CN108360269B - Preparation method of cow hair powder filler modified aqueous dry-method polyurethane base - Google Patents
Preparation method of cow hair powder filler modified aqueous dry-method polyurethane base Download PDFInfo
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- CN108360269B CN108360269B CN201810356752.XA CN201810356752A CN108360269B CN 108360269 B CN108360269 B CN 108360269B CN 201810356752 A CN201810356752 A CN 201810356752A CN 108360269 B CN108360269 B CN 108360269B
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- 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
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- 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
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- 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
- D06N3/0063—Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds
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- 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 invention relates to a preparation method of a modified waterborne dry polyurethane base by a cow hair powder filler, which comprises the following steps: (1) removing impurities from cow hair, (2) rough preparation of cow hair powder filler, (3) refining of cow hair powder filler, (4) preparation of aqueous polyurethane slurry containing cow hair powder filler, (5) preparation of modified aqueous dry-process polyurethane base of cow hair powder filler. The cow hair filler prepared by the method has small granularity, light weight and high water absorption, and the prepared waterborne dry-method polyurethane base has good foam structure and air permeability. The addition of the cow hair powder filler not only provides an effective way for resource utilization of the waste cow hair, but also improves the sanitary performance and the ecological degradability of the waterborne polyurethane synthetic leather.
Description
Technical Field
The invention belongs to the field of biomass material resource utilization and leather/synthetic leather, and particularly relates to a preparation method of a modified waterborne dry-method polyurethane base by using a cow hair powder filler.
Background
In recent years, the vigorous development of leather industry provides powerful material guarantee for improving the living standard of people. However, due to the particularity of the leather making process, the industry rapidly develops and simultaneously causes certain environmental pollution problems, such as the discarding of chromium-containing solid wastes, the discharge of high ammonia nitrogen and high-chroma waste liquid such as liming unhairing, dyeing fatliquoring and the like, and the accumulation of terminal leather making sludge. With the enhancement of social environmental awareness, the whole body of national scientific research strength is increased, and the application of some emerging tanning technologies, such as chrome-free tanning, liming chrome tanning waste liquid recycling, high-absorption dyeing and greasing material use and the like, effectively relieves the environmental pressure of tanning, and people do not have the concept closer to leather green manufacturing than today. Although the continuous implementation of the environmental protection technology greatly changes the dirty and messy carved impression of the traditional tanning industry, the problems after the application of some new technologies begin to emerge recently, in particular the rapid popularization of the hair-protecting and unhairing process for replacing the 'hair destroying and rotting method' in the traditional cow leather production, and although the COD and BOD values in the wastewater are obviously reduced, the abandoned cow hairs which are fallen off are difficult to use for a while and start to be accumulated in large quantities, thus becoming a troublesome problem which a tannery must face.
On the other hand, artificial leather and synthetic leather are used as supplements to natural leather, are various in color and variety and low in price, and are popular with people in the market all the time. Nowadays, artificial leather and synthetic leather exceed limited genuine leather products in quantity for a long time, even are better than natural leather in strength, but because of lacking polar groups or peptide bonds of natural skin collagen, water and moisture permeability is insufficient, compatibility with skin is poor, and sanitary performance is often inferior to genuine leather. In the manufacturing of synthetic leather, the aqueous dry polyurethane BASE (BASE) refers to a synthetic leather semi-finished product with a cellular structure and a soft coating formed by directly coating synthetic leather BASE cloth with foamed Polyurethane (PU) slurry by utilizing the principle that aqueous resin can be mechanically foamed and drying. The base can be made into a finished product of the polyurethane synthetic leather after dry veneering or surface finishing, such as surface printing, embossing, buffing and the like. The dry method Bass for producing the waterborne polyurethane synthetic leather mainly comprises the raw materials of waterborne polyurethane resin, filling materials, surfactants and the like. Regarding the current fillers for preparing the bass, wood powder (microcrystalline cellulose) is the most common, and light calcium carbonate, calcium sulfate, wollastonite and the like are the second fillers.
Disclosure of Invention
The invention provides a preparation method of a cow hair powder filler modified waterborne dry method polyurethane base, aiming at solving the problems of poor water vapor permeability, limited filler resources and the like of the treatment of waste cow hair and common synthetic leather and realizing the high added value conversion of the waste cow hair resources and the functional modification of the waterborne dry method polyurethane base.
A method for modifying waterborne dry-process polyurethane base by using cow hair powder comprises the following steps:
(1) removing impurities from the cow hair: rinsing and soaking the cattle hair for 20-40 min by using clean water with the weight 15-25 times of that of the cattle hair, picking up wood chips floating on the water surface and insoluble impurities deposited at the bottom, and spin-drying the hair by using a centrifugal machine; placing into an ultrasonic cleaner, soaking, rinsing for 2-3 times (30 min each time), removing soluble impurities, placing the obtained wet cattle hair in a tray, spreading uniformly, and drying in an oven;
(2) crude cow hair powder: putting the cattle hair subjected to impurity removal in the step (1) into a pulverizer, and sieving;
(3) and (3) refining the cow hair powder: putting the cow hair powder obtained in the step (2) into a ball milling tank, and adding the solution; sealing and ball milling; selecting grinding balls, and spray-drying the slurry into powder;
(4) preparing aqueous polyurethane slurry: adding a foaming agent, a thickening agent, a foam stabilizer and the cow hair powder filler prepared in the step (3) into the waterborne polyurethane, and mechanically stirring uniformly for foaming;
(5) preparation of aqueous dry polyurethane base: and (3) padding feelers on two edges of the clean base cloth which is ironed, scraping the slurry obtained in the step (4) on the base cloth by using a coating rod along the longitudinal direction of the feelers, and then putting the base cloth into an oven to be heated and dried in a gradient manner to obtain the waterborne dry-method polyurethane base cloth.
The soaking solution in the step (1) is an aqueous solution which is 20 times of the weight of the cattle hair and contains 2 percent of sodium dodecyl benzene sulfonate.
In the step (3), the ball milling tank is any one of a ceramic tank, an agate tank, a stainless steel tank and a tetrafluoroethylene tank; the grinding ball is any one of cobblestone ball, agate ball, zirconia ball and stainless steel ball.
In the step (3), the solution is any one of water, acetone and ethanol; the mass ratio of the cow hair to the grinding ball to the solution is 1: 150-250: 100-; the ball milling time is 6-12h, and the rotating speed is 35-45 Hz.
In the step (4), the solid content of the waterborne polyurethane is 35-50%; the addition amounts of the foaming agent, the thickening agent, the foam stabilizer and the cow hair powder filler are respectively 3-5%, 0.5-3%, 0.5-5% and 1-4% by mass of the polyurethane resin.
In the step (4), the mechanical stirring rotation speed is 1200-2500 r/min, and the mechanical foaming time is 20-50 min.
In the step (5), the drying temperature of the oven is 60-110 ℃, and the drying time is 20-30 min.
Drawings
FIG. 1 shows the appearance of common wood powder filler (left) and cow hair powder filler (right);
FIG. 2 is a graph showing the particle size distribution of a common wood powder filler (top) and a cow hair powder filler (bottom);
FIG. 3 SEM cross-sectional morphology of common aqueous PU base (left) and aqueous dry PU base (right) modified by cow hair powder filler.
The invention has the beneficial effects that:
(1) according to the invention, the waste cattle hair is converted into cattle hair powder after impurity removal and is used as the filler of the dry-process base of the waterborne polyurethane synthetic leather, so that waste is changed into valuable, and a new thought and way is provided for recycling the waste cattle hair.
(2) The invention comprehensively utilizes physical modes such as crushing, mechanical ball milling and the like, avoids the problems of excessive hydrolysis, indirect waste of keratin resources and easy secondary pollution caused by the use of chemical reagents in the traditional chemical treatment of the cow hair, and realizes the high-efficiency and high-value conversion of the waste cow hair.
(3) The invention prepares the powder filler for the waterborne polyurethane synthetic leather bass (shown in the right part of figure 1) by using the leather-making waste cattle hair, replaces the traditional materials such as wood powder (shown in the left part of figure 1), calcium carbonate and the like, saves natural resources, reduces the production cost, creates another economic benefit for the leather and synthetic leather industries, and has better application prospect.
(4) Compared with the traditional wet-process polyurethane base or the aqueous dry-process polyurethane base, the aqueous polyurethane synthetic leather base prepared by the invention has good moisture absorption and moisture permeability, sanitary performance and ecological degradability due to the addition of the natural cow hair protein powder filler.
Detailed Description
The following description is only a preferred embodiment of the present invention, and is only for the purpose of describing the present invention, and should not be construed as limiting the scope of the present invention.
Example 1:
a method for modifying waterborne dry-process polyurethane base by using cow hair powder comprises the following steps:
(1) pretreatment of cow hair: rinsing and soaking the cow hair with clear water with the weight of 20 times of the hair for 20min, then picking up the wood chips floating on the water surface and insoluble impurities such as stone residue and meat pieces deposited at the bottom, and then spin-drying the hair by using a centrifuge. The cattle hair after primary impurity removal is put into an ultrasonic cleaner, soaked and rinsed for 3 times by using an aqueous solution containing 2 percent sodium dodecyl benzene sulfonate and the weight of the cattle hair is 20 times of the weight of the cattle hair, ultrasonic vibration is simultaneously assisted, the soluble impurities such as grease, sulfide and the like are removed for 30 minutes each time, the obtained wet cattle hair is put into a tray, evenly spread and put into an oven for drying.
(2) Crude cow hair powder filler: and (3) putting the cattle hair treated in the step (1) into a grinder, grinding the cattle hair to be less than 1mm, and sieving the cattle hair with a 20-mesh sieve.
(3) And (3) refining the cow hair powder filler: putting the cattle hair treated in the step 2 into a stainless steel ball milling tank of a planetary ball mill, adding stainless steel balls, and then adding water, wherein the cattle hair: grinding balls: the mass ratio of water is 1: 250: 200, sealing and ball milling for 6h at the speed of 45 Hz. And (4) selecting the grinding balls, and spray-drying the slurry into powder.
(4) Preparing aqueous polyurethane slurry mixed with a cow hair powder filler: putting 35% of solid content of waterborne polyurethane into a dry PE plastic beaker, adding 5% of foaming agent, 3% of thickening agent, 5% of foam stabilizer and 1% of the cow hair powder filler (calculated by the mass of PU resin) prepared in the step 3, mechanically stirring uniformly at the rotating speed of 2500r/min, and mechanically foaming for 20 min.
(5) Preparing the modified aqueous dry polyurethane base by the cow hair powder filler: and (3) padding a feeler gauge on two edges of the clean base cloth which is subjected to ironing, scraping the prepared slurry in the step (4) on the base cloth by using a coating rod along the longitudinal direction of the feeler gauge, and then putting the base cloth into an oven for drying, wherein the drying temperature is increased from 70 ℃ to 110 ℃ in a gradient manner, and the drying time is 20 min.
Example 2:
a method for modifying waterborne dry-process polyurethane base by using cow hair powder comprises the following steps:
(1) pretreatment of cow hair: rinsing and soaking the cow hair with clear water with the weight of 25 times of the hair for 30min, then picking up the wood chips floating on the water surface and insoluble impurities such as stone residue and meat pieces deposited at the bottom, and then spin-drying the hair by using a centrifuge. The cattle hair after primary impurity removal is put into an ultrasonic cleaner, soaked and rinsed for 2 times by using aqueous solution containing 2 percent sodium dodecyl benzene sulfonate with the weight of 20 times of the cattle hair, and simultaneously ultrasonic oscillation is assisted for 30 minutes each time to remove soluble impurities such as grease, sulfide and the like, the obtained wet cattle hair is put into a tray, evenly spread and put into an oven for drying.
(2) Crude cow hair powder filler: and (3) putting the cattle hair treated in the step (1) into a grinder, grinding the cattle hair to be less than 1mm, and sieving the cattle hair with a 20-mesh sieve.
(3) And (3) refining the cow hair powder filler: putting the cattle hair treated in the step 2 into a ceramic ball milling tank of a planetary ball mill, adding zirconia balls, and then adding ethanol, wherein the cattle hair: grinding balls: the mass ratio of ethanol is 1: 150: 100, sealing and then ball-milling for 10 hours at the speed of 40 Hz. And (4) selecting the grinding balls, and spray-drying the slurry into powder.
(4) Preparing aqueous polyurethane slurry mixed with a cow hair powder filler: putting 45% of solid content waterborne polyurethane into a dry PE plastic beaker, adding 4% of foaming agent, 2% of thickening agent, 3% of foam stabilizer and 2% of the cow hair powder filler (calculated by the mass of PU resin) prepared in the step (3), mechanically stirring uniformly at the rotating speed of 2000r/min, and mechanically foaming for 30 min.
(5) Preparing the modified waterborne polyurethane synthetic leather base by the cow hair powder filler: and (3) padding a feeler gauge on two edges of the clean base cloth which is subjected to ironing, scraping the prepared slurry in the step (4) on the base cloth by using a coating rod along the longitudinal direction of the feeler gauge, and then putting the base cloth into an oven for drying, wherein the drying temperature is increased from 80 ℃ to 110 ℃ in a gradient manner, and the drying time is 25 min.
Example 3:
a method for modifying waterborne dry-process polyurethane base by using cow hair powder comprises the following steps: (1) pretreatment of cow hair: rinsing and soaking the cow hair for 40min by using clean water with the weight 15 times of the hair, picking up the wood chips floating on the water surface and insoluble impurities such as stone residue and meat blocks deposited at the bottom, and spin-drying the hair by using a centrifuge. The cattle hair after primary impurity removal is put into an ultrasonic cleaner, soaked and rinsed for 3 times by using an aqueous solution containing 2 percent sodium dodecyl benzene sulfonate and the weight of the cattle hair is 20 times of the weight of the cattle hair, ultrasonic vibration is simultaneously assisted, the soluble impurities such as grease, sulfide and the like are removed for 30 minutes each time, the obtained wet cattle hair is put into a tray, evenly spread and put into an oven for drying.
(2) Crude cow hair powder filler: and (3) putting the cattle hair treated in the step (1) into a grinder, grinding the cattle hair to be less than 1mm, and sieving the cattle hair with a 20-mesh sieve.
(3) And (3) refining the cow hair powder filler: putting the cowhair treated in the step 2 into an agate ball milling tank of a planetary ball mill, adding agate balls, and then adding acetone, wherein the cowhair: grinding balls: the mass ratio of acetone is 1: 200: 150, sealing and then ball-milling for 12h at the speed of 35 Hz. And (4) selecting the grinding balls, and spray-drying the slurry into powder.
(4) Preparing aqueous polyurethane slurry mixed with a cow hair powder filler: and (2) placing 50% of waterborne polyurethane in a dry PE plastic beaker, adding 3% of foaming agent, 0.5% of thickening agent, 2% of foam stabilizer and 4% of the cow hair powder filler (calculated by the mass of PU resin) prepared in the step (3), mechanically stirring uniformly at the rotating speed of 1800r/min, and mechanically foaming for 50 min.
(5) Preparing the modified waterborne polyurethane synthetic leather base by the cow hair powder filler: and (3) padding a feeler gauge on two edges of the clean base cloth which is subjected to ironing, scraping the prepared slurry in the step (4) on the base cloth by using a coating rod along the longitudinal direction of the feeler gauge, and then putting the base cloth into an oven for drying, wherein the drying temperature is increased from 60 ℃ to 105 ℃ in a gradient manner, and the drying time is 30 min.
Comparative example
A process for an aqueous dry polyurethane base comprising the steps of:
(1) preparing aqueous polyurethane slurry mixed with a cow hair powder filler: putting 45% of solid content waterborne polyurethane into a dry PE plastic beaker, adding 4% of foaming agent, 2% of thickening agent, 3% of foam stabilizer and 2% of wood powder (calculated by the mass of PU resin), mechanically stirring uniformly at the rotating speed of 2000r/min, and mechanically foaming for 30 min.
(2) Preparing the modified waterborne polyurethane synthetic leather base by the cow hair powder filler: and (3) padding a feeler gauge on two edges of the clean base cloth which is subjected to ironing, scraping the prepared slurry in the step (4) on the base cloth by using a coating rod along the longitudinal direction of the feeler gauge, and then putting the base cloth into an oven for drying, wherein the drying temperature is increased from 80 ℃ to 110 ℃ in a gradient manner, and the drying time is 25 min.
The particle size analysis of the common wood powder sold in the market and the cattle hair powder filler developed by the invention is carried out by a micron-sized laser particle sizer, and the result is shown in figure 2; as can be seen from FIG. 2, the particle size of the cow hair powder filler prepared by the invention is similar to that of common wood powder, the average particle size is about 45 μm, and the particle size distribution of most particles is within 20-100 μm.
And Scanning Electron Microscope (SEM) analysis was performed on the cross-sections of the articles of example 2 and comparative example, the results are shown in fig. 3; as can be seen from fig. 3, compared with the aqueous dry-process bass prepared from the common wood powder filler, the aqueous dry-process polyurethane bass modified by the cow hair powder filler has a pore-shaped structure with different sizes, has a pore-forming effect similar to a wet-process coating process, has a better soft hand feeling, and has good water permeability, moisture permeability and other sanitary properties due to the open pores on the surface of the bass coating.
Claims (5)
1. A method for modifying waterborne dry-process polyurethane base by using cow hair powder is characterized by comprising the following steps:
(1) removing impurities from the cow hair: rinsing and soaking the cattle hair for 20-40 min by using clean water with the weight 15-25 times of that of the cattle hair, picking up wood chips floating on the water surface and insoluble impurities deposited at the bottom, and spin-drying the hair by using a centrifugal machine; placing into an ultrasonic cleaner, soaking in the solution, rinsing for 2-3 times (30 min each time), removing soluble impurities, placing the wet cattle hair in a tray, spreading uniformly, and drying in an oven;
(2) crude cow hair powder: putting the cattle hair subjected to impurity removal in the step (1) into a pulverizer, and sieving;
(3) and (3) refining the cow hair powder: putting the cow hair powder obtained in the step (2) into a ball milling tank, and adding the solution; sealing and ball milling; selecting grinding balls, and spray-drying the slurry into powder;
(4) preparing aqueous polyurethane slurry: adding a foaming agent, a thickening agent, a foam stabilizer and the cow hair powder filler prepared in the step (3) into the waterborne polyurethane, and mechanically stirring uniformly for foaming;
(5) preparation of aqueous dry polyurethane base: padding feelers on two edges of the clean base cloth which is ironed, scraping the slurry obtained in the step (4) on the base cloth by using a coating rod along the longitudinal direction of the feelers, and then putting the base cloth into an oven to be heated and dried in a gradient manner to obtain the waterborne dry-method polyurethane base;
the solution soaked in the step (1) is an aqueous solution which is 20 times of the weight of the cattle hair and contains 2% of sodium dodecyl benzene sulfonate;
in the step (3), the solution is any one of water, acetone and ethanol; the mass ratio of the cow hair to the grinding ball to the solution is 1: 150-250: 100-; the ball milling time is 6-12h, and the rotating speed is 35-45 Hz.
2. The preparation method according to claim 1, wherein in the step (3), the ball mill pot is any one of a ceramic pot, an agate pot, a stainless steel pot and a tetrafluoroethylene pot; the grinding ball is any one of cobblestone ball, agate ball, zirconia ball and stainless steel ball.
3. The preparation method according to claim 1, wherein in the step (4), the solid content of the aqueous polyurethane is 35-50%; the addition amounts of the foaming agent, the thickening agent, the foam stabilizer and the cow hair powder filler are respectively 3-5%, 0.5-3%, 0.5-5% and 1-4% by mass of the polyurethane resin.
4. The preparation method as claimed in claim 1, wherein in the step (4), the rotation speed of the mechanical stirring is 1200-2500 r/min, and the mechanical foaming time is 20-50 min.
5. The preparation method according to claim 1, wherein in the step (5), the drying temperature of the oven is 60-110 ℃, and the drying time is 20-30 min.
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| CN110204679B (en) * | 2019-05-20 | 2021-08-31 | 齐鲁工业大学 | Preparation method of modified environment-friendly waterborne polyurethane and polyurethane prepared by same |
| CN115323803A (en) * | 2022-08-17 | 2022-11-11 | 广东汇齐新材料有限公司 | Completely-recyclable environment-friendly thermoplastic foaming artificial leather material and preparation method thereof |
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| CN102080332A (en) * | 2010-12-27 | 2011-06-01 | 陕西科技大学 | Preparation method of waterborne polyurethane synthetic leather base |
| CN102182066A (en) * | 2010-11-30 | 2011-09-14 | 江苏宝泽高分子材料股份有限公司 | Soft crazy-horse resin for clothing leather and preparation method thereof |
| CN106118034A (en) * | 2016-08-16 | 2016-11-16 | 合肥科天水性科技有限责任公司 | A kind of dry method clothing leather bass and preparation technology thereof |
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| CN102182066A (en) * | 2010-11-30 | 2011-09-14 | 江苏宝泽高分子材料股份有限公司 | Soft crazy-horse resin for clothing leather and preparation method thereof |
| CN102080332A (en) * | 2010-12-27 | 2011-06-01 | 陕西科技大学 | Preparation method of waterborne polyurethane synthetic leather base |
| CN106118034A (en) * | 2016-08-16 | 2016-11-16 | 合肥科天水性科技有限责任公司 | A kind of dry method clothing leather bass and preparation technology thereof |
| CN106478957A (en) * | 2016-10-12 | 2017-03-08 | 温州大学 | The preparation method of keratin grafting water-based polyurethane polymer leather retanning packing material |
| CN107190349A (en) * | 2017-05-10 | 2017-09-22 | 天津中智科技发展有限公司 | A kind of method that utilization yak hair prepares nanofiber |
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