CN106049055B - A kind of preparation method of highly hygroscopic penetrability Sea-island Composite Fiber Synthetic Leather base fabric - Google Patents
A kind of preparation method of highly hygroscopic penetrability Sea-island Composite Fiber Synthetic Leather base fabric Download PDFInfo
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- CN106049055B CN106049055B CN201610393907.8A CN201610393907A CN106049055B CN 106049055 B CN106049055 B CN 106049055B CN 201610393907 A CN201610393907 A CN 201610393907A CN 106049055 B CN106049055 B CN 106049055B
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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
- D06M14/34—Polyamides
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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
- 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
- D06M2101/34—Polyamides
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Abstract
The invention discloses a kind of preparation methods of highly hygroscopic penetrability Sea-island Composite Fiber Synthetic Leather base fabric, first prepare sulfhydrylation Sea-island Composite Fiber Synthetic Leather base fabric, after being modified followed by vinyl collagen solution to its surface to get.After the present invention process such as impregnates, adsorbs, pads, is crosslinked, washes to sulfhydrylation Sea-island Composite Fiber Synthetic Leather base fabric using the collagen after vinyl modified, can by vinyl collagen in the form of covalent bond grafting and modifying in sulfhydrylation Sea-island Composite Fiber Synthetic Leather base fabric, the moisture absorption water vapour permeability for increasing Sea-island Composite Fiber Synthetic Leather base fabric, successfully solves the problems, such as that superfine fiber synthetic leather base cloth moisture absorption water vapour permeability is poor.The simple process, no pollution to the environment have preferable economic benefit and social benefit.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of highly hygroscopic penetrability sea-island composite fiber conjunction
At the preparation method of leather base cloth.
Background technique
Fypro active group in Sea-island Composite Fiber Synthetic Leather base fabric (ISFSLB) is seldom, with collagenous fibres
Compare, only its 10% or so, therefore the hygroscopicity of superfine fiber chemical leather and penetrability are poor.According to data: natural leather
Crust leather vapor pervious amount 700g/ (m2Left and right for 24 hours), and the vapor pervious amount of ISFSLB is only 400g/ (m2Left and right for 24 hours), it is excellent
The features such as good chemical-resistant, weatherability, is welcomed by the people, but its poor moisture absorption water vapour permeability prevents it from extensive
Applied to clothes.
The country has carried out a series of research, someone to the raising of the water vapour permeability of Sea-island Composite Fiber Synthetic Leather base fabric
The methods of research formic acid hydrolysis, sulphuric acid hydrolysis, triethanolamine hydrolysis, protease hydrolytic and pancreatin hydrolysis, close superfine fibre
Fypro in finished leather exposes more polar groups.But excessively hydrolysis can destroy the intensity of Fypro, to ask
More surface polar groups, somebody studies slightly hydrolyze with formic acid after with aluminium tannin and exposure carboxylic group coordination,
By phenolic hydroxyl group modification on Fypro, achieve the purpose that increase fiber surface polar group number.In addition, someone successively grinds
Study carefully and appropriate hydrolysis is carried out to superfine fiber synthetic leather base cloth with sulfuric acid, using glutaraldehyde as crosslinking agent, by polyamide-amide
(PAMAM) macromolecules cross-linking increases the water vapour permeability of superfine fiber synthetic leather base cloth on Fypro.It is subsequent also to use
G0.5PAMAM-COOH and G1PAMAM-COOH are modified superfine fiber synthetic leather base cloth.Somebody studies to be located in advance with sulfuric acid
Reason, using organic phosphine tanning agent FP as crosslinking agent, improves superfine fiber chemical leather on Fypro for collagen cross-linking
The penetrability of base fabric.The base fabric water vapour permeability that above method obtains all is promoted, but continues to mention to modified base fabric water vapor permeability
It rises and the exploration of mechanism of modification needs further to study.
The research model that the present invention is ISFSLB with pure Fypro (Nylon), it is right with vinyl collagen (CMA)
Fypro (Nylon-SH) after the sulfhydrylation of surface carries out grafting and modifying research, and obtains CMA grafting and modifying Fypro
(Nylon-S-CMA).On this basis, the best practice of CMA graft-polyamide fiber is applied to the grafting and modifying of ISFSLB
In research, and CMA grafting and modifying ISFSLB (ISFSLB-S-CMA) product is obtained, successfully prepares a kind of highly hygroscopic penetrability
The Sea-island Composite Fiber Synthetic Leather base fabric of energy, the simple process, no pollution to the environment have preferable economic benefit and society
Benefit.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of highly hygroscopic penetrability Sea-island Composite Fiber Synthetic Leather base fabric,
Improve the problem of sea-island composite fiber moisture absorption water vapour permeability difference.
The technical scheme adopted by the invention is as follows a kind of system of highly hygroscopic penetrability Sea-island Composite Fiber Synthetic Leather base fabric
Preparation Method is specifically implemented according to the following steps:
Step 1, sulfhydrylation Sea-island Composite Fiber Synthetic Leather base fabric (USFSLB-SH) is prepared, it is spare；
Step 2, it prepares vinyl collagen solution (CMA), it is spare；
Step 3, step 1 gained sulfhydrylation Sea-island Composite Fiber Synthetic Leather base fabric is placed in step 2 gained ethylene base rubber
In former protein solution, Fypro in Sea-island Composite Fiber Synthetic Leather base fabric (USFSLB) is carried out under ultraviolet irradiation condition
Surface grafting modification to get.
It is of the invention to be further characterized in that,
In step 1, the detailed process of Sea-island Composite Fiber Synthetic Leather base fabric sulfhydrylation are as follows:
Step 1.1: the Sea-island Composite Fiber Synthetic Leather sample cloth (about 12g ± 0.5g) of 170 × 130mm is cut, with third
Ketone ultrasonic cleaning 30min at normal temperature is put into the NaOH solution that concentration is 10% after taking-up and impregnates 1h, rushed with a large amount of water
It washes, is subsequently placed at 50 DEG C of baking oven drying；
Step 1.2: by step 1.1, treated that superfine fibre is arranged in phosphoric acid solution and the mixed liquor of formalin,
After reacting 15h at 60 DEG C, takes out and rinsed with a large amount of water, 50 DEG C dry to obtain hydroxylating Sea-island Composite Fiber Synthetic Leather base fabric
(USFSLB-OH)；
Step 1.3: hydroxylating Sea-island Composite Fiber Synthetic Leather base fabric being placed in isopropanol, then (3- is added thereto
Mercaptopropyi) trimethyoxysilane (MPS), it is then filled with nitrogen thereto, places it at 70 DEG C and reacts 12h, reaction knot
It takes out after beam, is sufficiently cleaned 3 times with isopropanol, dried in 60 DEG C of environment, obtain sulfhydrylation Sea-island Composite Fiber Synthetic Leather base
Cloth.
In step 1.2, the concentration of phosphoric acid solution is 85%, and the concentration of formalin is 37%；Phosphoric acid solution in mixed liquor
Amount ratio with formalin is 1:100~2:100.
In step 1.3, the amount ratio of hydroxylating Sea-island Composite Fiber Synthetic Leather base fabric and isopropanol is 12:100 (W/
V)；The amount ratio of hydroxylating Sea-island Composite Fiber Synthetic Leather base fabric and (3- mercaptopropyi) trimethyoxysilane is 12:0.7
(W/V)。
In step 2, the specific preparation process of vinyl collagen are as follows:
It weighs collagen to be placed in phosphate buffer solution, under the conditions of 70 DEG C ± 2 DEG C, stirs 0.5~1h, make it sufficiently
Dissolution, obtains collagen solution；It is molten that methacrylic anhydride is added drop-wise to collagen under water bath condition at a temperature of 40~60 DEG C
In liquid, 1~3h of stirring obtains vinyl collagen solution (CMA) to collagen dialysis treatment.
The number-average molecular weight of collagen is 178580；The pH of phosphate buffer solution is 7.4, collagen and phosphoric acid buffer
The amount ratio of solution is 1:8~12 (w/v)；The mass concentration of methacrylic anhydride is 94%, methacrylic anhydride and collagen egg
The amount ratio of white solution is 0.1:5~2.4:5 (V/W)；Rate of addition is 1mL/min.
Dialysis treatment process are as follows: by solution pour into trapped molecular weight be 3500D bag filter in, use deionized water as
Dialyzate, 40 DEG C ± 2 DEG C at a temperature of, dialysis for 24 hours.
In step 3, the detailed process of Fypro surface grafting modification are as follows:
Photoinitiator is taken to be added in step 2 gained vinyl collagen solution, the ultrasonic oscillation 30min at 40 DEG C,
Mixed liquor, then by step 1 sulfhydrylation Sea-island Composite Fiber Synthetic Leather base fabric be put into ultrasonic vibration 0.5 in mixed liquor~
1h rolls extra collagen (CMA) with padding machine under the pressure of 0.3MPa, is put into the ultraviolet friendship of a length of 365nm of ultraviolet light wave
Join and carry out 4~6h of ultraviolet irradiation in instrument, irradiation is 30~50kGy, is dried at a temperature of 30 DEG C ± 5 DEG C, then at 40 DEG C ± 2
DEG C water in be cleaned by ultrasonic 30min after, take out, dry to get.
Photoinitiator is ultraviolet initiator2959；Photoinitiator is dense in vinyl collagen solution
Degree is 0.005%~0.01%.
The mass ratio of sulfhydrylation Sea-island Composite Fiber Synthetic Leather base fabric and vinyl collagen solution is 1:4~5.
The invention has the advantages that being closed using the collagen after vinyl modified to sulfhydrylation sea-island composite fiber
It, can be by vinyl collagen and sulfhydrylation after the process such as being impregnated, being adsorbed, padded, is crosslinked, washed at leather base cloth
Sea-island Composite Fiber Synthetic Leather base fabric grafting, fiber surface formed space net structure, close covered fiber, preparation
The moisture absorption water vapour permeability of the composite modified Sea-island Composite Fiber Synthetic Leather base fabric of collagen enhances, and improves synthetic leather base cloth
Sanitation performance successfully solves the problems, such as that superfine fiber synthetic leather base cloth moisture absorption water vapour permeability is poor, the simple process, to environment without
Pollution has preferable economic benefit and social benefit.
Detailed description of the invention
Fig. 1 is a kind of preparation method sulfhydrylation sea of highly hygroscopic penetrability Sea-island Composite Fiber Synthetic Leather base fabric of the present invention
Influence of the formaldehyde dosage to USFSLB degree of hydroxylation in island superfine fiber synthetic leather base cloth preparation process (USFSLB-SH)；
Fig. 2 is a kind of preparation method sulfhydrylation sea of highly hygroscopic penetrability Sea-island Composite Fiber Synthetic Leather base fabric of the present invention
Influence of the MPS dosage to USFSLB degree of hydroxylation in island superfine fiber synthetic leather base cloth preparation process (USFSLB-SH)；
Fig. 3 is that difference takes in a kind of preparation method of highly hygroscopic penetrability Sea-island Composite Fiber Synthetic Leather base fabric of the present invention
Influence of the vinyl collagen of Dai Du to modified USFSLB water vapour permeability；
Fig. 4 is that a kind of preparation method difference of highly hygroscopic penetrability Sea-island Composite Fiber Synthetic Leather base fabric of the present invention replaces
Spend influence of the vinyl collagen to modified USFSLB moisture pick-up properties；
The water vapour permeability comparison that Fig. 5 is the USFSLB after distinct methods are modified；
The moisture pick-up properties comparison that Fig. 6 is the USFSLB after distinct methods are modified；
Fig. 7 is a kind of preparation method difference irradiation of highly hygroscopic penetrability Sea-island Composite Fiber Synthetic Leather base fabric of the present invention
The infrared spectrum on Fypro surface under time.
Specific embodiment
The following describes the present invention in detail with reference to the accompanying drawings and specific embodiments.
A kind of preparation method of highly hygroscopic penetrability Sea-island Composite Fiber Synthetic Leather base fabric of the present invention, specifically according to following
Step is implemented:
Step 1, the superfine fibre sample (about 12g ± 0.5g) for cutting 170 × 130mm, with acetone ultrasonic wave at normal temperature
30min is cleaned, is put into after taking-up in 10%NaOH solution and impregnates 1h, is rinsed after taking-up with a large amount of water, 50 DEG C of baking oven drying are placed in,
85% phosphoric acid solution and formalin is placed in volume ratio to be reacted in the mixed solution of 1:100~2:100 at 60 DEG C
It after 15h, takes out and is rinsed with a large amount of water, 50 DEG C dry to obtain hydroxylating Sea-island Composite Fiber Synthetic Leather base fabric (USFSLB-OH), will
USFSLB-OH is placed in isopropanol, then thereto be added (3- mercaptopropyi) trimethyoxysilane (MPS), USFSLB-OH with
The mass volume ratio 12:0.7 of MPS；Then it is filled with nitrogen into sample cup, sample cup is placed at 70 DEG C and reacts 12h, reaction knot
It takes out after beam, is sufficiently cleaned 3 times with isopropanol, drying obtains sulfhydrylation Sea-island Composite Fiber Synthetic Leather base in 60 DEG C of baking ovens
Cloth (USFSLB-SH).
Step 2, it weighs the collagen that molecular mass is 178580 to be placed in phosphate buffer solution (pH 7.4), at 70 DEG C
Under the conditions of ± 2 DEG C, 0.5~1h is stirred, it is dissolved sufficiently, obtains collagen solution；Water bath condition at a temperature of 40~60 DEG C
Lower that methacrylic anhydride is added drop-wise in collagen solution, the volume mass ratio of methacrylic anhydride and collagen is 0.1:
5~2.4:5 (mL/g), 1~3h of stirring obtain vinyl collagen solution (CMA) to collagen dialysis treatment.
Step 3, take photoinitiator (2959) the vinyl collagen solution after step 2 dialysis is added
In, after mixing, step 1 gained USFSLB-SH is put into wherein by ultrasonic oscillation 30min at 40 DEG C, then ultrasound vibration
Dynamic 0.5~1h, rolls extra collagen with padding machine under the pressure of 0.3MPa, is put into the ultraviolet of a length of 365nm of ultraviolet light wave
It is crosslinked in instrument and carries out 4~6h of ultraviolet irradiation, dry at a temperature of 30 DEG C ± 5 DEG C, be then cleaned by ultrasonic in 40 DEG C ± 2 DEG C of water
After 30min, takes out, dry.
The present invention will be described in terms of principle below:
Vinyl collagen solution is grafted the route of sulfhydrylation superfine fiber synthetic leather base cloth (USFSLB-SH) specifically such as
Under: the fabric of island-in-sea type for reacting to obtain surface sulfhydrylation with (3- mercaptopropyi) trimethyoxysilane (MPS) with USFSLB-OH is ultra-fine
Fiber synthetic leather base cloth (USFSLB-SH).Then by USFSLB-SH be put into containing certain density photoinitiator (2959) in vinyl collagen (CMA) solution (solid content 6% ± 0.5%), at 40 DEG C, ultrasound shake
After dynamic 30min, taking-up is put into UV crosslinking instrument, is carried out ultraviolet light and is caused crosslinking, and " click " reaction is completed.Crosslinking terminates
Sample is placed on afterwards in 40 DEG C of distilled water and carries out ultrasonic cleaning 30min, dried after taking-up alternative.
Using sulfydryl-alkene " click chemistry " method, by the USFSLB with sulfydryl and with the vinyl collagen of C=C key
Albumen can carry out Radical Addition under the conditions of ultraviolet light irradiation.Photoinitiator causes under the conditions of ultraviolet irradiation to be obtained
Primary group of free radicals, primary group of free radicals capture the hydrogen on sulfydryl-SH to obtain sulfydryl free radical, and it is bis- that sulfydryl free radical encounters C=C
Key carries out Radical Addition, to make collagen grafting and modifying on Fypro surface.
The present invention also tests the moisture absorption penetrability using the modified base fabric of the method for the present invention using penetrability and hygroscopicity
It can, in which:
(1) water vapour permeability of modified Sea-island Composite Fiber Synthetic Leather base fabric is expressed by static rate of perviousness, specific to survey
Examination process are as follows: take the sample of Φ 55mm, then sample be placed in climatic chamber and carries out air conditioning, air conditioning method according to
QB/T 3812.12-1999 regulation carries out, the condition of adjusting are as follows: and 20 DEG C ± 2 DEG C of temperature, relative humidity 65% ± 2%, base fabric
When weight alternation amount is no more than 0.25%, it can think to reach balance.Take 30mL distilled water in test cup after air conditioning
In, sample and rubber washer are successively put, then tightens aluminium lid, weighs moisture vapor transmission cup gross mass, and record data.Then saturating
Wet cup is put into having in the drier that relative density is the 1.84g/mL concentrated sulfuric acid, is weighed again after standing for 24 hours.
In formula:
SWVT --- static rate of perviousness, unit are the every 10 square centimeters of 24 hours [mg/10cm of milligram2It is for 24 hours] or gram every
Square meters per hour [g/m2·24h]
Δ m --- the difference that same test group zoarium weighs twice, unit are (mg)；
The difference that the same test group zoarium of Δ m' --- blank sample weighs twice, unit are (mg)；Do not do blank test
When, Δ m'=0.
A --- efficiency test area (10cm2), unit is square centimeter (cm2)；
T --- test period, unit are 24 hours (for 24 hours).
(2) modified Sea-island Composite Fiber Synthetic Leather base fabric moisture absorption performance measurement: wicking rate is that characterization is knitted
Object moisture absorption and the main indicator for leading wet ability.Sampling: length is cut not less than 250mm, the long cloth of width about 30mm is as examination
Sample.20 DEG C are put it into before test, air conditioning carries out wicking rate afterwards for 24 hours in the climatic chamber of relative humidity 65%
Measurement.
Measurement: sample is hung up, and is immersed in the beaker containing mixing test solution away from bottom end 15mm, observation and metering liquid
Rise time used in 30mm height, unit, s from liquid level along sample.It is measured by wicking rate, liquid passes through capillary
Pipe effect, the wicking height that the unit time reaches on textile material.
Embodiment 1
Step 1, the super superfine fibre sample (about 12g ± 0.5g) of 170 × 130mm is cut, it is ultrasonic at normal temperature with acetone
Wave cleans 30min, is put into 10%NaOH solution after taking-up and impregnates 1h, is rinsed after taking-up with a large amount of water, is placed in 50 DEG C of baking ovens and dries
It is dry, 85% phosphoric acid solution and formalin is placed in volume ratio as in the mixed solution of 1:100, after reacting 15h at 60 DEG C,
It takes out and is rinsed with a large amount of water, 50 DEG C of drying obtain hydroxylating superfine fibre (USFSLB-OH), the superfine fibre after hydroxylating is set
In in the sample cup of 100mL isopropanol, 0.7mLMPS is added, is then filled with nitrogen into sample cup, sample cup is placed in 70 DEG C
Lower reaction 12h, takes out after reaction, is sufficiently cleaned 3 times with isopropanol, and drying obtains sulfhydrylation fabric of island-in-sea type in 60 DEG C of baking ovens
Superfine fiber synthetic leather base cloth.
Step 2, the collagen 5.0g that number average molecular weight is 178580 is weighed, 50mL phosphate buffer solution (pH is placed in
7.4) in, 0.5h is stirred, it is dissolved sufficiently, obtains collagen solution；By 0.1mL methyl under water bath condition at a temperature of 40 DEG C
Acrylic anhydride is added drop-wise in gained collagen solution with 1mL/min rate, is stirred 2h, is obtained vinyl collagen solution；It will
Vinyl collagen solution is placed in the bag filter of molecular size range 3500D, uses deionized water as dialyzate, in 40 DEG C of temperature
The lower dialysis of degree for 24 hours, degree of substitution be 15% vinyl collagen (CMA).
Step 3, the concentration by photoinitiator in CMA solution be 0.005%, weigh photoinitiator (
2959) be added step 2 dialysis after vinyl collagen solution in, at 40 DEG C ultrasonic oscillation 30min after mixing,
Step 1 gained USFSLB-SH is put into wherein, subsequent ultrasonic vibration 0.5h, it is extra to be rolled under the pressure of 0.3MPa with padding machine
Collagen is put into progress ultraviolet irradiation 4h in the UV crosslinking instrument of a length of 365nm of ultraviolet light wave, dries at a temperature of 30 DEG C,
Then it after being cleaned by ultrasonic 30min in 40 DEG C of water, takes out, dries.
Embodiment 2
Step 1, the super superfine fibre sample (about 12g ± 0.5g) of 170 × 130mm is cut, it is ultrasonic at normal temperature with acetone
Wave cleans 30min, is put into 10%NaOH solution after taking-up and impregnates 1h, is rinsed after taking-up with a large amount of water, is placed in 50 DEG C of baking ovens and dries
It is dry, 85% phosphoric acid solution and formalin is placed in volume ratio as in the mixed solution of 2:100, after reacting 15h at 60 DEG C,
It takes out and is rinsed with a large amount of water, 50 DEG C of drying obtain hydroxylating superfine fibre (USFSLB-OH), the superfine fibre after hydroxylating is set
In in the sample cup of 100mL isopropanol, 0.7mLMPS is added, is then filled with nitrogen into sample cup, sample cup is placed in 70 DEG C
Lower reaction 12h, takes out after reaction, is sufficiently cleaned 3 times with isopropanol, and drying obtains sulfhydrylation fabric of island-in-sea type in 60 DEG C of baking ovens
Superfine fiber synthetic leather base cloth.
Step 2, the collagen 5.0g that number average molecular weight is 178580 is weighed, 50mL phosphate buffer solution (pH is placed in
7.4) in, 0.5h is stirred, it is dissolved sufficiently, obtains collagen solution；By 0.3mL methyl under water bath condition at a temperature of 40 DEG C
Acrylic anhydride is added drop-wise in gained collagen solution with 1mL/min rate, is stirred 3h, is obtained modified collagen solution；
Modified collagen solution is placed in the bag filter of molecular size range 3500D, uses deionized water as dialyzate, 40
Dialyse at a temperature of DEG C for 24 hours, degree of substitution be 50% vinyl collagen (CMA).
Step 3, the concentration by photoinitiator in CMA solution be 0.006% weigh photoinitiator (
2959) in the vinyl collagen solution after step 2 dialysis is added, the ultrasonic oscillation 30min at 40 DEG C, with step 1
USFSLB-SH is uniformly mixed, and subsequent ultrasonic vibration 0.5h rolls extra collagen with padding machine under the pressure of 0.3MPa, puts
Enter progress ultraviolet irradiation 6h in the UV crosslinking instrument of a length of 365nm of ultraviolet light wave, is dried at a temperature of 30 DEG C, then at 40 DEG C
After being cleaned by ultrasonic 30min in water, takes out, dry.
Embodiment 3
Step 1, the super superfine fibre sample (about 12g ± 0.5g) of 170 × 130mm is cut, it is ultrasonic at normal temperature with acetone
Wave cleans 30min, is put into 10%NaOH solution after taking-up and impregnates 1h, is rinsed after taking-up with a large amount of water, is placed in 50 DEG C of baking ovens and dries
It is dry, 85% phosphoric acid solution and formalin is placed in volume ratio to react 15h at 60 DEG C in the mixed solution of 1.5:100
Afterwards, it takes out and is rinsed with a large amount of water, 50 DEG C of drying obtain hydroxylating superfine fibre (USFSLB-OH), by the ultra-fine fibre after hydroxylating
Dimension is placed in the sample cup of 100mL isopropanol, and 0.7mLMPS is added, is then filled with nitrogen into sample cup, sample cup is placed in
12h is reacted at 70 DEG C, is taken out after reaction, is sufficiently cleaned 3 times with isopropanol, and drying obtains sulfhydrylation sea in 60 DEG C of baking ovens
Island superfine fiber synthetic leather base cloth.
Step 2, the collagen 5.0g that number average molecular weight is 178580 is weighed, 50mL phosphate buffer solution (pH is placed in
7.4) in, 0.5h is stirred, it is dissolved sufficiently, obtains collagen solution；By 1.2mL methyl under water bath condition at a temperature of 40 DEG C
Acrylic anhydride is added drop-wise in gained collagen solution with 1mL/min rate, is stirred 1h, is obtained modified collagen solution；
Modified collagen solution is placed in the bag filter of molecular size range 3500D, uses deionized water as dialyzate, 40
Dialyse at a temperature of DEG C for 24 hours, degree of substitution be 73% vinyl collagen (CMA).
Step 3, the concentration by photoinitiator in CMA solution be 0.01% weigh photoinitiator (2959)
It, will be obtained by step 1 at 40 DEG C after ultrasonic oscillation 30min in vinyl collagen solution after step 2 dialysis is added
USFSLB-SH is put into wherein, and subsequent ultrasonic vibration 0.5h rolls extra collagen with padding machine under the pressure of 0.3MPa, puts
Enter progress ultraviolet irradiation 4h in the UV crosslinking instrument of a length of 365nm of ultraviolet light wave, is dried at a temperature of 30 DEG C, then at 40 DEG C
After being cleaned by ultrasonic 30min in water, takes out, dry.
Embodiment 4
Step 1, the super superfine fibre sample (about 12g ± 0.5g) of 170 × 130mm is cut, it is ultrasonic at normal temperature with acetone
Wave cleans 30min, is put into 10%NaOH solution after taking-up and impregnates 1h, is rinsed after taking-up with a large amount of water, is placed in 50 DEG C of baking ovens and dries
It is dry, 85% phosphoric acid solution and formalin is placed in volume ratio as in the mixed solution of 1:100, after reacting 15h at 60 DEG C,
It takes out and is rinsed with a large amount of water, 50 DEG C of drying obtain hydroxylating superfine fibre (USFSLB-OH), the superfine fibre after hydroxylating is set
In in the sample cup of 100mL isopropanol, 0.7mLMPS is added, is then filled with nitrogen into sample cup, sample cup is placed in 70 DEG C
Lower reaction 12h, takes out after reaction, is sufficiently cleaned 3 times with isopropanol, and drying obtains sulfhydrylation fabric of island-in-sea type in 60 DEG C of baking ovens
Superfine fiber synthetic leather base cloth.
Step 2, the collagen 5.0g that number average molecular weight is 178580 is weighed, 50mL phosphate buffer solution (pH is placed in
7.4) in, 0.5h is stirred, it is dissolved sufficiently, obtains collagen solution；By 1.8mL methyl under water bath condition at a temperature of 40 DEG C
Acrylic anhydride is added drop-wise in gained collagen solution with 1mL/min rate, is stirred 2h, is obtained modified collagen solution；
Modified collagen solution is placed in the bag filter of molecular size range 3500D, uses deionized water as dialyzate, 40
Dialyse at a temperature of DEG C for 24 hours, degree of substitution be 83% vinyl collagen (CMA).
Step 3, taking concentration of the photoinitiator in CMA solution is 0.006%.Weigh photoinitiator (
2959) in the vinyl collagen solution after step 2 dialysis is added, at 40 DEG C after ultrasonic oscillation 30min, by step 1
Gained USFSLB-SH is put into wherein, and subsequent ultrasonic vibration 0.5h rolls extra collagen egg with padding machine under the pressure of 0.3MPa
It is white, it is put into progress ultraviolet irradiation 5h in the UV crosslinking instrument of a length of 365nm of ultraviolet light wave, dries at a temperature of 30 DEG C, then exists
After being cleaned by ultrasonic 30min in 40 DEG C of water, takes out, dry.
Embodiment 5
Step 1, the super superfine fibre sample (about 12g ± 0.5g) of 170 × 130mm is cut, it is ultrasonic at normal temperature with acetone
Wave cleans 30min, is put into 10%NaOH solution after taking-up and impregnates 1h, is rinsed after taking-up with a large amount of water, is placed in 50 DEG C of baking ovens and dries
It is dry, 85% phosphoric acid solution and formalin is placed in volume ratio as in the mixed solution of 1:100, after reacting 15h at 60 DEG C,
It takes out and is rinsed with a large amount of water, 50 DEG C of drying obtain hydroxylating superfine fibre (USFSLB-OH), the superfine fibre after hydroxylating is set
In in the sample cup of 100mL isopropanol, 0.7mLMPS is added, is then filled with nitrogen into sample cup, sample cup is placed in 70 DEG C
Lower reaction 12h, takes out after reaction, is sufficiently cleaned 3 times with isopropanol, and drying obtains sulfhydrylation fabric of island-in-sea type in 60 DEG C of baking ovens
Superfine fiber synthetic leather base cloth.
Step 2, the collagen 5.0g that number average molecular weight is 178580 is weighed, 50mL phosphate buffer solution (pH is placed in
7.4) in, 0.5h is stirred, it is dissolved sufficiently, obtains collagen solution；By 1.5mL methyl under water bath condition at a temperature of 40 DEG C
Acrylic anhydride is added drop-wise in gained collagen solution with 1mL/min rate, is stirred 2h, is obtained modified collagen solution；
Modified collagen solution is placed in the bag filter of molecular size range 3500D, uses deionized water as dialyzate, 40
Dialyse at a temperature of DEG C for 24 hours, degree of substitution be 79% vinyl collagen (CMA).
Step 3, the concentration by photoinitiator in CMA solution be 0.01% weigh photoinitiator (2959)
In vinyl collagen solution after step 2 dialysis is added, ultrasonic oscillation 30min after mixing, will be walked at 40 DEG C
Rapid 1 gained USFSLB-SH is put into wherein, and subsequent ultrasonic vibration 0.5h rolls extra collagen with padding machine under the pressure of 0.3MPa
Albumen is put into progress ultraviolet irradiation 4h in the UV crosslinking instrument of a length of 365nm of ultraviolet light wave, dries at a temperature of 30 DEG C, then
After being cleaned by ultrasonic 30min in 40 DEG C of water, takes out, dry.
As shown in Figure 1, in the increase USFSLB of formaldehyde dosage hydroxyl quantity increasing, when formaldehyde dosage be 100mL
When, hydroxyl quantity in USFSLB is close to maximum value.When being further continued for increasing formaldehyde dosage, the hydroxyl quantity in USFSLB is also no longer
Increase, tends to be constant.I.e. formaldehyde dosage is 100mL, and measured absorbance is 0.5909, calculates to modify on 12gUSFSLB
There are about the hydroxyl of 0.1335mmol.Fig. 2 is influence of the dosage of MPS to USFSLB sulfhydrylation degree.As shown in Figure 2, with
The increase of MPS dosage, sulfydryl quantity is increasing in USFSLB, the mercapto when MPS dosage is between 0.5~0.7mL, in USFSLB
Base content is most.MPS dosage about 0.5~0.7mL, corresponding absorbance value are 0.704~0.707, calculate to obtain 12gUSFSLB
There are about the sulfydryls of 0.902~0.9145mmol in upper modification.Because 12gUSFSLB-OH surface hydroxyl number is about 0.1335mmol,
Sulfydryl is 8:1~9:1 with react molar ratio (SH/OH) of hydroxyl on supposition USFSLB, i.e. is connected with 8~9 mercaptos on 1 hydroxyl
Base.
Fig. 3 is influence of the degree of substitution to the static rate of perviousness (SWVT) of USFSLB-S-CMA of CMA.It can be seen that
The static rate of perviousness of USFSLB-S-CMA reduces afterwards as the increase of degree of substitution first increases.The USFSLB- when degree of substitution is 50%
The static water vapour permeability of S-CMA preferably (2221.5g/m2For 24 hours), with unmodified USFSLB (1554.7g/m2It compares for 24 hours)
43% is improved compared with SWVT value.This is because the C=C quantity with the increase of vinyl collagen degree of substitution, on strand
More, under the conditions of ultraviolet irradiation, sulfydryl (- SH) on the surface USFSLB-SH is reacted with unsaturation C=C key addition polymerization
Efficiency is higher, and the collagen amount of USFSLB-SH surface grafting crosslinking is more, and a large amount of hydrophilic radical on collagen makes
The water vapour permeability of USFSLB gets a promotion.But when the degree of substitution of CMA is increasing, the water vapour permeability of USFSLB-S-CMA is anti-
And it reduces.This may be because, on the one hand, the detection of static water vapour permeability be measurement under certain temperature humidity USFSLB-S-
CMA is in the weight that interior steam is penetrated and discharged for 24 hours.And the CMA film around Fypro is attached to the absorption energy of water
Power is very strong, in contrast, possesses ability also very by force to vapour molecule.So after steam is quickly absorbed,
There is no so fast largely to discharge, therefore the weight of penetrability detection combination body does not significantly reduce, so as to cause
The value variation of SWVT is unobvious.On the other hand, the penetrability of fabric is a small amount of gaseous state moisture of evaporation because the water inside and outside fabric steams
Draught head and to external diffusion and migrated to outer space by interfibrous gap.So penetrability may depend primarily on material
Microcellular structure, the followed by quantity of polar group.Therefore the degree of substitution for working as CMA is bigger, the C=C on collagen molecules chain
Key is more and more, and the sulfydryl on the surface USFSLB-SH is further increased with C=C key reaction efficiency, while vinyl collagen
Between the contact probability of C=C key also increase, be also cross-linked with each other reaction between collagen, generates continuous network structure, causes
The amount for being grafted to the collagen on fiber surface increases, and occupies original fibre gap, leads to the moisture-inhibiting of USFSLB-S-CMA
Performance decline.
Fig. 4 is influence of the CMA degree of substitution to the wicking rate (LWR) of USFSLB-S-CMA.As shown in figure, with
The LWR of the increase of CMA degree of substitution, USFSLB-S-CMA is increasing sharply, when degree of substitution is 73%, the liquid of USFSLB-S-CMA
Body wicking rate is up to 0.597mm/s.Increase compared with the wicking rate (0.085mm/s) of unmodified USFSLB
602.4%.When degree of substitution is 50%, the static penetrability maximum (2221.5g/m of USFSLB-S-CMA2For 24 hours), but liquid
Body wicking rate is not maximum (0.364mm/s).It was found that penetrability is poor instead greatly for degree of substitution, but hygroscopicity is fine.Experiment is
Verified, the amount for the collagen that the big CMA of degree of substitution is grafted in the fibre is more, and the CMA that degree of substitution is 73% is in fiber
The amount of the collagen of upper grafting is more than the CMA that degree of substitution is 50%.This illustrate USFSLB-S-CMA hygroscopicity promoted with
How much collagen amount has relationship, i.e. the collagen amount of fiber surface grafting is more, and the hygroscopicity of USFSLB-S-CMA is got over
It is good.This may be because the hygroscopicity of fabric is that fiber surface of the most of gaseous state moisture of evaporation in fabric condenses into liquid
State water and a large amount of sweat of human body discharge suck fabric with liquid water, then are diffused into fabric surface evaporation discharge.Simultaneously
Polar group on collagen has compatibility to hydrone, and in the state of having liquid water, collagen amount is more, corresponding parent
Aqueous group is more, and water absorbing properties are stronger, so that the moisture pick-up properties of performance is better.Speculate the moisture absorption of USFSLB
Property depends primarily on the quantity of the polar group inside it.
Figures 5 and 6 are the penetrability (SWVT) and hygroscopicity (LWR) of the USFSLB under different modifying method respectively.For not
Same method of modifying, USFSLB surface hydroxylation (USFSLB-OH), surface sulfhydrylation (USFSLB-SH), CMA coating modification
USFSLB (USFSLB/CMA) compares its maximum penetrability and hygroscopicity with CMA grafting and modifying USFSLB (USFSLB-S-CMA)
Comparison is as illustrated in Figures 5 and 6.Compared with unmodified USFSLB, the SWVT of USFSLB-OH improves 28.7%, LWR and improves
208.2%；The SWVT of USFSLB-SH, which improves 14.4%, LWR, but reduces 67%；The SWVT of USFSLB/CMA is improved
32.6%, LWR improve about 477.7%；The SWVT of USFSLB-S-CMA improves 43%, LWR and improves 602.4%.SWVT
The water vapour permeability of material is mainly reflected, and LWR reflects the moisture pick-up properties of material.USFSLB is modified in vinyl collagen
During find, the moisture absorption water vapour permeability of USFSLB/CMA and USFSLB-S-CMA have a distinct increment, and USFSLB-S-
The moisture absorption penetrability of CMA is better than USFSLB/CMA.
Fig. 7 is infrared spectrum of the sulfhydrylation Fypro without collagen grafting and modifying, and b, c, d are purple respectively in figure
The infrared spectrum of resulting collagen grafting and modifying sulfhydrylation polyamide under outer smooth irradiation time 3h, 4h, 5h.In Fig. 7-a,
3296cm-1The peak at place is the stretching vibration peak of N-H in polyamide molecule, with the increase of irradiation time, when irradiation time reaches 4h
When (such as Fig. 7-c), peak shape herein broadens, this is because a part of CMA and sulfydryl react and be grafted to Fypro
Surface, hydrogen bond association has occurred in the presence of a large amount of N-H in CMA, so that peak shape broadens.When irradiation time reaches 5h
(such as Fig. 7-d), respectively in 3232cm-1And 3340cm-1There are two big Bao Feng in place, this is from secondary acyl in collagen
The stretching vibration peak of N-H (containing hydrogen bond) on amine and primary amide, in addition, depositing due to primary amine relatively large number of in collagen
In lower wave number area 900cm-1~650cm-1Between have appearance, this is N-H out-of-plane deformation vibration peak, but due to by hydrogen bond
Influence, peak shape disperses.Thus it proves, vinyl collagen C=C and sulfydryl react and be successfully grafted to polyamide
On fiber surface.
Claims (10)
1. a kind of preparation method of highly hygroscopic penetrability Sea-island Composite Fiber Synthetic Leather base fabric, which is characterized in that specifically according to
Following steps are implemented:
Step 1, sulfhydrylation Sea-island Composite Fiber Synthetic Leather base fabric is prepared, it is spare；
Step 2, vinyl collagen solution is prepared, it is spare；
Step 3, step 1 gained sulfhydrylation Sea-island Composite Fiber Synthetic Leather base fabric is placed in step 2 gained vinyl collagen egg
In white solution, Fypro surface grafting in Sea-island Composite Fiber Synthetic Leather base fabric is carried out under ultraviolet irradiation condition and is repaired
Decorations to get.
2. a kind of preparation method of highly hygroscopic penetrability Sea-island Composite Fiber Synthetic Leather base fabric according to claim 1,
It is characterized in that, in step 1, the detailed process of Sea-island Composite Fiber Synthetic Leather base fabric sulfhydrylation are as follows:
Step 1.1: cutting the Sea-island Composite Fiber Synthetic Leather sample cloth of 170 × 130mm, ultrasonic wave is clear at normal temperature with acetone
30min is washed, is put into after taking-up in the NaOH solution that concentration is 10% and impregnates 1h, rinsed with a large amount of water, be subsequently placed at 50 DEG C of baking ovens
Drying；
Step 1.2: by step 1.1, treated that superfine fibre is arranged in phosphoric acid solution and the mixed liquor of formalin, 60
After reacting 15h at DEG C, takes out and rinsed with a large amount of water, 50 DEG C dry to obtain hydroxylating Sea-island Composite Fiber Synthetic Leather base fabric；
Step 1.3: hydroxylating Sea-island Composite Fiber Synthetic Leather base fabric being placed in isopropanol, then (3- sulfydryl is added thereto
Propyl) trimethyoxysilane, it is then filled with nitrogen thereto, places it at 70 DEG C and reacts 12h, take out after reaction,
It is sufficiently cleaned 3 times with isopropanol, is dried in 60 DEG C of environment, obtain sulfhydrylation Sea-island Composite Fiber Synthetic Leather base fabric.
3. a kind of preparation method of highly hygroscopic penetrability Sea-island Composite Fiber Synthetic Leather base fabric according to claim 2,
It is characterized in that, the concentration of phosphoric acid solution is 85% in step 1.2, the concentration of formalin is 37%；Phosphoric acid is molten in mixed liquor
Liquid and the amount ratio of formalin are 1:100~2:100.
4. a kind of preparation method of highly hygroscopic penetrability Sea-island Composite Fiber Synthetic Leather base fabric according to claim 2,
It is characterized in that, the amount ratio of hydroxylating Sea-island Composite Fiber Synthetic Leather base fabric and isopropanol is 12:100 in step 1.3；
The amount ratio of hydroxylating Sea-island Composite Fiber Synthetic Leather base fabric and (3- mercaptopropyi) trimethyoxysilane is 12:0.7.
5. a kind of preparation method of highly hygroscopic penetrability Sea-island Composite Fiber Synthetic Leather base fabric according to claim 1,
It is characterized in that, in step 2, the specific preparation process of vinyl collagen are as follows:
It weighs collagen to be placed in phosphate buffer solution, under the conditions of 70 DEG C ± 2 DEG C, stirs 0.5~1h, keep it sufficiently molten
Solution, obtains collagen solution；Methacrylic anhydride is added drop-wise to collagen solution under water bath condition at a temperature of 40~60 DEG C
In, 1~3h of stirring obtains vinyl collagen solution to collagen dialysis treatment.
6. a kind of preparation method of highly hygroscopic penetrability Sea-island Composite Fiber Synthetic Leather base fabric according to claim 5,
It is characterized in that, the number-average molecular weight of the collagen is 178580；The pH of phosphate buffer solution be 7.4, collagen with
The amount ratio of phosphate buffer solution is 1:8~12；The mass concentration of methacrylic anhydride is 94%, methacrylic anhydride and collagen
The amount ratio of protein solution is 0.1:5~2.4:5；Rate of addition is 1mL/min.
7. a kind of preparation method of highly hygroscopic penetrability Sea-island Composite Fiber Synthetic Leather base fabric according to claim 5,
It is characterized in that, dialysis treatment process are as follows: pour into solution in the bag filter that trapped molecular weight is 3500D, use deionized water
As dialyzate, 40 DEG C ± 2 DEG C at a temperature of, dialysis is for 24 hours.
8. a kind of preparation method of highly hygroscopic penetrability Sea-island Composite Fiber Synthetic Leather base fabric according to claim 1,
It is characterized in that, in step 3, the detailed process of Fypro surface grafting modification are as follows:
Photoinitiator is taken to be added in step 2 gained vinyl collagen solution, the ultrasonic oscillation 30min at 40 DEG C is obtained mixed
Liquid is closed, step 1 sulfhydrylation Sea-island Composite Fiber Synthetic Leather base fabric is then put into 0.5~1h of ultrasonic vibration in mixed liquor,
Extra collagen is rolled with padding machine under the pressure of 0.3MPa, is put into the UV crosslinking instrument of a length of 365nm of ultraviolet light wave and carries out
4~6h of ultraviolet irradiation is dried at a temperature of 30 DEG C ± 5 DEG C, after being then cleaned by ultrasonic 30min in 40 DEG C ± 2 DEG C of water, is taken
Out, dry to get.
9. a kind of preparation method of highly hygroscopic penetrability Sea-island Composite Fiber Synthetic Leather base fabric according to claim 8,
It is characterized in that, the photoinitiator is ultraviolet initiator2959；Light draws in vinyl collagen solution
The concentration for sending out agent is 0.005%~0.01%.
10. a kind of preparation method of highly hygroscopic penetrability Sea-island Composite Fiber Synthetic Leather base fabric according to claim 8,
It is characterized in that, the mass ratio of the sulfhydrylation Sea-island Composite Fiber Synthetic Leather base fabric and vinyl collagen solution is 1:
4~5.
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