized water cleaning, after anhydrous magnesium sulfate is dried, reaction product is rotated to obtain, obtains containing double bond
Naphthoic acid monomer, i.e. intermediate monomer；
(2) preparation of light trigger support type spandex
A, in pre-polymerization tank, be firstly added DMAC and PTMG, then according to NCO/OH mol ratios be 1.4~2.0 ratio, add
4,4-MDI, prepolymerization reaction is fully carried out,
After B, step A reaction terminate, light trigger is added into the system of pre-polymerization tank, is sufficiently stirred for obtaining light trigger distribution
Even oligomer solution, then it is transferred to chain extension tank,
C, in chain extension tank, under low temperature, control be added dropwise the DMAC containing Diamines chain extender, the mixed amine of monoamine terminator it is molten
Liquid carries out chain growth, chain termination, and finally giving blending has the polyurethane urea solutions of light trigger,
D, the polyurethane urea solutions obtained by step C are sufficiently stirred for disperseing, are cured, obtaining polyurethane-urea spinning solution, by
Dry spinning system and technique, polyurethane-urea spinning solution is carried out spinneret stretching, high temperature drying, finish oil, coiling and molding,
Obtain being blended the spandex of light trigger；
(3) spandex surface grafting polymerization intermediate monomer
First the intermediate monomer obtained in step (1) is dissolved in organic solvent, obtains being dissolved with the organic solution of intermediate monomer,
The spandex that the blending obtained in step (2) has light trigger is infiltrated on wherein again, in irradiating 5-15min under ultraviolet light, taken out
Spandex after infiltration, successively using chloroform, ethanol, deionized water washing, vacuum drying, obtaining surface grafting polymerization has middle single
The spandex of body；
(4) preparation of fluorescence spandex material
The spandex that the surface grafting polymerization obtained in step (3) has intermediate monomer is fully infiltrated on to the DMF solution of synergy modes
In, the ratio of spandex and solution is 0.5-1:10g/mL, then at 40-45 DEG C when, concentration be added dropwise thereto under stirring be
The DMF solution of 0.4-0.5mol/L europium nitrate, control europium nitrate, the 6-Hydroxy-2-naphthoic acid in step (1), synergy modes
Mol ratio between three is 1.2:1:1.4, continue stirring reaction after 30-45 minutes completion of dropping 12 hours, take out after infiltration
Spandex, successively using ethanol, deionized water wash, vacuum drying, obtain fluorescence modification spandex material.
2. the preparation method of fluorescence spandex material as claimed in claim 1, it is characterised in that：6- hydroxyls described in step (1)
The mol ratio of the addition of base -2- naphthoic acids and catalyst of triethylamine is 1:0.8—1.2；The 6-Hydroxy-2-naphthoic acid and third
The mol ratio of the addition of alkene acyl chlorides is 1:1.4.
3. the preparation method of fluorescence spandex material as claimed in claim 1, it is characterised in that：In step (2) described in step A
DMAC and PTMG mass ratio is 0.5-0.8:1.
4. the preparation method of fluorescence spandex material as claimed in claim 1, it is characterised in that：In step (2) described in step B
Light trigger is 2- hydroxy-2-methyl -1- phenyl -1- acetone or 1- hydroxycyclohexyl phenyl ketones, the use of the light trigger
Measure as 4% -6% of PTMG and 4,4-MDI mass summation in step A.
5. the preparation method of fluorescence spandex material as claimed in claim 1, it is characterised in that：In step (2) described in step C
Diamines in Diamines chain extender is that the monoamine in ethylenediamine, 1,2- propane diamine, the monoamine terminator is dimethylamine, diethyl
Amine or di-n-propylamine.
6. the preparation method of fluorescence spandex material as claimed in claim 1, it is characterised in that：In step (2) described in step D
It is sufficiently stirred in dispersion process, antioxidant, ultraviolet absorber, delustering agent or lubricant is added into polyurethane urea solutions.
7. the preparation method of fluorescence spandex material as claimed in claim 1, it is characterised in that：It is organic described in step (3)
Solvent is DMF or chloroform.
8. the preparation method of fluorescence spandex material as claimed in claim 1, it is characterised in that：In step (3), during infiltration, altogether
The ratio being mixed between the spandex of light trigger and the organic solution for being dissolved with intermediate monomer is 0.5-1:10g/mL.
9. the preparation method of fluorescence spandex material as claimed in claim 1, it is characterised in that：Collaboration described in step (4)
Part is 2,2-bipyridyl or Phen.
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| CN108517580B (en) * | 2018-03-14 | 2021-06-22 | 江阴中绿化纤工艺技术有限公司 | Method for recycling spandex waste liquid |
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