CN108841163A - Modified polyurethane resin and preparation method thereof, modified polyurethane artificial leather and application - Google Patents
Modified polyurethane resin and preparation method thereof, modified polyurethane artificial leather and application Download PDFInfo
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- CN108841163A CN108841163A CN201810738482.9A CN201810738482A CN108841163A CN 108841163 A CN108841163 A CN 108841163A CN 201810738482 A CN201810738482 A CN 201810738482A CN 108841163 A CN108841163 A CN 108841163A
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/16—Drying; Softening; Cleaning
- B32B38/164—Drying
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2497/00—Characterised by the use of lignin-containing materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The present invention provides a kind of modified polyurethane resin and preparation method thereof, modified polyurethane artificial leather and application, micro-nano lignocellulose is dispersed in the modified polyurethane resin.Micro-nano lignocellulose is added in polyurethane resin, mechanical performance, corrosion-resistant, thermal stability and the ageing-resistant performance of polyurethane resin can be increased, enhance the mechanical properties such as stretching, the tearing of polyurethane resin, and reduce the dilatancy of polyurethane resin, when preparing polyurethane artificial leather with modified polyurethane resin, it can be under the premise of keeping polyurethane artificial leather feel, preferable intensity is made it have, while also there are wearability, elasticity, gas permeability, scratch resistance, bacteria mildew-proof, anti-aging and antistatic etc. performances.
Description
Technical field
The invention belongs to polyurethane resin field, it is related to a kind of modified polyurethane resin and preparation method thereof, modified poly- ammonia
Ester artificial leather and application.
Background technique
Polyurethane material is to develop extraordinary material in recent years, since polyurethane resin has excellent elasticity, so that
Polyurethane material has the toughness of far superior to phenolic aldehyde, epoxy resin substrate, can be widely applied, such as prepare polyurethane people
Fabricate-leather；Polyurethane artificial leather goods have excellent performance, along with the fast development of superfiber leather, at present in clothes, shoes
The fields such as packet, furniture, automobile are all widely used, and become the indispensable consumer goods.With the raising of people's level of consumption,
Requirement to article is also higher and higher, requirement of the fields such as shoes packet, fur clothing chaparajos, sofa to polyurethane artificial leather necessary not only for
It has certain intensity, should also have the function of wear-resisting, ventilative, antibacterial, mould proof etc..
Nano-cellulose the features such as haveing excellent performance, is received more and more attention since its is from a wealth of sources.By raw material fibre
Dimension element, lignocellulosic etc. are by handling and special process prepares nano-cellulose with certain draw ratio, wooden nanometer
The nano-fiber materials such as fiber, and these nano-fiber materials not only can be used as the reinforcing material of resin composite materials, also
The thermal expansivity of resin can be reduced, but since there are bad dispersibilities, appearance in the resin matrixes such as polyurethane for nano-cellulose
Problem easy to reunite can reduce the mechanical performance of the resins such as polyurethane instead.
CN101698697B discloses a kind of polyurethane resin and its synthetic method, passes through the synthesis in polyurethane resin
Cellulose acetate is added in journey, to enhance the flow leveling of polymer；CN102504167B discloses nitrocellulose modified water
The preparation method of property polyurethane resin, is added nitrocellulose, it is therefore an objective to as light in the reaction process of polyurethane resin
Before agent is added, and cellulose acetate and nitrocellulose are added, need by being modified acquisition to cellulose.
CN106883371A discloses a kind of modified polyurethane resin and preparation method thereof, also in the synthesis process of polyurethane resin
Middle addition cellulose solves the anti-aging and hydrophobic performance of polyurethane.
Graphene is to appeal highest New Two Dimensional carbon material in recent years, based on performances such as its excellent mechanics, electricity, heat,
Become the favorite of new material.And these excellent performances are only single layers in graphene or several layers of can show completely
Come.After obtaining the Nobel Prize because single-layer graphene is prepared from two scientists in 2010, many researchers are opened
Beginning is dedicated to its preparation and application.It is easy to reunite mainly there is the hardly possible dispersion of graphene in the application process of composite material
The problems such as；CN107523038A discloses a kind of graphene compound polyurethane material and preparation method thereof, and preparation method is that will mix
There is pultrusion after the polyurethane resin composite fibre reinforcing material of graphene nano material, in mixed process, there are still stones
The dispersion problem of black alkene；CN106832189A discloses a kind of preparation method of graphene compound polyurethane material, first by stone
Black alkene is dispersed in polyalcohol and is uniformly mixed, and is then reacted again, solves point of the graphene in polyurethane resin material
It dissipates, is prepared for the good compound polyurethane material of heating conduction, but for the other performance of polyurethane material, obviously do not change
It is kind；CN106400506B discloses a kind of aqueous polyurethane spinning sizing agent modified based on graphene, including modified graphene, water
Property polyurethane, ethylene glycol, nano-titanium dioxide, calcium carbonate, hydroxylated cellulose and water, preparation method is first by modified graphene
It is reacted with polyurethane solutions microwave radiation, then adds hydroxylated cellulose etc., to improve the film forming of slurry, stability etc.,
On the basis of graphene modified polyurethane, hydroxylated cellulose is improved into properties of product as a kind of additive.
The addition of cellulose, modified cellulose pointedly improves the partial properties of polyurethane resin (as levelling
Agent, brightener), but the raising of the raising of the comprehensive performance for polyurethane resin, especially mechanical property is not significant, and fine
The addition of dimension element, modified cellulose is added in the reaction process of polyurethane resin, there is certain limitation to reaction condition, is grasped
Make complicated.
In view of the above problems, being badly in need of studying a kind of new polyurethane resin at present, good mechanical property is made it have, together
When can simplify its preparation process, save the cost reduces environmental pollution.
Summary of the invention
The purpose of the present invention is to provide a kind of modified polyurethane resin and preparation method thereof, modified polyurethane artificial leather and
Using, it is therefore intended that the mechanical property for improving polyurethane resin enhances the performances such as stretching, the tearing of polyurethane resin, Jin Erjin
The performance of one step improvement polyurethane resin end product.
For this purpose, the present invention uses following technical scheme：
In a first aspect, being dispersed in the modified polyurethane resin micro- the present invention provides a kind of modified polyurethane resin
Nano lignin cellulose.
In the present invention, described " micro-nano lignocellulose " refers to the micro-nano cellulose containing lignin component,
It can be understood as containing lignin, and cellulosic material of the diameter dimension within 1nm~1 μm.
Micro-nano lignocellulose, micro-nano lignin fibre are dispersed in modified polyurethane resin provided by the invention
The lignin contained in element has preferable oil-soluble, can form binding site with the lipophilic group in polyurethane resin, because
This is the present invention provides a kind of new nano cellulose material containing lignin and solves nano-cellulose in polyurethane tree
In rouge the problem of bad dispersibility；Micro-nano lignocellulose is dispersed in modified polyurethane resin provided by the invention, it can be with
Improve the mechanical property of polyurethane resin, enhances the performances such as the stretching of polyurethane resin product, and then end product can be improved
Mechanical property；Also, the addition of micro-nano lignocellulose not only has humidification to resin material, can also increase
It is the corrosion-resistant of resin, thermal stability, ageing-resistant, and the advantages that reduce the dilatancy of resin.
Preferably, grapheme material is also dispersed in the modified polyurethane resin.
It is dispersed with grapheme material in modified polyurethane resin provided by the invention, contains in micro-nano lignocellulose
Numerous hydroxyls can interact with grapheme material, increase dispersibility of the grapheme material in polyurethane resin, thus
Improve the performance of polyurethane resin.When preparing polyurethane artificial leather with polyurethane resin, polyurethane artificial leather can kept
Under the premise of feel, higher intensity is made it have, while also there is wearability, elasticity, gas permeability, scratch resistance, bacteria mildew-proof, resist
Aging and the performances such as antistatic.
Preferably, the grapheme material be by mechanically pulling off method, oxidation-reduction method, pyrolysis method, intercalation stripping method,
Chemical vapour deposition technique, liquid phase stripping method or biomass by hydro-thermal carbonizatin method are prepared.
Preferably, the average platelet thickness of the grapheme material is≤20nm, such as 15nm, 10nm, 8nm, 3nm etc.,
It is preferred that 3~10nm.
Preferably, the mass ratio of the grapheme material and micro-nano lignocellulose is (0.01-1):1, such as
0.02:1,0.05:1,0.1:1,0.3:1,0.5:1,0.6:1,0.8:1 etc..
Preferably, the micro-nano lignocellulose accounts for the 0.1-20wt% of modified polyurethane resin, such as 0.5%,
1%, 2%, 5%, 10%, 15% etc..
Preferably, length >=1 μm of the micro-nano lignocellulose, such as 2 μm, 5 μm, 10 μm etc., diameter 5-
250nm, such as 10nm, 50nm, 100nm, 150nm, 200nm etc..
Preferably, the micro-nano lignocellulose contains the lignin component of 10~35wt%, such as 15wt%,
20wt%, 25wt%, 30wt% etc..
Second aspect, the present invention provides the preparation method of modified polyurethane resin as described in relation to the first aspect, the system
Preparation Method includes the following steps：
(1) cellulosic material containing lignin is added in organic solvent, obtains stock dispersion liquid；
(2) stock dispersion liquid removed by mechanical pretreatment, ground, obtain the first pretreatment product；
(3) first part's polyurethane resin is added in the first pretreatment product, is uniformly mixed, obtains the second pretreatment production
Object；
(4) homogeneous removing is carried out to the second pretreatment product, obtains third pretreatment product；
(5) third pretreatment product and second part polyurethane resin are mixed, obtains the modified polyurethane resin.
It is provided by the invention that preparation method is simple；The lignin contained in micro-nano lignocellulose of the invention
With preferable oil-soluble, binding site can be formed with the lipophilic group in polyurethane, therefore micro-nano lignin can be made
Cellulose can be well dispersed in polyurethane resin.
The present invention prepares micro-nano lignocellulose in such a way that mechanical prestripping and high pressure homogenizer combine, and can keep away
Exempt to directly adopt blocking of the high pressure homogenizer in shattering process, reduces abrasion.
In the prior art, the preparation process of nano-cellulose needs to carry out bleaching, so-called bleaching to raw material
It needs to remove the lignin in raw material using strong acid, highly basic or organic solvent etc..Micro-nano lignin fibre provided by the invention
The preparation method of plain dispersion liquid has directly obtained the micro-nano containing lignin structure to remove lignin without being chemically treated
Rice cellulose.
Preferably, in the stock dispersion liquid of step (1), the concentration of the cellulosic material containing lignin is 1-
20wt%, such as 5wt%, 10wt%, 15wt% etc., preferably 3-10wt%.
Preferably, in the cellulosic material containing lignin, the content of the lignin is 10-30wt%, such as
15wt%, 20wt%, 25wt% etc..
Preferably, step (1) organic solvent be acetone, butanone, formamide, acetamide, n,N-Dimethylformamide,
In DMAC N,N' dimethyl acetamide, ethyl acetate and acetonitrile any one or at least two combination.
Preferably, after step (1) obtains stock dispersion liquid, stock dispersion liquid is heated to reflux 10-30min, such as
12min, 15min, 18min, 20min, 25min etc..
The cellulosic material containing lignin can be promoted to soften using being heated to reflux, be allowed to be conducive to subsequent mechanical pre-
Processing.
Preferably, step (2) described mechanical pretreatment includes any one in ball milling, mill and sand milling or at least two
Combination, further preferably be sanded.
Preferably, during the mechanical pretreatment, the temperature of stock dispersion liquid is kept to be not higher than the organic solvent
Boiling point.
Preferably, before step (2) carry out mechanical pretreatment, grapheme material is added in stock dispersion liquid.
Grapheme material interacts with the raw material for preparing micro-nano lignocellulose, not only contributes to micro-nano wooden
The generation of cellulose fiber element, at the same in the micro-nano lignocellulose generated numerous hydroxyls for containing can further with graphene
Material interaction, can increase dispersibility of the grapheme material in polyurethane resin.
Preferably, step (3) first part's polyurethane resin accounts for the 1-3wt% of polyurethane resin gross mass, such as
1.5wt%, 2wt%, 2.5wt% etc..
Preferably, step (4) the homogeneous removing is carried out using high pressure homogenizer.
Preferably, temperature is kept to be not higher than the boiling point of the organic solvent in homogeneous stripping process.
Preferably, the pressure of step (4) homogeneous removing is 50-150MPa, for example, 60MPa, 80MPa, 100MPa,
120MPa, 140MPa etc., preferably 60-80MPa.
Preferably, the cycle-index of step (4) homogeneous removing is 3-7 times, for example, 4 times, 5 times, it is 6 inferior.
Polyurethane resin of the present invention can be selected according to the actual situation, such as Xu Chuan Chemical Co., Ltd. provides
The polyurethane resins such as XCM-7002, XCM-7003, XCM-7035A, XCM-7006, XCM-7106H.
The third aspect, the present invention provides a kind of modified polyurethane artificial leather, the modified polyurethane artificial leather is by first
Modified polyurethane resin described in aspect is prepared.
Modified polyurethane resin provided by the invention can be directly utilized, prepares polyurethane people using commonly used in the prior art
The technique (such as dry method process hides or wet process process hides) of fabricate-leather prepares modified polyurethane artificial leather, and illustratively, the modification is poly-
The preparation method of urethane artificial leather includes the following steps：
(A) modified polyurethane resin as described in first aspect is diluted, then dilution is coated in release paper, is dry
It is dry, obtain fabric resin；
(B) bottom material resin is coated on the fabric resin that step (A) is obtained, is dried to the matter of the solvent in bottom material resin
Amount percentage composition is 40%-50% (such as 42%, 45%, 48% etc.), then with base fabric pressing, drying, obtains being modified poly- ammonia
Ester artificial leather.
In the present invention, bottom material resin can be selected according to the actual situation, such as can be wanted according to differences such as viscosity
Ask selection Xu Chuan Chemical Co., Ltd. provide XC-900, XC-900L, XC-900H, XC-900F, XC-900HF, XC-800W,
The bottom material resin of the models such as XCS series.
Fourth aspect, the present invention provides the modified polyurethane artificial leathers according to the third aspect in automobile, furniture, family
It spins, the application in Medical Devices or luggage dress ornament.
Compared with the existing technology, the invention has the advantages that：
(1) micro-nano lignocellulose, micro-nano lignin are dispersed in modified polyurethane resin provided by the invention
The lignin contained in cellulose has preferable oil-soluble, can form binding site with the lipophilic group in polyurethane, because
This is the present invention provides a kind of new micro nanometer fiber cellulosic material containing lignin and solves micro-nano cellulose in poly- ammonia
In ester resin the problem of bad dispersibility；
(2) it is dispersed with micro-nano lignocellulose in modified polyurethane resin provided by the invention, poly- ammonia can be improved
The mechanical property of ester resin enhances the performances such as stretching, the tearing of polyurethane resin product, and then can improve the power of end product
Learn performance；
(3) grapheme material is dispersed in modified polyurethane resin provided by the invention, in micro-nano lignocellulose
The have micro-nano cellulose and grapheme material compared with polyhydroxy contained interacts, and can increase grapheme material in poly- ammonia
Dispersibility in ester resin, while the addition of graphene also contributes to point of the micro-nano lignocellulose in polyurethane resin
It dissipates, the two synergistic effect realizes the uniform and stable dispersion in polyurethane resin；
(4) micro-nano lignocellulose and grapheme material are added in polyurethane resin, polyurethane can be increased
Mechanical performance, corrosion-resistant, thermal stability and ageing-resistant performance, and reduce the dilatancy of polyurethane matrix, when with polyurethane
When resin prepares polyurethane artificial leather, it can be made it have good preferable under the premise of keeping polyurethane artificial leather feel
Intensity, while also there are wearability, elasticity, gas permeability, scratch resistance, bacteria mildew-proof, anti-aging and antistatic etc. performances；
(5) preparation method provided by the invention can not be prepared by removing lignin containing the micro- of lignin structure
Nano-cellulose.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.Those skilled in the art should be bright
, the described embodiments are merely helpful in understanding the present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
A kind of modified polyurethane resin, wherein being dispersed with the micro-nano lignocellulose of 10wt% and the graphite of 1wt%
The mass ratio of alkene material, grapheme material and micro-nano lignocellulose is 0.1:1.
It wherein, include the lignin of 20wt%, the length of micro-nano lignocellulose in micro-nano lignocellulose
It is 2 μm, diameter 100nm；Grapheme material is by mechanically pulling off method and is prepared, average platelet thickness 6nm.
Preparation method is as follows：
(1) the cellulosic material adding into acetone containing 20wt% lignin is then refluxed for heating 20min, obtains concentration
For the stock dispersion liquid of 10wt%；
(2) grapheme material is added in stock dispersion liquid, then removed, ground by sanded treatment, obtains
One pretreatment product；
(3) polyurethane resin for accounting for that polyurethane resin gross mass is 2wt% is added in the first pretreatment product, mixing is equal
It is even, obtain the second pretreatment product；
(4) the second pretreatment product is put into high pressure homogenizer, homogeneous removing is carried out at 100MPa, homogeneous removing
Cycle-index is 5 times, obtains third pretreatment product；
(5) third pretreatment product and remaining polyurethane resin are mixed, obtains modified polyurethane resin.
Embodiment 2-8
Difference with embodiment 1 is only that, in modified polyurethane resin provided in this embodiment, the matter of grapheme material
Amount percentage composition be 0.1%, and (mass ratio of grapheme material and micro-nano lignocellulose is 0.01:1, embodiment 2),
10% (mass ratio of grapheme material and micro-nano lignocellulose be 1:1,
Embodiment 3), 12% (mass ratio of grapheme material and micro-nano lignocellulose be 1.2:1, embodiment 4),
It does not include grapheme material (embodiment 5) in modified polyurethane resin provided in this embodiment.
Difference with embodiment 1 is only that, is in the mass ratio of holding grapheme material and micro-nano lignocellulose
0.1:It include the micro-nano that mass percentage is 0.1% in the case that 1 is constant, in modified polyurethane resin provided in this embodiment
Rice lignocellulose (embodiment 6), 20% micro-nano lignocellulose (embodiment 7), 24% micro-nano lignin
Cellulose (embodiment 8).
Embodiment 9
A kind of modified polyurethane resin, wherein being dispersed with the micro-nano lignocellulose of 10wt% and the graphite of 1wt%
The mass ratio of alkene material, grapheme material and micro-nano lignocellulose is 0.1:1.
It wherein, include the lignin of 10wt% in micro-nano lignocellulose, micro-nano lignocellulose length is 1
μm, diameter 4nm；Grapheme material is prepared by liquid phase stripping method, average platelet thickness 3nm.
Preparation method is as follows：
(1) it will be added in n,N-Dimethylformamide containing the cellulosic material of 10wt% lignin, be then refluxed for heating
10min obtains the stock dispersion liquid that concentration is 3wt%；
(2) grapheme material is added in stock dispersion liquid, then removed, ground by ball milling, sanded treatment, obtained
To the first pretreatment product；
(3) polyurethane resin for accounting for that polyurethane resin gross mass is 1wt% is added in the first pretreatment product, mixing is equal
It is even, obtain the second pretreatment product；
(4) the second pretreatment product is put into high pressure homogenizer, homogeneous removing is carried out at 50MPa, homogeneous removing
Cycle-index is 3 times, obtains third pretreatment product；
(5) third pretreatment product and remaining polyurethane resin are mixed, obtains modified polyurethane resin.
Embodiment 10
A kind of modified polyurethane resin, wherein being dispersed with the micro-nano lignocellulose of 10wt% and the graphite of 1wt%
The mass ratio of alkene material, grapheme material and micro-nano lignocellulose is 0.1:1.
It wherein, include the lignin of 35wt% in micro-nano lignocellulose, micro-nano lignocellulose length is
10 μm, diameter 200nm；Grapheme material is prepared by liquid phase stripping method, average platelet thickness 10nm.
Preparation method is as follows：
(1) it will be added in ethyl acetate containing the cellulosic material of 30wt% lignin, be then refluxed for heating 30min, obtain
The stock dispersion liquid for being 1wt% to concentration；
(2) grapheme material is added in stock dispersion liquid, then removed, ground by ball milling, mill processing, obtained
To the first pretreatment product；
(3) polyurethane resin for accounting for that polyurethane resin gross mass is 3wt% is added in the first pretreatment product, mixing is equal
It is even, obtain the second pretreatment product；
(4) the second pretreatment product is put into high pressure homogenizer, homogeneous removing is carried out at 150MPa, homogeneous removing
Cycle-index is 7 times, obtains third pretreatment product；
(5) third pretreatment product and remaining polyurethane resin are mixed, obtains modified polyurethane resin.
Comparative example 1
Difference with embodiment 1 is only that, in this comparative example, micro-nano lignocellulose equivalent is replaced with nanometer
The combination of cellulose and lignin, wherein the mass ratio of nano-cellulose and lignin is remained unchanged with embodiment 1；I.e. this is right
Ratio provide polyurethane material in, including mass percentage be 0.08% nano-cellulose, 0.02% lignin and
0.5% grapheme material.
Comparative example 2
Difference with embodiment 1 is only that, is only dispersed with and embodiment 1 in the modified polyurethane resin that this comparative example provides
The identical grapheme material of mass percentage does not include micro-nano lignocellulose, i.e. the quality percentage of grapheme material
Content is 1%.
Performance test
The embodiment 1-10 and comparative example 1-2 modified polyurethane resin provided is tested for the property：
(1) in product micro-nano lignocellulose detection：Modified polyurethane resin is dissolved or is swollen with solvent, is made
The micro-nano lignocellulose dispersion of partially/whole in a solvent, is centrifuged and cleans removing graphene, obtain micro-nano lignin
Then whether micro-nano lignocellulose is dispersed in water detection lignin and cellulose with chemistry key connection by cellulose：
Carboxymethyl-modification is carried out to the product being dispersed in water, product degree of substitution is made to be greater than 1, and lignin degree of substitution is small
In 0.4 (being verified by lignin model compound).It is centrifugated after taking modified product to be sufficiently stirred, by supernatant and sediment
Freeze-drying obtains the hydrotrope and sediment respectively, and measurement sediment accounts for the mass fraction and micro-nano wood of carboxymethylated product
Hemicellulose and content of lignin in quality cellulose fibre judge to change between lignin and cellulose according to its contents of precipitate
The presence for learning key, further determines that the presence of micro-nano lignocellulose；
1 is shown in Table for the test result for the modified polyurethane resin that embodiment 1 and comparative example 2 provide：
Table 1
Polysaccharide compound carboxymethyl-modification degree of substitution is dissolvable in water in water when being greater than 0.4, and lignin carboxy methylation
Degree is not soluble in water less than 0.4.If hemicellulose and lignin, which exist, stablizes chemical bonding, even if hemicellulose carboxymethyl
Change degree of substitution and be greater than 0.4, still has portion of cellulose and be present in carboxymethylated product precipitating.
As can be seen from Table 1, micro-nano lignocellulose lignin and hemicellulose quality before modified that embodiment 1 provides
Measuring score summation is 27.1%, much smaller than the mass percentage of modified sediment, it was demonstrated that there is part carboxymethylated cellulosic
It is present in carboxymethylated product precipitating, i.e., exists between cellulose and lignin and stablize chemical bond, to prove in embodiment 1
The presence of micro-nano lignocellulose.And after 1 product carboxy methylation of comparative example, content of lignin 15.8%, with sediment
Mass fraction matches, and illustrates that there is no carboxymethyl celluloses in sediment, i.e. cellulose and lignin is without chemical bonds.
(2) tensile strength：By the measurement of GB/T 528-2009 vulcanized rubber or thermoplastic elastomer tensile stress-strain performance
Standard is tested；
(3) tearing strength：It is carried out by the measurement standard of GB/T 529-2008 vulcanized rubber or thermoplastic elastomer tearing strength
Test.
2 are shown in Table to the test result of the embodiment 1-10 and comparative example 1-2 polyurethane material provided：
Table 2
In the present invention, we characterized using the mechanical performance of modified polyurethane resin micro-nano lignocellulose and
Dispersion performance of the grapheme material in modified polyurethane resin, because micro-nano lignocellulose and grapheme material are changing
Property polyurethane resin in dispersibility it is better, then mechanical performance is better；Conversely, the mechanical performance of modified polyurethane resin is better,
Then prove that the dispersibility of micro-nano lignocellulose and grapheme material is better.
By embodiment and performance test it is found that the better mechanical property of modified polyurethane resin provided by the invention,
In, tensile strength is in 60MPa or more, and tearing strength is in 55N/mm or more, i.e., micro-nano lignocellulose and grapheme material
Dispersibility in modified polyurethane resin is preferably；By embodiment 1 and embodiment 4-5,8 comparison it is found that when the present invention provides
Modified polyurethane resin in the content of micro-nano lignocellulose, micro-nano lignocellulose and grapheme material ratio
When being worth in the preferred range, the mechanical performance of modified polyurethane resin provided by the invention is more excellent, wherein tensile strength
In 75MPa or more, tearing strength is in 62N/mm or more；By the comparison of embodiment 1 and comparative example 1 it is found that provided by the invention change
The micro-nano lignocellulose dispersed in property polyurethane resin can not equivalent replace with the group of lignin and nano-cellulose
It closes, by the comparison of embodiment 1,5 and comparative example 2 it is found that being dispersed with micro-nano wood in modified polyurethane resin provided by the invention
Quality cellulose and grapheme material can mutually promote, and synergistic effect improves its uniform and stable point in polyurethane resin
It dissipates, to enhance the performance of polyurethane resin.
Application examples 1
The application example provides a kind of modified polyurethane artificial leather answering as modified polyurethane resin provided by the invention
With.
In the application example, used fabric resin is the modified polyurethane resin that embodiment 1 provides, and polyurethane tree
Rouge is provided by Xu Chuan Chemical Co., Ltd., model XCS-2565C；Used bottom material resin is mentioned by Xu Chuan Chemical Co., Ltd.
For model XC-900H.
Preparation method is as follows：
(1) modified polyurethane resin for obtaining embodiment 1 dilutes, and then dilution has been coated in modeling release paper,
Then dry at 100 DEG C, obtain fabric resin；
(2) bottom material resin is coated on the fabric resin that step (1) obtains, 15s is dried at 110 DEG C to bottom material resin
In the mass percentage of solvent be 45%, then pressed with base fabric, it is dry at 120 DEG C, it is artificial to obtain modified polyurethane
Leather.
The modified polyurethane artificial leather that the application example provides can be used as vamp, luggage.
Application examples 2
Difference with application examples 1 is only that, the model XCS-5230DY for the polyurethane resin that the application example provides, bottom material
The model XAC-88H of resin is provided by Xu Chuan Chemical Co., Ltd..
The modified polyurethane artificial leather that the application example provides can be used as dress ornament.
Application examples 3
Difference with application examples 1 is only that, the model XCY-5565A for the polyurethane resin that the application example provides, bottom material
The model XCA-4050 of resin is provided by Xu Chuan Chemical Co., Ltd..
The modified polyurethane artificial leather that the application example provides can be used as luggage, sofa.
The Applicant declares that the present invention is explained by the above embodiments modified polyurethane resin and its preparation side of the invention
Method, modified polyurethane artificial leather and application, but the invention is not limited to above-mentioned method detaileds, that is, do not mean that the present invention is necessary
Relying on above-described embodiment could implement.It should be clear to those skilled in the art, any improvement in the present invention, to this
The equivalence replacement of each raw material of invention product and addition, the selection of concrete mode of auxiliary element etc., all fall within protection of the invention
Within range and the open scope.
Claims (10)
1. a kind of modified polyurethane resin, which is characterized in that it is fine to be dispersed with micro-nano lignin in the modified polyurethane resin
Dimension element.
2. modified polyurethane resin according to claim 1, which is characterized in that also disperse in the modified polyurethane resin
There is grapheme material；
Preferably, the grapheme material is to be by mechanically pulling off method, oxidation-reduction method, pyrolysis method, intercalation stripping method, chemistry
Vapour deposition process, liquid phase stripping method or biomass by hydro-thermal carbonizatin method are prepared；
Preferably, the average platelet thickness of the grapheme material is≤20nm, preferably 3~10nm；
Preferably, the mass ratio of the grapheme material and micro-nano lignocellulose is (0.01-1):1.
3. modified polyurethane resin according to claim 1, which is characterized in that the micro-nano lignocellulose, which accounts for, to be changed
The 0.1-20wt% of property polyurethane resin；
Preferably, length >=1 μm of the micro-nano lignocellulose, diameter 5-250nm；
Preferably, the micro-nano lignocellulose contains the lignin component of 10~35wt%.
4. the preparation method of modified polyurethane resin described in any one of -3 according to claim 1, which is characterized in that described
Preparation method includes the following steps：
(1) cellulosic material containing lignin is added in organic solvent, obtains stock dispersion liquid；
(2) stock dispersion liquid removed by mechanical pretreatment, ground, obtain the first pretreatment product；
(3) first part's polyurethane resin is added in the first pretreatment product, is uniformly mixed, obtains the second pretreatment product；
(4) homogeneous removing is carried out to the second pretreatment product, obtains third pretreatment product；
(5) third pretreatment product and second part polyurethane resin are mixed, obtains the modified polyurethane resin.
5. the preparation method according to claim 4, which is characterized in that described to contain in the stock dispersion liquid of step (1)
The concentration of the cellulosic material of lignin is 1-20wt%, preferably 3-10wt%；
Preferably, in the cellulosic material containing lignin, the content of the lignin is 10-30wt%；
Preferably, step (1) organic solvent is acetone, butanone, formamide, acetamide, n,N-Dimethylformamide, N, N-
In dimethyl acetamide, ethyl acetate and acetonitrile any one or at least two combination；
Preferably, after step (1) obtains stock dispersion liquid, stock dispersion liquid is heated to reflux 10-30min.
6. preparation method according to claim 4 or 5, which is characterized in that step (2) described mechanical pretreatment includes ball
In mill, mill and sand milling any one or at least two combination, be further preferably sanded；
Preferably, before step (2) carry out mechanical pretreatment, grapheme material is added in stock dispersion liquid.
7. the preparation method according to any one of claim 4-6, which is characterized in that step (3) described first part
Polyurethane resin accounts for the 1-3wt% of polyurethane resin gross mass.
8. the preparation method according to any one of claim 4-7, which is characterized in that step (4) the homogeneous removing
It is carried out using high pressure homogenizer；
Preferably, the pressure of step (4) the homogeneous removing is 50-150MPa, preferably 60-80MPa；
Preferably, the cycle-index of step (4) the homogeneous removing is 3-7 times.
9. a kind of modified polyurethane artificial leather, which is characterized in that the modified polyurethane artificial leather is by appointing in claim 1-3
Modified polyurethane resin described in one is prepared.
10. modified polyurethane artificial leather according to claim 9 is in automobile, furniture, home textile, Medical Devices or luggage dress ornament
In application.
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| CN201810738482.9A CN108841163A (en) | 2018-07-06 | 2018-07-06 | Modified polyurethane resin and preparation method thereof, modified polyurethane artificial leather and application |
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| CN201810738482.9A CN108841163A (en) | 2018-07-06 | 2018-07-06 | Modified polyurethane resin and preparation method thereof, modified polyurethane artificial leather and application |
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| CN111549540A (en) * | 2020-05-25 | 2020-08-18 | 天守(福建)超纤科技股份有限公司 | Method for manufacturing one-way solvent-free polyurethane resin artificial leather |
| CN116554673A (en) * | 2023-05-16 | 2023-08-08 | 广东技塑新材料股份有限公司 | Degradable TPU (thermoplastic polyurethane) for shoe material and preparation method thereof |
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| CN116554673A (en) * | 2023-05-16 | 2023-08-08 | 广东技塑新材料股份有限公司 | Degradable TPU (thermoplastic polyurethane) for shoe material and preparation method thereof |
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Application publication date: 20181120 |