CN105175670B - A kind of amino resins modified aqueous polyurethane and preparation method and application - Google Patents
A kind of amino resins modified aqueous polyurethane and preparation method and application Download PDFInfo
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- CN105175670B CN105175670B CN201510633677.3A CN201510633677A CN105175670B CN 105175670 B CN105175670 B CN 105175670B CN 201510633677 A CN201510633677 A CN 201510633677A CN 105175670 B CN105175670 B CN 105175670B
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- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
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- C08G18/30—Low-molecular-weight compounds
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- 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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- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
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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
- C09D175/04—Polyurethanes
Abstract
The invention belongs to technical field of coatings, a kind of amino resins modified aqueous polyurethane and preparation method and application is disclosed.The amino resins modified aqueous polyurethane is prepared from by the component of following parts by weight：34.6~39.2 parts of dihydric alcohol, 24.5~29.8 parts of diisocyanate, 0.03~0.09 part of dibutyl tin laurate, 1~4 part of Isosorbide-5-Nitrae butanediol, 2,2 2~6 parts of dihydromethyl propionic acids, 2~8 parts of amino resins, 0.5~1.25 part of p-methyl benzenesulfonic acid, 2~6 parts of nertralizer, 1.2~1.9 parts of small molecule chain extender.The present invention uses prepolymerized method and changes the incorporation way of amino resins; products therefrom has that good, water-fast heat endurance, solvent resistant, hardness is high, water absorption rate is low and the excellent properties such as good mechanical performance; paint film baking temperature prepared therefrom is low, technique simple, meets the concept of environmental protection chemical industry.
Description
Technical field
The invention belongs to technical field of coatings, and in particular to a kind of amino resins modified aqueous polyurethane and preparation method thereof
With application.
Background technology
Polyurethane refers to the high molecular polymer for containing urethano (- NHCOO-) in strand, and it is by soft chain segment and hard chain
Duan Zucheng.Soft chain segment is generally polyethers, PEPA, assigns resin flexibility and toughness, hard segment be generally diisocyanate with
The condensation polymer of small molecule dihydric alcohol or diamine.Because the controllable property of the soft and hard segments of polyurethane is strong, so it possesses attachment
The many merits such as power is good, hardness is high, wearability is good, are widely used in the multiple fields such as leather, weaving, automobile, building materials, medicine.
But, because aqueous polyurethane introduces the deficiency of more hydrophilic radical and its degree of cross linking inherently, cause paint film
Hardness, water resistance, solvent resistance and heat resistance it is not good enough.Therefore, it is necessary to be carried out to aqueous polyurethane cross-linking modified.
Methyl-etherified high imino group melmac in part is the amino resins with methoxy and imino group, merely
Paint film as obtained by this amino resins through high temperature from condensation curing is hard and crisp, and poor adhesive force, but with it to aqueous
Polyurethane is modified, and can improve the degree of cross linking of system, so as to improve the hardness of paint film, water resistance, solvent resistance, heat resistance
With reduction water absorption rate etc..General blending and modifying, due to both consistency problems, effect is not highly desirable and bin stability
It is bad, also it is exactly that baking condition is higher, so to carry out chemical modification to it.
Patent CN104212330 A disclose a kind of preparation method of water-polyurethane/amido resin compounded emulsion, the method
Homemade aqueous polyurethane and amino resins are simply subjected to simple physical mixed, although the obtained paint film degree of cross linking and resistance to
Water corrosion resistance is increased, but this complex emulsions need up to 150 DEG C of solidification temperature, and simple physical blending is made
The describing property of aqueous polyurethane and amino resins is not fine in architectonical, causes emulsion intercalation method bad.
The content of the invention
In place of shortcoming and defect in order to solve above prior art, primary and foremost purpose of the invention is to provide a kind of amino
Resin modified aqueous polyurethane.
Another object of the present invention is to provide the preparation method of above-mentioned amino resins modified aqueous polyurethane.
It is still another object of the present invention to provide application of the above-mentioned amino resins modified aqueous polyurethane in paint.
The object of the invention is achieved through the following technical solutions：
A kind of amino resins modified aqueous polyurethane, is prepared from by the component of following mass parts：
The preferred polycaprolactone glycol of described dihydric alcohol, polypropylene glycol and polyadipate ethylene glycol -1,4- butanediol esters two
It is more than one or both of alcohol.
The preferred toluene di-isocyanate(TDI) of described diisocyanate (TDI), diphenyl methane -4,4- diisocyanate
(MDI), more than one or both of IPDI (IPDI) and hexamethylene diisocyanate (HDI).
Described amino resins preferably has the high imino group melamine of part methyl-etherified of molecular structural formula shown in formula (1)
Resin；Imino group (- NH-) in the high imino group melmac of part methyl-etherified is acted in acidic catalyst p-methyl benzenesulfonic acid
Multiple spot reaction occurs for the carboxyl (- COOH) in lower and system to reach cross-linking modified effect；
Described nertralizer is preferably more than triethylamine, N, one or both of N- dimethylethanolamines and ammoniacal liquor.
During described small molecule chain extender is preferably diethyl toluene diamine, 3,5- dimethythiotoluene diamines and ethylenediamine
One or more.
The preparation method of above-mentioned amino resins modified aqueous polyurethane, including following preparation process：
(1) prepared by base polyurethane prepolymer for use as：At 60~80 DEG C, by dihydric alcohol, diisocyanate and di lauric dibutyl
Tin is added in reactor, is reacted 1~3 hour；
(2) chain extension：At 60~80 DEG C, the BDO for being dissolved in acetone is added drop-wise in reactor, reaction 30~60
Minute, 2, the 2- dihydromethyl propionic acids for being dissolved in 1-METHYLPYRROLIDONE are then added, are reacted 2~4 hours；
(3) salt is neutralized into：At 50~60 DEG C, acetone reduction viscosity is added, nertralizer, stirring insulation 10~30 is added
Minute；
(4) amino resins is modified：At 50~60 DEG C, the amino resins and p-methyl benzenesulfonic acid that are dissolved in distilled water are added to
In reactor, react 0.5~1 hour, obtain the amino resins modified polyurethane of thick shape；
(5) emulsification and rear chain extension：Under agitation, deionization is added into the amino resins modified polyurethane of thick shape
Water, disperses 5~10 minutes, adds small molecule chain extender, disperses 20~30 minutes, obtains the poly- ammonia of amino resins modified water-soluble
Ester.
Preferably, described in step (2) 1-METHYLPYRROLIDONE and the mass ratio of 2,2- dihydromethyl propionic acid for (2~
2.5):1。
Preferably, the amino resins and p-methyl benzenesulfonic acid described in step (4) are dissolved in after water by ultrasonic vibration treatment 30
Minute makes it be uniformly dispersed.
Preferably, the mixing speed of stirring condition described in step (5) is 6000~7000r/min.
Application of the above-mentioned amino resins modified aqueous polyurethane in paint, the component with paint is matched somebody with somebody by weight percentage
Than as follows：
Preferably, described defoamer is preferably EVONIK Foamex805；Described wetting agent is preferably
Disperbyk-181。
The preparation method and resulting product of the present invention has the following advantages that and beneficial effect：
(1) present invention uses prepolymerized method, makes the imino group in the high imino group melmac of part methyl-etherified
With the carboxyl reaction in aqueous polyurethane, methyl-etherified high imino group melmac in part is successfully linked into aqueous poly- ammonia
In ester, increase the degree of cross linking of system so that resin hardness of paint film is improved, water resistance, solvent resistance, heat resistance strengthen, absorb water
Rate is reduced, tensile strength and elongation at break increase；
(2) present invention introduces the method for amino resins compared to blending method, the particle diameter of gained resin is more homogeneous, stability
More preferably, products therefrom is all good compared with blending method in the performances such as heat endurance, hardness and adhesive force.
Embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
Embodiment 1
(1) prepared by base polyurethane prepolymer for use as：At 75 DEG C, 39.2g polycaprolactone glycols, 29.8g isophorones two are added different
Cyanate (IPDI) and 0.08g dibutyl tin laurates, react 2 hours, using di-n-butylamine-acetone method to NCO residual volumes
Titrated, when NCO residual volumes are close or less than theoretical value reaches reaction end；
(2) chain extension：At 75 DEG C, weigh 2.5g BDOs and be dissolved in 3g acetone and be added drop-wise in reactor, react 30 points
Clock, weighs 5.4g dihydromethyl propionic acids and is dissolved in 7g 1-METHYLPYRROLIDONEs, be added in reactor, reacts 2 hours, using two
N-butylamine-acetone method is titrated to NCO residual volumes, when NCO residual volumes are close or less than theoretical value reaches reaction end；
(3) salt is neutralized into：It is cooled at 50 DEG C~60 DEG C, adds 10g acetone reduction viscosity, add in 3.8g triethylamines
With into salt, 10 minutes are incubated, room temperature is cooled to, obtains the polyurethane of clear viscous shape；
(4) amino resins is modified：At 50~60 DEG C, by the high imino group melmac of 4g parts methyl-etherified and 0.6g
P-methyl benzenesulfonic acid is dissolved in 10g distilled water and is added to through ultrasonic vibration in reactor after 30 minutes, reacts 30 minutes, obtains thick shape
Amino resins modified polyurethane；
(5) emulsification and rear chain extension：Under conditions of low whipping speed is 7000r/min, it is modified to thick amino resins
Polyurethane adds 145g deionized waters, first disperses 5 minutes, adds the ethylenediamine that 1.5g is dissolved in 5g deionized waters, disperses 25
Minute, obtain amino resins modified aqueous polyurethane.
Embodiment 2
(1) prepared by base polyurethane prepolymer for use as：At 75 DEG C, 34.6g polypropylene glycols, 24.5g toluene di-isocyanate(TDI)s are added
(TDI) and 0.08g dibutyl tin laurates, react 2 hours, NCO residual volumes are dripped using di-n-butylamine-acetone method
It is fixed, when NCO residual volumes are close or less than theoretical value reaches reaction end；
(2) chain extension：At 75 DEG C, weigh 2.5g BDOs and be dissolved in 4g acetone and be added drop-wise in reactor, react 30 points
Clock, weighs 5.8g dihydromethyl propionic acids and is dissolved in 7g 1-METHYLPYRROLIDONEs, be added in reactor, reacts 2 hours, using two
N-butylamine-acetone method is titrated to NCO residual volumes, when NCO residual volumes are close or less than theoretical value reaches reaction end；
(3) salt is neutralized into：Less than 50 DEG C are cooled to, 10g acetone reduction viscosity is added, adds 3.9g N, N- dimethyl
Monoethanolamine neutralizes into salt, is incubated 10 minutes, is cooled to room temperature, obtains thick polyurethane；
(4) amino resins is modified：At 50~60 DEG C, by the high imino group melmac of 2g parts methyl-etherified and
0.25g p-methyl benzenesulfonic acid is dissolved in 10g distilled water after ultrasonic vibration 30 minutes, is added in reactor, reacts 30 minutes, obtains
The amino resins modified polyurethane of thick shape；
(5) emulsification and rear chain extension：Under conditions of low whipping speed is 7000r/min, it is modified to thick amino resins
Polyurethane adds 150g deionized waters, first disperses 5 minutes, adds the diethyltoluene two that 1.9g is dissolved in 5g deionized waters
Amine, disperses 25 minutes, obtains amino resins modified aqueous polyurethane.
Embodiment 3
(1) prepared by base polyurethane prepolymer for use as：At 75 DEG C, 37.2g polypropylene glycols, 29g toluene di-isocyanate(TDI)s (TDI) are added
With 0.08g dibutyl tin laurates, react 1.5 hours, NCO residual volumes are titrated using di-n-butylamine-acetone method, when
NCO residual volumes are close or less than theoretical value reaches reaction end；
(2) chain extension：At 75 DEG C, weigh 1.8g BDOs and be dissolved in 3g acetone and be added drop-wise in reactor, react 30 points
Clock, weighs 4.3g dihydromethyl propionic acids and is dissolved in 6g 1-METHYLPYRROLIDONEs, be added in reactor, reacts 2 hours, using two
N-butylamine-acetone method is titrated to NCO residual volumes, when NCO residual volumes are close or less than theoretical value reaches reaction end；
(3) salt is neutralized into：Less than 50 DEG C are cooled to, 10g acetone reduction viscosity is added, adds 2.8g N, N- dimethyl
Monoethanolamine neutralizes into salt, is incubated 10 minutes, is cooled to room temperature, obtains thick polyurethane；
(4) amino resins is modified：At 50~60 DEG C, by the high imino group melmac of 8g parts methyl-etherified and
1.25g p-methyl benzenesulfonic acid is dissolved in 20g distilled water after ultrasonic vibration 30 minutes, is added in reactor, reacts 30 minutes, obtains
The amino resins modified polyurethane of thick shape；
(5) emulsification and rear chain extension：Low whipping speed be 7000r/min under conditions of, to thick polyurethane-part first
It is etherified high imino group melmac acid modified alcoholic and adds 153g deionized waters, first disperses 5 minutes, add 1.8g and be dissolved in 5g
Ethylenediamine in deionized water, disperses 25 minutes, obtains amino resins modified aqueous polyurethane.
Comparative example 1
(1) prepared by base polyurethane prepolymer for use as：At 75 DEG C, 39.2g polycaprolactone glycols, 29.8g isophorones two are added different
Cyanate (IPDI) and 0.08g dibutyl tin laurates, react 2 hours, using di-n-butylamine-acetone method to NCO residual volumes
Titrated, when NCO residual volumes are close or less than theoretical value reaches reaction end；
(2) chain extension：At 75 DEG C, weigh 2.5g BDOs and be dissolved in 3g acetone and be added drop-wise in reactor, react 30 points
Clock, weighs 5.4g dihydromethyl propionic acids and is dissolved in 7g 1-METHYLPYRROLIDONEs, be added in reactor, reacts 2 hours, using two
N-butylamine-acetone method is titrated to NCO residual volumes, when NCO residual volumes are close or less than theoretical value reaches reaction end；
(3) salt is neutralized into：It is cooled at 50 DEG C~60 DEG C, adds 10g acetone reduction viscosity, add in 3.8g triethylamines
With into salt, 10 minutes are incubated, room temperature is cooled to, obtains the polyurethane of clear viscous shape；
(4) emulsification and rear chain extension：Under conditions of low whipping speed is 7000r/min, it is modified to thick amino resins
Polyurethane adds 145g deionized waters, first disperses 5 minutes, adds the ethylenediamine that 1.5g is dissolved in 5g deionized waters, disperses 25
Minute, obtain aqueous polyurethane.
(5) blending and modifying：The high imino group trimerization of 4g part methyl-etherifieds is directly added in aqueous polyurethane obtained above
Melamine resin and 0.6g p-methyl benzenesulfonic acid, and stirred with glass bar.
Amino resins modified aqueous polyurethane obtained by example 1~3 and comparative example 1 is carried out with paint, the component with paint
It is as follows by weight percentage：
Defoamer is EVONIK Foamex805, and wetting agent is Disperbyk-181.
The paint film sample of embodiment 1~3 is toasted 20 minutes at 80 DEG C, and the paint film sample of comparative example 1 toasts 30 points at 130 DEG C
Clock.
Performance to emulsion and paint film is tested, as a result as shown in table 1.Wherein particle diameter is using dynamic light scattering laser grain
Instrument (DLS, Malvern, ZS-Nano-S) is spent to determine；Water absorption rate is weighed by the way that glued membrane to be cut into 25mm X 25mm square
(m1), it is placed in running water and soaks 24 hours at room temperature, film surface moisture is sucked with blotting paper, weighs (m2), by (m1-
m2)/m1The formula of X 100% are calculated；Tensile strength, elongation at break use general tensile testing machine (Instron
Corporation, Series IX) determine；Hardness of paint film is determined by GB/T 6739-2006；Adhesive force presses GB/T 9286-
1998 determine；Solvent resistance by paint film by being soaked in 24h in dimethylbenzene, and observation paint film change is determined.
The embodiment 1~3 of table 1 and the emulsion of comparative example 1 and paint film property test result
Present invention introduces the method for amino resins compared to blending method, gained emulsion and paint film it can be seen from the result of table 1
Properties increase, be mainly reflected in water absorption rate reduction, draw high intensity increase, elongation at break increase, hardness increase
High, adhesive force is improved, solvent resistance enhancing.With increasing for amino resins consumption, the increase of the system degree of cross linking, thus paint film are showed
Decline to draw high the performances such as intensity raising, water absorption rate and elongation at break.
Above-described embodiment is preferably embodiment, but embodiments of the present invention are not by above-described embodiment of the invention
Limitation, other any Spirit Essences without departing from the present invention and the change made under principle, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (9)
1. a kind of amino resins modified aqueous polyurethane, it is characterised in that be prepared from by the component of following mass parts：
The method of the preparation comprises the following steps：
(1) prepared by base polyurethane prepolymer for use as：At 60~80 DEG C, dihydric alcohol, diisocyanate and dibutyl tin laurate are added
Enter into reactor, react 1~3 hour；
(2) chain extension：At 60~80 DEG C, the BDO for being dissolved in acetone is added drop-wise in reactor, reacted 30~60 minutes,
Then 2, the 2- dihydromethyl propionic acids for being dissolved in 1-METHYLPYRROLIDONE are added, are reacted 2~4 hours；
(3) salt is neutralized into：At 50~60 DEG C, acetone reduction viscosity is added, nertralizer, 10~30 points of stirring insulation is added
Clock；
(4) amino resins is modified：At 50~60 DEG C, the amino resins and p-methyl benzenesulfonic acid that are dissolved in distilled water are added to reaction
In device, react 0.5~1 hour, obtain the amino resins modified polyurethane of thick shape；
(5) emulsification and rear chain extension：Under agitation, deionized water is added into the amino resins modified polyurethane of thick shape, point
Dissipate 5~10 minutes, add small molecule chain extender, disperse 20~30 minutes, obtain amino resins modified aqueous polyurethane.
2. a kind of amino resins modified aqueous polyurethane according to claim 1, it is characterised in that：Described dihydric alcohol is
Refer to more than one or both of polycaprolactone glycol, polypropylene glycol and polyadipate ethylene glycol -1,4- butyl glycol ester diols.
3. a kind of amino resins modified aqueous polyurethane according to claim 1, it is characterised in that：Two described isocyanic acids
Ester refers to toluene di-isocyanate(TDI), diphenyl methane -4,4- diisocyanate, IPDI and hexa-methylene two
It is more than one or both of isocyanates.
4. a kind of amino resins modified aqueous polyurethane according to claim 1, it is characterised in that：Described amino resins
For the high imino group melmac of part methyl-etherified with molecular structural formula shown in formula (1),
5. a kind of amino resins modified aqueous polyurethane according to claim 1, it is characterised in that：Described nertralizer is
It is more than triethylamine, N, one or both of N- dimethylethanolamines and ammoniacal liquor.
6. a kind of amino resins modified aqueous polyurethane according to claim 1, it is characterised in that：Described small molecule expands
Chain agent is more than one or both of diethyl toluene diamine, 3,5- dimethythiotoluene diamines and ethylenediamine.
7. a kind of amino resins modified aqueous polyurethane according to claim 1, it is characterised in that：Described in step (2)
1-METHYLPYRROLIDONE and 2,2- dihydromethyl propionic acids mass ratio be (2~2.5):1；Amino tree described in step (4)
Fat and p-methyl benzenesulfonic acid are dissolved in after water makes it be uniformly dispersed in 30 minutes by ultrasonic vibration treatment；Stirring bar described in step (5)
The mixing speed of part is 6000~7000r/min.
8. application of the amino resins modified aqueous polyurethane in paint described in any one of claim 1~6, its feature exists
In the component components by weight percentage with paint is as follows：
9. a kind of application of the amino resins modified aqueous polyurethane according to claim 8 in paint, it is characterised in that
Described defoamer is Foamex805；Described wetting agent is Disperbyk-181.
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| CN107090069B (en) * | 2017-05-27 | 2019-09-17 | 杭州传化精细化工有限公司 | A kind of secondary the aqueous polyurethane preparation method of chain extension and its dispersion liquid of preparation afterwards |
| CN110591629A (en) * | 2019-08-14 | 2019-12-20 | 萍乡高恒材料科技有限公司 | Single-component self-exhaust moderate-peeling-force polyurethane pressure-sensitive adhesive composition |
| CN111440479A (en) * | 2020-05-15 | 2020-07-24 | 珠海乐通新材料科技有限公司 | Gravure ink for pure water type heat shrinkable film label and preparation method thereof |
| CN111777982A (en) * | 2020-07-30 | 2020-10-16 | 深圳市安伯斯科技有限公司 | Yellowing-resistant solvent-free polyurethane composite adhesive and preparation method thereof |
| CN113831725A (en) * | 2021-11-12 | 2021-12-24 | 成都市红宝丽新材料科技发展有限公司 | Polyurethane-coated flame-retardant sealing rubber strip with high production efficiency and preparation method thereof |
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