CN106087451A - A kind of preparation method of air previous polyurethane artificial leather - Google Patents
A kind of preparation method of air previous polyurethane artificial leather Download PDFInfo
- Publication number
- CN106087451A CN106087451A CN201610721480.XA CN201610721480A CN106087451A CN 106087451 A CN106087451 A CN 106087451A CN 201610721480 A CN201610721480 A CN 201610721480A CN 106087451 A CN106087451 A CN 106087451A
- Authority
- CN
- China
- Prior art keywords
- polyether
- add
- modified silicone
- polyurethane
- artificial leather
- 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
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/147—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the isocyanates used
-
- 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
-
- 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
- C08G18/61—Polysiloxanes
-
- 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
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
- D06N3/0061—Organic fillers or organic fibrous fillers, e.g. ground leather waste, wood bark, cork powder, vegetable flour; Other organic compounding ingredients; Post-treatment with organic compounds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/146—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the macromolecular diols used
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/12—Permeability or impermeability properties
- D06N2209/121—Permeability to gases, adsorption
- D06N2209/123—Breathable
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/28—Artificial leather
Abstract
The present invention relates to the preparation method of a kind of air previous polyurethane artificial leather, belong to synthetic leather preparing technical field.The present invention is with octamethylcy-clotetrasiloxane, γ aminoethylaminopropyl trimethoxy silane is raw material, through open loop, polymerization obtains amino-modified silicone oil, react with PTMG again and obtain polyether-containing aminopolysiloxane, then react with isophorone diisocyanate and obtain performed polymer, then with 2, the operations such as 2 dihydromethyl propionic acids etc. are neutralized after reacting obtain polyether-type amino-modified silicone polyurethane, Acetobacter gluconicum is obtained Bacterial cellulose with the fermentation of polyether-type amino-modified silicone polyurethane, after mixing with part polyether-type amino-modified silicone polyurethane the most again, add after then auxiliary agent stirs coating and solidify, washing, it is dried and waits operation, obtain air previous polyurethane artificial leather good permeability prepared by the air previous polyurethane artificial leather present invention, breathability reaches 720mL/cm2More than h, comfortable and easy to wear, light；And its water permeability is superior, water penetration reaches 952g/m2More than 24h.
Description
Technical field
The present invention relates to the preparation method of a kind of air previous polyurethane artificial leather, belong to synthetic leather preparing technical field.
Background technology
Synthetic leather is a kind of using various fabricbases as base material, on base material application of resin make it have various decorative pattern, pattern,
Function and feel.At present, the synthetic leather application in fields such as clothing, sport shoes, sofa and case and bag is more and more extensive, at very great Cheng
The rare restriction come to relevant preparation industrial belt of animal skins is compensate on degree.From industrial significance, it is not only suitable for modernization rule
Mould produces, simultaneously the most again can protecting ecology, reduce environmental pollution, take full advantage of non-natural resource.
Containing two kinds of chain segment components of soft or hard in polyurethane molecular, it is possible to form special micro phase separation structure, make polyurethane
Resin has abrasion resistance, resistance to tortuosity, ageing resistance and the adhesive fastness of excellence, and film forming is pliable and tough and be rich in rigidity simultaneously.Tool
There are the many merits such as good mechanical property.Synthetic Leather is with polyurethane resin as raw material, by special processing work
Artificial leather product prepared by skill, it is possible to obtain the appearance very much like with natural leather, soft, corium texture
By force.Polyurethane also gives the prominent tolerance to cold of synthetic leather, excellent wear-resisting, scratch resistance and resistance to ag(e)ing etc., and relatively
Being more readily processed control, with low cost in natural leather Synthetic Leather, combination property is more excellent than artificial polyvinyl chloride leather
Different, it is the ideal substitute products of current natural leather.Therefore, the Synthetic Leather manufactured with polyurethane resin for raw material
As artificial leather development interim product, the most in a large number substitute natural leather and be widely used in clothing, shoemaking, case and bag,
The industries such as furniture.
Synthetic Leather (PU synthetic leather) but in waterproof and breathable performance, still have a certain distance.This is because high physics
The surface of the Synthetic Leather of performance has one layer of fine and close polyurethane epithelium so that breathability is substantially poor than natural leather,
Can make us producing the sense of discomfort such as wet sultry, cold.Although breathability can be improved in right amount by methods such as punchings, but poly-ammonia can be destroyed
The bond structure of ester, causes serviceability to decline.
Summary of the invention
The technical problem to be solved: for current Synthetic Leather poor air permeability, can make us producing vexed
The sense of discomfort such as wet hot, cold, and its punching is improved breathability, then the problem that can reduce its serviceability, the present invention is with prestox
Cyclotetrasiloxane, γ-aminoethylaminopropyl trimethoxy silane is raw material, with Tetramethylammonium hydroxide as catalyst, through open loop,
Polymerization obtains amino-modified silicone oil, then reacts with PTMG and obtain polyether-containing aminopolysiloxane, then with different Buddhist
Your ketone di-isocyanate reaction obtains performed polymer, then with 2, the operation such as is neutralized after the reaction such as 2-dihydromethyl propionic acid and obtains
Polyether-type amino-modified silicone polyurethane, obtains antibacterial by Acetobacter gluconicum and the fermentation of polyether-type amino-modified silicone polyurethane fine
Dimension element, after mixing with part polyether-type amino-modified silicone polyurethane the most again, adds after then auxiliary agent stirs coating and coagulates
Gu, wash, the operation such as be dried, obtain air previous polyurethane artificial leather, air previous polyurethane artificial leather good permeability prepared by the present invention,
There is good hygroscopicity, skin-friendly, wear light, comfortable, with low cost.
For solving above-mentioned technical problem, the technical solution used in the present invention is:
(1) weigh 100～200g octamethylcy-clotetrasiloxanes to join in the there-necked flask with thermometer and reflux, and
Be placed in oil bath pan, be warming up to 110～120 DEG C, add 0.1～0.3g Tetramethylammonium hydroxide, stirring reaction 30～
40min, adds 8～12g γ-aminoethylaminopropyl trimethoxy silane, stirring reaction 4～5h, sequentially add 100～
200g PTMG, 20～30g isopropanol, be cooled to 90～100 DEG C, stirring reaction 5～6h, and reaction terminates, will
Product carries out decompression and distills to the 1/5 of original volume, obtains polyether-containing aminopolysiloxane mixture；
(2) above-mentioned polyether-containing aminopolysiloxane mixture is joined in the there-necked flask with thermometer and reflux, then
It is placed in water-bath, is warming up to 60～70 DEG C, add 10～20g isophorone diisocyanate, stirring reaction 1～2h, obtain
To performed polymer, sequentially adding 10～15g2,2-dihydromethyl propionic acid, 3～5g1,4-butanediol, stirring is reacted 2～3h, is reacted
Terminate, be cooled to 5～10 DEG C, add mass fraction be 10% sodium hydroxide acetone soln regulation pH be 7, then add 100
～200mL acetone, filter after stirring 3～5min, obtain colloid, i.e. polyether-type amino-modified silicone polyurethane, standby；
(3) weigh successively 8～12g glucoses, 10～15g yeast powder, 3～5g calcium carbonate, 15～20g agar and 800～
1000mL deionized water, after stirring, moves in sterilization tank, and at 100～110 DEG C, sterilizing 10～20min, are cultivated
Base, by the 8～10% of inoculum concentration, is inoculated into Acetobacter gluconicum in culture medium, is subsequently placed in shaking table, 20～30 DEG C, 150
～under 160r/min, cultivate 12～24h, then it is centrifuged separating, under 1000～1200r/min, is centrifuged 20～30min, abandons
Precipitation is gone to obtain Acetobacter gluconicum bacterium solution；
(4) 20～30g glucoses, 5～8g yeast extract, 5～8g peptone, 1～3g citric acid, 2～4g phosphoric acid hydrogen are weighed successively
Polyether-type amino-modified silicone polyurethane that dipotassium, 40～50g step (2) are standby and 800～1000mL deionized waters, stirring is all
After even, moving in sterilization tank, at 100～110 DEG C, sterilizing 10～20min, obtain fermentation medium, then move into fermentation tank
In, take 100～200mL above-mentioned Acetobacter gluconicum bacterium solution and join in fermentation tank, 25～35 DEG C of bottom fermentations 4～5 days, fermentation knot
Bundle, is warming up to 110～120 DEG C of sterilizings 10～20min, is taken out by the bacteria cellulose film on tunning surface, uses deionized water
It is washed till neutrality, obtains Bacterial cellulose；
(5) the polyether-type amino-modified silicone polyurethane weighing 50～60g steps (2) standby joins in blender, adds
Above-mentioned Bacterial cellulose and 300～400mL deionized waters, high-speed stirred 30～40min under 8000～10000r/min, then add
Enter 0.3～0.5g dodecylbenzene sodium sulfonate, stir 20～30min, obtain slurry, slurry is spread evenly across one side fleece
Being placed in coagulating basin solidification 8～12min, controlling solidification temperature is 20～30 DEG C, is subsequently placed in rinsing bowl and washes, then
It is placed in baking oven, is dried 2～3h at 95～105 DEG C, then naturally cools to room temperature, i.e. can get air previous polyurethane artificial leather.
Air previous polyurethane artificial leather peel strength prepared by the present invention reaches more than 40.5N, and water penetration reaches 952g/m2·
More than 24h, breathability reaches 720mL/cm2More than h, thermostability reaches more than 195.2 DEG C.
The present invention is compared with additive method, and Advantageous Effects is:
(1) the air previous polyurethane artificial leather good permeability that prepared by the present invention, breathability reaches 720mL/cm2More than h, dress is relaxed
Suitable, light；
(2) the air previous polyurethane artificial leather water permeability that prepared by the present invention is superior, and water penetration reaches 952g/m2More than 24h；
(3) air previous polyurethane artificial leather that prepared by the present invention is with low cost, and preparation technology is simple, contributes to industrialized production.
Detailed description of the invention
First weigh 100～200g octamethylcy-clotetrasiloxanes and join the there-necked flask with thermometer and reflux
In, be placed in oil bath pan, be warming up to 110～120 DEG C, add 0.1～0.3g Tetramethylammonium hydroxide, stirring reaction 30～
40min, adds 8～12g γ-aminoethylaminopropyl trimethoxy silane, stirring reaction 4～5h, sequentially add 100～
200g PTMG, 20～30g isopropanol, be cooled to 90～100 DEG C, stirring reaction 5～6h, and reaction terminates, will
Product carries out decompression and distills to the 1/5 of original volume, obtains polyether-containing aminopolysiloxane mixture；By above-mentioned polyether modified amino silicon
Oil mixture joins in the there-necked flask with thermometer and reflux, then is placed in water-bath, is warming up to 60～70
DEG C, add 10～20g isophorone diisocyanate, stirring reaction 1～2h, obtain performed polymer, sequentially add 10～15g2,
2-dihydromethyl propionic acid, 3～5g1,4-butanediol, stirring reaction 2～3h, reaction terminates, and is cooled to 5～10 DEG C, adds matter
Amount mark be 10% sodium hydroxide acetone soln regulation pH be 7, then add 100～200mL acetone, mistake after stirring 3～5min
Filter, obtains colloid, and i.e. polyether-type amino-modified silicone polyurethane, standby；Weigh 8～12g glucoses, 10～15g ferment the most successively
Female powder, 3～5g calcium carbonate, 15～20g agar and 800～1000mL deionized waters, after stirring, move in sterilization tank,
At 100～110 DEG C, sterilizing 10～20min, obtain culture medium, by the 8～10% of inoculum concentration, Acetobacter gluconicum are inoculated into cultivation
On base, it is subsequently placed in shaking table, under 20～30 DEG C, 150～160r/min, cultivates 12～24h, be then centrifuged separating,
It is centrifuged 20～30min under 1000～1200r/min, discards precipitation and obtain Acetobacter gluconicum bacterium solution；Weigh 20～30g the most successively
The polyethers that glucose, 5～8g yeast extract, 5～8g peptone, 1～3g citric acid, 2～4g dipotassium hydrogen phosphate, 40～50g are standby
Type amino-modified silicone polyurethane and 800～1000mL deionized waters, after stirring, move in sterilization tank, 100～110
At DEG C, sterilizing 10～20min, obtain fermentation medium, then move in fermentation tank, take 100～200mL above-mentioned Acetobacter gluconicum
Bacterium solution joins in fermentation tank, 25～35 DEG C of bottom fermentations 4～5 days, fermentation ends, be warming up to 110～120 DEG C of sterilizings 10～
20min, takes out the bacteria cellulose film on tunning surface, is washed with deionized water to neutrality, obtains Bacterial cellulose；Finally
Weigh 50～60g standby polyether-type amino-modified silicone polyurethane and join in blender, add above-mentioned Bacterial cellulose
With 300～400mL deionized waters, high-speed stirred 30～40min under 8000～10000r/min, add 0.3～0.5g ten
Dialkyl benzene sulfonic acids sodium, stirs 20～30min, obtains slurry, slurry is spread evenly across one side fleece and is placed on coagulating basin
Middle solidification 8～12min, controlling solidification temperature is 20～30 DEG C, is subsequently placed in rinsing bowl and washes, then is placed in baking oven,
It is dried 2～3h at 95～105 DEG C, then naturally cools to room temperature, i.e. can get air previous polyurethane artificial leather.
Example 1
First weigh 200g octamethylcy-clotetrasiloxane to join in the there-necked flask with thermometer and reflux, be placed in
In oil bath pan, it is warming up to 120 DEG C, adds 0.3g Tetramethylammonium hydroxide, stirring reaction 40min, add 12g γ-ammonia second
Base aminopropyl trimethoxysilane, stirring reaction 5h, sequentially add 200g PTMG, 30g isopropanol, cooling
To 100 DEG C, stirring reaction 6h, reaction terminates, and product carries out decompression and distills to the 1/5 of original volume, obtain polyether modified amino
Silicon oil mixture；Above-mentioned polyether-containing aminopolysiloxane mixture is joined the there-necked flask with thermometer and reflux
In, then be placed in water-bath, it is warming up to 70 DEG C, adds 20g isophorone diisocyanate, stirring reaction 2h, obtain pre-polymerization
Body, sequentially adds 15g2,2-dihydromethyl propionic acid, 5g1,4-butanediol, stirring reaction 3h, and reaction terminates, and is cooled to 10 DEG C,
Add mass fraction be 10% sodium hydroxide acetone soln regulation pH be 7, then add 200mL acetone, mistake after stirring 5min
Filter, obtains colloid, and i.e. polyether-type amino-modified silicone polyurethane, standby；Weigh 12g glucose, 15g yeast powder, 5g the most successively
Calcium carbonate, 20g agar and 1000mL deionized water, after stirring, move in sterilization tank, sterilizing 20min at 110 DEG C,
To culture medium, by the 10% of inoculum concentration, Acetobacter gluconicum is inoculated in culture medium, is subsequently placed in shaking table, at 30 DEG C, 160r/
Cultivating 24h under min, be then centrifuged separating, under 1200r/min, centrifugal 30min, discards precipitation and obtains Acetobacter gluconicum bacterium
Liquid；Weigh 30g glucose, 8g yeast extract, 8g peptone, 3g citric acid, 4g dipotassium hydrogen phosphate, standby the gathering of 50g the most successively
Ether type amino-modified silicone polyurethane and 1000mL deionized water, after stirring, move in sterilization tank, sterilizing at 110 DEG C
20min, obtains fermentation medium, then moves in fermentation tank, takes 200mL above-mentioned Acetobacter gluconicum bacterium solution and joins fermentation tank
In, in 35 DEG C of bottom fermentations 5 days, fermentation ends, it is warming up to 120 DEG C of sterilizing 20min, by the bacteria cellulose film on tunning surface
Take out, be washed with deionized water to neutrality, obtain Bacterial cellulose；Finally weigh polyether-type amino-modified silicone standby for 60g to gather
Urethane joins in blender, adds above-mentioned Bacterial cellulose and 400mL deionized water, high-speed stirred under 10000r/min
40min, adds 0.5g dodecylbenzene sodium sulfonate, stirs 30min, obtains slurry, slurry is spread evenly across one side napping
Cloth is placed in coagulating basin solidification 12min, and controlling solidification temperature is 30 DEG C, is subsequently placed in rinsing bowl and washes, then is placed in
In baking oven, at 105 DEG C of dry 3h, then naturally cool to room temperature, i.e. can get air previous polyurethane artificial leather.
After testing, air previous polyurethane artificial leather peel strength prepared by the present invention reaches 40.6N, and water penetration reaches 954g/
m224h, breathability reaches 725mL/cm2H, thermostability reaches 196.2 DEG C.
Example 2
First weigh 100g octamethylcy-clotetrasiloxane to join in the there-necked flask with thermometer and reflux, be placed in
In oil bath pan, it is warming up to 110 DEG C, adds 0.1g Tetramethylammonium hydroxide, stirring reaction 30min, add 8g γ-aminoethyl
Aminopropyl trimethoxysilane, stirring reaction 4h, sequentially add 100g PTMG, 20g isopropanol, be cooled to
90 DEG C, stirring reaction 5h, reaction terminates, and product carries out decompression and distills to the 1/5 of original volume, obtain polyether-containing aminopolysiloxane
Mixture；Above-mentioned polyether-containing aminopolysiloxane mixture is joined in the there-necked flask with thermometer and reflux, then
It is placed in water-bath, is warming up to 60 DEG C, add 10g isophorone diisocyanate, stirring reaction 1h, obtain performed polymer, then
Being sequentially added into 10g2,2-dihydromethyl propionic acid, 3g1,4-butanediol, stirring reaction 2h, reaction terminates, and is cooled to 5 DEG C, adds
Mass fraction be 10% sodium hydroxide acetone soln regulation pH be 7, then add 100mL acetone, filter after stirring 3min,
To colloid, i.e. polyether-type amino-modified silicone polyurethane, standby；Weigh the most successively 8g glucose, 10g yeast powder, 3g calcium carbonate,
15g agar and 800mL deionized water, after stirring, move in sterilization tank, and at 100 DEG C, sterilizing 10min, obtains culture medium,
By the 8% of inoculum concentration, Acetobacter gluconicum is inoculated in culture medium, is subsequently placed in shaking table, 20 DEG C, cultivate under 150r/min
12h, is then centrifuged separating, and under 1000r/min, centrifugal 20min, discards precipitation and obtain Acetobacter gluconicum bacterium solution；Then depend on
Secondary weigh 20g glucose, 5g yeast extract, 5g peptone, 1g citric acid, 2g dipotassium hydrogen phosphate, polyether-type amino silicone standby for 40g
Oil modified urethanes and 800mL deionized water, after stirring, move in sterilization tank, and at 100 DEG C, sterilizing 10min, is sent out
Ferment culture medium, then moves in fermentation tank, takes 100mL above-mentioned Acetobacter gluconicum bacterium solution and joins in fermentation tank, issues at 25 DEG C
Ferment 4 days, fermentation ends, it is warming up to 110 DEG C of sterilizing 10min, the bacteria cellulose film on tunning surface is taken out, uses deionization
It is washed to neutrality, obtains Bacterial cellulose；Finally weigh polyether-type amino-modified silicone polyurethane standby for 50g and join stirring
In machine, add above-mentioned Bacterial cellulose and 300mL deionized water, high-speed stirred 30min under 8000r/min, add
0.3g dodecylbenzene sodium sulfonate, stirs 20min, obtains slurry, slurry is spread evenly across one side fleece and is placed on solidification
Solidifying 8min in groove, controlling solidification temperature is 20 DEG C, is subsequently placed in rinsing bowl and washes, then be placed in baking oven, at 95 DEG C
It is dried 2h, then naturally cools to room temperature, i.e. can get air previous polyurethane artificial leather.
After testing, air previous polyurethane artificial leather peel strength prepared by the present invention reaches 41.5N, and water penetration reaches 960g/
m224h, breathability reaches 724mL/cm2H, thermostability reaches 197.2 DEG C.
Example 3
First weigh 150g octamethylcy-clotetrasiloxane to join in the there-necked flask with thermometer and reflux, be placed in
In oil bath pan, it is warming up to 115 DEG C, adds 0.2g Tetramethylammonium hydroxide, stirring reaction 35min, add 10g γ-ammonia second
Base aminopropyl trimethoxysilane, stirring reaction 4h, sequentially add 150g PTMG, 25g isopropanol, cooling
To 95 DEG C, stirring reaction 5h, reaction terminates, and product carries out decompression and distills to the 1/5 of original volume, obtain polyether modified amino silicon
Oil mixture；Above-mentioned polyether-containing aminopolysiloxane mixture is joined in the there-necked flask with thermometer and reflux,
It is placed in again in water-bath, is warming up to 65 DEG C, add 15g isophorone diisocyanate, stirring reaction 2h, obtain performed polymer,
Sequentially adding 12g2,2-dihydromethyl propionic acid, 4g1,4-butanediol, stirring reaction 2h, reaction terminates, and is cooled to 7 DEG C, then adds
Enter mass fraction be 10% sodium hydroxide acetone soln regulation pH be 7, then add 150mL acetone, filter after stirring 4min,
Obtaining colloid, i.e. polyether-type amino-modified silicone polyurethane, standby；Weigh 10g glucose, 12g yeast powder, 4g carbonic acid the most successively
Calcium, 17g agar and 900mL deionized water, after stirring, move in sterilization tank, and at 105 DEG C, sterilizing 15min, is cultivated
Base, by the 9% of inoculum concentration, is inoculated into Acetobacter gluconicum in culture medium, is subsequently placed in shaking table, 25 DEG C, train under 155r/min
Supporting 20h, be then centrifuged separating, under 1100r/min, centrifugal 25min, obtains Acetobacter gluconicum bacterium solution；Weigh the most successively
25g glucose, 7g yeast extract, 6g peptone, 2g citric acid, 3g dipotassium hydrogen phosphate, polyether-type amino-modified silicone standby for 45g
Polyurethane and 900mL deionized water, after stirring, move in sterilization tank, and at 105 DEG C, sterilizing 15min, obtains fermentation culture
Base, then moves in fermentation tank, takes 150mL above-mentioned Acetobacter gluconicum bacterium solution and joins in fermentation tank, 30 DEG C of bottom fermentations 5 days,
Fermentation ends, is warming up to 115 DEG C of sterilizing 15min, is taken out the bacteria cellulose film on tunning surface, be washed with deionized water to
Neutrality, obtains Bacterial cellulose；Finally weigh polyether-type amino-modified silicone polyurethane standby for 55g and join in blender,
Add above-mentioned Bacterial cellulose and 350mL deionized water, high-speed stirred 35min under 9000r/min, add 0.4g 12
Sodium alkyl benzene sulfonate, stirs 25min, obtains slurry, slurry is spread evenly across one side fleece and is placed in coagulating basin solidification
10min, controlling solidification temperature is 25 DEG C, is subsequently placed in rinsing bowl and washes, then is placed in baking oven, at 100 DEG C of dry 3h,
Then naturally cool to room temperature, i.e. can get air previous polyurethane artificial leather.
After testing, air previous polyurethane artificial leather peel strength prepared by the present invention reaches 40.8N, and water penetration reaches 962g/
m224h, breathability reaches 725mL/cm2H, thermostability reaches 195.6 DEG C.
Claims (1)
1. the preparation method of an air previous polyurethane artificial leather, it is characterised in that concrete preparation process is:
(1) weigh 100～200g octamethylcy-clotetrasiloxanes to join in the there-necked flask with thermometer and reflux, and
Be placed in oil bath pan, be warming up to 110～120 DEG C, add 0.1～0.3g Tetramethylammonium hydroxide, stirring reaction 30～
40min, adds 8～12g γ-aminoethylaminopropyl trimethoxy silane, stirring reaction 4～5h, sequentially add 100～
200g PTMG, 20～30g isopropanol, be cooled to 90～100 DEG C, stirring reaction 5～6h, and reaction terminates, will
Product carries out decompression and distills to the 1/5 of original volume, obtains polyether-containing aminopolysiloxane mixture；
(2) above-mentioned polyether-containing aminopolysiloxane mixture is joined in the there-necked flask with thermometer and reflux, then
It is placed in water-bath, is warming up to 60～70 DEG C, add 10～20g isophorone diisocyanate, stirring reaction 1～2h, obtain
Performed polymer, sequentially adds 10～15g2, and 2-dihydromethyl propionic acid, 3～5g1,4-butanediol, stirring reaction 2～3h, reaction is tied
Bundle, be cooled to 5～10 DEG C, add mass fraction be 10% sodium hydroxide acetone soln regulation pH be 7, then add 100～
200mL acetone, filters after stirring 3～5min, obtains colloid, and i.e. polyether-type amino-modified silicone polyurethane, standby；
(3) weigh successively 8～12g glucoses, 10～15g yeast powder, 3～5g calcium carbonate, 15～20g agar and 800～
1000mL deionized water, after stirring, moves in sterilization tank, and at 100～110 DEG C, sterilizing 10～20min, are cultivated
Base, is inoculated into Acetobacter gluconicum in culture medium by inoculum concentration 8～10%, is subsequently placed in shaking table, 20～30 DEG C, 150～
Cultivate 12～24h under 160r/min, be then centrifuged separating, under 1000～1200r/min, be centrifuged 20～30min, discard
Precipitation obtains Acetobacter gluconicum bacterium solution；
(4) 20～30g glucoses, 5～8g yeast extract, 5～8g peptone, 1～3g citric acid, 2～4g phosphoric acid hydrogen are weighed successively
Polyether-type amino-modified silicone polyurethane that dipotassium, 40～50g step (2) are standby and 800～1000mL deionized waters, stirring is all
After even, moving in sterilization tank, at 100～110 DEG C, sterilizing 10～20min, obtain fermentation medium, then move into fermentation tank
In, take 100～200mL above-mentioned Acetobacter gluconicum bacterium solution and join in fermentation tank, 25～35 DEG C of bottom fermentations 4～5 days, fermentation knot
Bundle, is warming up to 110～120 DEG C of sterilizings 10～20min, is taken out by the bacteria cellulose film on tunning surface, uses deionized water
It is washed till neutrality, obtains Bacterial cellulose；
(5) the polyether-type amino-modified silicone polyurethane weighing 50～60g steps (2) standby joins in blender, adds
Above-mentioned Bacterial cellulose and 300～400mL deionized waters, high-speed stirred 30～40min under 8000～10000r/min, then add
Enter 0.3～0.5g dodecylbenzene sodium sulfonate, stir 20～30min, obtain slurry, slurry is spread evenly across one side fleece
Being placed in coagulating basin solidification 8～12min, controlling solidification temperature is 20～30 DEG C, is subsequently placed in rinsing bowl and washes, then
It is placed in baking oven, is dried 2～3h at 95～105 DEG C, then naturally cools to room temperature, i.e. can get air previous polyurethane artificial leather.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610721480.XA CN106087451A (en) | 2016-08-25 | 2016-08-25 | A kind of preparation method of air previous polyurethane artificial leather |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610721480.XA CN106087451A (en) | 2016-08-25 | 2016-08-25 | A kind of preparation method of air previous polyurethane artificial leather |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106087451A true CN106087451A (en) | 2016-11-09 |
Family
ID=57225861
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610721480.XA Pending CN106087451A (en) | 2016-08-25 | 2016-08-25 | A kind of preparation method of air previous polyurethane artificial leather |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106087451A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109401282A (en) * | 2018-09-11 | 2019-03-01 | 苏州市雄林新材料科技有限公司 | A kind of dress ornament highly-flexible TPU film and preparation method thereof |
| CN109485927A (en) * | 2018-10-31 | 2019-03-19 | 际华三五三七制鞋有限责任公司 | PU surrounding edge Antiskid rubber outer bottom shoes and preparation method thereof |
| EP3476996A1 (en) * | 2017-10-27 | 2019-05-01 | Sanko Tekstil Isletmeleri San. Ve Tic. A.S. | A process for preparing a composite textile article including a biopolymer layer produced by microoorganisms |
| CN110305577A (en) * | 2019-06-12 | 2019-10-08 | 黄琳 | A kind of preparation method of folding aqueous transfer coating |
| CN110498896A (en) * | 2019-08-29 | 2019-11-26 | 江苏宝泽高分子材料股份有限公司 | A kind of organic-silicon-modified water for synthetic leather rubs auxiliary agent and preparation method thereof |
| CN111732708A (en) * | 2020-06-04 | 2020-10-02 | 旭川化学（苏州）有限公司 | Soft high-resilience aqueous polyurethane resin and preparation method and application thereof |
| CN113661282A (en) * | 2019-04-11 | 2021-11-16 | 德普伊新特斯产品公司 | Bacterial-derived nanocellulose textile materials |
| CN113771467A (en) * | 2021-09-16 | 2021-12-10 | 清远市齐力合成革有限公司 | Imitation silicon leather synthetic leather |
| CN114539308A (en) * | 2022-01-22 | 2022-05-27 | 巩义市泛锐熠辉复合材料有限公司 | Preparation method and application of polyurethane foam bonding auxiliary agent |
| WO2023218225A1 (en) * | 2022-05-12 | 2023-11-16 | Polybion, S.L. | Composite material comprising polyurethane and tanned bacterial cellulose, and method for manufacturing the same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1470544A (en) * | 2003-06-24 | 2004-01-28 | 中国科学院广州化学研究所 | Method for preparing amino silicone oil modified polyurethane |
| CN102634035A (en) * | 2012-03-30 | 2012-08-15 | 南京工业大学 | Organic silicon polyether polyol and preparation method thereof and method for preparing polyurethane elastomer |
| CN104480731A (en) * | 2014-10-23 | 2015-04-01 | 合肥金伶俐服饰有限公司 | Air-permeable PU synthetic leather and producing method thereof |
-
2016
- 2016-08-25 CN CN201610721480.XA patent/CN106087451A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1470544A (en) * | 2003-06-24 | 2004-01-28 | 中国科学院广州化学研究所 | Method for preparing amino silicone oil modified polyurethane |
| CN102634035A (en) * | 2012-03-30 | 2012-08-15 | 南京工业大学 | Organic silicon polyether polyol and preparation method thereof and method for preparing polyurethane elastomer |
| CN104480731A (en) * | 2014-10-23 | 2015-04-01 | 合肥金伶俐服饰有限公司 | Air-permeable PU synthetic leather and producing method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 张俐娜: "《基于生物质的环境友好材料》", 30 June 2011, 化学工业出版社 * |
| 朱和国等: "《复合材料原理》", 31 July 2017, 国防工业出版社 * |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3476996B1 (en) | 2017-10-27 | 2020-09-16 | Sanko Tekstil Isletmeleri San. Ve Tic. A.S. | A process for preparing a composite textile article including a biopolymer layer produced by microoorganisms |
| EP3476996A1 (en) * | 2017-10-27 | 2019-05-01 | Sanko Tekstil Isletmeleri San. Ve Tic. A.S. | A process for preparing a composite textile article including a biopolymer layer produced by microoorganisms |
| WO2019081473A1 (en) | 2017-10-27 | 2019-05-02 | Sanko Tekstil Isletmeleri San. Ve Tic. A.S. | A process for preparing a composite textile article including a biopolymer layer produced by microoorganisms |
| CN109722906A (en) * | 2017-10-27 | 2019-05-07 | 尚科纺织企业工业及贸易公司 | The method of compound textile fabrics of the manufacture comprising biopolymerization nitride layer |
| CN109722906B (en) * | 2017-10-27 | 2023-11-14 | 尚科纺织企业工业及贸易公司 | Method for manufacturing a composite textile product comprising a biopolymer layer |
| CN109401282A (en) * | 2018-09-11 | 2019-03-01 | 苏州市雄林新材料科技有限公司 | A kind of dress ornament highly-flexible TPU film and preparation method thereof |
| CN109485927A (en) * | 2018-10-31 | 2019-03-19 | 际华三五三七制鞋有限责任公司 | PU surrounding edge Antiskid rubber outer bottom shoes and preparation method thereof |
| CN113661282A (en) * | 2019-04-11 | 2021-11-16 | 德普伊新特斯产品公司 | Bacterial-derived nanocellulose textile materials |
| CN113661282B (en) * | 2019-04-11 | 2023-06-02 | 德普伊新特斯产品公司 | Nanocellulose textile material derived from bacteria |
| CN110305577A (en) * | 2019-06-12 | 2019-10-08 | 黄琳 | A kind of preparation method of folding aqueous transfer coating |
| CN110498896A (en) * | 2019-08-29 | 2019-11-26 | 江苏宝泽高分子材料股份有限公司 | A kind of organic-silicon-modified water for synthetic leather rubs auxiliary agent and preparation method thereof |
| CN111732708A (en) * | 2020-06-04 | 2020-10-02 | 旭川化学（苏州）有限公司 | Soft high-resilience aqueous polyurethane resin and preparation method and application thereof |
| CN113771467A (en) * | 2021-09-16 | 2021-12-10 | 清远市齐力合成革有限公司 | Imitation silicon leather synthetic leather |
| CN114539308A (en) * | 2022-01-22 | 2022-05-27 | 巩义市泛锐熠辉复合材料有限公司 | Preparation method and application of polyurethane foam bonding auxiliary agent |
| WO2023218225A1 (en) * | 2022-05-12 | 2023-11-16 | Polybion, S.L. | Composite material comprising polyurethane and tanned bacterial cellulose, and method for manufacturing the same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106087451A (en) | A kind of preparation method of air previous polyurethane artificial leather | |
| CN106521986B (en) | A kind of water-based two-sided matte woven fabric PU synthetic leather and preparation method thereof | |
| CN102978965B (en) | Method for preparing ultra-soft high-elastic polyurethane leather | |
| CN109098008A (en) | A kind of suede nap ultra-soft albumen leather | |
| CN102863850A (en) | Disposable rain-proof antibacterial shoe covers and preparation method thereof | |
| CN110592956A (en) | Water-based directly-coated microfiber sofa leather | |
| CN105482334B (en) | A kind of disposable feel slurry for artificial flowers and its preparation method and application | |
| CN105965992A (en) | Production method of zero-dermatoglyph imitation leather composite sofa fabric | |
| CN102675576B (en) | Preparation method of antimicrobial moldproof MDI (methylenediphenyl diisocyanate) polyurethane foam | |
| CN105482074B (en) | A kind of anionic polyurethane modified organic silicon emulsion and preparation method thereof | |
| CN106188124B (en) | The preparation method of novel ester organosilicon quaternary ammonium salt | |
| CN111500799B (en) | Alkali leather high-pH value silica gel precursor sol-gel chromium-free ecological silane tanning process | |
| CN108409939A (en) | A kind of underwear chest pad of the sponge containing chitin and preparation method thereof | |
| CN110317316B (en) | Preparation method of antibacterial and stain-resistant polyurethane for synthetic leather | |
| CN107351509A (en) | A kind of two-sided leather production technology | |
| CN203807860U (en) | Waterproof and moisture permeable grid printed fabric | |
| CN101288988A (en) | Lace PVC tablecloth manufacturing method | |
| CN110952338A (en) | Super-simulation leather, cow and sheep crystal transparent synthetic leather fabric and preparation method thereof | |
| CN107419550A (en) | A kind of preparation method of simulated leather knitted composite fabric | |
| CN112482018A (en) | Production process of nano real silk crease-resistant knitted garment | |
| CN109177417B (en) | Multilayer composite fabric, composite process and application of fabric | |
| CN103741490B (en) | Textile shuttle-woven fabric anti tear finishing agent and preparation method | |
| CN210886739U (en) | Transparent synthetic leather fabric with super-simulation leather, cow and sheep crystals | |
| CN113322684A (en) | Artificial leather capable of being directly embossed and preparation method thereof | |
| CN106009620A (en) | Highly-soft flame-retardant TPU synthetic leather and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20161109 |