CN110527047A - A kind of biology base waterborne polyurethane resin and its preparation method and application - Google Patents
A kind of biology base waterborne polyurethane resin and its preparation method and application Download PDFInfo
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- CN110527047A CN110527047A CN201910801782.1A CN201910801782A CN110527047A CN 110527047 A CN110527047 A CN 110527047A CN 201910801782 A CN201910801782 A CN 201910801782A CN 110527047 A CN110527047 A CN 110527047A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
Abstract
The invention discloses a kind of biology base waterborne polyurethane resins and its preparation method and application, including at least following mass component: the biology base macromolecular polyol of 70-100 mass parts, the biological based isocyanate of 15-30 mass parts, the graphene oxide etc. of 0.02-0.2 mass parts.The present invention can improve the performances such as the folding quality, wear-resisting property, mechanical property of biology base waterborne polyurethane resin.
Description
Technical field
The invention belongs to polyurethane resin synthesis technical fields, and in particular to a kind of biology base waterborne polyurethane resin and its
Preparation method and application.
Background technique
Biology base macromolecular polyol and biological based isocyanate are most of all from vegetable oil series, resourceful,
And cheap, raw material are easy to obtain；Biological fundamental mode waterborne polyurethane resin has degradability and environmental-friendly
Feature meets instantly environmentally protective concept；The development of biological fundamental mode waterborne polyurethane resin can be lacked with even without petroleum
The polyalcohol of series, using the polyalcohol of vegetable oil series, excessive use that can not only be energy saving can also promote agricultural
Development, therefore, the exploitation of biological fundamental mode waterborne polyurethane resin has a very important significance.However, current biology base
There is also folding quality, wear-resisting property, solvent resistances, that is, resistance to DOP performance, mechanical property, storage performance for waterborne polyurethane resin
And the defect that the performances such as constant temperature and humidity performance are not high enough.
Summary of the invention
In view of the foregoing deficiencies of prior art, the purpose of the present invention is to provide a kind of biological base water polyurethane trees
Rouge and its preparation method and application can significantly improve the folding quality, wear-resisting property, resistance to DOP performance, power of waterborne polyurethane resin
Learn the performances such as performance, storage performance and constant temperature and humidity performance.
To achieve the goals above or other purposes, the present invention is achieved by the following technical solutions, a kind of biology
Base water polyurethane resin includes at least following mass component:
Wherein, the graphene oxide is the graphene oxide containing hydroxyl and carboxyl, for aqueous to the biology base
Polyurethane resin carries out chemical modification.
In one embodiment, the mass fraction of nitrogen is 4%-10% in the graphene oxide.
In one embodiment, the biology base macromolecular polyol includes castor oil, castor oil derivative polyalcohol, dimerization
Any one or more combination in sour polyalcohol and 1,3-PD polyether polyol.
In one embodiment, the biological based isocyanate includes dimer acid diisocyanate, biology base Isosorbide-5-Nitrae-Ding Eryi
Cyanate, biology base 1, any one or more combination in penta diisocyanate of 5-.
In one embodiment, the small molecule polyol chain extender includes trimethylolpropane, glycerol, butanediol, second two
Any one or more combination in pure and mild cyclohexanedimethanol.
In one embodiment, the small molecule polyamine chain extender includes ethylenediamine, hexamethylene diamine, in isophorone diamine
Any one or more combination.
In one embodiment, the carboxylic acid type hydrophilic chain extender includes any in dihydromethyl propionic acid and dihydroxy butyric acid
One or more combinations.
In one embodiment, the neutralizer include in triethylamine, diethanol amine and triethanolamine any one or it is more
Kind.
The present invention relates to a kind of preparation methods of waterborne polyurethane resin, include at least following steps,
The graphene oxide of 0.02-0.2 mass parts is configured to graphene oxide solution；
By the life of the biology base macromolecular polyol, 15-30 mass parts of the graphene oxide solution, 70-100 mass parts
The small molecule polyol chain extender of object based isocyanate, the carboxylic acid type hydrophilic chain extender of 1-3 mass parts and 3-8 mass parts carries out
It is mixed, obtains Waterborne Polyurethane Prepolymer；
Under stirring, by the Waterborne Polyurethane Prepolymer, the neutralizer of 1-4 mass parts, deionized water and 3-8 matter
The small molecule amine rear chain extender mixing for measuring part, obtains the biology base waterborne polyurethane resin.
The invention further relates to application of the biology base waterborne polyurethane resin in clothing leather described in one kind.
The present invention introduces graphene oxide in biology base waterborne polyurethane resin synthesis process, to improve biology base
The performance of waterborne polyurethane resin.The graphene oxide that the present invention uses has the structures such as hydroxyl and carboxyl, is easy to aqueous poly-
Urethane carries out chemical modification.Biology base waterborne polyurethane resin mainly utilizes biological fundamental mode isocyanates and biology base macromolecular
Polyols preparation introduces graphene in biology base waterborne polyurethane resin synthesis process and carries out chemical modification, utilizes oxygen
The special construction of graphite alkene improves the properties of biological base water polyurethane.It is found by test, graphene oxide makes
Folding quality, wear-resisting property, solvent resistance, mechanical property, storage performance and the perseverance of biological base water polyurethane fabric resin
Constant temperature and humidity performance has a more substantial increase.The present invention is during preparing biology base aqueous polyurethane dispersion without being added
Organic solvent avoids environmental pollution, has reached low-carbon, environmental protection, energy-efficient target.
Detailed description of the invention
Fig. 1 is the method flow schematic diagram of one embodiment of the invention.
Specific embodiment
Illustrate embodiments of the present invention below by way of particular specific embodiment, those skilled in the art can be by this explanation
Other advantages and efficacy of the present invention can be easily understood for content disclosed by book.The present invention can also be by addition different specific
Embodiment is embodied or practiced, and the various details in this specification can also not carried on the back based on different viewpoints and application
From carrying out various modifications or alterations under spirit of the invention.It should be noted that in the absence of conflict, following embodiment and reality
The feature applied in example can be combined with each other.It is also understood that term used in the embodiment of the present invention is specific in order to describe
Specific embodiment, rather than limiting the scope of protection of the present invention.The test of actual conditions is not specified in the following example
Method, usually according to normal condition, or according to condition proposed by each manufacturer.
When embodiment provides numberical range, it should be appreciated that except non-present invention is otherwise noted, two ends of each numberical range
Any one numerical value can be selected between point and two endpoints.Unless otherwise defined, the present invention used in all technologies and
The grasp and record of the invention of scientific term and those skilled in the art to the prior art, can also use and this hair
Any method, equipment and the material of the similar or equivalent prior art of bright method as described in the examples, equipment, material is realized
The present invention.
Note that be such as not particularly illustrated, it is described herein shown in " % " and " part " refer respectively to " quality % " and " quality
Part ".
As shown in Figure 1, providing a kind of preparation method of biology base waterborne polyurethane resin, following steps are included at least,
S1, graphene oxide is configured to graphene oxide solution；
It is S2, the graphene oxide solution, biology base macromolecular polyol, biological based isocyanate, carboxylic acid type is hydrophilic
Chain extender and small molecule polyol chain extender are mixed, and Waterborne Polyurethane Prepolymer is obtained；
S3, under stirring, will expand after the Waterborne Polyurethane Prepolymer, neutralizer, deionized water and small molecule amine
Chain agent mixing, obtains the biology base waterborne polyurethane resin.
Specifically, in step sl, the graphene oxide of 0.02-0.2 mass parts is configured to graphene oxide solution.With
Such as the graphene oxide of 0.02-0.2 mass parts is configured to graphene oxide solution by N-Methyl pyrrolidone, wherein described
Graphene oxide is the graphene oxide containing hydroxyl and carboxyl, is changed for carrying out chemistry to biology base waterborne polyurethane resin
Property.The mass fraction of nitrogen is 4%-10% in the graphene oxide.Graphene oxide containing hydroxyl and carboxyl is conducive to pair
Biological base water polyurethane is modified, and the nitrogen content in graphene oxide has significant shadow to the performance of biological base water polyurethane
It rings.
Specifically, in step s 2, the graphene oxide solution, the biology base macromolecular of 70-100 mass parts is polynary
Alcohol, the biological based isocyanate of 15-30 mass parts, small point of the carboxylic acid type hydrophilic chain extender of 1-3 mass parts and 3-8 mass parts
Sub- polyol chain extender is mixed, and Waterborne Polyurethane Prepolymer is obtained；In step s 2, detailed process are as follows: by 70-
The biology base macromolecular polyol of 100 mass parts and the biological based isocyanate of 15-30 mass parts stir 1-3 at 80-90 DEG C
Hour, be then added the graphene oxide solution, 80-90 DEG C stirring 1-1.5 hours, (temperature of cooling is in 65-75 after cooling
Within the scope of DEG C) the carboxylic acid type hydrophilic chain extender of 1-3 mass parts is added, the small molecule polyol chain extender of 3-8 mass parts is warming up to
Predetermined temperature (predetermined temperature is within the scope of 65-75 DEG C) stirs 2-4 hours, obtains Waterborne Polyurethane Prepolymer.Present invention preparation
Waterborne Polyurethane Prepolymer it is easy to operate, dispersion is easier, and synthesis process is easy to control.The biology base macromolecular polyol packet
Include in castor oil, castor oil derivative polyalcohol, dimeric dibasic acid polyalcohol and 1,3-PD polyether polyol any one or
Multiple combinations.The biology based isocyanate includes dimer acid diisocyanate, biology base Isosorbide-5-Nitrae-fourth diisocyanate, biology base
Any one or more combination in 1,5- penta diisocyanate.The small molecule polyol chain extender includes trihydroxy methyl third
Any one or more combination in alkane, glycerol, butanediol, ethylene glycol and cyclohexanedimethanol.The carboxylic acid type hydrophilic chain extender
Including any one or more combination in dihydromethyl propionic acid and dihydroxy butyric acid.
Specifically, in step s3, under stirring, by the Waterborne Polyurethane Prepolymer, the neutralization of 1-4 mass parts
The small molecule amine rear chain extender of agent, deionized water and 3-8 mass parts mixes, and obtains the biology base waterborne polyurethane resin.Tool
Body process are as follows: the Waterborne Polyurethane Prepolymer is cooled to 1-20 DEG C, is transferred to high speed after the neutralizer of 1-4 mass parts is added
In dispersion machine, deionized water is added under high-speed stirred, the small molecule amine rear chain extender of 3-8 mass parts is added after 1-3 minutes, obtains
The Waterborne Polyurethane Prepolymer.The small molecule polyamine chain extender includes ethylenediamine, hexamethylene diamine, in isophorone diamine
Any one or more combination.The neutralizer includes any one or more in triethylamine, diethanol amine and triethanolamine.
The present invention is illustrated with some specific embodiments.
In various embodiments, the mass fraction of nitrogen includes 4-4.5%, 6-7%, 8-9% in graphene oxide,
9.5%-10% and 5%-6%.The nitrogen content of graphene oxide has a significant impact the performance of biological base water polyurethane, example
Such as, the influence of graphene oxide is different under different technology conditions, and nitrogen content is not that the higher the better, nor it is more low more
Difference, in various raw material ranges of the invention, the mass fraction of nitrogen is within the scope of 4%-10%, the aqueous poly- ammonia of modified biology base
Ester resin comprehensive performance is preferable.The quality of graphene oxide includes 0.05-1g, 1.5-3g.Castor oil derivative polyalcohol, castor
Sesame oil, dimeric dibasic acid polyalcohol dosage include 75-80g, 95-100g, 85-90g.The dosage of dimer acid diisocyanate includes
15-18g, 20-25g.The ratio of biology base macromolecular polyol and biological based isocyanate of the invention is to biology base obtained
The performance of aqueous polyurethane has certain influence, for example, constant temperature and humidity performance, wear-resisting property etc..Trimethylolpropane, ethylenediamine
Dosage includes 3-4g, 5-6g, 7-8g, and trimethylolpropane is identical as the dosage of ethylenediamine, it is therefore an objective to keep chain extension more abundant, more
Conducive to the modification of graphene oxide.The step of stirring at 80-90 DEG C, which is included at 85 DEG C, stirs.Predetermined temperature is at 65-75 DEG C
It include 65 DEG C, 65-66 DEG C, 70 DEG C, 75 DEG C in range.
Embodiment 1
A kind of preparation method of biology base waterborne polyurethane resin, comprising the following steps:
75-80g castor oil derivative polyalcohol (relative molecular mass 1000) is weighed, is put into reactor, is being stirred
20-25g dimer acid diisocyanate is added under state, is kept for 80-90 DEG C of temperature, stirs 2-3 hours.0.05-1g is added to prepare
Graphene oxide solution (graphene oxide 0.02-0.04g), graphene oxide solution for example matched by N-Methyl pyrrolidone
It makes, is kept for 80-90 DEG C of temperature, stir 2-3 hours.It is cooled to 65-66 DEG C of addition 2.5-3g dihydromethyl propionic acid (DMPA),
3-4g trimethylolpropane is warming up to 70-71 DEG C, and keeps 70-71 DEG C of stirring 2-3 hours, and biology base water polyurethane is made
Performed polymer.
Waterborne Polyurethane Prepolymer is cooled to 5-8 DEG C, 1-1.5g triethylamine is added, stirs 10-15 minutes, then shifts
To high-speed emulsifying machine, 200g-220g deionized water is added under 1400-1600 revs/min of revolving speed, 3- is added after 1-3 minutes
Biology base waterborne polyurethane resin is made in 4g ethylenediamine.
In the embodiment, graphene oxide is the graphene oxide containing hydroxyl and carboxyl, wherein the mass fraction of nitrogen is
4-4.5% is modified biology base waterborne polyurethane resin using the graphene oxide of above-mentioned condition, the aqueous poly- ammonia of biology base
Folding quality, wear-resisting property, solvent resistance, mechanical property, storage performance and the constant temperature and humidity performance of ester have to be mentioned by a relatively large margin
The biology base waterborne polyurethane resin is applied in fabric by height, and the peel strength of fabric can reach 70-80KN/m and resistance to
Mill performance reaches 15-20 ten thousand times.
Embodiment 2
A kind of preparation method of biology base waterborne polyurethane resin, comprising the following steps:
95-100g castor oil (relative molecular mass 1000) is weighed, is put into reactor, is added under stirring
15-18g dimer acid diisocyanate is kept for 80-90 DEG C of temperature, is stirred 2-3 hours.The graphite oxide that 0.05-1g is prepared is added
Alkene solution (graphene oxide 0.02-0.04g), graphene oxide solution are for example formulated by N-Methyl pyrrolidone, are protected
80-90 DEG C of temperature is held, is stirred 2-3 hours.It is cooled to 65-66 DEG C of addition 3-4g dihydromethyl propionic acid (DMPA), tri- hydroxyl first of 7-8g
Base propane is warming up to 70-71 DEG C, and keeps 70-71 DEG C of stirring 2-3 hours, and biology base Waterborne Polyurethane Prepolymer is made.
Waterborne Polyurethane Prepolymer is cooled to 5-8 DEG C, 1-1.5g triethylamine is added, stirs 10-15 minutes, then shifts
To high-speed emulsifying machine, 200g-220g deionized water is added under 1400-1600 revs/min of revolving speed, 7- is added after 1-3 minutes
Biology base waterborne polyurethane resin is made in 8g ethylenediamine.
In the embodiment, graphene oxide is the graphene oxide containing hydroxyl and carboxyl, wherein the mass fraction of nitrogen is
6-7% is modified biology base waterborne polyurethane resin using the graphene oxide of above-mentioned condition, biological base water polyurethane
Folding quality, wear-resisting property, solvent resistance, mechanical property, storage performance and constant temperature and humidity performance have a more substantial increase,
The biology base waterborne polyurethane resin is applied in fabric, the peel strength of fabric can reach 100-110KN/m and resistance to
Mill performance reaches 20-25 ten thousand times.
Embodiment 3
A kind of preparation method of biology base waterborne polyurethane resin, comprising the following steps:
85-90g dimeric dibasic acid polyalcohol (relative molecular mass 1000) is weighed, is put into reactor, under stirring
20-25g dimer acid diisocyanate is added, is kept for 80-90 DEG C of temperature, stirs 2-3 hours.The oxidation that 0.05-1g is prepared is added
Graphene solution (graphene oxide 0.02-0.04g), graphene oxide solution for example by N-Methyl pyrrolidone prepare and
At 80-90 DEG C of temperature of holding is stirred 2-3 hours.It is cooled to 70-71 DEG C of addition 2.5-3g dihydromethyl propionic acid (DMPA), 3-4g
Trimethylolpropane is warming up to 75-76 DEG C, and keeps 75-76 DEG C of stirring 2-3 hours, and biology base water polyurethane pre-polymerization is made
Body.
Waterborne Polyurethane Prepolymer is cooled to 5-8 DEG C, 1-1.5g triethylamine is added, stirs 10-15 minutes, then shifts
To high-speed emulsifying machine, 200g-220g deionized water is added under 1400-1600 revs/min of revolving speed, 3- is added after 1-3 minutes
Biology base waterborne polyurethane resin is made in 4g ethylenediamine.
In the embodiment, graphene oxide is the graphene oxide containing hydroxyl and carboxyl, wherein the mass fraction of nitrogen is
8-9% is modified biology base waterborne polyurethane resin using the graphene oxide of above-mentioned condition, biological base water polyurethane
Folding quality, wear-resisting property, solvent resistance, mechanical property, storage performance and constant temperature and humidity performance have a more substantial increase,
The biology base waterborne polyurethane resin is applied in fabric, the peel strength of fabric can reach 105-118KN/m and resistance to
Mill performance reaches 25-28 ten thousand times.
Embodiment 4
A kind of preparation method of biology base waterborne polyurethane resin, comprising the following steps:
75-80g castor oil derivative polyalcohol (relative molecular mass 1000) is weighed, is put into reactor, is being stirred
20-25g dimer acid diisocyanate is added under state, is kept for 80-90 DEG C of temperature, stirs 2-3 hours.It is added what 1.5-3g was prepared
Graphene oxide solution (graphene oxide 0.06-0.08g), graphene oxide solution are for example prepared by N-Methyl pyrrolidone
It forms, is kept for 80-90 DEG C of temperature, stir 2-3 hours.It is cooled to 65-66 DEG C of addition 2.5-3g dihydromethyl propionic acid (DMPA), 3-
4g trimethylolpropane is warming up to 70-71 DEG C, and keeps 70-71 DEG C of stirring 2-3 hours, and it is pre- that biology base water polyurethane is made
Aggressiveness.
Waterborne Polyurethane Prepolymer is cooled to 5-8 DEG C, 1-1.5g triethylamine is added, stirs 10-15 minutes, then shifts
To high-speed emulsifying machine, 200g-220g deionized water is added under 1400-1600 revs/min of revolving speed, 3- is added after 1-3 minutes
Biology base waterborne polyurethane resin is made in 4g ethylenediamine.
In the embodiment, graphene oxide is the graphene oxide containing hydroxyl and carboxyl, wherein the mass fraction of nitrogen is
4-4.5%, the quality of graphene oxide solution are 1.5-3g, and the quality of graphene oxide is 0.06-0.08g, uses above-mentioned item
The graphene oxide of part is modified biology base waterborne polyurethane resin, the folding quality of biological base water polyurethane, wear-resisting
Performance, solvent resistance, mechanical property, storage performance and constant temperature and humidity are preferable, by the biological base water polyurethane tree
Rouge is applied in fabric, and the peel strength of fabric can reach 85-90KN/m and wear-resisting property reaches 18-22 ten thousand times.
Comparative example 1
A kind of preparation method of biology base waterborne polyurethane resin, comprising the following steps:
75-80g castor oil derivative polyalcohol (relative molecular mass 1000) is weighed, is put into reactor, is being stirred
20-25g dimer acid diisocyanate is added under state, is kept for 80-90 DEG C of temperature, stirs 2-3 hours.65-66 DEG C is cooled to add
Enter 2.5-3g dihydromethyl propionic acid (DMPA), 3-4g trimethylolpropane is warming up to 70-71 DEG C, and keeps 70-71 DEG C of stirring 2-
3 hours, biology base Waterborne Polyurethane Prepolymer is made.
Waterborne Polyurethane Prepolymer is cooled to 5-8 DEG C, 1-1.5g triethylamine is added, stirs 10-15 minutes, then shifts
To high-speed emulsifying machine, 200g-220g deionized water is added under 1400-1600 revs/min of revolving speed, 3- is added after 1-3 minutes
Biology base waterborne polyurethane resin is made in 4g ethylenediamine.
In the embodiment, graphene oxide is not added, the folding resistance of biology base water polyurethane made from the embodiment
Energy, wear-resisting property, solvent resistance, mechanical property, storage performance and constant temperature and humidity performance are without being added graphene oxide institute
The performance of biology base waterborne polyurethane resin obtained is high.The biology base waterborne polyurethane resin is applied in fabric, face
The peel strength of material can reach 30-40KN/m and wear-resisting property reaches 100,000 times.
Application note of the invention: by biology base waterborne polyurethane resin prepared by the present invention specifically answering in clothing leather
With, first by biology base waterborne polyurethane resin prepared by the present invention be used as precoat be coated in release paper on, then in release paper
On the successively bed of material and initial bed in coating, the middle bed of material and initial bed select biology base waterborne polyurethane resin of the invention and its
His type of resin, obtains clothing leather after drying.
Performance detection
To the section Example of the invention biological base water polyurethane fabric resin progressive as obtained by embodiment 1-5
It can test:
(1) folding quality: the test of room temperature folding machine, folding test result are as shown in table 1.
(2) wear-resisting property: the test of Martindale's wear resistant instrument, the results are shown in Table 1 for wear-resisting test.
(3) solvent resistance: i.e. resistance to DOP performance, the test of DOP solvent soaking, test result are as shown in table 1.
(4) mechanical property: tension tester test, tensile strength test results are as shown in table 1.
(5) storage performance: 50 DEG C of baking ovens place test, and test result is as shown in table 1.
(6) constant temperature and humidity is tested: the test of constant temperature and humidity tester, constant temperature and humidity test result are as shown in table 1.
1. performance test table of table
It can be obtained from table 1, compared to biology base waterborne polyurethane resin made from no addition graphene oxide, oxygen is added
The folding quality of biology base waterborne polyurethane resin made from graphite alkene, wear-resisting property, resistance to DOP performance, mechanical property, storage
Performance and constant temperature and humidity performance have a more substantial increase.Also it can be obtained from side, the graphene oxide under different technology conditions
Influence of the nitrogen content to biology base waterborne polyurethane resin.
In addition, it should also be understood that, one or more method and step mentioned in the present invention does not repel before and after the combination step
It can also be inserted into other methods step there may also be other methods step or between these explicitly mentioned steps, unless separately
It is described；It should also be understood that unless otherwise indicated, the number of various method steps is only the convenient tool of identification various method steps, and
It is non-that to limit the arrangement order of various method steps or limit the scope of the invention, relativeness is altered or modified,
Without material changes in technical content, when being also considered as the enforceable scope of the present invention.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should be covered by the claims of the present invention.
Claims (10)
1. a kind of biology base waterborne polyurethane resin, which is characterized in that include at least following mass component:
Wherein, the graphene oxide is the graphene oxide containing hydroxyl and carboxyl, is used for poly- ammonia aqueous to the biology base
Ester resin carries out chemical modification.
2. biology base waterborne polyurethane resin according to claim 1, which is characterized in that nitrogen in the graphene oxide
Mass fraction is 4%-10%.
3. biology base waterborne polyurethane resin according to claim 1, which is characterized in that the biology base macromolecular is polynary
Alcohol includes any one in castor oil, castor oil derivative polyalcohol, dimeric dibasic acid polyalcohol and 1,3-PD polyether polyol
Kind or multiple combinations.
4. biology base waterborne polyurethane resin according to claim 1, which is characterized in that the biology based isocyanate packet
Dimer acid diisocyanate, biology base Isosorbide-5-Nitrae-fourth diisocyanate, biology base 1 are included, any one in penta diisocyanate of 5-
Or multiple combinations.
5. biology base waterborne polyurethane resin according to claim 1, which is characterized in that the small molecule polyol chain extension
Agent includes any one or more combination in trimethylolpropane, glycerol, butanediol, ethylene glycol and cyclohexanedimethanol.
6. waterborne polyurethane resin according to claim 1, which is characterized in that the small molecule polyamine chain extender includes
Ethylenediamine, hexamethylene diamine, any one or more combination in isophorone diamine.
7. biology base waterborne polyurethane resin according to claim 1, which is characterized in that the carboxylic acid type hydrophilic chain extender
Including any one or more combination in dihydromethyl propionic acid and dihydroxy butyric acid.
8. biology base waterborne polyurethane resin according to claim 1, which is characterized in that the neutralizer includes three second
Any one or more in amine, diethanol amine and triethanolamine.
9. a kind of preparation method of biology base waterborne polyurethane resin, which is characterized in that following steps are included at least,
The graphene oxide of 0.02-0.2 mass parts is configured to graphene oxide solution；
By the graphene oxide solution, the biology base macromolecular polyol of 70-100 mass parts, 15-30 mass parts biology base
The small molecule polyol chain extender of isocyanates, the carboxylic acid type hydrophilic chain extender of 1-3 mass parts and 3-8 mass parts is mixed
Stirring obtains Waterborne Polyurethane Prepolymer；
Under stirring, by the Waterborne Polyurethane Prepolymer, the neutralizer of 1-4 mass parts, deionized water and 3-8 mass parts
Small molecule amine rear chain extender mixing, obtain the biology base waterborne polyurethane resin.
10. a kind of such as application of the described in any item biology base waterborne polyurethane resins of claim 1-8 in clothing leather.
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Application publication date: 20191203 |