CN107353394A - A kind of coating, polyurethane and preparation method thereof - Google Patents
A kind of coating, polyurethane and preparation method thereof Download PDFInfo
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- CN107353394A CN107353394A CN201710732421.7A CN201710732421A CN107353394A CN 107353394 A CN107353394 A CN 107353394A CN 201710732421 A CN201710732421 A CN 201710732421A CN 107353394 A CN107353394 A CN 107353394A
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- chain extender
- polyurethane
- glycol
- isocyanates
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
- C08G18/722—Combination of two or more aliphatic and/or cycloaliphatic polyisocyanates
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- 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
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- C08G18/3206—Polyhydroxy compounds aliphatic
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- C08G18/30—Low-molecular-weight compounds
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- C08G18/30—Low-molecular-weight compounds
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- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4202—Two or more polyesters of different physical or chemical nature
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- 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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- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
- C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
- C08G18/425—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids the polyols containing one or two ether groups
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- 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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- 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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- 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
- C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
- C08G18/4676—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing sulfur
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- 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
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- 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
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6625—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/34
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
Abstract
A kind of coating, polyurethane and preparation method thereof, belong to paint field.Polyurethane is mainly dispersed through as emulsion by the prepolymer with hydrophilic radical, then is polymerized under the conditions of existing for polyamine chain extender.Wherein, the prepolymer with hydrophilic radical is mainly made by isocyanates, sulfonate-type polyol, polymer polyatomic alcohol, hydroxyl-containing epoxy resin reaction.The preparing raw material of polyurethane includes the following components counted in parts by weight：7.00~13.00 parts of isocyanates, 8.00~12.00 parts of sulfonate-type polyol, 12.00~15.00 parts of polymer polyatomic alcohol, 1.00~4.00 parts of hydroxyl-containing epoxy resin, 0.10~0.50 part of hydrophilic chain extender, 0.10~0.50 part of small molecule chain extender, 0.20~0.70 part of crosslinking agent, 0.01~0.05 part of catalyst, 0.10~1.00 part of nertralizer, 1.00~3.00 parts of polyamine chain extender, 54.00~90.00 parts of water.
Description
Technical field
The present invention relates to paint field, in particular to a kind of coating, polyurethane and preparation method thereof.
Background technology
Polyurethane refers to one kind polymer containing carbamate groups on high polymer main chain, has wear-resisting well
Property, Scratch Resistance, preferable physical and mechanical properties, also with the adjustable and excellent low temperature resistant flexural property of soft durometer, have simultaneously
There is the adjustable characteristic of the sub- size of water-dispersible grain.At present, polyurethane is widely used in the fields such as coating, elastomer.In recent years, with
The raising of environmental requirement, the research and development of environment-protecting polyurethane product, the theme of polyurethane researcher exploration is increasingly becoming,
It is wherein especially more prominent with no-solvent type polyurethane and aqueous polyurethane.Aqueous polyurethane refer in polyurethane one kind using water as point
The polyurethane resin material of dispersion media.It has the excellent specific property such as non-ignitable, low VOCs, safe and environment-friendly, is widely used at fabric
The fields such as reason, leather finish, adhesive, coating, ink.In recent years, the research on aqueous polyurethane is in physical and chemical performance
Aspect achieves more breakthrough, improves consolidating for aqueous polyurethane and contains and performance, greatly expands its application.
Although the research of current aqueous polyurethane is just fast-developing, also having emerged in large numbers many has excellent physical chemical property
Water-base polyurethane material, but the research of the extraordinary water-base polyurethane material with property still has larger bottleneck,
Wherein especially with more difficult from the research and development of delustring aqueous polyurethane.For example, there is delustring in existing water-base polyurethane material
Performance is weaker, or the balance of high extinction effect and stability of emulsion is bad, or high extinction effect and resin emulsion stability is flat
The problems such as weighing apparatus is still bad.
The content of the invention
It is an object of the invention to provide a kind of coating, polyurethane and preparation method thereof, has to obtain from extinction
Polyurethane, while keep its extinction effect and stably, and improve tensile strength performance, improve Bearable dry and wet wipe characteristic.
According to the first aspect of the invention, there is provided a kind of polyurethane.
Polyurethane has from extinction.
Polyurethane is mainly to be dispersed through by the prepolymer with hydrophilic radical for emulsion, then in bar existing for polyamine chain extender
Be polymerized under part, the prepolymer with hydrophilic radical mainly by isocyanates, sulfonate-type polyol, polymer polyatomic alcohol, contain
The reaction of hydroxyl epoxy resin is made.
Prepare the following components that the raw material of polyurethane includes counting in parts by weight：7.00~13.00 parts of isocyanates, sulfonic acid
8.00~12.00 parts of salt form polyalcohol, 12.00~15.00 parts of polymer polyatomic alcohol, hydroxyl-containing epoxy resin 1.00~4.00
Part, 0.10~0.50 part of hydrophilic chain extender, 0.10~0.50 part of small molecule chain extender, 0.20~0.70 part of crosslinking agent, catalyst
0.01~0.05 part, 0.10~1.00 part of nertralizer, 1.00~3.00 parts of polyamine chain extender, 54.00~90.00 parts of water.
According to the second aspect of the invention, there is provided a kind of preparation method of above-mentioned polyurethane.Preparation method includes：
Under conditions of heating, make isocyanates and sulfonate-type polyol, polymer polyatomic alcohol, hydroxyl-containing epoxy resin
Contact and sudden reaction occurs and obtain first polymer；
Solvent, hydrophilic chain extender, small molecule chain extender, crosslinking agent, catalyst and molten are added after first polymer cooling
Agent is reacted, and adds nertralizer, water carries out disperseing to form aqueous emulsion；
The aqueous solution dissolved with polyamine chain extender is added in the aqueous emulsion, and continued in heating, vacuum environment
Reaction, reaction terminate rear desolvation.
According to the third aspect of the invention we, there is provided a kind of coating.Coating mainly includes foregoing polyurethane.
The beneficial effect of the embodiment of the present invention：
Polyurethane provided in an embodiment of the present invention, using specific raw material, formula and technique, obtain with ultralow light
Pool, without solid delustring composition, high tensile, excellent feel, excellent Bearable dry and wet wipe performance it is water-based poly- from extinction type
Urethane.The compatibility of polyurethane and other kinds resin is excellent, can be widely applied to all kinds of low luster coatings, as dumb light woodcare paint,
Dumb light printing mortar, dumb light leather finish, packaging dumb light coating etc..
Embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the present invention.It is unreceipted specific in embodiment
Condition person, the condition suggested according to normal condition or manufacturer are carried out.Agents useful for same or the unreceipted production firm person of instrument, it is
The conventional products that can be obtained by commercially available purchase.
Coating, polyurethane below for the embodiment of the present invention and preparation method thereof are specifically described：
Based on the deficiencies in the prior art, a kind of polyurethane is inventors herein proposed.Described polyurethane is a kind of resistance to from delustring
Dry and wet wipes high-strength water-based polyurethane.In some instances, it is 0, tensile break strength to obtain polyurethane to have 60 ° of angle gloss
27MPa, elongation at break ＞ 400% characteristic.
Prepare the following components that the raw material of polyurethane includes counting in parts by weight：7.00~13.00 parts of isocyanates, sulfonic acid
8.00~12.00 parts of salt form polyalcohol, 12.00~15.00 parts of polymer polyatomic alcohol, hydroxyl-containing epoxy resin 1.00~4.00
Part, 0.10~0.50 part of hydrophilic chain extender, 0.10~0.50 part of small molecule chain extender, 0.20~0.70 part of crosslinking agent, catalyst
0.01~0.05 part, 0.10~1.00 part of nertralizer, 1.00~3.00 parts of polyamine chain extender, 54.00~90.00 parts of water.
Further, the following components that the raw material of polyurethane includes counting in parts by weight is prepared：Isocyanates 8.00~
12.00 parts, 9.00~11.00 parts of sulfonate-type polyol, 13.00~14.00 parts of polymer polyatomic alcohol, hydroxyl-containing epoxy resin
2.00~3.00 parts, 0.20~0.30 part of hydrophilic chain extender, 0.30~0.40 part of small molecule chain extender, crosslinking agent 0.40~0.60
Part, 0.02~0.04 part of catalyst, 0.40~0.80 part of nertralizer, 1.60~2.80 parts of polyamine chain extender, water 60.00~
80.00 parts.
Wherein, isocyanates can be monoisocyanates or polyisocyanates.As a kind of optional example, isocyanates bag
Include IPDI, diphenylmethane diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, two
Methylenebis phenyl isocyanate, toluene di-isocyanate(TDI), tetramethyl group diisocyanate, XDI, to benzene
Any of group diisocyanate.
Wherein, the number-average molecular weight of sulfonate-type polyol is 400, or 1000, or 1500, or 2000.
Wherein, the alcohol hydroxyl value of polymer polyatomic alcohol is 50~120mg KOH/g.In some instances, polymer polyatomic alcohol
Alcohol hydroxyl value be 65~75KOH/g, or 80~90KOH/g, or 100~110KOH/g.Alcohol hydroxyl value is that the content of hydroxyl is (or dense
Degree), refer to the amount of institute's hydroxyl in the sample of Unit Weight, unit is mgKOH/g.Hydroxyl value is surveyed using acid-base titration.Appropriate
Alcohol hydroxyl value while reactivity is improved, can keep the proper viscosity of reaction system, so as to carry the physics and chemistry of original text polyurethane
Can, such as hardness, heat resistance.The hydroxyl value of polymer polyatomic alcohol is high, then isocyanates increases with its reactivity enhancing, main reaction
By force；If the hydroxyl value of polymer polyatomic alcohol is low, the increased response of isocyanates and water, main reaction speed is caused not catch up with foaming anti-
Speed is answered, easily causes bubble phenomenon of collapsing.When the content rise of hydroxyl value, the used in amounts increase of isocyanates, not to isocyanates
Amount is adjusted, very few equivalent to isocyanates addition, so as to cause poor foam crackle, resilience, intensity difference, the permanent change of compression
The problems such as shape increases.Added excessively equivalent to isocyanates conversely, hydroxyl value content reduces, formation of foam macropore can be caused and closed
Hole, hardness increase, curing time length cause the appearance of the problems such as heartburn.
Polymer polyatomic alcohol can be any of PEPA, polyether polyamine or two kinds of mixture.One
In a little examples, polymer polyatomic alcohol can be polybutylene glyool adipate, polyadipate diglycol ester, gather oneself two
Sour butanediol glycol ester glycol, polyneopentyl glycol adipate glycol, polybutyleneadipate diglycol esterdiol,
Polypropylene glycol adipate glycol, poly-epsilon-caprolactone glycol, PPOX ether glycol, PCDL, PolyTHF
Any of ether glycol, polyethylene glycol oxide ether glycol or a variety of compositions, (such as weight ratio is 1 to such as two kinds of composition:1
Polybutylene glyool adipate and polyadipate diglycol ester), (such as weight ratio is 1 for three kinds of composition:2:4
Polybutyleneadipate glycol ester glycol, polypropylene glycol adipate glycol, poly-epsilon-caprolactone glycol), four kinds of combination
Thing.
Preferably, PEPA is the condensation product of adipic acid and polyalcohol, wherein, polyalcohol includes butanediol, second
Any of glycol, neopentyl glycol or propane diols or a variety of mixtures.PPG be polypropylene glycol, polyethylene glycol,
One or more mixtures in PTMG.
Wherein, hydrophilic chain extender include sulfamate, dihydromethyl propionic acid, dimethylolpropionic acid, dihydromethyl propionic acid,
Any of hydroxy sulfonate is a variety of.
Wherein, small molecule chain extender includes butanediol, 1,2-PD, 1,3-PD, ethylene glycol, a contracting diethyl two
Any of alcohol, triethylene-glycol, 1,4 cyclohexane dimethanol, 1,6-HD, neopentyl glycol are a variety of.
Wherein, polyamine chain extender includes appointing in ethylenediamine, hexamethylene diamine, hydrazine hydrate, diethylenetriamine, triethylene tetramine
It is a kind of.
Wherein, crosslinking agent includes appointing in triethanolamine, trimethylolpropane, three-functionality-degree PPG, castor oil
It is one or more.
Wherein, catalyst is organo-metallic catalyst.As a kind of optional example, organic metal include antimony organic and/
Or organo-bismuth.Organo-bismuth can be isooctyl acid bismuth, Yue Gui Jiao acid bismuths, any of bismuth neodecanoate.
Wherein, nertralizer include triethylamine, dimethyl acetamide, N, N- dimethylethanolamines, N, N- diethyl ethylene diamines,
Any of ammoniacal liquor is a variety of.
Based on foregoing polyurethane, the invention also provides a kind of coating.Coating includes foregoing polyurethane, and optional
Pigment, filler, auxiliary agent etc..In use, coating is deposited in the form of being dissolved in the thick liquid formed in organic solvent or water
.Its occupation mode can be blade coating, spraying etc., can specifically be selected according to being actually needed.
Inventor also proposed a kind of preparation method of foregoing polyurethane.
Polyurethane is mainly dispersed through for emulsion, then in condition existing for polyamine chain extender by the prepolymer with hydrophilic radical
Under be polymerized.Wherein, the prepolymer with hydrophilic radical mainly by isocyanates, sulfonate-type polyol, polymer polyatomic alcohol,
Hydroxyl-containing epoxy resin reaction is made.
The preparation method of polyurethane is described in detail below.
Making the method for polyurethane includes：
Step S101, under conditions of heating, isocyanates and sulfonate-type polyol, polymer polyatomic alcohol are made, containing hydroxyl
Base epoxy contacts and sudden reaction occurs.
As the isocyanates of a part for raw material, sulfonate-type polyol, polymer polyatomic alcohol, hydroxyl-containing epoxy resin
It is preferred that dewater treatment is carried out, to reduce the interference of the polymerisation of the isocyanates of moisture and alcohol and adverse effect.
The present invention some examples in, the method for dewater treatment can be make isocyanates, sulfonate-type polyol,
Polymer polyatomic alcohol, hydroxyl-containing epoxy resin are respectively in independent equipment or instrument, by heat drying.For example, 90~
Vacuum dehydration 1~2 hour at 130 DEG C, further, dry temperature can also be 100~110 DEG C, or 106~125 DEG C.
Respectively to each raw material drying after, preferably by sulfonate-type polyol, polymer polyatomic alcohol, hydroxyl-containing epoxy resin
Mixture is thoroughly mixed to form, is then mixed again with isocyanates, and carries out sudden reaction in a heated condition.Can as one kind
The specific embodiment of choosing, the temperature of sudden reaction is 70~90 DEG C, the time is 2~4 hours.Preferably, the temperature of sudden reaction
For 73~82 DEG C.It is highly preferred that the temperature of sudden reaction is 84~89 DEG C.
The first polymer that preliminary polymerization occurs can be obtained by this step.
Step S102, solvent, hydrophilic chain extender are added after first polymer cooling, small molecule chain extender, crosslinking agent, is urged
Agent and solvent are reacted, and add nertralizer, water carries out disperseing to form aqueous emulsion.
The demand of soft and hard segments ratio in the degree of cross linking, polymer chain based on adjustment polymer etc., makes the first polymerization
Further polymerisation occurs for thing, to obtain improved structural strength, chemical stability.
Wherein, foregoing first polymer is to react to obtain under conditions of 70~90 DEG C, time is 2~4 hours, therefore,
When it is cooled to 50~70 DEG C, solvent, hydrophilic chain extender, small molecule chain extender, crosslinking agent, catalyst and solvent are reacted,
And reacted 5~8 hours at 50~70 DEG C.
More preferably, solvent, hydrophilic chain extender, small molecule chain extender, crosslinking agent, catalyst and solvent are repeatedly to add
Mode is contacted with first polymer, reacted.For example, when first polymer is cooled to 50~70 DEG C, hydrophilic chain extender, small is added
Molecule chain extender and crosslinking agent, catalyst and solvent, keep obtaining pre-polymerization to carry out reaction in 5~8 hours at 50~70 DEG C
Thing, and prepolymer contains hydrophilic radical, such as hydroxyl.Wherein, solvent can be selected acetone, and its dosage for pre-polymerization amount of substance 30~
50%.
Further, added into prepolymer nertralizer, water be stirred it is dispersed to have the function that, so as to prepare
Aqueous emulsion.
Step S103, the aqueous solution dissolved with polyamine chain extender is added in aqueous emulsion, and in heating, vacuum environment
Sustained response, reaction terminate rear desolvation.
It should be noted that it is " from extinction " described in the polyurethane having from extinction provided in the present invention
Refer to, do not need additional extinction material in polyurethane, wax, diatomite, kaolin, the aerosil being such as typically used
Deng in other words, low glossiness is the intrinsic attribute of its (polyurethane).
The coating to the present invention, polyurethane and preparation method thereof are described in further detail with reference to embodiments.
Embodiment 1
A kind of polyurethane is present embodiments provided, its preparation method is as described below, wherein, the dosage of each raw material is with weight
Part meter.
By 80.00 parts of polybutylene glyool adipates (Mn=2000), 80.00 parts of polypropylene oxide glycol (Mn=
2000) and 130.00 parts of sulfonate type polyester diols (Mn=1500) vacuumize water removal 2h in 120 DEG C, 0.09MPa.Add
47.04 parts of hexamethylene diisocyanates, 62.16 parts of IPDIs, stir and keep 80 DEG C of reaction 2h.Add
50.00 parts of acetone, 1.50 parts of dihydromethyl propionic acids, 2.90 parts of butanediols, 6.25 parts of trimethylolpropanes and 0.36 part of catalyst,
60 DEG C of reaction 5h of keeping temperature.Add 1.80 parts of triethylamine nertralizers to neutralize, after 1min, in dispersant rotating speed 1100r/min bars
600 parts of water emulsifications are added under part, and keep rotating speed to disperse；14.00 parts of ethylenediamine is added in 150 parts of water and stirred, is delayed
It is slow to add in emulsion, continue to be kept stirring for 30min.Emulsion is kept stirring for 2h under 60 DEG C, 0.09MPa vacuum conditions, removed
Solvent acetone, you can obtain from delustring aqueous polyurethane emulsion.
Embodiment 2
By 80.00 parts of polyadipate diglycol butyl glycol ester diols (Mn=2000), 80.00 parts of PolyTHFs
Ether glycol (Mn=2000) and 130.00 parts of sulfonate type polyester diols (Mn=1500) vacuumize in 120 DEG C, 0.09MPa and removed
Water 2h.47.04 parts of hexamethylene diisocyanates, 62.16 parts of IPDIs are added, stirs and is kept for 80 DEG C instead
Answer 2h.Add 50.00 parts of acetone, 1.50 parts of dihydromethyl propionic acids, 2.90 parts of butanediols, 6.25 parts of trimethylolpropanes and 0.36
Part catalyst, 60 DEG C of reaction 5h of keeping temperature.Add 1.80 parts of triethylamine nertralizers to neutralize, after 1min, in dispersant rotating speed
600 parts of water emulsifications are added under the conditions of 1100r/min, and keep rotating speed to disperse；14.00 parts of ethylenediamine is added in 150 parts of water
Stir, be slowly added in emulsion, continue to be kept stirring for 30min.Emulsion is kept under 60 DEG C, 0.09MPa vacuum conditions
Stir 2h, desolvation acetone, you can obtain from delustring aqueous polyurethane emulsion.
Embodiment 3
By 80.00 parts of polyadipate diglycol butyl glycol ester diols (Mn=2000), 80.00 parts of PPOXs
Glycol (Mn=2000) and 130.00 parts of sulfonate type polyester diols (Mn=1500) vacuumize water removal in 120 DEG C, 0.09MPa
2h.47.04 parts of hexamethylene diisocyanates, 73.36 parts of dicyclohexyl methyl hydride diisocyanates are added, stirs and is kept for 80 DEG C
React 2h.Add 50.00 parts of acetone, 2.00 parts of dihydromethyl propionic acids, 2.56 parts of butanediols, 6.25 parts of trimethylolpropanes and
0.36 part of catalyst, 60 DEG C of reaction 5h of keeping temperature.Add 2.00 parts of triethylamine nertralizers to neutralize, after 1min, turn in dispersant
600 parts of water emulsifications are added under the conditions of fast 1100r/min, and keep rotating speed to disperse；27.00 parts of hexamethylene diamine is added into 150 parts of water
In stir, be slowly added in emulsion, continue to be kept stirring for 30min.Emulsion is protected under 60 DEG C, 0.09MPa vacuum conditions
Hold stirring 2h, desolvation acetone, you can obtain from delustring aqueous polyurethane emulsion.
Embodiment 4
By 80.00 parts of polyadipate ethylene glycol butyl glycol ester diols (Mn=2000), 80.00 parts of polypropylene oxide glycols
(Mn=2000) and 130.00 parts of sulfonate type polyester diols (Mn=1500) vacuumize water removal 2h in 120 DEG C, 0.09MPa.
146.72 parts of dicyclohexyl methyl hydride diisocyanates are added, stirs and keeps 80 DEG C of reaction 2h.Add 50.00 parts of acetone, 1.00
Part dihydromethyl propionic acid, 3.23 parts of butanediols, 6.25 parts of trimethylolpropanes and 0.36 part of catalyst, 60 DEG C of reactions of keeping temperature
5h.Add 1.00 parts of triethylamine nertralizers to neutralize, after 1min, 600 portions of water and milk are added under the conditions of dispersant rotating speed 1100r/min
Change, and keep rotating speed to disperse；14.00 parts of ethylenediamine is added in 150 parts of water and stirred, is slowly added in emulsion, is continued
It is kept stirring for 30min.Emulsion is kept stirring for 2h, desolvation acetone, you can obtain under 60 DEG C, 0.09MPa vacuum conditions
From delustring aqueous polyurethane emulsion.
Embodiment 5
By 80.00 parts of polyneopentyl glycol adipate glycol (Mn=2000), 80.00 parts of PTMG (Mn
=2000) and 130.00 parts of sulfonate type polyester diols (Mn=1500) vacuumize water removal 2h in 120 DEG C, 0.09MPa.Add
124.32 parts of IPDIs, stir and keep 80 DEG C of reaction 2h.Add 50.00 parts of acetone, 2.50 parts of dihydroxy first
Base propionic acid, 2.22 parts of butanediols, 6.25 parts of trimethylolpropanes and 0.36 part of catalyst, 60 DEG C of reaction 5h of keeping temperature.Add
2.50 parts of triethylamine nertralizers neutralize, and after 1min, 600 parts of water emulsifications are added under the conditions of dispersant rotating speed 1100r/min, and protect
Rotating speed is held to disperse；27.00 parts of hexamethylene diamine is added in 150 parts of water and stirred, is slowly added in emulsion, continues to be kept stirring for
30min.Emulsion is kept stirring for 2h, desolvation acetone under 60 DEG C, 0.09MPa vacuum conditions, you can obtain from delustring water
Property polyaminoester emulsion.
Embodiment 6
By 80.00 parts of PCDLs (Mn=2000), 80.00 parts of PTMGs (Mn=2000) and
130.00 parts of sulfonate type polyester diols (Mn=1500) vacuumize water removal 2h in 120 DEG C, 0.09MPa.Add 124.32 parts
IPDI, stir and keep 80 DEG C of reaction 2h.Add 50.00 parts of acetone, 3.00 parts of dihydromethyl propionic acids,
1.88 parts of butanediols, 6.25 parts of trimethylolpropanes and 0.36 part of catalyst, 60 DEG C of reaction 5h of keeping temperature.Add 3.00 part three
Ethamine nertralizer neutralizes, and after 1min, 600 parts of water emulsifications is added under the conditions of dispersant rotating speed 1100r/min, and keep rotating speed point
Dissipate；15.98 parts of diethylenetriamine is added in 150 parts of water and stirred, is slowly added in emulsion, continues to be kept stirring for
30min.Emulsion is kept stirring for 2h, desolvation acetone under 60 DEG C, 0.09MPa vacuum conditions, you can obtain from delustring water
Property polyaminoester emulsion.
Embodiment 7
By 80.00 parts of polyadipate diglycol butyl glycol ester diols (Mn=2000), 80.00 parts of PPOXs
Glycol (Mn=2000) and 130.00 parts of sulfonate type polyester diols (Mn=1500) vacuumize water removal in 120 DEG C, 0.09MPa
2h.47.04 parts of hexamethylene diisocyanates, 73.36 parts of dicyclohexyl methyl hydride diisocyanates are added, stirs and is kept for 80 DEG C
React 2h.Add 50.00 parts of acetone, 1.00 parts of dihydromethyl propionic acids, 3.23 parts of butanediols, 6.25 parts of trimethylolpropanes and
0.36 part of catalyst, 60 DEG C of reaction 5h of keeping temperature.Add 1.00 parts of triethylamine nertralizers to neutralize, after 1min, turn in dispersant
600 parts of water emulsifications are added under the conditions of fast 1100r/min, and keep rotating speed to disperse；17.03 parts of triethylene tetramine is added 150
Stirred in part water, be slowly added in emulsion, continue to be kept stirring for 30min.By emulsion in 60 DEG C, 0.09MPa vacuum conditions
Under be kept stirring for 2h, desolvation acetone, you can obtain from delustring aqueous polyurethane emulsion.
Embodiment 8
By 86.67 parts of polycaprolactone glycols (Mn=2000), 86.67 parts of PTMGs (Mn=2000) and
120.00 parts of sulfonate type polyester diols (Mn=1500) vacuumize water removal 2h in 120 DEG C, 0.09MPa.Add 47.04 part six
Methylene diisocyanate, 62.16 parts of IPDIs, stir and keep 80 DEG C of reaction 2h.Add 50.00 part third
Ketone, 1.50 parts of dihydromethyl propionic acids, 2.90 parts of butanediols, 6.25 parts of trimethylolpropanes and 0.36 part of catalyst, keeping temperature
60 DEG C of reaction 5h.Add 1.50 parts of triethylamine nertralizers to neutralize, after 1min, added under the conditions of dispersant rotating speed 1100r/min
600 parts of water emulsifications, and keep rotating speed to disperse；17.67 parts of TEPA is added in 150 parts of water and stirred, is slowly added
Enter in emulsion, continue to be kept stirring for 30min.Emulsion is kept stirring for 2h, desolvation under 60 DEG C, 0.09MPa vacuum conditions
Acetone, you can obtain from delustring aqueous polyurethane emulsion.
Comparative example 1
(1) by PTMG of 20g (20mmol) molecular weight for 1000,19 (7.5mmol) dihydroxymethyls third
Acid vacuum dehydration at 120 DEG C in a kettle.After stopping vacuum, 60 DEG C are cooled to, a small amount of dibutyl tin laurate is added and urges
Agent and 11g IPDIs (50mmol), 80 DEG C are warming up to, react 3h.(2) 50 DEG C are cooled to, to step (1)
0.7g (7mmol) triethylamine neutralization reaction 30min is added in product.(3) continue to be cooled to less than 30 DEG C, will be dissolved with 0.5g
(thinned water amount accounts for gross water requirement in whole reaction to the aqueous solution of (2.6mmol) 2- (2 one amino-ethyl) tarine sodium
80%) emulsification, chain extension 10min in reactor are added to.(4) add the aqueous solution containing 0.6g hydrazine hydrates and carry out secondary chain extension
1h, room temperature is down to, filtering and discharging, obtains polyurethane resin.
Test example 1
This is tested for being detected to the glossiness of embodiment 1~8 and the polyurethane of the offer of comparative example 1.Referring in particular to, in
Chinese's name republic national standard, 20 °, 60 ° and 85 ° bright lusters of colored paint paint film of the paint and varnish without metallic pigments
Determine (GB9754-88).As a result it is as shown in table 1.
Table 1 polyurethane, 60 ° of glossiness
Test example 2
This tests the rubbing fastness and Detection of Stability of the polyurethane for providing embodiment 1~8.Referring in particular to China
Name republic national standard, textile color stability experiment colour fastness to rubbing (GB/T 3920-2008)；Chinese name republicanism
State's national standard, coating storage stability test method (GB6753.3-86).As a result it is as shown in table 2.
The polyurethane rubbing fastness of table 2 and stability
In table 2, skinning, pressure, the grade scoring of corrosion and stale flavor are：10=is without, 8=is very slight, 6=is slight, 4=
It is medium, 2=is more serious, 0=is serious.
The grade scoring of sedimentation degree is：10=suspends completely.Compared with the reset condition of colored paint, do not change.8=has
It is obvious to settle sense of touch and occur a small amount of deposited pigments on toolsetting.No obvious resistance is elapsed with toolsetting knife face.6=
The pigment cake significantly settled.The war portion of container is fallen on through pigment cake with the gravity energy of toolsetting.Have one with the passage of toolsetting knife face
Fixed resistance.The block of cohesion part can be transferred on toolsetting.4=can not fall on the war portion of container with the deadweight of toolsetting.Adjust
Knife passes through pigment cake, then is elapsed and had any problem with toolsetting sword, and is elapsed along tank side and adjust sword, and blade has light resistance.But can
Colored paint is easily re-mixed into uniform state.2=is pushed away when firmly making toolsetting penetrate pigment sedimentation layer with toolsetting knife is beautiful
Move it is highly difficult, along tank side passage toolsetting sword sword have obvious resistance.But colored paint can be re-mixed into uniform state.0=forms
The tight hard blocks of very H.By stirring by hand these lump can not be made to re-mix into liquid again in 3~5min uniform
Colored paint.
The grade scoring of particle, blob of viscose or sliding block on paint film is：10=without, 8=is very slight, 6=is slight, 4=is medium,
2=is more serious, 0=is serious.
It can be seen from the result of above test example 1 and test example 2, stabilization that polyurethane provided in an embodiment of the present invention has
Property, and there are preferable Gloss properties, it is then 0 in 60 ° of angle gloss, hence it is evident that the polyurethane in limited comparative example 1, i.e. this hair
The polyurethane of bright offer reached take into account from extinction and stability the advantages of.
Although illustrate and describing the present invention with specific embodiment, but will be appreciated that without departing substantially from the present invention's
Many other change and modification can be made in the case of spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (10)
1. a kind of polyurethane, it is characterised in that the polyurethane has from extinction, and the polyurethane is mainly by band hydrophilic group
The prepolymer of group is dispersed through as emulsion, then be polymerized under the conditions of existing for polyamine chain extender, described with hydrophilic radical
Prepolymer is mainly made by isocyanates, sulfonate-type polyol, polymer polyatomic alcohol, hydroxyl-containing epoxy resin reaction；
Prepare the following components that the raw material of the polyurethane includes counting in parts by weight：7.00~13.00 parts of isocyanates, sulfonic acid
8.00~12.00 parts of salt form polyalcohol, 12.00~15.00 parts of polymer polyatomic alcohol, hydroxyl-containing epoxy resin 1.00~4.00
Part, 0.10~0.50 part of hydrophilic chain extender, 0.10~0.50 part of small molecule chain extender, 0.20~0.70 part of crosslinking agent, catalyst
0.01~0.05 part, 0.10~1.00 part of nertralizer, 1.00~3.00 parts of polyamine chain extender, 54.00~90.00 parts of water.
2. polyurethane according to claim 1, it is characterised in that the raw material including counting with the following group in parts by weight
Point：8.00~12.00 parts of isocyanates, 9.00~11.00 parts of sulfonate-type polyol, polymer polyatomic alcohol 13.00~14.00
Part, 2.00~3.00 parts of hydroxyl-containing epoxy resin, 0.20~0.30 part of hydrophilic chain extender, small molecule chain extender 0.30~0.40
Part, 0.40~0.60 part of crosslinking agent, 0.02~0.04 part of catalyst, 0.40~0.80 part of nertralizer, polyamine chain extender 1.60
~2.80 parts, 60.00~80.00 parts of water.
3. polyurethane according to claim 1, it is characterised in that the number-average molecular weight of the sulfonate-type polyol is
400, or 1000, or 1500, or 2000；
The alcohol hydroxyl value of the polymer polyatomic alcohol is 50~120mg KOH/g, and the polymer polyatomic alcohol includes polyadipate fourth
Glycol esterdiol, polyadipate diglycol ester, polybutyleneadipate glycol ester glycol, polyadipate neopentyl glycol
Esterdiol, polybutyleneadipate diglycol esterdiol, polypropylene glycol adipate glycol, poly-epsilon-caprolactone glycol,
Any of PPOX ether glycol, PCDL, PTMG, polyethylene glycol oxide ether glycol；
Preferably, the polymer polyatomic alcohol includes PEPA and/or PPG, wherein, the PEPA
It is the condensation product of adipic acid and polyalcohol, the polyalcohol includes appointing in butanediol, ethylene glycol, neopentyl glycol or propane diols
One or more, the PPG include polypropylene glycol, polyethylene glycol, one kind in PTMG or more
Kind.
4. polyurethane according to claim 1, it is characterised in that the hydrophilic chain extender includes sulfamate, dihydroxy
Any of methylpropanoic acid, dimethylolpropionic acid, dihydromethyl propionic acid, hydroxy sulfonate are a variety of；The small molecule chain extension
Agent includes butanediol, 1,2- propane diols, 1,3- propane diols, ethylene glycol, diglycol, triethylene-glycol, 1,4- hexamethylenes
Any of alkane dimethanol, 1,6- hexylene glycols, neopentyl glycol are a variety of, the polyamine chain extender include ethylenediamine, oneself two
Any of amine, hydrazine hydrate, diethylenetriamine, triethylene tetramine.
5. polyurethane according to claim 1, it is characterised in that the crosslinking agent includes triethanolamine, trihydroxy methyl third
Any of alkane, three-functionality-degree PPG, castor oil are a variety of；The catalyst is organo-metallic catalyst, described
Organic metal includes antimony organic and/or organo-bismuth, and the organo-bismuth includes isooctyl acid bismuth, the moon osmanthus Jiao acid bismuth, in bismuth neodecanoate
It is any；The nertralizer includes triethylamine, dimethyl acetamide, N, N- dimethylethanolamines, N, N- diethyl ethylene diamines, ammonia
Any of water is a variety of.
6. polyurethane according to claim 1, it is characterised in that the isocyanates includes isophorone diisocyanate
Ester, diphenylmethane diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, methyl diphenylene diisocyanate,
Toluene di-isocyanate(TDI), tetramethyl group diisocyanate, XDI, to any in phenyl diisocyanate
Kind.
7. such as the preparation method of polyurethane according to any one of claims 1 to 6, it is characterised in that the preparation method bag
Include：
Under conditions of heating, isocyanates is set to be contacted with sulfonate-type polyol, polymer polyatomic alcohol, hydroxyl-containing epoxy resin
And sudden reaction occurs and obtains first polymer；
Solvent, hydrophilic chain extender, small molecule chain extender, crosslinking agent, catalyst and molten are added after first polymer cooling
Agent is reacted, and adds nertralizer, water carries out disperseing to form aqueous emulsion；
The aqueous solution dissolved with polyamine chain extender is added in the aqueous emulsion, and the sustained response in heating, vacuum environment,
Reaction terminates rear desolvation.
8. the preparation method of polyurethane according to claim 7, it is characterised in that isocyanates and sulfonate type are more making
Before the step of first alcohol, polymer polyatomic alcohol, hydroxyl-containing epoxy resin contact and sudden reaction occur, isocyanates, sulfonate
Type polyalcohol, polymer polyatomic alcohol, hydroxyl-containing epoxy resin vacuum dehydration 1~2 hour at 90~130 DEG C；
Isocyanates and sulfonate-type polyol, polymer polyatomic alcohol, the temperature of hydroxyl-containing epoxy resin sudden reaction for 70~
90 DEG C, the time be 2~4 hours；
The step of solvent, hydrophilic chain extender, small molecule chain extender, crosslinking agent, catalyst and solvent are reacted is added described
In, reaction temperature is 50~70 DEG C, the time is 5~8 hours.
9. polyurethane according to claim 7, it is characterised in that polyamine chain extender is being added to the step of the aqueous emulsion
In rapid, the aqueous emulsion is in the dispersity of stirring, and the polyamine chain extender is to be slowly added to the aqueous emulsion.
10. a kind of coating, it is characterised in that including polyurethane such as according to any one of claims 1 to 6.
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| US10907004B2 (en) | 2018-12-28 | 2021-02-02 | Industrial Technology Research Institute | Waterborne polyurethane and preparation method thereof |
| CN110423329A (en) * | 2019-08-29 | 2019-11-08 | 江苏宝泽高分子材料股份有限公司 | One kind is from extinction type waterborne polyurethane resin and preparation method thereof |
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| CN110669197A (en) * | 2019-09-24 | 2020-01-10 | 浙江禾欣科技有限公司 | Low-gloss body extinction type waterborne polyurethane resin and preparation method thereof |
| CN111040597A (en) * | 2019-12-18 | 2020-04-21 | 广东沐峰节能创新科技有限公司 | Micro-elastic sound insulation coating and preparation method thereof |
| CN111073482A (en) * | 2019-12-24 | 2020-04-28 | 珠海展辰新材料股份有限公司 | Water-based paint and preparation method thereof |
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