CN109651588A - Castor oil modified cation self-crosslinkable polyurethane polyurea water dispersion and preparation method and application - Google Patents
Castor oil modified cation self-crosslinkable polyurethane polyurea water dispersion and preparation method and application Download PDFInfo
- Publication number
- CN109651588A CN109651588A CN201811388429.7A CN201811388429A CN109651588A CN 109651588 A CN109651588 A CN 109651588A CN 201811388429 A CN201811388429 A CN 201811388429A CN 109651588 A CN109651588 A CN 109651588A
- Authority
- CN
- China
- Prior art keywords
- component
- castor oil
- water dispersion
- oil modified
- glycol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4045—Mixtures of compounds of group C08G18/58 with other macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/58—Epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—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
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6696—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
-
- C—CHEMISTRY; METALLURGY
- 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
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- 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
- C09D5/002—Priming paints
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention relates to a kind of castor oil modified self crosslinking cationic polyurethane-polyurea aqueous dispersion and preparation method thereof and in the application of wooden ware sealing priming paint, the dispersion includes (a) castor oil polyhydric alcohol, (b) isocyanates, (c) at least one amine containing tertiary amino group, (d) at least one epoxy resin, (e) low molecular compound containing hydroxyl in addition to component (c), (f) low molecular compound containing amido in addition to component (c), (g) non-ionic hydrophilic compound and (h) at least one neutralizer.The castor oil modified self crosslinking cationic polyurethane-polyurea aqueous dispersion of gained of the invention introduces the amine containing tertiary amine group by rear chain extension mode, play hydrophilic interaction, when being applied to wooden ware sealing priming paint in the later period, the tertiary amine group can be catalyzed epoxy group and form self-crosslinking, excellent adhesion and closure are made it have, while chemicals anti-corrosion performance is excellent.
Description
Technical field
The present invention relates to a kind of preparation method of castor oil modified cationic self-crosslinkable polyurethane polyurea water dispersion and its
In the application of wooden ware sealing priming paint.
Background technique
Aqueous woodware paint is constantly subjected to the concern of coating material production quotient and people due to the advantage in terms of its environmental protection, but is constructing
With there is also many insoluble problems, such as water colour paint, especially white paint or light colour paint, film is dry in extension process
Change colour immediately after dry, causes inconsistent with desired color.Its main cause is that timber is pigment that is hydrophilic, containing
(tannic acid) also has hydrophily, and water is one of main constituent of water paint.When coating is coated on wood surface, wood
Colored component in material can be dissolved into rapidly the continuous phase of coating --- in water, just as being added to color again in coating, thus
Change the form and aspect of coating.Reduce water colo(u)r or tannic acid exudation most simple effective method first is that coating close bottom
Paint.Resin cation can react formation with the tannic acid and amount of grease substance molecule formation ionic bond in timber
Salts substances coated is fixed on interface, and exudation will not be migrated under high temperature, super-humid conditions, coating surface is caused to be oxidized change
Color, to influence the appearance of film.
Castor oil is a kind of natural reproducible vegetable oil, has special structure, not only has hydroxyl, also contains double bond,
Belong to bifunctionality compound.Hydroxyl in castor oil can directly and-NCO reaction, and three-functionality-degree compound therein can be with
Increase the degree of cross linking of polyurethane, improve water resistance and mechanical performance, carbon-carbon double bond therein can form high property by oxidation cross-linked
The self-crosslinking polymer material of energy, nonpolarity fatty acid long-chain therein, further increases the substrate wetting, water-fast of polyurethane
Property etc..
Epoxy resin contains epoxy group, hydroxyl, and it is excellent to have that modulus is high, intensity is high and chemical resistance is good, thermal stability is good etc.
Point it is water-fast, resistance to can to have become at present raising aqueous polyurethane by way of blending and graft copolymerization in conjunction with polyurethane
The important means of the items comprehensive performance such as solvent nature and tensile strength.
Although having more document and patent report at present, but still there are poor adhesive force, closure enters permeability, chemistry
Product patience, poor water resistance, hardness is low, the problems such as stability difference.As 102093533 A of CN discloses a kind of cationic
Aqueous polyurethane wooden ware sealing priming paint, uses TDI, N220 and MDEA for primary raw material, but uses N220 for soft segment, synthesis
The hardness of WPU is small, poor adhesive force, while lotion contains low admittedly, is weak in terms of the fillibility and feel of film.
Summary of the invention
It is an object of the present invention to existing cation water-based wooden ware sealing priming paint there are aiming at the problem that, one kind is provided
The preparation method of the dual modified self crosslinking cationic polyurethane-polyurea aqueous dispersion of castor oil, epoxy resin and its woodenware seal
The application of priming paint is closed, which introduces the amine containing tertiary amine group by using the mode of rear chain extension, hydrophilic interaction is played, rear
When phase is applied to wooden ware sealing priming paint, which can be catalyzed epoxy group and form self-crosslinking, be formed finer and close netted
Structure, the continuous exudation for blocking tannic acid in timber make it have excellent adhesion and closure, while chemicals patience
It can be excellent.The long carbocyclic aliphatic chain being had by introducing castor oil polyhydric alcohol can reduce the surface energy of lotion, improve lotion in timber
On enter permeability；Unsaturated double-bond in castor oil polyhydric alcohol occur as the extension of time will be slow it is oxidation cross-linked, further
It improves hardness and grinability makes it have good hardness and grinability.
According to the first aspect of the invention, a kind of castor oil modified cationic self-crosslinkable polyurethane polyureas water dispersion is provided
Body comprising following components:
(a) castor oil polyhydric alcohol, 10~45wt%, preferably 15~40wt%,
(b) isocyanates, 10~50wt%, preferably 20-40wt%,
(c) at least one amine containing tertiary amino group, the amine containing tertiary amino group, which contains at least one, to be in NCO
The functional group of reactivity, 1~8wt%, preferably 2~5wt%,
(d) at least one epoxy resin, 10~20wt%, preferably 12~18wt%,
(e) low molecular compound containing hydroxyl in addition to component (c), 0~10wt%, preferably 2~10wt%,
(f) low molecular compound containing amido in addition to component (c), 0~10wt%, preferably 2~10wt%,
(g) non-ionic hydrophilic compound, 0.2~5wt%, preferably 0.5~3wt%,
(h) at least one neutralizer, for can be with component (c) at the acidic materials of salt, dosage makes the degree of neutralization to be
50-150%, preferably 60%-120%, more preferable 80-100%,
Wherein, the wt% is counted on the basis of component (a)-(g) total weight.
Further, castor oil modified cationic self-crosslinkable polyurethane polyurea water dispersion be by component (a), (b), (d),
(e) it is reacted in the presence of the solvent with (g), obtains isocyanate terminated performed polymer, then neutralized with component (h), add group
Divide (c) and (f) chain extension, add water dispersion, partially or completely removes solvent and obtain.
The castor oil modified cationic self-crosslinkable polyurethane polyurea water dispersion of the one kind provided according to the present invention, preferred institute
Stating its hydroxyl value of component (a) castor oil polyhydric alcohol is 158-163mgKOH/g.
The castor oil modified cationic self-crosslinkable polyurethane polyurea water dispersion of the one kind provided according to the present invention, preferred institute
State component (b) diisocyanate, including toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, isophorone diisocyanate
One of ester, hexamethylene diisocyanate and dicyclohexyl methyl hydride diisocyanate are a variety of；Preferably hexa-methylene two
One or both of isocyanates and dicyclohexyl methyl hydride diisocyanate.
The castor oil modified cationic self-crosslinkable polyurethane polyurea water dispersion of the one kind provided according to the present invention, preferred institute
At least one amine containing tertiary amino group of component (c) is stated, the amine containing tertiary amino group contains at least one can be with NCO in anti-
Answer active functional group, including 3- dimethylamine propylamine, N, one in bis- (3- aminopropyl) methylamines of N-, dimethyl dipropylenetriamine
Kind is a variety of, wherein at least one can be selected from amino in the functional group of reactivity with NCO.
The castor oil modified cationic self-crosslinkable polyurethane polyurea water dispersion of the one kind provided according to the present invention, the component
(d) at least one epoxy resin is the epoxy resin that epoxide number is 0.18-0.56, and preferably epoxide number is 0.30-0.54's
Bisphenol A type epoxy resin, such as one of E44, E51, E42, E20 or the mixture of two or more arbitrary proportions, more preferably
It is the bisphenol A type epoxy resin that epoxide number is about 0.44.
The castor oil modified cationic self-crosslinkable polyurethane polyurea water dispersion of the one kind provided according to the present invention, preferred institute
State low molecular compound of the component (e) containing hydroxyl, including ethylene glycol, 1,2-PD, 1,3-PD, 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- cyclohexanediol, 1,4- cyclohexanediol, 2- ethyl -3- propyl pentanediol, 2,2- dimethyl-penten two
One of alcohol, diethylene glycol (DEG), glycerine, trimethylolpropane are a variety of；It is preferably selected from ethylene glycol, 1,2- propylene glycol, 1,2- fourth
Glycol, diethylene glycol (DEG), is more preferably selected from diethylene glycol (DEG) at 1,3 butylene glycol.
The castor oil modified cationic self-crosslinkable polyurethane polyurea water dispersion of the one kind provided according to the present invention, preferred institute
State low molecular compound of the component (f) containing amido be selected from ethylenediamine, hydroxyethyl ethylenediamine, 1,3- propane diamine, 1,2- propane diamine,
One of 1,4- butanediamine, 1,5- pentanediamine, 1,6- hexamethylene diamine, hexamethylenediamine and isophorone diamine are a variety of；It is preferred that
Selected from isophorone diamine.
The castor oil modified cationic self-crosslinkable polyurethane polyurea water dispersion of the one kind provided according to the present invention, preferred institute
Component (g) non-ionic hydrophilic compound is stated, selected from the polyethers containing polyethoxy, being preferably selected from containing ethylene oxide number is 4
~200 single functionality polyethoxy ether, particularly preferably selected from the number-average molecular weight that ethylene oxide number is 12~75 be 200~
8000 poly glycol monomethyl ether.
The castor oil modified cationic self-crosslinkable polyurethane polyurea water dispersion of the one kind provided according to the present invention, preferred institute
State at least one neutralizer of component (h) be can acidic materials with component (c) at salt, such as formic acid, acetic acid, methane sulfonic acid, benzene
One of sulfonic acid, phosphoric acid etc. are a variety of, preferably formic acid, acetic acid, more preferable acetic acid.
The solvent is preferably ketones solvent, further preferred acetone or methyl ethyl ketone, and the dosage of solvent can be component
(a) 1.0-2.1 times of-(g) total weight, preferably 1.2-1.8 times.
According to the second aspect of the invention, above-mentioned castor oil modified cationic self-crosslinkable polyurethane polyureas water dispersion is provided
The preparation method of body includes the following steps: that (such as ketones solvent is such as by component (a), (b), (d), (g) and first part's solvent
Acetone), catalyst is put into reaction kettle in 50~95 DEG C, preferably 60-90 DEG C, preferably lower reaction, and component (e) and the is then added
Two partial solvents (such as ketones solvent such as acetone) at 50~95 DEG C, preferably 60-90 DEG C the reaction was continued obtain it is isocyanate terminated
Performed polymer is added Part III solvent (such as ketones solvent such as acetone), and cooling (such as to 20-40 DEG C, preferably 30-35 DEG C) will
Component (h) addition neutralized (such as 2-30 minutes, preferably from about 5min, until 50-150%, preferably 60%-120%, more preferably
The degree of neutralization of 80-100%), component (c) is added and component (f) carries out chain extension (such as 10-40min, preferably from about 15min), then
Add water dispersion, by distillation fraction or completely removes solvent.
Total dosage of solvent can be 1.0-2.1 times of component (a)-(g) total weight, preferably 1.2-1.8 times, and first
The mass ratio of partial solvent and second part solvent and Part III solvent can be 1:0.3~3:5~13, and preferably 1:0.7~
1.5:7~12.Add in water dispersion, the additive amount of water should make the solid content of dispersion of the invention with 25-50wt%, especially
The solid content of 30-40wt%.
The present invention is introduced the amine containing tertiary amino group by the way of rear chain extension, adopted by using the tertiary amine of special construction
It is reacted with amino with isocyanates, is different from common N methyldiethanol amine, tertiary ammonia plays hydrophilic interaction in dispersion process,
When applied to wooden ware sealing priming paint, it can be catalyzed the self-crosslinking of epoxy and epoxy, do not need extra catalyst, by introducing epoxy,
In the film forming procedure of wooden ware sealing priming paint, the self-crosslinking of epoxy and epoxy itself under the catalysis of tertiary amine is preferably closed.
Invention further provides above-mentioned castor oil modified cationic self-crosslinkable polyurethane polyurea water dispersions in woodenware
The application of seal coat.
The beneficial effects of the present invention are: the amine containing tertiary amine group is introduced by using the mode of rear chain extension, is being dispersed
Hydrophilic interaction is played in the process, and when being applied to wooden ware sealing priming paint in the later period, which can be catalyzed epoxy group and be formed certainly
Crosslinking forms finer and close reticular structure, block tannic acid in timber continuous exudation make it have excellent adhesion and
Closure, while chemicals anti-corrosion performance is excellent.The long carbocyclic aliphatic chain being had by introducing castor oil polyhydric alcohol, can reduce lotion
Surface can, improve lotion enter permeability on timber；Unsaturated double-bond in castor oil polyhydric alcohol with the time extension meeting
Slowly occur oxidation cross-linked, further increases hardness and grinability makes it have good hardness and grinability.
Specific embodiment
The embodiment preferred embodiment that the present invention will be described in more detail will be passed through below.Although embodiment describes this hair
Bright preferred embodiment, however, it is to be appreciated that may be realized in various forms the implementation of the invention without that should be illustrated here
Mode is limited.
One, the source of reaction raw materials
1, component (a)
Castor oil polyhydric alcohol (158-163mgKOH/g of hydroxyl value): (Tongliao, Inner Mongolia chemical industry)
2, component (b)
HMDI:(Wanhua Chemical Group Co., Ltd.)
3, component (c)
Dimethyl dipropylenetriamine: (analyzing pure, Xin Dian chemical material (Shanghai) Co., Ltd.)
4, component (d)
Epoxy resin: (Sinopec)
5, component (e)
Diethylene glycol (DEG) (analyzes pure, traditional Chinese medicines chemical reagent Co., Ltd)
6. component (f)
Isophorone diamine: (technical grade, Wanhua Chemical Group Co., Ltd.)
7, component (g)
Poly glycol monomethyl ether, the Hunan molecular weight 1200:(petrochemical industry Co., Ltd)
8, component (h)
Acetic acid (analyzes pure, traditional Chinese medicines chemical reagent Co., Ltd).
Two, evaluating method:
1, water-fast/acid/base/alcohol test: reference GB/T 4893.1-2005,
It is acidproof: under room temperature, cotton white paper piece to be soaked with 10% acetum and is placed it on paint film, is taken afterwards for 24 hours
The scraps of paper are walked, paint film situation of change is observed；
It is alkaline-resisting: under room temperature, cotton white paper piece is soaked with 10% sodium carbonate liquor and is placed it on paint film, for 24 hours after
It takes the scraps of paper away, observes paint film situation of change；
Resistance to alcohol: under room temperature, soaking cotton white paper piece with 50% ethanol solution and place it on paint film, places two
Block respectively at 1h, is for 24 hours taken 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 paint film, take the scraps of paper, observation paint away afterwards for 24 hours
Film situation of change.
2, sealing effect is tested:
Plate is dyed with a certain amount of tannic acid solution, it is to be dried for 24 hours after, gently grind off wolline with 400 mesh sand paper, brush
1 aqueous wooden ware seal coat is applied, after spontaneously drying 4h, then brushes 1 seal coat, is spontaneously dried for 24 hours, finally, spraying 2
White water-borne lacquer as woodenware finish (is based on ten thousand Hua Huaxue4221 lotions), see whether tannic acid migration in the table of film
Face.
Formula used is shown in Table 1 when seal coat:
1 seal coat formula of table
| The trade mark | Quality/g | |
| Lotion (35% solid content) | Self-control | 82 |
| Substrate wetting agents | BYK346 | 0.3 |
| Levelling agent | Tego410 | 0.3 |
| Coalescing agent | DPNB | 5.0 |
| Thickener | U605 | 1.2 |
| Defoaming agent | BYK 024 | 0.2 |
| Water | 10 |
Embodiment 1:
Castor oil polyhydric alcohol, 40g epoxy resin E44,5.2g poly glycol monomethyl ether by 80g Jing Guo dehydration,
90gHMDI and 35g acetone is added in the 1L four round flask equipped with import and export of nitrogen, stirs the mixture at 80~90 DEG C
Until NCO reaches 7.09wt%.50~55 DEG C of addition 10g diethylene glycol (DEG)s are cooled to, 28g acetone is warming up to 60 DEG C of stirrings and continues instead
3.84wt% should be reached until NCO.310g acetone is added, cools in 30-35 DEG C of addition 2.94g acetic acid and about 5min, then
6g dimethyl dipropylenetriamine is added and 8g isophorone diamine carries out chain extension 15min, is then mixed this by adding 558g water
Object dispersion is closed, continues to stir 5min after dispersion.It is separated by distillation out acetone again and obtains solvent-free dispersion later,
Its solid content with 35wt%, average grain diameter 100nm, pH value are 5.
Embodiment 2:
Castor oil polyhydric alcohol, 40g epoxy resin E44,5.2g poly glycol monomethyl ether by 60g Jing Guo dehydration,
90gHMDI and 35g acetone is added in the 1L four round flask equipped with import and export of nitrogen, stirs the mixture at 80~90 DEG C
Until NCO reaches 8.99wt%.50~55 DEG C of addition 13g diethylene glycol (DEG)s are cooled to, 28g acetone is warming up to 60 DEG C of stirrings and continues instead
4.21wt% should be reached until NCO.287g acetone is added, cools in 30-35 DEG C of addition 2.94g acetic acid and about 5min, then
6g dimethyl dipropylenetriamine is added and 7g isophorone diamine carries out chain extension 15min, is then mixed this by adding 516g water
Object dispersion is closed, continues to stir 5min after dispersion.It is separated by distillation out acetone again and obtains solvent-free dispersion later,
Its solid content with 35wt%, average grain diameter 86nm, pH value are 5.2.
Embodiment 3:
Castor oil polyhydric alcohol, 40g epoxy resin E44,5.2g poly glycol monomethyl ether by 50g Jing Guo dehydration,
90gHMDI and 25g acetone is added in the 1L four round flask equipped with import and export of nitrogen, stirs the mixture at 80~90 DEG C
Until NCO reaches 10.05wt%.50~55 DEG C of addition 15g diethylene glycol (DEG)s are cooled to, 28g acetone is warming up to 60 DEG C of stirrings and continues instead
4.24wt% should be reached until NCO.278g acetone is added, cools in 30-35 DEG C of addition 2.94g acetic acid and about 5min, then
6g dimethyl dipropylenetriamine is added and 8g isophorone diamine carries out chain extension 15min, is then mixed this by adding 500g water
Object dispersion is closed, continues to stir 5min after dispersion.It is separated by distillation out acetone again and obtains solvent-free dispersion later,
Its solid content with 35wt%, average grain diameter 92nm, pH value are 4.8.
Embodiment 4:
Castor oil polyhydric alcohol, 35g epoxy resin E44,5.2g poly glycol monomethyl ether by 35g Jing Guo dehydration,
83gHMDI and 35g acetone is added in the 1L four round flask equipped with import and export of nitrogen, stirs the mixture at 80~90 DEG C
Until NCO reaches 11.14wt%.50~55 DEG C of addition 16g diethylene glycol (DEG)s are cooled to, 34g acetone is warming up to 60 DEG C of stirrings and continues instead
3.99wt% should be reached until NCO.249g acetone is added, cools in 30-35 DEG C of addition 2.94g acetic acid and about 5min, then
6g dimethyl dipropylenetriamine is added and 7g isophorone diamine carries out chain extension 15min, is then mixed this by adding 448g water
Object dispersion is closed, continues to stir 5min after dispersion.It is separated by distillation out acetone again and obtains solvent-free dispersion later,
Its solid content with 35wt%, average grain diameter 80nm, pH value are 5.2.
Embodiment 5:
Castor oil polyhydric alcohol, 20g epoxy resin E44,5.2g poly glycol monomethyl ether by 50g Jing Guo dehydration,
90gHMDI and 35g acetone is added in the 1L four round flask equipped with import and export of nitrogen, stirs the mixture at 80~90 DEG C
Until NCO reaches 11.02wt%.50~55 DEG C of addition 15g diethylene glycol (DEG)s are cooled to, 34g acetone is warming up to 60 DEG C of stirrings and continues instead
4.28wt% should be reached until NCO.253g acetone is added, cools in 30-35 DEG C of addition 2.94g acetic acid and about 5min, then
6g dimethyl dipropylenetriamine is added and 9g isophorone diamine carries out chain extension 15min, is then mixed this by adding 455g water
Object dispersion is closed, continues to stir 5min after dispersion.It is separated by distillation out acetone again and obtains solvent-free dispersion later,
Its solid content with 35wt%, average grain diameter 86nm, pH value are 5.0.
Comparative example 1:
Polyneopentyl glycol adipate glycol, 6g poly glycol monomethyl ether, 90gHMDI by 232g Jing Guo dehydration and
49g acetone is added in the 1L four round flask equipped with import and export of nitrogen, and the mixture is stirred at 80~90 DEG C until NCO reaches
To 5.0wt%.50~55 DEG C of addition 11.8g diethylene glycol (DEG)s are cooled to, 43g acetone, being warming up to 60 DEG C of stirrings, the reaction was continued until NCO
Reach 2.21wt%.399g acetone is added, cools in 30-35 DEG C of additions 6.38g acetic acid and about 5min, then addition 13g bis-
Methyl dipropylenetriamine and 4g isophorone diamine carry out chain extension 15min, are then dispersed the mixture by addition 832g water,
Continue to stir 5min after dispersion.It is separated by distillation out acetone again and obtains solvent-free dispersion later, has
The solid content of 35wt%, average grain diameter 76nm, pH value are 4.6.
Comparative example 2:
Polyneopentyl glycol adipate glycol, 38g castor oil, 5.2g polyethyleneglycol first by 180g Jing Guo dehydration
Ether, 92gHMDI and 51g acetone are added in the 1L four round flask equipped with import and export of nitrogen, and it is mixed that this is stirred at 80~90 DEG C
Object is closed until NCO reaches 4.66wt%.50~55 DEG C of addition 8g diethylene glycol (DEG)s are cooled to, 57g acetone is warming up to 60 DEG C of stirrings and continues
Reaction reaches 2.49wt% until NCO.440g acetone is added, cools in 30-35 DEG C of addition 4.91g acetic acid and about 5min, so
10g dimethyl dipropylenetriamine is added afterwards and 6g isophorone diamine carries out chain extension 15min, it then should by addition 791g water
Mixture dispersion continues to stir 5min after dispersion.It is separated by distillation out acetone again and obtains solvent-free dispersion later
Body, the solid content with 35wt%, average grain diameter 160nm, pH value are 4.8.
Comparative example 3:
Polyneopentyl glycol adipate glycol, 3g poly glycol monomethyl ether by 263.5g Jing Guo dehydration,
104gHMDI and 40g acetone is added in the 1L four round flask equipped with import and export of nitrogen, stirs the mixing at 80~90 DEG C
Object reaches 2.09wt% until NCO.50~55 DEG C are cooled to, 18.72gN- methyl diethanolamine 60g acetone is warming up to 60 DEG C and stirs
Mix that the reaction was continued until NCO reaches 1.86wt%.It cools in 30-35 DEG C of addition 9.43g acetic acid and about 5min, is then added
15.2g isophorone diamine carries out chain extension 15min, is then dispersed the mixture by adding 606g water, after dispersion after
Continuous stirring 5min.It is separated by distillation out acetone again and obtains solvent-free dispersion later, the solid with 35wt% contains
Amount, average grain diameter 186nm, pH value is 4.8.
Lotion made from each embodiment and comparative example is prepared into anti-wooden ware sealing according to formulation for coating material provided by table 1 above
Priming paint, and be tested for the property.The performance test results of obtained seal coat are shown in Table 2:
2 seal coat test result of table
It can be seen that by the test result of embodiment and comparative example using castor oil modified prepared by this patent method
When self crosslinking cationic polyurethane-polyurea aqueous dispersion is applied to wooden ware sealing priming paint, there is good sealing effect and excellent
Chemical-resistant.
It will be understood by those skilled in the art that under the introduction of this specification, the present invention can be made some modifications or
Adjustment.These modifications or adjustment should also be as within the scope of the claims in the present invention.
Claims (10)
1. a kind of castor oil modified cationic self-crosslinkable polyurethane polyurea water dispersion comprising following components:
(a) castor oil polyhydric alcohol, 10~45wt%, preferably 15~40wt%, it is preferable that component (a) castor oil polyhydric alcohol
Hydroxyl value is 158-163mgKOH/g,
(b) isocyanates, 10~50wt%, preferably 20-40wt%,
(c) at least one amine containing tertiary amino group, the amine containing tertiary amino group, which contains at least one, to be in react with NCO
Active functional group, 1~8wt%, preferably 2~5%,
(d) at least one epoxy resin, 10~20wt%, preferably 12~18wt%,
(e) low molecular compound containing hydroxyl in addition to component (c), 0~10wt%, preferably 2~10wt%,
(f) low molecular compound containing amido in addition to component (c), 0~10wt%, preferably 2~10wt%,
(g) non-ionic hydrophilic compound, 0.2~5wt%, preferably 0.5~3wt%,
(h) at least one neutralizer, being can be with component (c) at the acidic materials of salt, and dosage makes degree of neutralization be 50-
150%, preferably 60%-120%, more preferable 80-100%,
Wherein, the wt% is counted on the basis of component (a)-(g) total weight.
2. castor oil modified self crosslinking cationic polyurethane-polyurea aqueous dispersion according to claim 1, which is characterized in that
The castor oil modified cationic self-crosslinkable polyurethane polyurea water dispersion is with (g) by component (a), (b), (d), (e) molten
It is reacted in the presence of agent, obtains isocyanate terminated performed polymer, then neutralized with component (h), added component (c) and (f) expands
Chain adds water dispersion, partially or completely removes solvent and obtains.
3. castor oil modified self crosslinking cationic polyurethane-polyurea aqueous dispersion according to claim 1 or 2, feature exist
In component (b) isocyanates is selected from toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, two isocyanide of isophorone
One of acid esters, hexamethylene diisocyanate and dicyclohexyl methyl hydride diisocyanate are a variety of；Preferably hexa-methylene
One or both of diisocyanate and dicyclohexyl methyl hydride diisocyanate.
4. castor oil modified self crosslinking cationic polyurethane-polyurea water dispersion described in any one of -3 according to claim 1
Body, which is characterized in that at least one amine containing tertiary amino group of the component (c), which contains at least one, to be in react work with NCO
The functional group of property, is preferably selected from 3- dimethylamine propylamine, N, and one in bis- (3- aminopropyl) methylamines of N-, dimethyl dipropylenetriamine
Kind is a variety of.
5. castor oil modified self crosslinking cationic polyurethane-polyurea water dispersion described in any one of -4 according to claim 1
Body, which is characterized in that at least one epoxy resin of component (d) is the epoxy resin that epoxide number is 0.18-0.56, preferably
Epoxide number is the bisphenol A type epoxy resin of 0.30-0.54.
6. castor oil modified self crosslinking cationic polyurethane-polyurea water dispersion described in any one of -5 according to claim 1
Body, which is characterized in that low molecular compound of the component (e) containing hydroxyl is selected from ethylene glycol, 1,2-PD, 1,3- third
Glycol, 1,2- butanediol, 1,3 butylene glycol, 1,4- butanediol, 1,5- pentanediol, 3- methylpentane -1,5- pentanediol, 1,6- oneself
Glycol, neopentyl glycol, 1,4- cyclohexane dimethanol, 1,2- cyclohexanediol, 1,4- cyclohexanediol, 2- ethyl -3- propyl pentanediol,
2,2- dimethyl-penten glycol, diethylene glycol (DEG), glycerine, trimethylolpropane it is one or more；It is preferably selected from ethylene glycol, 1,2- third
Glycol, 1,3 butylene glycol, diethylene glycol (DEG), is more preferably selected from diethylene glycol (DEG) at 1,2- butanediol；And/or
Low molecular compound of the component (f) containing amido is selected from ethylenediamine, hydroxyethyl ethylenediamine, 1,3- propane diamine, 1,2-
One of propane diamine, 1,4- butanediamine, 1,5- pentanediamine, 1,6- hexamethylene diamine, hexamethylenediamine and isophorone diamine are more
Kind；It is preferably selected from isophorone diamine.
7. castor oil modified cation self-crosslinkable polyurethane polyureas water dispersion described in any one of -6 according to claim 1
Body, which is characterized in that component (g) non-ionic hydrophilic compound be selected from the polyethers containing polyethoxy, be preferably selected from containing
The single functionality polyethoxy ether that ethylene oxide number is 4~200, the number for being particularly preferably 12~75 selected from ethylene oxide number
The poly glycol monomethyl ether that average molecular weight is 200~8000.
8. castor oil modified cation self-crosslinkable polyurethane polyureas water dispersion described in any one of -7 according to claim 1
Body, which is characterized in that at least one neutralizer of the component (h) be can with component (c) at the acidic materials of salt, as formic acid,
One of acetic acid, methane sulfonic acid, benzene sulfonic acid, phosphoric acid are a variety of, preferably formic acid or acetic acid, more preferable acetic acid.
9. the system of castor oil modified cation self-crosslinkable polyurethane polyurea water dispersion described in any one of claim 1-8
Preparation Method, the preparation method include the following steps: that, by component (a), (b), (d), (g) and first part's solvent, catalyst is thrown
Enter in 50~95 DEG C, preferably 60-90 DEG C in reaction kettle, then component (e) and second part solvent is added 50 in preferably lower reaction
~95 DEG C, preferably 60-90 DEG C the reaction was continued obtains isocyanate terminated performed polymer, Part III solvent is added, by group after cooling
(h) addition is divided to carry out being neutralized to 50-150%, preferably 60%-120%, the degree of neutralization of more preferable 80-100% is added component (c)
Then plus water dispersion chain extension is carried out with component (f), by distillation fraction or completely removes solvent；
Preferably, the mass ratio of first part's solvent and second part solvent and Part III solvent is 1:0.3~3:5~13,
It is preferred that 1:0.7~1.5:7~12.
10. claim 1-8 described in any item are changed by the castor oil that preparation method as claimed in claim 9 obtains
Property cation self-crosslinkable polyurethane polyurea water dispersion be used for wooden ware sealing priming paint application.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811388429.7A CN109651588B (en) | 2018-11-21 | 2018-11-21 | Castor oil modified cationic self-crosslinking polyurethane polyurea aqueous dispersion, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811388429.7A CN109651588B (en) | 2018-11-21 | 2018-11-21 | Castor oil modified cationic self-crosslinking polyurethane polyurea aqueous dispersion, preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109651588A true CN109651588A (en) | 2019-04-19 |
| CN109651588B CN109651588B (en) | 2021-09-07 |
Family
ID=66112160
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811388429.7A Active CN109651588B (en) | 2018-11-21 | 2018-11-21 | Castor oil modified cationic self-crosslinking polyurethane polyurea aqueous dispersion, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109651588B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110964433A (en) * | 2019-12-15 | 2020-04-07 | 安徽匠星联创新材料科技有限公司 | Spraying type castor oil-based polyurethane damping material and preparation method thereof |
| CN111019087A (en) * | 2019-12-23 | 2020-04-17 | 万华化学集团股份有限公司 | Polyurethane-polyurea aqueous dispersion for synthetic leather, and preparation method and application thereof |
| CN112778487A (en) * | 2019-11-05 | 2021-05-11 | 万华化学集团股份有限公司 | Aqueous dispersion of polyurethane or polyurethane-urea, preparation method and application thereof |
| CN112842937A (en) * | 2019-11-12 | 2021-05-28 | 万华化学集团股份有限公司 | Hair conditioner containing aqueous nonionic polyurethane dispersion |
| CN115093532A (en) * | 2022-05-12 | 2022-09-23 | 广州冠志新材料科技有限公司 | Cationic hydroxyl polyurethane dispersoid, water-based wood coating, and preparation method and application thereof |
| US12227610B2 (en) | 2019-11-05 | 2025-02-18 | Wanhua Chemical Group Co., Ltd. | Aqueous dispersion comprising polyurethane or polyurethane-urea, preparation method therefor and use thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432798A (en) * | 2011-08-19 | 2012-05-02 | 陕西科技大学 | Preparation method of epoxy resin modified cationic waterborne polyurethane emulsion |
| CN102775578A (en) * | 2012-08-15 | 2012-11-14 | 中国海洋石油总公司 | Cation-nonionic mixed aqueous polyurethane emulsion and preparation method thereof |
| CN102786637A (en) * | 2011-05-17 | 2012-11-21 | 上海富臣化工有限公司 | Composite modified aqueous polyurethane resin and its preparation method |
| CN103173183A (en) * | 2013-03-23 | 2013-06-26 | 广东新展化工新材料有限公司 | Polyurethane modified epoxy resin adhesive and preparation method thereof |
| CN103848949A (en) * | 2014-03-07 | 2014-06-11 | 安徽正和橡塑合金有限公司 | Process of synthetizing polyurethane |
| CN104356343A (en) * | 2014-11-04 | 2015-02-18 | 佛山市功能高分子材料与精细化学品专业中心 | Epoxy resin and castor oil double-modified polyurethane leather finishing agent and preparation method thereof |
| CN105218778A (en) * | 2015-10-21 | 2016-01-06 | 中山大桥化工集团有限公司 | A kind of epoxy-terminated waterborne polyurethane resin and preparation method thereof |
| CN106188457A (en) * | 2016-07-14 | 2016-12-07 | 武汉理工大学 | Cross-linking type castor oil-base aqueous polyurethane emulsion and preparation method thereof in a kind of |
| CN106752829A (en) * | 2017-01-05 | 2017-05-31 | 辽宁恒星精细化工有限公司 | Corium non-ionic water polyurethane finishing agent and preparation method |
| CN106750080A (en) * | 2017-01-19 | 2017-05-31 | 佛山市功能高分子材料与精细化学品专业中心 | It is a kind of from extinction type modified aqueous polyurethane coating and preparation method and application |
| CN107216705A (en) * | 2017-05-16 | 2017-09-29 | 枣阳市同邦达科技有限公司 | A kind of cathode electrodip painting mill base grind resin and preparation method thereof |
-
2018
- 2018-11-21 CN CN201811388429.7A patent/CN109651588B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102786637A (en) * | 2011-05-17 | 2012-11-21 | 上海富臣化工有限公司 | Composite modified aqueous polyurethane resin and its preparation method |
| CN102432798A (en) * | 2011-08-19 | 2012-05-02 | 陕西科技大学 | Preparation method of epoxy resin modified cationic waterborne polyurethane emulsion |
| CN102775578A (en) * | 2012-08-15 | 2012-11-14 | 中国海洋石油总公司 | Cation-nonionic mixed aqueous polyurethane emulsion and preparation method thereof |
| CN103173183A (en) * | 2013-03-23 | 2013-06-26 | 广东新展化工新材料有限公司 | Polyurethane modified epoxy resin adhesive and preparation method thereof |
| CN103848949A (en) * | 2014-03-07 | 2014-06-11 | 安徽正和橡塑合金有限公司 | Process of synthetizing polyurethane |
| CN104356343A (en) * | 2014-11-04 | 2015-02-18 | 佛山市功能高分子材料与精细化学品专业中心 | Epoxy resin and castor oil double-modified polyurethane leather finishing agent and preparation method thereof |
| CN105218778A (en) * | 2015-10-21 | 2016-01-06 | 中山大桥化工集团有限公司 | A kind of epoxy-terminated waterborne polyurethane resin and preparation method thereof |
| CN106188457A (en) * | 2016-07-14 | 2016-12-07 | 武汉理工大学 | Cross-linking type castor oil-base aqueous polyurethane emulsion and preparation method thereof in a kind of |
| CN106752829A (en) * | 2017-01-05 | 2017-05-31 | 辽宁恒星精细化工有限公司 | Corium non-ionic water polyurethane finishing agent and preparation method |
| CN106750080A (en) * | 2017-01-19 | 2017-05-31 | 佛山市功能高分子材料与精细化学品专业中心 | It is a kind of from extinction type modified aqueous polyurethane coating and preparation method and application |
| CN107216705A (en) * | 2017-05-16 | 2017-09-29 | 枣阳市同邦达科技有限公司 | A kind of cathode electrodip painting mill base grind resin and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| QIWEN YONG，等: "Preparation and characterization of a novel low gloss waterborne polyurethane resin", 《SURFACE & COATINGS TECHNOLOGY》 * |
| 周玉琴: "内交联阳离子型水性聚氨酯的合成", 《中国优秀硕士学位论文全文数据库工程科技I辑》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112778487A (en) * | 2019-11-05 | 2021-05-11 | 万华化学集团股份有限公司 | Aqueous dispersion of polyurethane or polyurethane-urea, preparation method and application thereof |
| US12227610B2 (en) | 2019-11-05 | 2025-02-18 | Wanhua Chemical Group Co., Ltd. | Aqueous dispersion comprising polyurethane or polyurethane-urea, preparation method therefor and use thereof |
| CN112842937A (en) * | 2019-11-12 | 2021-05-28 | 万华化学集团股份有限公司 | Hair conditioner containing aqueous nonionic polyurethane dispersion |
| CN112842937B (en) * | 2019-11-12 | 2023-03-31 | 万华化学集团股份有限公司 | Hair conditioner containing aqueous nonionic polyurethane dispersion |
| CN110964433A (en) * | 2019-12-15 | 2020-04-07 | 安徽匠星联创新材料科技有限公司 | Spraying type castor oil-based polyurethane damping material and preparation method thereof |
| CN111019087A (en) * | 2019-12-23 | 2020-04-17 | 万华化学集团股份有限公司 | Polyurethane-polyurea aqueous dispersion for synthetic leather, and preparation method and application thereof |
| CN111019087B (en) * | 2019-12-23 | 2022-01-07 | 万华化学集团股份有限公司 | Polyurethane-polyurea aqueous dispersion for synthetic leather, and preparation method and application thereof |
| CN115093532A (en) * | 2022-05-12 | 2022-09-23 | 广州冠志新材料科技有限公司 | Cationic hydroxyl polyurethane dispersoid, water-based wood coating, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109651588B (en) | 2021-09-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109651588A (en) | Castor oil modified cation self-crosslinkable polyurethane polyurea water dispersion and preparation method and application | |
| US5401582A (en) | Aqueous polyurethane formulations | |
| EP0578645B1 (en) | Method for producing motor car repair paints | |
| CN109824555B (en) | Sulfamic acid and preparation method and application thereof | |
| RU2543894C2 (en) | Novel solvents in obtaining polyurethane dispersions | |
| CN101437863B (en) | Oil-based aqueous polyurethane dispersions | |
| DE2446440A1 (en) | PROCESS FOR THE PRODUCTION OF POLYURETHANES | |
| DE1694152A1 (en) | Process for the production of microporous surfaces | |
| CN100491430C (en) | Water-dilutable polyurethane dispersions | |
| JPS58173169A (en) | Water-dispersible binder for cationic electrodeposition paint and manufacture | |
| AT409134B (en) | OXYDATIVE DRYING POLYURETHANE DISPERSIONS | |
| EP0208908B1 (en) | Ionically modified pur spreading pastes and their use | |
| EP0807648B1 (en) | Latent curing aqueous polyurethane dispersions | |
| CN111218202A (en) | Water-based single-component super-strong stain-resistant white paint suitable for woodware and preparation method thereof | |
| CN101003609A (en) | Resins for universal use | |
| AU701707B2 (en) | Method of forming multi-layer paint films, base coat composition and method of painting | |
| CN110294830A (en) | A kind of self-crosslinkable polyurethane-polyurea water dispersion and its preparation method and application | |
| DE2015603A1 (en) | ||
| CN114213955B (en) | Low-odor water-based double-component matte clear finish and preparation method thereof | |
| DE10221220A1 (en) | Aqueous polyurethane preparations | |
| DE60020527T2 (en) | Aqueous dispersion of a blocked reactive site containing polyurethene | |
| CN109181443A (en) | A kind of water soluble acrylic acid Baking Paint and preparation method thereof | |
| DE3246812C2 (en) | ||
| CN114989707B (en) | Polyurea coatings | |
| EP2162582A2 (en) | Aqueous formulations and the use thereof for coloring or coating substrates |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20200927 Address after: 264006 No. 17 Tianshan Road, Yantai economic and Technological Development Zone, Shandong Applicant after: Wanhua Chemical Group Co.,Ltd. Applicant after: Wanhua chemical (Ningbo) Co.,Ltd. Address before: 264002 No. 17 Tianshan Road, Yantai economic and Technological Development Zone, Shandong Applicant before: Wanhua Chemical Group Co.,Ltd. Applicant before: Wanhua chemical (Ningbo) Co.,Ltd. Applicant before: SHANGHAI WANHUA KEJU CHEMICAL TECHNOLOGY DEVELOPMENT Co.,Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |