CN106866918A - A kind of urethane composition and preparation method - Google Patents
A kind of urethane composition and preparation method Download PDFInfo
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- CN106866918A CN106866918A CN201510919093.2A CN201510919093A CN106866918A CN 106866918 A CN106866918 A CN 106866918A CN 201510919093 A CN201510919093 A CN 201510919093A CN 106866918 A CN106866918 A CN 106866918A
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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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
- C08K5/00—Use of organic ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
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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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
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- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a kind of urethane composition and preparation method thereof.The composition includes：Polyurethane and melanin；Counted by 100 weight portions of polyurethane；The weight portion of melanin 0.05~30.Preparation method includes：Melanin is well mixed in 500~1000mL solvents first, polyalcohol, isocyanates are added in melanin solution again, stirring, heating carry out prepolymerization reaction and obtain performed polymer, it is subsequently added chain extender, (or being added without) curing agent is added, 80~120 DEG C of reactions are obtained the urethane composition.The tensile strength and elongation at break of compound polyurethane material prepared by the present invention are significantly improved.
Description
Technical field
The present invention relates to compositions field, further say, be to be related to a kind of urethane composition and preparation side
Method.
Background technology
Polyurethane (PU) is to carry repetition by polyalcohol and the obtained class main chain of polyisocyanates reaction
The general name of the polymer of-NHCOO- groups.Because raw materials used functional group number purpose is different, line can be divided into
The high molecular polymer of type structure and three-dimensional-structure.Polyester or the flexible soft section of polyethers composition and amino first in structure
The rigidity hard section such as acid esters, urea groups is alternately connected；Because of soft, hard segment thermodynamic differences, soft section and hard section exist
Can each self aggregation, formation soft section phase and hard section phase, generation microphase-separated in polymer.Due to this uniqueness
Micro phase separation structure, makes it have many excellent performances, and has very strong bonding force with multiple material, from
And it is widely used as the fields such as petrochemical industry, transporting equipment, building, household electrical appliances, packaging and shipbuilding, it is described as
The new material of great development power.But because the design feature of itself makes its mechanical property be difficult to further raising,
Which has limited its application field, therefore improve the mechanical property of polyurethane as study hotspot.
At present, researcher mainly lifts the mechanical property of polyurethane using two methods, and one kind is the poly- ammonia of regulation and control
Soft in ester structure, hard segment ratio, another kind is by adding SiO2, montmorillonite, talcum, mica and
The reinforcements such as fiber are strengthened, although intensity is increased, but reduce the extension at break of polyurethane
Rate.
The content of the invention
To solve the problems, such as that polyurethane mechanical property is not good in the prior art, the invention provides a kind of polyurethane
Composition and preparation method.The present invention uses melanin modified polyurethane, improves the mechanical property of polyurethane.
An object of the present invention is to provide a kind of urethane composition.
Including：
Polyurethane and melanin；
Counted by 100 weight portions of polyurethane；The weight portion of melanin 0.05~30, preferably 0.1~20 weight portion；
More preferably 0.2~10 weight portion.
Melanoidins prepared by the natural extraction of melanin choosing, chemical synthesis and biological fermentation process, can use existing
Melanin prepared by the preparation method of common melanin in technology, preferably chemical synthesis process.
The polyurethane includes thermoplastic polyurethane and heat-curable urethane.
The second object of the present invention is to provide a kind of preparation method of urethane composition.
Including：
Melanin is well mixed in a solvent first, then by polyalcohol, that isocyanates is added to melanin is molten
In liquid, stirring, heating carry out prepolymerization reaction and obtain performed polymer, are subsequently added chain extender, add (or be not added with
Enter) curing agent, 80~120 DEG C of prepared urethane compositions of reaction.
Described polyalcohol includes that PPG, PEPA, polycarbonate polyol, polyolefin are more
The one or more combination of first alcohol, acrylic polyol and non-amine type dihydroxylic alcohols.
Described polyether polyol is polyethylene glycol, polypropylene glycol, polyoxypropyleneglycol, PTMG
One or more combination in glycol, molecular weight is 1000~4000；Described PEPA is polycaprolactone
Dihydroxylic alcohols, PCDL, polyadipate -1,4- butyl glycol ester diols and polyhexamethylene adipate glycol
One or more combination.
Described isocyanates include diisocyanate and with 3 or multiple isocyanate groups compound.
Such as methylene diphenyl isocyanate, 1B diisocyanate, 1B triisocyanate, toluene
- 2,4- diisocyanate, diphenyl-methane -4,4 '-diisocyanate, IPDI, hydrogenation hexichol
Dicyclohexylmethane diisocyanate, 1,6- hexamethylene diisocyanates, the isocyanatomethyl benzene of 1-3 bis-, 1 isocyano
Close -2 (4- isocyanatophenyls) methylbenzenes, 1,1- di-2-ethylhexylphosphine oxides (4- isocyanic acids benzene), the isocyanato-s of 2,4- bis-
- 1- methylbenzenes, the isocyanic acid benzene of Isosorbide-5-Nitrae-two, 1,1- di-2-ethylhexylphosphine oxide (4- isocyanatocyclohexanes) and their two
One kind or its any combination in aggressiveness；Described polyisocyanates is by multicyclic aliphatic polyisocyanate containing one kind
There is the polyfunctional compound of 3 or multiple isocyanate groups obtained in cyanate.
Described chain extender is 3,3 '-two chloro- 4,4 '-diaminodiphenyl-methanes, ethylenediamine, glycerine, trihydroxy
Propane, triethylene glycol, ethylene glycol, butanediol, 1,6 1 hexylene glycols, diglycol, neopentyl glycol or 2-
One or more in methyl-1,3-propanediol.
Described curing agent is not particularly limited, and can use curing agent commonly used in the art.Such as two is sub-
Ethyl triamine, 4- aminomethyl-1,2s, 8- octanediamines, 2,2 ', 2 "-triamido triethylamine, three -1,1,1- amino
Ethylethanaminium, 1,2,3- triaminopropanes, three-(3- aminopropyls) amine, N, N, N ', N '-four-(2- amino-ethyls)-
The one or more combinations such as the polyethers system such as ethylenediamine, polyoxy alkylidene triamine triamine.
Described solvent is dimethylformamide, acetone, butanone, toluene, dimethylbenzene, hexamethylene, diformazan
One or more combination in sulfoxide, chloroform, dichloromethane and ethyl acetate.
The class that in the composition prepared by the natural extraction of melanin modifying agent choosing, chemical synthesis and biological fermentation process
Melanin.
The mass ratio (0.2-5) of both described polyalcohol and isocyanate-monomer:1, chain extender and performed polymer
Mass ratio is (1~20):100, curing agent is (1~10) with the mass ratio of performed polymer:100.
Beneficial effect：
1. a small amount of melanin can increase substantially the tensile strength of polyurethane, tension fracture elongation rate, tear
The mechanical properties such as resistance to spalling, prepare high-strength and high ductility polyurethane；
2. the preparation method of high-strength and high ductility polyurethane of the present invention is similar with general polyurethane, simple and easy to apply, easily
In industrialization.
Specific embodiment
With reference to embodiment, the present invention is further illustrated.
The preparation of melanin
(1) preparation of melanin 1：By dopamine hydrochloride (the Shanghai Aladdin limited public affairs of biochemical technology share
Department provides, specification：AR) it is dissolved in deionized water, stirs, heat up, adds a certain amount of NaOH, 4
After individual hour, reaction terminates, and by centrifugation, obtainsMelanin 1；
(2) preparation of DOPA-Melanoidins melanin 2：By DOPA, (Shanghai Aladdin biochemical technology share has
Limit company provides, specification：AR), dibenzoyl peroxide (Chemical Reagent Co., Ltd., Sinopharm Group, specification：
AR) it is dissolved in dimethylsulfoxide solvent (Chemical Reagent Co., Ltd., Sinopharm Group, specification：AR in), adjust molten
Liquid after 20 times of reaction, can be arrived in acidity through centrifugationMelanin 2；
(3) preparation of melanin 3：Inkfish (Wuxi Nanchan Temple food market) is bought from market, inkfish ink is taken
Juice, it is centrifugedMelanin 3。
Comparative example 1
PolyTHF 60g, methylene diphenyl isocyanate 30g are weighed respectively, and both are added into 900mL
It is well mixed in acetone solvent, 90 DEG C of reaction 3h are cooled to room temperature and obtain prepolymer；Add chain extender 1,4-
Butanediol 1.8g, after stirring 3h, 24h is reacted during prepolymer is placed into 90 DEG C of baking ovens, is obtained after completion of the reaction
Polyurethane.Wherein chain extender and the mass ratio of prepolymer is 2:100.
Embodiment 1
PolyTHF 60g, methylene diphenyl isocyanate 30g are weighed respectively, add 900mL to contain
0.45gMelanin 1Acetone soln in, be well mixed after, 90 DEG C reaction 3h, be cooled to room temperature and obtain pre-polymerization
Thing；Chain extender BDO 1.8g is added, after stirring 3h, 24h is reacted during prepolymer is placed into 90 DEG C of baking ovens,
Urethane composition is obtained after completion of the reaction.Melanin 1It is 0.5 weight portion.Wherein chain extender and prepolymer
Mass ratio be 2:100.
Embodiment 2
Except adding 900mL to contain 0.9gMelanin 1Acetone soln beyond, i.e.,Melanin 1It is 1 weight
Part, other conditions are same as Example 1.
Embodiment 3
Except adding 900mL to contain 4.5gMelanin 1Acetone soln beyond, i.e.,Melanin 1It is 5 weight
Part, other conditions are same as Example 1.
Embodiment 4
Except adding 900mL to contain 9gMelanin 1Acetone soln beyond, i.e.,Melanin 1It is 10 weight
Part, other conditions are same as Example 1.
Comparative example 2
Polymerized monomer raw material polyethylene glycol 60g and 1B diisocyanate 30g is weighed respectively, is added to
After being well mixed in the DMSO solvents of 800mL, 90 DEG C of reaction 3h are cooled to room temperature and obtain prepolymer；Plus
Enter chain extender ethylenediamine 3.6g, after stirring 3h, prepolymer is positioned over 80 DEG C of baking oven reaction 2h, then heat up
To 100 DEG C, 24h is reacted；Polyurethane is obtained after completion of the reaction.Wherein chain extender is with the mass ratio of prepolymer
4:100。
Embodiment 5
Polymerized monomer raw material polyethylene glycol 60g and 1B diisocyanate 30g is weighed respectively, is added
800mL contains 4.5gMelanin 2DMSO solution in, be well mixed after, 90 DEG C reaction 3h, cooling
Prepolymer is obtained to room temperature；Chain extender ethylenediamine 3.6g is added, after stirring 3h, prepolymer 80 DEG C is positioned over
Baking oven reacts 2h, then is warming up to 100 DEG C, reacts 24h, and urethane composition is obtained after completion of the reaction.Black Element 2It is 5 weight portions.Wherein chain extender and the mass ratio of prepolymer is 4:100.
Embodiment 6
Except adding 800mL to contain 9gMelanin 2DMSO solution beyond, i.e.,Melanin 2It is 10
Weight portion.Other conditions are same as Example 5.
Embodiment 7
Except adding 800mL to contain 13.5gMelanin 2DMSO solution beyond, i.e.,Melanin 2It is 15
Weight portion.Other conditions are same as Example 5.
Embodiment 8
Except adding 800mL to contain 18gMelanin 2DMSO solution beyond, i.e.,Melanin 2It is 20
Weight portion.Other conditions are same as Example 5.
Comparative example 3
Polymerized monomer raw material polyadipate -1,4- butyl glycol ester diols 40g and the isocyanide of 1B three are weighed respectively
Acid esters 40g, is added to after being well mixed in the DMF of 800mL, 90 DEG C of reaction 4h, is cooled to room temperature and obtains
To prepolymer；Add chain extender 1,6- hexylene glycol 15g, curing agent 4- aminomethyl-1,2s, 8- octanediamines 0.9g
After stirring 3h, prepolymer is positioned over 90 DEG C of baking oven reaction 24h, polyurethane is obtained after completion of the reaction.Wherein
Chain extender is 19 with the mass ratio of prepolymer:100, curing agent is 1 with the mass ratio of prepolymer:100.
Embodiment 9
Polymerized monomer raw material polyadipate -1,4- butyl glycol ester diols 40g and the isocyanide of 1B three are weighed respectively
Acid esters 40g, adds 800mL to contain 4g'sMelanin 3DMF solution in, be well mixed after, 90 DEG C
Reaction 4h, is cooled to room temperature and obtains prepolymer；Add chain extender 1,6- hexylene glycol 15g, curing agent 4- amino first
Base -1, after 8- octanediamines 0.9g stirrings 3h, 90 DEG C of baking oven reaction 24h is positioned over by prepolymer, and reaction is finished
After obtain urethane composition.Melanin 3It is 5 weight portions.Wherein chain extender is with the mass ratio of prepolymer
19:100, curing agent is 1 with the mass ratio of prepolymer:100.
Embodiment 10
Except adding 800mL to contain 8gMelanin 3DMF solution beyond, i.e.,Melanin 3It is 10 weights
Amount part.Other conditions are same as Example 9.
Embodiment 11
Except adding 800mL to contain 12gMelanin 3DMF solution beyond, i.e.,Melanin 3It is 15 weights
Amount part.Other conditions are same as Example 9.
Embodiment 12
Except adding 800mL to contain 16gMelanin 3DMF solution beyond, i.e.,Melanin 3It is 20 weights
Amount part.Other conditions are same as Example 9.
Comparative example 4
Polymerized monomer raw material PCDL 65g and toluene di-isocyanate(TDI) 25g are weighed respectively, are added
It is well mixed in the DMF solvent of 800mL, 90 DEG C of reaction 3h are cooled to room temperature and obtain prepolymer；Add
After chain extender diglycol 5g, curing agent diethylenetriamines 4.5g stirring 3h, prepolymer is placed
90 DEG C of baking ovens react 24h, and polyurethane is obtained after completion of the reaction.Wherein chain extender is with the mass ratio of prepolymer
5.6:100, curing agent is 5 with the mass ratio of prepolymer:100.
Embodiment 13
Polymerized monomer raw material PCDL 65g and toluene di-isocyanate(TDI) 25g are weighed respectively, are added
800mL contains 10gMelanin 1DMF solution in be well mixed, 90 DEG C reaction 3h, be cooled to room temperature and obtain
To prepolymer；Chain extender diglycol 5g is added, after curing agent diethylenetriamines 4.5g stirrings 3h,
Prepolymer is placed into 90 DEG C of baking oven reaction 24h, urethane composition is obtained after completion of the reaction.Melanin 1For
11 weight portions.Wherein chain extender and the mass fraction ratio of prepolymer is 5.6:100, the matter of curing agent and prepolymer
Amount is than being 5:100.
Comparative example 5
Isocyanato- -1- the methylbenzenes of polymerized monomer raw material polycaprolactone diols 50g and 2,4- bis- are weighed respectively
30g, adds well mixed, 80 DEG C of reaction 2h in the toluene solvant of 800mL, is cooled to room temperature and obtains pre-polymerization
Thing；Chain extender Glycerin 10g is added, after stirring 3h, prepolymer 100 DEG C of baking oven reaction 24h is placed into,
Polyurethane is obtained after completion of the reaction.Wherein chain extender and the mass ratio of prepolymer is 12.5:100.
Embodiment 14
Isocyanato- -1- the methylbenzenes of polymerized monomer raw material polycaprolactone diols 50g and 2,4- bis- are weighed respectively
30g, adds 800mL to contain 10gMelanin 1Toluene solution in be well mixed, 80 DEG C reaction 2h, cooling
Prepolymer is obtained to room temperature；Chain extender Glycerin 10g is added, after stirring 3h, prepolymer 100 DEG C is placed
Baking oven reacts 24h, and urethane composition is obtained after completion of the reaction.Melanin 1It is 12.5 weight portions.Wherein
Chain extender is 12.5 with the mass ratio of prepolymer:100.
Comparative example 6
Polymerized monomer raw material PCDL 40g, methylene diphenyl isocyanate 35g are weighed respectively
With IPDI 15g, well mixed, 90 DEG C of reaction 3h in 800mL DMF solutions are added,
It is cooled to room temperature and obtains prepolymer；Add chain extender diglycol 10g, curing agent three -1,1,1- amino second
After base ethane 9g stirrings 3h, prepolymer is placed into baking oven insulation reaction, 80 DEG C of reaction temperature, reaction time
2h, then it is warming up to 100 DEG C, 24h is reacted, polyurethane is obtained after completion of the reaction.Wherein chain extender and prepolymer
Mass ratio be 11:100, curing agent is 10 with the mass ratio of prepolymer:100.
Embodiment 15
Polymerized monomer raw material PCDL 40g, methylene diphenyl isocyanate 35g are weighed respectively
With IPDI 15g, 800mL is added to contain 15gMelanin 2DMF solution in mixing it is equal
Even, 90 DEG C of reaction 3h are cooled to room temperature and obtain prepolymer；Chain extender diglycol 10g is added, Gu
Agent three -1, after 1,1- amino-ethyl ethane 9g stirrings 3h, baking oven insulation reaction, reaction temperature is placed by prepolymer
80 DEG C of degree, reaction time 2h, then it is warming up to 100 DEG C, and 24h is reacted, polyurethane is obtained after completion of the reaction.Melanin 2It is 17 weight portions.Wherein chain extender and the mass ratio of prepolymer is 11:100, curing agent and pre-polymerization
The mass ratio of thing is 10:100.
Comparative example 7
Polymerized monomer raw material polypropylene glycol 40g, 1,6- hexamethylene diisocyanate 35g and hydrogenation are weighed respectively
Methyl diphenylene diisocyanate 20g, the DMF solvent for being added to 800mL is well mixed, 90 DEG C of reactions
3h, is cooled to room temperature and obtains prepolymer；Chain extender triethylene glycol 15g is added, after stirring 3h, prepolymer is put
80 DEG C of baking oven reaction 2h are put, 100 DEG C are then heated to, 24h is reacted, polyurethane is obtained after completion of the reaction.
Wherein chain extender and the mass ratio of prepolymer is 16:100.
Embodiment 16
Polymerized monomer raw material polypropylene glycol 40g, 1,6- hexamethylene diisocyanate 35g and hydrogenation are weighed respectively
Methyl diphenylene diisocyanate 20g, is added to 800mL containing 5gMelanin 2DMF solution in mix
Uniformly, 90 DEG C of reaction 3h, are cooled to room temperature and obtain prepolymer；Chain extender triethylene glycol 15g is added, 3h is stirred
Afterwards, prepolymer is placed into 80 DEG C of baking oven reaction 2h, then heats to 100 DEG C, react 24h, reaction is finished
After obtain urethane composition.Melanin 2It is 5 weight portions.Wherein chain extender is with the mass ratio of prepolymer
16:100。
Embodiment 17
Contain 10g except 800mL is added toMelanin 2DMF solution, i.e.,Melanin 2It is 10 weight portions.
Other conditions are identical with embodiment 16.
Comparative example 8
Polymerized monomer raw material polyoxypropyleneglycol 30g and 1,1- di-2-ethylhexylphosphine oxide (4- isocyanic acids benzene) are weighed respectively)
60g, adds well mixed, 80 DEG C of reaction 2h in the DMF solvent of 800mL, is cooled to room temperature and obtains pre-polymerization
Thing；Chain extender Glycerin 10g is added, after stirring 3h, prepolymer 100 DEG C of baking oven reaction 24h is placed into,
Polyurethane is obtained after completion of the reaction.Wherein chain extender and the mass ratio of prepolymer is 11:100.
Embodiment 18
Polymerized monomer raw material polyoxypropyleneglycol 30g and 1,1- di-2-ethylhexylphosphine oxide (4- isocyanic acids benzene) are weighed respectively)
60g, adds 800mL to contain 10gMelanin 1DMF solvent in be well mixed, 80 DEG C reaction 2h, cooling
Prepolymer is obtained to room temperature；Chain extender Glycerin 10g is added, after stirring 3h, prepolymer 100 DEG C is placed
Baking oven reacts 24h, and polyurethane is obtained after completion of the reaction.Melanin 1It is 11 weight portions.Wherein chain extender with
The mass ratio of prepolymer is 11:100.
Comparative example 9
The isocyanatomethyl benzene of polymerized monomer raw material polyhexamethylene adipate glycol 75g and 1-3 bis- is weighed respectively
15g, adds well mixed, 80 DEG C of reaction 2h in the acetone solvent of 800mL, is cooled to room temperature and obtains pre-polymerization
Thing；Chain extender neopentyl glycol 18g is added, after stirring 3h, prepolymer is positioned in 110 DEG C of baking ovens and is reacted
24h, obtains polyurethane after completion of the reaction.Wherein chain extender and the mass ratio of prepolymer is 20:100.
Embodiment 19
The isocyanatomethyl benzene of polymerized monomer raw material polyhexamethylene adipate glycol 75g and 1-3 bis- is weighed respectively
15g, adds 800mL to contain 10gMelanin 1Acetone soln in be well mixed, 80 DEG C reaction 2h, cooling
Prepolymer is obtained to room temperature；Chain extender neopentyl glycol 20g is added, after stirring 3h, prepolymer 110 DEG C is positioned over
24h is reacted in baking oven, urethane composition is obtained after completion of the reaction.Melanin 1It is 11 weight portions.Wherein
Chain extender is 20 with the mass ratio of prepolymer:100.
Comparative example 10
Weigh the isocyanato- -1- of polymerized monomer raw material polyadipate -1,4- butyl glycol ester diols 15g and 2,4- bis-
Methylbenzene 75g, adds well mixed, 80 DEG C of reaction 2h in the acetone solvent of 800mL, is cooled to room temperature and obtains
To prepolymer；Chain extender 2- methyl isophthalic acids, ammediol 18g is added after stirring 4h, prepolymer to be placed into 110 DEG C
24h is reacted in baking oven, polyurethane is obtained after completion of the reaction.Wherein chain extender is with the mass ratio of prepolymer
20:100。
Embodiment 20
Weigh the isocyanato- -1- of polymerized monomer raw material polyadipate -1,4- butyl glycol ester diols 15g and 2,4- bis-
Methylbenzene 75g, adds 800mL to contain 15g'sMelanin 3It is well mixed in acetone soln, 80 DEG C of reaction 2h,
It is cooled to room temperature and obtains prepolymer；Add chain extender 2- methyl isophthalic acids, ammediol 18g, after stirring 4h, by advance
Polymers reacts 24h in placing 110 DEG C of baking ovens, and urethane composition is obtained after completion of the reaction.Melanin 3It is 17
Weight portion.Wherein chain extender and the mass ratio of prepolymer is 20:100.
To above-mentioned sample, according to GB/T528-2009 standards for calibration battens, and universal material testing is used
Machine carries out Mechanics Performance Testing (test temperature is 25 DEG C, and rate of extension is 200mm/min), gained mechanics
Performance data lists table 1 in.
Table 1
In sum, the mechanical property of embodiment illustrates to add apparently higher than the mechanical property of corresponding comparative example
After melanin, the tensile strength and elongation at break of polyurethane are significantly improved, and obtain high-strength and high ductility polyurethane
Composition.
Claims (8)
1. a kind of urethane composition, it is characterised in that the composition includes：
Polyurethane and melanin；
Counted by 100 weight portions of polyurethane；The weight portion of melanin 0.05~30.
2. urethane composition as claimed in claim 1, it is characterised in that：
The weight portion of melanin 0.1~20.
3. urethane composition as claimed in claim 2, it is characterised in that：
The weight portion of melanin 0.2~10.
4. urethane composition as claimed in claim 3, it is characterised in that：
The polyurethane includes thermoplastic polyurethane and heat-curable urethane.
5. a kind of preparation method of urethane composition as described in one of Claims 1 to 4, it is characterised in that institute
The method of stating includes：
Melanin is well mixed in 500~1000mL solvents first, then polyalcohol, isocyanates are added
Enter in melanin solution, stirring, heating carry out prepolymerization reaction and obtain performed polymer, are subsequently added chain extender,
(or being added without) curing agent is added, 80~120 DEG C of reactions are obtained the urethane composition；
Described solvent is dimethylformamide, acetone, butanone, toluene, dimethylbenzene, hexamethylene, diformazan
One or more combination in sulfoxide, chloroform, dichloromethane and ethyl acetate；
Described chain extender is 3,3 '-two chloro- 4,4 '-diaminodiphenyl-methanes, ethylenediamine, glycerine, trihydroxy
Propane, triethylene glycol, ethylene glycol, butanediol, 1,6-HD, diglycol, neopentyl glycol or 2-
One or more in methyl-1,3-propanediol.
6. preparation method as claimed in claim 5, it is characterised in that：
Described polyalcohol includes that PPG, PEPA, polycarbonate polyol, polyolefin are more
The one or more combination of first alcohol, acrylic polyol and non-amine type dihydroxylic alcohols；
Described isocyanates include diisocyanate and with 3 or multiple isocyanate groups compound.
7. preparation method as claimed in claim 5, it is characterised in that：
Described PPG is polyethylene glycol, polypropylene glycol, polyoxypropyleneglycol, PolyTHF
One or more combination in ether glycol, molecular weight is 1000~4000；
Described PEPA is polycaprolactone diols, PCDL, polyadipate -1,4- fourths two
The one or more combination of alcohol esterdiol and polyhexamethylene adipate glycol；
Described isocyanates is methylene diphenyl isocyanate, 1B diisocyanate, 1B
Triisocyanate, Toluene-2,4-diisocyanate, 4- diisocyanate, diphenyl-methane -4,4 '-diisocyanate, isophorone two be different
Cyanate, hydrogenated diphenyl methane diisocyanate, 1,6- hexamethylene diisocyanates, the isocyanic acids of 1-3 bis-
Methylbenzene, 1- isocyanato-s -2 (4- isocyanatophenyls) methylbenzene, 1,1- di-2-ethylhexylphosphine oxides (4- isocyanic acids benzene),
2,4- bis- isocyanato- -1- methylbenzenes, the isocyanic acid benzene of Isosorbide-5-Nitrae-two, 1,1- di-2-ethylhexylphosphine oxide (4- isocyanato- hexamethylenes
Alkane) and their dimer in one kind or its any combination.
8. the preparation method as described in one of claim 5~7, it is characterised in that：
The mass ratio (0.2-5) of both described polyalcohol and isocyanate-monomer:1, chain extender and performed polymer
Mass ratio is (1~20):100, curing agent is (1~10) with the mass ratio of performed polymer:100.
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| CN107325526A (en) * | 2017-07-10 | 2017-11-07 | 湖北大学 | A kind of ultraviolet compounded film of heat-resistant and preparation method thereof |
| CN110122983A (en) * | 2019-06-17 | 2019-08-16 | 浙江伟星实业发展股份有限公司 | A kind of waterproof slide fastener processing method |
| WO2019245941A1 (en) * | 2018-06-21 | 2019-12-26 | Steven Baranowitz | Impact resistant material |
| CN110862512A (en) * | 2019-12-03 | 2020-03-06 | 青岛科技大学 | Biomass particle composite polyurethane elastomer and preparation method thereof |
| CN111848923A (en) * | 2020-07-28 | 2020-10-30 | 湘江涂料科技有限公司 | Preparation method of water-based polyisocyanate curing agent |
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| CN102666671A (en) * | 2009-10-23 | 2012-09-12 | 首尔大学校产学协力团 | Nano-sized melanin particles and method of producing same |
| CN104672407A (en) * | 2015-02-05 | 2015-06-03 | 西南林业大学 | Preparation method of natural melanin-acrylic acid composite superabsorbent resin |
| CN104744662A (en) * | 2015-03-25 | 2015-07-01 | 南京东亚橡塑制品有限公司 | Shoe sole made of polyester based polyurethane material and preparation process of shoe sole |
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| US20090323179A1 (en) * | 2006-02-24 | 2009-12-31 | Mgc Filsheet Co., Ltd. | Laminated body for optical purposes that includes a melanin-containing layer and an optical product which includes the laminate |
| CN102666671A (en) * | 2009-10-23 | 2012-09-12 | 首尔大学校产学协力团 | Nano-sized melanin particles and method of producing same |
| CN104672407A (en) * | 2015-02-05 | 2015-06-03 | 西南林业大学 | Preparation method of natural melanin-acrylic acid composite superabsorbent resin |
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| CN107325526A (en) * | 2017-07-10 | 2017-11-07 | 湖北大学 | A kind of ultraviolet compounded film of heat-resistant and preparation method thereof |
| WO2019245941A1 (en) * | 2018-06-21 | 2019-12-26 | Steven Baranowitz | Impact resistant material |
| CN110122983A (en) * | 2019-06-17 | 2019-08-16 | 浙江伟星实业发展股份有限公司 | A kind of waterproof slide fastener processing method |
| CN110862512A (en) * | 2019-12-03 | 2020-03-06 | 青岛科技大学 | Biomass particle composite polyurethane elastomer and preparation method thereof |
| CN111848923A (en) * | 2020-07-28 | 2020-10-30 | 湘江涂料科技有限公司 | Preparation method of water-based polyisocyanate curing agent |
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Application publication date: 20170620 |