CN110294830A - A kind of self-crosslinkable polyurethane-polyurea water dispersion and its preparation method and application - Google Patents
A kind of self-crosslinkable polyurethane-polyurea water dispersion and its preparation method and application Download PDFInfo
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- CN110294830A CN110294830A CN201910571686.2A CN201910571686A CN110294830A CN 110294830 A CN110294830 A CN 110294830A CN 201910571686 A CN201910571686 A CN 201910571686A CN 110294830 A CN110294830 A CN 110294830A
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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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
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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
- C08G18/30—Low-molecular-weight compounds
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- 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
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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
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3823—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
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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
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
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- 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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
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- 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
- C08G18/65—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
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- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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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
- C08G18/65—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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6655—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
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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
- C08G18/65—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
- C08G18/6633—Compounds of group C08G18/42
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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
- C08G18/65—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
- C08G18/6633—Compounds of group C08G18/42
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/07—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from polymer solutions
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- 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
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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Abstract
The present invention provides a kind of preparation methods of the chain extender of polyurethane-polyurea ketocarbonyl-containing, and using the polyurethane-polyurea water dispersion of the chain extender.Secondary amine reactive hydrogen containing connection amide group in the chain extender.The fields such as woodwork coating and industrial paint can be used for using the polyurethane-polyurea water dispersion of such ketocarbonyl-containing chain extender, paint film also has splendid pressure mottling resistance energy, splendid chemical resistance and higher hardness under high humidity conditions.
Description
Technical field
The invention belongs to technical field of aqueous paint, and in particular to a kind of self-crosslinkable polyurethane-polyurea water dispersion and its
Preparation method and purposes.
Background technique
Aqueous polyurethane-polyurea aqueous dispersion is nontoxic, tasteless, non-ignitable using water as decentralized medium, is a kind of environmentally friendly
High molecular material is widely used in woodcare paint field.In the production process of aqueous polyurethane wood lacquer, in order to improve work effect
Rate and depot storage capacity, need it is painted after furniture surface rate of drying is fast, furniture stack do not generate each other impression,
(such as humidity 80%) can also construct under conditions of high humility, this just itself proposes polyurethane-polyurea moisture body very high
It is required that.Not only there are high hardness, water-fast chemical-resistant after paint film is dry, also to have under high humidity conditions good anti-
Impression performance.
Ketone carbonyl and the cross-linking reaction of acyl hydrazine and its derivative are to improve a kind of method of paint film property.Patent
CN101516950A provides a kind of method for synthesizing ketocarbonyl-containing monomer, is reacted using the monomer of ketocarbonyl-containing with epoxide
Hydroxyl is generated, is introduced into polyurethane segment by being reacted with isocyanates, hydrazides is added by the later period and obtains cross-linking effect.
Patent US2010197856A1 is described by being introduced into the 3- acetylpropyl alcohol containing acetyl group into polyester segment,
Hydrazides is added to improve the degree of cross linking by the later period, but 3- acetylpropyl alcohol is a kind of envelope of single functionality for isocyanates
Agent is held, later period cross-linking effect is bad.
Patent CN105131236A describe prepared using plant oil modified polyalcohol and ketocarbonyl-containing chain extender it is aqueous
Polyaminoester emulsion, water-fast, alcohol resistance and high rigidity with higher.The preparation method and patent of its ketocarbonyl-containing monomer
CN101516950A is similar, and the later period needs to remove unreacted acid monomers, technique by techniques such as repeatedly neutralization, extraction, elution
Complexity, post-processing difficulty are big.
Patent CN1197463A is synthesized in the presence of solvent, catalyst using diene ketone compound and diethanol amine containing double
Carbonyls, but purity is lower, the later period needs to remove solvent, there is a problem of that solvent, catalyst removal are not clean, makes simultaneously
Standby dispersion is because the residual of diene ketone compound causes storage stability poor.
To sum up, slow, slow drying speed that there are reaction speeds in existing aqueous polyurethane dispersion technology, because crosslinking degree is low
And water-fast chemical resistance is poor and is difficult to the problem of meeting resistance to compression trace requirement.
Summary of the invention
Current polyurethane-polyurea water dispersion there are aiming at the problem that, the purpose of the present invention is to provide a kind of dry speed
Spend the ambient self-crosslinking polyurethane-polyurea moisture that fast, water-fast chemical-resistant is excellent, pressure mottling resistance can be excellent under high humidity
Granular media.
Another object of the present invention is to provide the preparation methods of the polyurethane-polyurea water dispersion.
Another object of the present invention is to provide a kind of self-crosslinkable polyurethane-polyurea water dispersion product and application thereof.
For achieving the above object and reach above-mentioned technical effect, the present invention adopts the following technical scheme:
A kind of polyurethane-polyurea water dispersion, with solid part total weight of each component, the dispersion is anti-by following component
It should be made:
(a) rilanit special, 6~20wt%；
(b) macromolecule polyol that degree of functionality is 2~4,40~60wt%；
(c) isocyanates, 20~40wt%；
(d) chemical combination at least one isocyanate-reactive groups and at least one ion or potential ionic group
Object, 1~3wt%；
(e) antalkali, 0.5~2.5wt%；
(f) containing hydroxyl and/or amido, the small molecule compound that degree of functionality is 2~4,0~4wt%；
(g) non-ionic hydrophilic compound of single functionality, 0.5~1.6%；
(h) ketone carbonyl chain extender, 1~5wt%；
(i) hydrazide-based compound, 0.7~1.2wt%；
Wherein, component (h) at least contains a secondary amine group being connected directly with amide group β carbon.
In the present invention, the solid content of the polyurethane-polyurea water dispersion is 25~50wt%, preferably 30~
40wt%, in terms of dispersion gross mass.
In the present invention, the structural formula of the component (h) is as follows:
Wherein, R is containing hydroxyl and/or containing the alkyl of secondary amine group, and K is 1 or 0.In formula (1) in amide group-
The reactionless activity of NH is not belonging to secondary amine structure.
In the present invention, the component (h) is prepared by the following method:
Diacetone Acrylamide carries out bulk polymerization, Diacetone Acrylamide and formula with the compound with formula (2) structure
(2) molar ratio of primary amine group is 1:(0.9~1.2 in structural material), 50~120 DEG C of reaction temperature, 1~10h of reaction time,
Obtain the compound with formula (1) structure；
Wherein, m and n is 0 or 1, and simultaneously be 0, R containing hydroxyl and/or to contain the alkyl of secondary amine group；With formula
(2) compound of structure preferably comprises the hydramine and/or polyamines of primary amine group, more preferable 3- amino -1- methylaminopropane, 3- ammonia
Base -1- ethylamino propane, 3 amino 1 cyclohexylamino propane, 3- amino -1- methylamino butane, N- aminoethyl ethanolamine, 2- ammonia
One of base-2- methyl-1-propyl alcohol, ethanol amine and diethylenetriamine is a variety of, further preferred ethanol amine and/or N- ammonia second
Ethylethanolamine.In Michael addition reaction, since carbonyl is strong electron-withdrawing group group, cause the electron cloud of the carbon atom in methylene
Density reduces, and in the presence of alkali, is easy to lose proton and form more stable carbanion, the carbanion of generation remakes
Reaction after participating in for nucleopilic reagent, there are two proton hydrogen for primary amine group tool, and primary amine groups are located at chain end, and steric hindrance is small
In secondary amine, makes the reactivity of primary amine groups much higher than secondary amine, there can be very high conversion ratio under lower reaction temperature.
In the present invention, the hydroxyl in the H and R of secondary amine group that is formed after primary amine group reaction in the component (h) and/or
The H of secondary amine group participates in the chain extending reaction to component (c) jointly.
In the present invention, the hydroxyl value of the component (a) is 140-160mgKOH/g.
In the present invention, the component (b) is selected from normal polyester polyalcohol, polytetrahydrofuran diol, polycarbonate polyol
With one of polycaprolactone polyol or a variety of；It is preferred that polycarbonate polyol.
In the present invention, the component (c) be selected from cyclic structure isocyanates, preferably 4,4 '-dicyclohexyl methyl hydrides
Diisocyanate (HMDI), benzene dimethylene diisocyanate (XDI), isophorone diisocyanate (IPDI) and durol
One of dimethylene diisocyanate (TMXDI) is a variety of, more preferable 4,4'-Dicyclohexylmethane diisocyanate
(HMDI)。
In the present invention, the component (d) is selected from dihydromethyl propionic acid, 2,2- dimethylolpropionic acid, dihydroxymethyl acetic acid, two
Hydroxy succinic acid, N- (2- aminoethyl) -2- aminoethane sulphonic acid, N- (3- aminopropyl) -2-aminoethanesulfonic acid, N- (3- amino
Propyl) one of-Homotaurine and N- (2- aminoethyl)-Homotaurine or a variety of, preferably in above-mentioned raw materials
It is one or more and at least contain dihydromethyl propionic acid.
In the present invention, the component (e) is one of triethylamine, dimethylethanolamine and sodium hydroxide or a variety of, excellent
Select triethylamine.The component can partly or entirely convert ionic functional group for the potential ionic functional group in component (d).
In the present invention, component (f) molecular weight 60~500, component (f) includes component (f1) and/or component (f2),
Middle component (f1) be selected from ethylene glycol, 1,2- propylene glycol, 1,3- propylene glycol, 1,2- butanediol, 1,3 butylene glycol, 1,4- butanediol,
1,5- pentanediol, 3- methylpentane -1,5- pentanediol, 1,6-HD, neopentyl glycol, 1,4- cyclohexane dimethanol, 1,2- ring
Hexylene glycol, 1,4- cyclohexanediol, 2- ethyl -3- propyl pentanediol, 2,2- dimethyl-penten glycol, diethylene glycol (DEG), glycerine and three hydroxyls
One of methylpropane is a variety of, preferably 1,4-butanediol and/or neopentyl glycol；Component (f2) is selected from hydrazine, ethylenediamine and different
One of isophoronediamine is a variety of.
In the present invention, the component (g) is selected from the list that number of repeat unit is 20~75, number-average molecular weight is 900~3500
Degree of functionality polyethoxy ether, the polyethyleneglycol first that preferred repeat units number is 20~75, number-average molecular weight is 900~3500
Ether, the poly glycol monomethyl ether that more preferable molecular weight is 1000~1200.
In the present invention, the component (i), which is selected from, contains polycarboxylic two hydrazides and/or polyhydrazide, preferably adipic dihydrazide；
Hydrazides group and component (h) ketone carbonyl molar ratio are (0.6~1.4): 1.
In the present invention, the hydroxyl in the H and R of secondary amine group that is formed after primary amine group reaction in the component (h) and/or
After the H of secondary amine group participates in the chain extending reaction to component (c) jointly, the carbonyl of component (h) can continue to be selfed with component (i)
Connection reaction.
A kind of preparation method of polyurethane-polyurea water dispersion, the preparation method include the following steps:
(1) component (a), (b), (c), (d), (g) and solvent are put into reaction kettle, is stirred to react, obtain end isocyanic acid
The performed polymer of ester；
(2) component (f1) and solvent is added, is added at this time if the component (h) selected is single-amino compound, continues anti-
It answers；
(3) after reaction, solvent is added to dilute and cool down, component (e) is added and carries out neutralization reaction；
(4) under high velocity agitation, it adds water in prepolymer solution and is dispersed, is added component (f2), if component (h)
It is then added at this time for the compound of polyamino, continues to be stirred to react；
(5) solvent is removed, component (i) is added and stirs evenly to get polyurethane-polyurea water dispersion is arrived.
In the present invention, the preparation method step (1) of aqueous dispersion is reacted at 60~90 DEG C.
In the present invention, 45~60 DEG C of chargings are first cooled in the preparation method step (2) of aqueous dispersion, then it is warming up to 60~
75 DEG C of reactions.
In the present invention, the solvent in the preparation method step (2) of aqueous dispersion and (3) is acetone.
In the present invention, the preparation method step (3) of aqueous dispersion is cooled to≤40 DEG C.
In the present invention, which in 800~1000rpm is dispersed 5 by the preparation method step (4) of aqueous dispersion~
10min。
In the present invention, the reaction time of the preparation method step (4) of aqueous dispersion is 5-20min.
A kind of self-crosslinkable polyurethane-polyurea water dispersion product, the aqueous dispersion product are by the polyurethane-polyurea
The product that aqueous dispersion obtains, or the product being prepared by the polyurethane-polyurea water dispersion preparation method.
The purposes of a kind of polyurethane-polyurea water dispersion or polyurethane-polyurea water dispersion product, the polyurethane-polyurea
Aqueous dispersion or polyurethane-polyurea water dispersion product are used for water-borne wood coating, water-based industrial paint field.
The present invention during preparing aqueous dispersion, it is surprisingly found that: with formula (2) structure primary amine group it is anti-
When the H for the secondary amine group that should be formed afterwards participates in chain extending reaction together with the H of the active group on R, chain extension production is greatly improved
The indexs such as hardness, resistance to compression trace and the chemical resistance of object, this may be to react acquisition due to the secondary amine group and isocyanates
A urea bond and neighbouring amido bond together form a bigger polar group group, improve whole cohesive energy, and
Synergistic effect is generated with the three-dimensional structure that subsequent ketone hydrazine is cross-linked to form, to improve every physical index of product.
In the present invention, rilanit special is introduced in polyurethane-polyurea system, the crosslinked action of rilanit special assigns
The lower elasticity of paint film and extensibility, improve toughness and chemical resistance performance, the long carbon saturated aliphatic chain of rilanit special
Section, improves water repellency, smooth degree and the photostability of surface of the paint film, reduces the intrusion because of chemical substance especially water
The problem of paint film intensity caused by caused internal plasticization declines；Meanwhile the introducing of ketone carbonyl makes resulting dispersion be provided with friendship
Join point, obtains the dispersion of room-temperature self crosslinking with additional crosslinking agent (hydrazide compound) cooperation；Ketone carbonyl containing polyamino
Compound is more flexible on additive amount compared with the compound merely containing hydroxyl, and technological operation is easier, while itself and isocyanide
What acid esters reacted is the bigger urea bond of bond energy, and last film forming has higher mechanical performance.
It is known method with the method that the aqueous dispersion prepares varnish in the present invention, such as can be by polyurethane-polyurea
Aqueous dispersion is added in container, is placed under the conditions of rate of dispersion 1200rpm and is dispersed, the substrate being uniformly mixed then is added
Wetting agent, coalescing agent, thickener, fungicide and deionized water, maintain that rate of dispersion is constant continues to disperse after adding
15min can be prepared by aqueous one-component varnish.
Compared with prior art, the positive effect of the present invention is:
(1) ketone hydrazine crosslinking technological is applied in polyurethane-polyurea dispersions using the chain extender of special construction, is improved
The cohesive energy of material, every physical property that the three-dimensional structure generation synergistic effect being cross-linked to form with ketone hydrazine further improves product refer to
Mark, wherein impression will not be generated at 4Psi, chemical resistance greatly improves, hardness can reach H~2H；
(2) the polyurethane collocation with ketone hydrazine crosslinking technological is obtained containing the rilanit special for being saturated long carbocyclic aliphatic chain
Aqueous dispersion with excellent properties, coating prepared therefrom further improve resistance to compression in addition to water-fast and wearability improves
Trace, chemical resistance and hardness.
Detailed description of the invention
Fig. 1 is the NMR spectra of 1 ketocarbonyl-containing monomeric compound I of embodiment；
Fig. 2 is the NMR spectra of 1 synthetic product of comparative example.
Specific embodiment
Below by technical solution and technical effect the present invention will now be described by way of example.It should be understood that the present invention should not be by
Embodiments set forth herein is limited.
Primary raw material information:
Rilanit special: hydroxyl value 158mgKOH/g, Qingdao Tong Kai Chemical Co., Ltd.；
Polycaprolactone glycol: number-average molecular weight 2000, Daicel trade (Shanghai) Co., Ltd.；
Polycarbonate glycol 981: number-average molecular weight 1000, Japanese NPU company.
4,4'-Dicyclohexylmethane diisocyanate (HMDI): technical grade, Wanhua Chemical Group Co., Ltd.；
Hexamethylene diisocyanate (HDI): technical grade, Wanhua Chemical Group Co., Ltd.；
Isophorone diisocyanate (IPDI): technical grade, Wanhua Chemical Group Co., Ltd.
Ethylenediamine: pure, traditional Chinese medicines chemical reagent Co., Ltd is analyzed；
Ethanol amine: pure, traditional Chinese medicines chemical reagent Co., Ltd is analyzed；
N- aminoethyl ethanolamine: pure, traditional Chinese medicines chemical reagent Co., Ltd is analyzed；
Diacetone Acrylamide: pure, traditional Chinese medicines chemical reagent Co., Ltd is analyzed；
Triethylamine: pure, traditional Chinese medicines chemical reagent Co., Ltd is analyzed；
Adipic dihydrazide (ADH): pure, traditional Chinese medicines chemical reagent Co., Ltd is analyzed；
Dihydromethyl propionic acid (DMPA): technical grade, Bai Situo chemical company；
Poly glycol monomethyl ether: technical grade, molecular weight 1200, Han Nong Chemical Co., Ltd.；
1,4-butanediol: pure, traditional Chinese medicines chemical reagent Co., Ltd is analyzed；
Diglycol: pure, traditional Chinese medicines chemical reagent Co., Ltd is analyzed.
Detection method:
Diacetone Acrylamide conversion ratio: HPLC analyzes (sample being made into the solution of 4mg/ml, solvent is tetrahydrofuran),
It is tested at 40 DEG C with the flow rate of 1ml/min).
Dispersions of polyurethanes: being diluted to the concentration of 0.5wt% with water by average grain diameter, uses the Nano- of Malvern company
The measurement of ZS90 type laser particle analyzer, 25 DEG C of test temperature.
PH value: being counted using the 827PHLAB type PH that Wan Tong company, Switzerland produces and measured, and 25 DEG C of test temperature.
NCO% measurement: " in HG/T2409-92 base polyurethane prepolymer for use as different according to People's Republic of China's chemical industry standard
The measurement of cyanic acid ester group content " measure NCO% content in polyurethane synthesis process.The potentiometric titrimeter type of Wan Tong company, Switzerland
Number 905Titrando.
Nuclear-magnetism test: Bruker company 400MHz nuclear-magnetism tester, test condition: pulse train zgig30,90 ° of pulsewidths
12.2 microseconds, spectrum width 240ppm, spectrum center 20ppm, relaxation extend 10 seconds time, sampling number 2480, sampling number 64K, sky
White number 4.
Embodiment 1
Synthesize ketocarbonyl-containing monomeric compound I:
172g ethanol amine, 470g Diacetone Acrylamide are added in 1000ml reaction flask, stirring is warming up to 85 DEG C, heat preservation
React 4h.It discharges up to target product, Diacetone Acrylamide conversion ratio 98.8%.Its structural formula is as follows, nuclear-magnetism test knot
Fruit sees attached drawing 1.
Embodiment 2
Synthesize ketocarbonyl-containing monomeric compound II:
320g N- aminoethyl ethanolamine, 470g Diacetone Acrylamide are added in 1000ml reaction flask, stirring is warming up to
80 DEG C, insulation reaction 4h.It discharges up to target product, Diacetone Acrylamide conversion ratio 98.2%.Its structural formula is as follows:
Embodiment 3
Synthesize ketocarbonyl-containing monomeric compound III:
100g diethylenetriamine, 324g Diacetone Acrylamide are added in 1000ml reaction flask, stirring is warming up to 85 DEG C,
Insulation reaction 4h.It discharges up to target product, Diacetone Acrylamide conversion ratio 97.2%.Its structural formula is as follows:
Embodiment 4
Synthesize ketocarbonyl-containing monomeric compound IV:
200g ethanol amine, 470g Diacetone Acrylamide are added in 1000ml reaction flask, stirring is warming up to 60 DEG C, heat preservation
React 8.5h.It discharges up to target product, Diacetone Acrylamide conversion ratio 99.2%.Its structural formula is the same as 1 carbonyl containing ketone of embodiment
Based compound I.
Embodiment 5
Synthesize ketocarbonyl-containing monomeric compound V:
155g ethanol amine, 470g Diacetone Acrylamide are added in 1000ml reaction flask, stirring is warming up to 105 DEG C, protects
Temperature reaction 2h.It discharges up to target product, Diacetone Acrylamide conversion ratio 97%.Its structural formula is the same as 1 ketocarbonyl-containing of embodiment
Compound I.
Comparative example 1
Hydramine containing secondary amine group is reacted with Diacetone Acrylamide.
105.14g diethanol amine, 169.2g Diacetone Acrylamide are added in 1000ml reaction flask, stirring is warming up to 85
DEG C, insulation reaction 6h, yield 74.6%, and Diacetone Acrylamide distillation is serious in reaction, is in bottle wall more than liquid level
Its crystal, conversion ratio are only 73%.Its nuclear-magnetism test result is shown in attached drawing 2.It is not further to be applied.
Embodiment 6
Polycarbonate glycol, 40g rilanit special by 220g Jing Guo dehydration, 4g poly glycol monomethyl ether, 8g
DMPA, 135g HMDI and 30g acetone are added in the 1L four round flask equipped with import and export of nitrogen, are stirred at 80~90 DEG C
The mixture reaches 3.4wt% until NCO%.Cool to 50~55 DEG C of addition 10g ketocarbonyl-containing monomeric compound I and 48g third
Ketone, being warming up to 60 DEG C of stirrings, the reaction was continued until NCO% reaches 2.3wt%.Cool to peace treaty in 40 DEG C of addition 6.3g triethylamines
5min, then by addition 840g water, 1000rpm by the mixture disperse 5min, after dispersion be added 5g ethylenediamine after
Continuous stirring chain extension 10min.3.5g ADH is added to stir evenly, then is separated by distillation out acetone and obtains solvent-free point later
Granular media, the solid content with 33wt%, average grain diameter 145nm, pH value 8.0.
Embodiment 7
Polycaprolactone glycol, 60g rilanit special, 4g poly glycol monomethyl ether, 9g by 210g Jing Guo dehydration
DMPA, 110g HMDI and 30g acetone are added in the 1L four round flask equipped with import and export of nitrogen, are stirred at 70~80 DEG C
The mixture reaches 3.3wt% until NCO%.Cool to 55~60 DEG C of addition 15g ketocarbonyl-containing monomeric compound I and 45g third
Ketone, being warming up to 70 DEG C of stirrings, the reaction was continued until NCO% reaches 1.7wt%.Cool to peace treaty in 40 DEG C of addition 7.1g triethylamines
The mixture is dispersed 5min in 1000rpm, 11g isophorone two is added after dispersion by 5min then by addition 850g
Amine continues to stir chain extension 10min, and 4.5g ADH is added and stirs evenly, then be separated by distillation out after acetone obtain it is solvent-free
Dispersion, the solid content with 34.8wt%, average grain diameter 175nm, pH value 8.1.
Embodiment 8
Polycaprolactone glycol, 50g rilanit special, 6g poly glycol monomethyl ether, 13g by 240g Jing Guo dehydration
DMPA, 120g HMDI and 30g acetone are added in the 1L four round flask equipped with import and export of nitrogen, are stirred at 60~70 DEG C
The mixture reaches 3.2wt% until NCO%.50~55 DEG C of addition 6g 1,4-butanediol and 48g acetone are cooled to, is warming up to
The reaction was continued until NCO% reaches 1.7wt% for 60 DEG C of stirrings.It cools in 35 DEG C of addition 7.1g triethylamines and about 5min, then
By adding 850g water, the mixture is dispersed into 5min in 1000rpm, 15g ketocarbonyl-containing monomer chemical combination is added after dispersion
Object II continues to stir chain extension 15min, and 4.3g ADH is added and stirs evenly, then is separated by distillation out acetone and obtains later without molten
The dispersion of agent, the solid content with 34.8wt%, average grain diameter 175nm, pH value 8.1.
Embodiment 9
Polycaprolactone glycol, 50g rilanit special, 6g poly glycol monomethyl ether, 13g by 240g Jing Guo dehydration
DMPA, 120g HMDI and 30g acetone are added in the 1L four round flask equipped with import and export of nitrogen, are stirred at 80~90 DEG C
The mixture reaches 3.15wt% until NCO%.50~55 DEG C of addition 6g 1,4-butanediol and 48g acetone are cooled to, is warming up to
The reaction was continued until NCO% reaches 1.7wt% for 60 DEG C of stirrings.It cools in 40 DEG C of addition 8.8g triethylamines and about 5min, then
By adding 870g water, the mixture is dispersed into 5min in 1000rpm, 12g ketocarbonyl-containing monomer chemical combination is added after dispersion
Object III, 2.5g isophorone diamine continue to stir chain extension 10min, and 4.6g ADH is added and stirs evenly, then is separated by distillation out
Solvent-free dispersion is obtained after acetone, the solid content with 32wt%, average grain diameter 114nm, pH value 8.1.
Embodiment 10
Polycarbonate glycol, 40g rilanit special by 220g Jing Guo dehydration, 4g poly glycol monomethyl ether, 8g
DMPA, 135g HMDI and 30g acetone are added in the 1L four round flask equipped with import and export of nitrogen, are stirred at 80~90 DEG C
The mixture reaches 3.47wt% until NCO%.Cool to 50~55 DEG C of addition 10g ketocarbonyl-containing monomeric compounds IV and 48g
Acetone, being warming up to 60 DEG C of stirrings, the reaction was continued until NCO% reaches 2.19wt%.40 DEG C of addition 6.3g triethylamines are cooled to neutralize
The mixture is dispersed 5min in 1000rpm, 5.38g second two is added after dispersion by about 5min then by addition 880g water
Amine continues to stir chain extension 10min, and 5g ADH is added and stirs evenly, then be separated by distillation out after acetone obtain it is solvent-free
Dispersion, the solid content with 33wt%, average grain diameter 134nm, pH value 8.4.
Embodiment 11
Polycarbonate glycol, 68g rilanit special by 150g Jing Guo dehydration, 4g poly glycol monomethyl ether, 6.5g
DMPA, 100g HMDI and 30g acetone are added in the 1L four round flask equipped with import and export of nitrogen, are stirred at 80~90 DEG C
The mixture reaches 2.05wt% until NCO%.Cool to 50~55 DEG C of addition 5g ketocarbonyl-containing monomeric compounds V and 48g third
Ketone, being warming up to 60 DEG C of stirrings, the reaction was continued until NCO% reaches 1.32wt%.Cool to peace treaty in 40 DEG C of addition 5.2g triethylamines
The mixture is dispersed 10min in 800rpm, 2.7g ethylenediamine is added after dispersion by 5min then by addition 690g water,
Continue to stir chain extension 10min, 2.5g ADH be added and stirs evenly, then be separated by distillation out after acetone obtain it is solvent-free
Dispersion, the solid content with 33wt%, average grain diameter 174nm, pH value 8.7.
Comparative example 2
Referring to embodiment 7, ketone carbonyl chain extender I is replaced with diglycol.
Polycaprolactone glycol, 60g rilanit special, 4g poly glycol monomethyl ether, 9g by 210g Jing Guo dehydration
DMPA, 110g HMDI and 30g acetone are added in the 1L four round flask equipped with import and export of nitrogen, are stirred at 70~80 DEG C
The mixture reaches 3.3wt% until NCO%.55~60 DEG C of addition 7g diglycols and 45g acetone are cooled to, is warming up to
The reaction was continued until NCO% reaches 1.7wt% for 70 DEG C of stirrings.It cools in 40 DEG C of addition 7.1g triethylamines and about 5min, then
By adding 850g water, the mixture is dispersed into 5min in 1000rpm, 11g isophorone diamine is added after dispersion and continues
Chain extension 10min is stirred, then is separated by distillation out acetone and obtains solvent-free dispersion later, consolidating with 34.8wt%
Body content, average grain diameter 166nm, pH value 8.1.
Comparative example 3
The comparative example replaces HMDI with HDI.
Polycaprolactone glycol, 60g rilanit special, 4g poly glycol monomethyl ether, 9g by 210g Jing Guo dehydration
DMPA, 76g HDI and 30g acetone are added in the 1L four round flask equipped with import and export of nitrogen, are somebody's turn to do in 70~80 DEG C of stirrings
Mixture reaches 4.2wt% until NCO%.55~60 DEG C of addition 15g ketocarbonyl-containing monomeric compound I and 45g acetone are cooled to,
Being warming up to 70 DEG C of stirrings, the reaction was continued until NCO% reaches 2.4wt%.Cool to peace treaty in 40 DEG C of addition 7.1g triethylamines
The mixture is dispersed 5min in 1000rpm, the different Fo Er of 12.2g is added after dispersion by 5min then by addition 850g water
Ketone diamines continues to stir chain extension 10min, and 4.5g ADH is added and stirs evenly, then is separated by distillation out acetone and obtains nothing later
The dispersion of solvent, the solid content with 34.8wt%, average grain diameter 175nm, pH value 8.1.
Comparative example 4
Rilanit special is not added in the comparative example.
Polycaprolactone glycol, 4g poly glycol monomethyl ether, 9g DMPA, 110g HMDI by 350g Jing Guo dehydration and
30g acetone is added in the 1L four round flask equipped with import and export of nitrogen, and the mixture is stirred at 70~80 DEG C until NCO%
Reach 3.0wt%.55~60 DEG C of addition 15g ketocarbonyl-containing monomeric compound I and 45g acetone are cooled to, 70 DEG C of stirrings are warming up to
The reaction was continued until NCO% reaches 1.6wt%.It cools in 40 DEG C of addition 7.1g triethylamines and about 5min, then passes through addition
The mixture is dispersed 5min in 1000rpm by 950g water, and 11g isophorone diamine is added after dispersion and continues to stir chain extension
10min is added 4.5g ADH and stirs evenly, then is separated by distillation out acetone and obtains solvent-free dispersion later, has
There are the solid content of 33.1wt%, average grain diameter 149nm, pH value 8.1.
The preparation of coating composition:
Lacquer formulation is shown in Table 1:
1 lacquer formulation table of table
Preparation method:
Polyurethane aqueous dispersion body is added in container, is placed under the conditions of rate of dispersion 1200rpm and disperses, is then added and stirs
Uniformly mixed Byk346, coalescing agent, thickener, fungicide and deionized water are mixed, maintains rate of dispersion constant after adding
Continue to disperse 15min, can be prepared by aqueous one-component woodwork coating (varnish).
Detection project and evaluating standard are shown in Table 2:
2 detection project of table and evaluating standard
Evaluation method:
Hardness: 120 microns of wet films are scraped on transparency glass plate with the paint prepared and use different hardness after drying at room temperature
Pencil survey its pencil hardness；
Surface drying: fingers-touch method measurement is scraped 120 microns of wet films on black and white paper jam with the paint prepared, is placed at room temperature for, opens after scraping
Beginning timing, and with the film scraped of finger interruption pressing, stop timing when adhering on finger without any resin to after pressing, therebetween
Every as surface drying time；
Resistance to compression trace under high humility: 120 microns of wet films are scraped on a glass with the finishing coat prepared, are put into 25 after scraping at once
DEG C, conserve 4h in the climatic chamber of 80% relative humidity, cover one layer of medical gauze in film coated surface after 4h, and press different weight
Counterweight take counterweight and gauze away after 25 DEG C, 80% relative humidities push 16h, whether there is or not impression prints for observation film coated surface
Mark.
Chemical resistance test:
Color, Lacper4101 polyaminoester emulsion priming paint twice are wiped in three-ply board, bottom, and 400 mesh sand paper are polished, and 2000 mesh sand paper are beaten
Mill, spray paint, room temperature surface drying, 50 DEG C of baking 16h tests
It is acidproof: under room temperature, cotton white paper piece to be soaked with 10% acetum and is placed it on plate, is taken away afterwards for 24 hours
The scraps of paper observe paint film situation of change；
It is alkaline-resisting: under room temperature, cotton white paper piece to be soaked with 10% sodium carbonate liquor and is placed it on plate, is taken afterwards for 24 hours
The scraps of paper are walked, paint film situation of change is observed；
Resistance to alcohol: under room temperature, soaking cotton white paper piece with 50% ethanol solution and place it on plate, places two pieces,
Respectively at 1h, for 24 hours take away afterwards, observation impregnate 1h, for 24 hours after paint film situation of change；
It is water-fast: under room temperature, with water-soaked cotton white paper piece and to place it on plate, take the scraps of paper away afterwards for 24 hours, observe paint film
Situation of change.
Test result is shown in Table 3:
3 test result of table
* it gives a mark mode, if " 5-4-5 " in embodiment indicates alkaline-resisting in order, resistance to alcohol, acidproof score, score higher generation
This of table performance is better.
The embodiment of the present invention is described above, above description is exemplary, and non-exclusive, and also not
It is limited to disclosed each embodiment.Without departing from the scope and spirit of illustrated each embodiment, for this technology
Many modifications and changes are obvious for the those of ordinary skill in field.
Claims (18)
1. a kind of polyurethane-polyurea water dispersion, which is characterized in that with solid part total weight of each component, the dispersion by
Following component reaction is made:
(a) rilanit special, 6~20wt%；
(b) macromolecule polyol that degree of functionality is 2~4,40~60wt%；
(c) isocyanates, 20~40wt%；
(d) compound at least one isocyanate-reactive groups and at least one ion or potential ionic group, 1
~3wt%；
(e) antalkali, 0.5~2.5wt%；
(f) containing hydroxyl and/or amido, the small molecule compound that degree of functionality is 2~4,0~4wt%；
(g) non-ionic hydrophilic compound of single functionality, 0.5~1.6%；
(h) ketone carbonyl chain extender, 1~5wt%；
(i) hydrazide-based compound, 0.7~1.2wt%；
Wherein, component (h) at least contains a secondary amine group being connected directly with amide group β carbon.
2. aqueous dispersion according to claim 1, which is characterized in that the structural formula of the component (h) is as follows:
Wherein, R is containing hydroxyl and/or containing the alkyl of secondary amine group, and K is 1 or 0.
3. aqueous dispersion according to claim 1 or 2, which is characterized in that the component (h) is prepared by the following method:
Diacetone Acrylamide carries out bulk polymerization with the compound with formula (2) structure, and Diacetone Acrylamide and formula (2) are tied
The molar ratio of primary amine group is 1:(0.9~1.2 in structure substance), 50~120 DEG C of reaction temperature, 1~10h of reaction time is obtained
Compound with formula (1) structure；
Wherein, m and n is 0 or 1, and simultaneously be 0, R containing hydroxyl and/or to contain the alkyl of secondary amine group；
Compound with formula (2) structure preferably comprises the hydramine and/or polyamines of primary amine group, more preferable 3- amino -1- first ammonia
Base propane, 3- amino -1- ethylamino propane, 3 amino 1 cyclohexylamino propane, 3- amino -1- methylamino butane, N- aminoethyl
One of ethanol amine, 2-amino-2-methyl-1-propanol, ethanol amine and diethylenetriamine are a variety of, further preferred ethanol amine
And/or N- aminoethyl ethanolamine.
4. aqueous dispersion according to any one of claim 1-3, which is characterized in that primary amine group in the component (h)
The H of hydroxyl and/or secondary amine group in the H and R of the secondary amine group formed after reaction participates in anti-to the chain extension of component (c) jointly
It answers.
5. aqueous dispersion according to claim 1, which is characterized in that the hydroxyl value of the component (a) is 140-160mgKOH/
g。
6. aqueous dispersion according to claim 1, which is characterized in that the component (b) is selected from normal polyester polyalcohol, gathers
One of erythritan, polycarbonate polyol and polycaprolactone polyol are a variety of；It is preferred that polycarbonate polyol.
7. aqueous dispersion according to claim 1, which is characterized in that the component (c) is selected from different with cyclic structure
Cyanate, preferably 4,4'-Dicyclohexylmethane diisocyanate, benzene dimethylene diisocyanate, isophorone diisocyanate
One of ester and tetramethylxylylene diisocyanate are a variety of, more preferable 4,4 '-dicyclohexyl methyl hydride diisocyanates
Ester.
8. aqueous dispersion according to claim 1, which is characterized in that the component (d) is selected from dihydromethyl propionic acid, 2,2-
Dimethylolpropionic acid, dihydroxymethyl acetic acid, dihydroxysuccinic acid, N- (2- aminoethyl) -2- aminoethane sulphonic acid, N- (3- amino
Propyl) in -2-aminoethanesulfonic acid, N- (3- aminopropyl)-Homotaurine and N- (2- aminoethyl)-Homotaurine
It is one or more, preferred one of above-mentioned raw materials or a variety of and at least contain dihydromethyl propionic acid.
9. dispersion according to claim 1, which is characterized in that the component (e) be triethylamine, dimethylethanolamine and
One of sodium hydroxide is a variety of, preferably triethylamine.
10. aqueous dispersion according to claim 1, which is characterized in that component (f) molecular weight 60~500, component
It (f) include component (f1) and/or component (f2), wherein component (f1) is selected from ethylene glycol, 1,2-PD, 1,3-PD, 1,
It is 2- butanediol, 1,3 butylene glycol, 1,4- butanediol, 1,5- pentanediol, 3- methylpentane -1,5- pentanediol, 1,6-HD, new
Pentanediol, 1,4- cyclohexane dimethanol, 1,2- cyclohexanediol, 1,4- cyclohexanediol, 2- ethyl -3- propyl pentanediol, 2,2- bis-
One of methyl pentanediol, diethylene glycol (DEG), glycerine and trimethylolpropane are a variety of, preferably 1,4-butanediol and/or new penta
Glycol；Component (f2) is selected from one of hydrazine, ethylenediamine and isophorone diamine or a variety of.
11. aqueous dispersion according to claim 1, which is characterized in that the component (g) be selected from number of repeat unit be 20~
75, the single functionality polyethoxy ether that number-average molecular weight is 900~3500, preferred repeat units number are 20~75, count equal molecule
The poly glycol monomethyl ether that amount is 900~3500, the poly glycol monomethyl ether that more preferable molecular weight is 1000~1200.
12. aqueous dispersion according to claim 1, which is characterized in that the component (i), which is selected from, contains polycarboxylic two hydrazides
And/or polyhydrazide, preferred adipic dihydrazide；Hydrazides group and component (h) ketone carbonyl molar ratio are (0.6~1.4): 1.
13. a kind of preparation method of such as polyurethane-polyurea water dispersion of any of claims 1-12, feature exist
In the preparation method includes the following steps:
(1) component (a), (b), (c), (d), (g) and solvent are put into reaction kettle, is stirred to react, obtains isocyanate terminated
Performed polymer；
(2) component (f1) and solvent is added, is added at this time if the component (h) selected is single-amino compound, the reaction was continued；
(3) after reaction, solvent is added to dilute and cool down, component (e) is added and carries out neutralization reaction；
(4) under high velocity agitation, it adds water in prepolymer solution and is dispersed, is added component (f2), if component (h) is more
The compound of amino is then added at this time, continues to be stirred to react；
(5) solvent is removed, component (i) is added and stirs evenly to get polyurethane-polyurea water dispersion is arrived.
14. preparation method according to claim 13, which is characterized in that step (1) is reacted at 60~90 DEG C.
15. preparation method according to claim 13, which is characterized in that 45~60 DEG C of chargings are first cooled in step (2),
It is warming up to 60~75 DEG C of reactions again.
16. preparation method according to claim 13, which is characterized in that step (3) is cooled to≤40 DEG C.
17. a kind of self-crosslinkable polyurethane-polyurea water dispersion product, which is characterized in that the aqueous dispersion product is to pass through right
It is required that the product that polyurethane-polyurea water dispersion described in any one of 1-12 obtains, or by any in claim 13-16
The product that polyurethane-polyurea water dispersion preparation method described in is prepared.
18. appointing in a kind of polyurethane-polyurea water dispersion of any of claims 1-12 or claim 13-16
Polyurethane-polyurea moisture described in the polyurethane-polyurea water dispersion or claim 17 of the preparation of preparation method described in one
The purposes of granular media product, the polyurethane-polyurea water dispersion or polyurethane-polyurea water dispersion product are applied for aqueous wooden ware
Material, water-based industrial paint field.
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| CN110982477A (en) * | 2019-12-20 | 2020-04-10 | 万华化学集团股份有限公司 | Water-based adhesive capable of being pasted in wet mode and preparation method and application thereof |
| CN112538152A (en) * | 2019-09-20 | 2021-03-23 | 万华化学集团股份有限公司 | Waterborne polyurethane-polyurea dispersion and preparation method and application thereof |
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| CN110982477A (en) * | 2019-12-20 | 2020-04-10 | 万华化学集团股份有限公司 | Water-based adhesive capable of being pasted in wet mode and preparation method and application thereof |
| CN110982477B (en) * | 2019-12-20 | 2022-04-22 | 万华化学集团股份有限公司 | Water-based adhesive capable of being pasted in wet mode and preparation method and application thereof |
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