A kind of urethane and preparation method thereof and application
Technical field
The present invention relates to a kind of novel, water-soluble type or water dispersant type polyaminoester, be suitable as the thickening material of Aquo System, this polyurethane thickener can carry out thickening and then change its rheological behaviour Aquo System.The invention still further relates to the preparation method and the application thereof of this urethane.
Background technology
Along with the raising gradually to environmental requirement, the water-based coating system has obtained using widely at present, like water emulsion coating, sizing agent, makeup, printing-ink etc.Be storage and the workability of improving Aquo System, add auxiliary agent usually and come viscosity and the rheological property of regulation system under different shearing conditions that this analog assistant is commonly called thickening material.Except that the required viscosity of system can be provided, this analog assistant also can improve the dispersion of color stuffing in the flowing property, system of system, the performances such as tack of coating system sometimes.
Traditional Aquo System is mainly water-soluble polymer with thickening material, and the molecular structure total hydrophilic does not contain hydrophobic structure, like cellulose family and acrylic thickener, these thickening materials through with system in water molecules form hydrogen bond and reach purpose the water thickening.This type thickening material can effectively improve the low-shear viscosity of system, but viscosity reduces rapidly when shear increasing, be prone in the coating procedure produce splash, film not plentiful, degradation defective under the coating film gloss.
Associative thickener is a kind of known for many years, is used for the thickening material of Aquo System.Usually, associative thickener contains a hydrophilic chief component, and this part is hydrophilic polymer chain, and it is through covalent linkage and the hydrophobic group formation associative thickener that links together.In Aquo System, the hydrophilic segment on this type thickening material is guaranteed dissolving or the dispersion of thickening material molecule in water through forming hydrogen bond with water; In water-based system, the hydrophobic part bridging on the thickening material can form in the Aquo System on emulsion, solid particulate and the micella of hydrophobic association effect and form the space multistory reticulated structure, realizes the thickening to Aquo System.This type of thickening material can be divided into hydrophobic alkali swelling type thickening material (HASE) and urethane associative thickeners (HEUR) and other types associative thickeners.The Aquo System that wherein adds HEUR has more excellent flow leveling, excellent film fullness ratio and film forming high gloss, thereby be widely used.
The preparation of associative thickener normally realizes through following mode: the isocyanic ester of difunctionality macromolecular alcohol and difunctionality carries out polyaddition reaction; Generate pure end capped polymkeric substance, the single functionality isocyanic ester that adds the band hydrophobic segment forms hydrophobic end capped polyurethane thickener; Or the isocyanic ester of the pure and mild difunctionality of difunctionality carries out polyaddition reaction and generates isocyanate-terminated polymkeric substance, through adding reactant (like the alcohol of simple function) the sealing polymkeric substance of single functionality, forms the water-soluble or water dispersion that has hydrophobic grouping.This synthesis mode had report in US4079028 and US4155892.
Though mentioned among the US4079028 and can adopt monofunctional amines to replace single functionality alcohol to seal macromolecular chain, and the performance characteristics of the end capped polyurethane thickener of monoamine of not mentioned ad hoc structure as blocking groups.As everyone knows, the deciding factor that plays thickening power in the polyurethane-type thickening material is its hydrophobic side, and mostly the hydrophobic grouping of traditional polyurethane thickener is the alkohol and amine of side chain or side chain.Therefore, the polyurethane thickener of some special hydrophobic capping group can obtain better performance at thickening efficiency and aspect other.
Summary of the invention
The object of the invention is to provide a kind of polyurethane thickener and preparation method thereof.But this urethane is a kind of novel, water-soluble type or water decentralized urethane.
Another object of the present invention is to be to provide a kind of polyurethane thickener preparation and the application in moisture coating system, tackiness agent and other Aquo Systems thereof.Compare with the product of market sale; The closed-end structure hydrophobicity of using among the present invention is bigger; The ability that in thickening material, forms hydrophobic association is stronger; Therefore the thickening efficiency of this type of thickening material has more significantly and improves, and the deflocculate performance that adds anti-minute water-based, the pigment of the water-based coating system of this type of thickening material all has preferably and improves.
In order to realize above goal of the invention, technical scheme of the present invention is following:
A kind of urethane, its structure is as follows:
Wherein,
R and R '
or
, and R and R 'the same or different;
A is the polyether Glycols residue;
B, C, D are the vulcabond residue;
M is 1~10 arbitrary integer.
Said polyether Glycols residue be in polyoxyethylene glycol (PEG) residue, W 166 (PPG) residue, polyethylene glycol-Ucar 35 (PEG-PPG) residue, the polytetramethylene glycol residue one or both or multiple.Wherein, the polymerization degree that forms the polyether Glycols of polyether Glycols residue is 90~455, and molecular weight is 500-20000 dalton, and preferred molecular weight is 2000-15000 dalton.
Said vulcabond residue be in aliphatic diisocyanate residue or the aromatic diisocyanate residue one or both or multiple, preferred fat (cyclo) aliphatic diisocyanates residue.Wherein the aliphatic diisocyanate residue is preferably one or both or three kinds in hexamethylene diisocyanate (HDI) residue, isophorone diisocyanate (IPDI) residue, dicyclohexyl methane diisocyanate (HMDI) residue; Or the aromatic diisocyanate residue is preferably tolylene diisocyanate (TDI) residue, 4, one or both in 4-diphenylmethanediisocyanate (MDI) residue.
The preparation method of urethane described in the present invention may further comprise the steps:
A) excessive vulcabond and polyether Glycols polycondensation forms isocyanate-terminated polymer segment;
The NCO of the polymer segment that b) forms in the step a) carries out end capping with the C6-C15 monoamine that contains alicyclic radical and/or aromatic ring yl and generates urethane.
In theory, the urethane among the present invention can adopt the whole bag of tricks of preparation urethane to prepare, and synthetic can under anhydrous situation, carrying out for example, can be adopted the dehydration of azeotropic dehydration or heating under vacuum; During reaction, adopt nitrogen to protect, prevent that steam from getting into.Can adopt solution method synthetic, also can adopt the body synthesis method synthetic.The synthetic solvent for use of solution method be can dissolve polyurethane inert organic solvents, preferably benzene,toluene,xylene, hexanaphthene, acetone, butanone, ETHYLE ACETATE, N-BUTYL ACETATE etc., solvent can add before reaction, also can in reaction, add; The preferred substance law that does not add organic solvent synthesizes.
Vulcabond described in the step a) of the present invention be in aliphatics or the aromatic diisocyanate one or both or multiple, one or both in the preferred fat (cyclo) aliphatic diisocyanates or multiple.Wherein aliphatic diisocyanate is preferably one or both or three kinds among HDI, IPDI or the HMDI, or aromatic diisocyanate is preferably among TDI or the MDI one or both.
Polyether Glycols described in the step a) is polyoxyethylene glycol (PEG), W 166 (PPG), polyethylene glycol-Ucar 35 (PEG-PPG), one or both in the polytetramethylene glycol or multiple; The polymerization degree of said polyether Glycols is 90~455, and molecular weight is 500-20000 dalton, and preferred molecular weight is 2000-15000 dalton.
The mol ratio of vulcabond described in the step a) and polyether Glycols is 1~2.
Described in the step b) of the present invention; The said C6-C15 monoamine that contains alicyclic radical and/or aromatic ring yl is one or both or three kinds among dicyclo monoamine
or
, and the consumption of preferred
accounts for the 80-100wt% of the total consumption of C6-C15 monoamine that contains alicyclic radical and/or aromatic ring yl.
Special single functionality amine, vulcabond and polyether Glycols are all in amount of substance, and the consumption calculating formula of said special single functionality amine is: 2 * h * (vulcabond-polyether Glycols), wherein, h is any number between the 0.5-2.
The urethane that step b) reaction of the present invention generates has following structure:
Wherein,
R and R '
or
, and R and R 'the same or different;
A is the polyether Glycols residue.Wherein, said polyether Glycols residue be in polyoxyethylene glycol (PEG) residue, W 166 (PPG) residue, polyethylene glycol-Ucar 35 (PEG-PPG) residue, the polytetramethylene glycol residue one or both or multiple.Wherein, the polymerization degree that forms the polyether Glycols of polyether Glycols residue is 90~455, and molecular weight is 500-20000 dalton, and preferred molecular weight is 2000-15000 dalton.
B is the vulcabond residue.Wherein, said vulcabond residue be in aliphatic diisocyanate residue or the aromatic diisocyanate residue one or both or multiple, preferred fat (cyclo) aliphatic diisocyanates residue.Wherein the aliphatic diisocyanate residue is preferably one or both or three kinds in hexamethylene diisocyanate (HDI) residue, isophorone diisocyanate (IPDI) residue, dicyclohexyl methane diisocyanate (HMDI) residue; Or the aromatic diisocyanate residue is preferably tolylene diisocyanate (TDI) residue, 4, one or both in 4-diphenylmethanediisocyanate (MDI) residue.
M is 1~10 arbitrary integer.
Usually, the temperature of reaction of step a) of the present invention and step b) does not all have strict qualification, can select 40-130 ℃, and preferred 50-110 ℃, more preferably 70-100 ℃, the temperature of reaction that selection is best can effectively reduce the generation of by product, improves the quality of product.
The reaction times of step a) of the present invention and step b) is respectively 0.5-3h.
Polyether Glycols in the step a) of the present invention need carry out the vacuum removal trace water before using, and water-content is less than 500ppm.
Step a) of the present invention and step b) need be used rare gas element protection, and said rare gas element is nitrogen or helium, nitrogen.
In addition, the preparation process of urethane of the present invention a) needs under the catalyzer condition, to carry out, said catalyzer be in organo-metallic catalyst and/or the amines catalyst one or both or multiple.Wherein, organo-metallic catalyst be in dibutyl tin laurate, stannous octoate, capric acid bismuth, Bismuth Octoate or the silver type catalyzer one or both or multiple; Amines catalyst is a triethylamine, 1, and one or both in 4-diazabicylo [2.2.2] octane.Catalyst consumption is the 0.005-0.2wt% of vulcabond and the two total consumption of polyether Glycols.
But urethane of the present invention is soluble in water or water/tensio-active agent or water/machine solvent in form solution or water dispersion-s, obtain association type polyurethane thickener preparation.
With urethane of the present invention is raw material, and preparation association type polyurethane thickener preparation comprises following component:
(1) water;
(2) urethane;
(3) one or both of organic solvent of choosing wantonly and/or tensio-active agent or multiple.
In the polyurethane thickener preparation according to the invention; Organic solvent is a volatile organic matter; Be preferably in low-molecular-weight alcohol, the ether one or both or multiple; Further be preferably methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, terepthaloyl moietie, Ucar 35, USP Kosher, butyl glycol ether, one or both in the Diethylene Glycol butyl ether or multiple.
Said tensio-active agent be in ionic or the non-ionics one or both or multiple; Be preferably in the nonionogenic tenside one or both or multiple, more preferably oxyethane and/or propylene oxide and C8-18 alcohol adduct in one or both or multiple.
Thickener preparation of the present invention comprises the water of 10~90wt%, the urethane of 10~60wt% and the auxiliary agent of 0~50wt%, and this per-cent is based on the gross weight of preparation.
The purposes of polyurethane thickener preparation according to the invention in aqueous coating system, tackiness agent and other Aquo Systems.
Polyurethane associative thickener of the present invention is applicable to the thickening of moisture or main aqueous system, such as fields such as rubber-emulsion paint, varnish, tackiness agent, leather, papermaking, printing ink, makeup, personal-care supplies.
Positively effect of the present invention is:
(1) urethane of the present invention is with the comparatively hydrophobic and end capped urethane of the special single functionality amine of inflexible, and with the thickener preparation of polyurethane preparation of the present invention, thickening efficiency is far above adopting the end capped polyurethane thickener of common single functionality amine.
(2) polyurethane preparation process of the present invention; Compare with the conventional urethane of prior art; Under the situation of not adding organic solvent, synthesize; Reaction raw materials is the high boiling substance (not being identified as volatile organic compounds usually) of boiling point >=250 ℃, therefore, does not contain volatile organic compounds (VOC) basically in the urethane of the present invention's preparation.
(3) thickener preparation of the present invention is in moisture or main aqueous system, shows excellent performance such as high thickening efficiency, good color development performance, good system consistency and stability in storage etc.
" choosing " expression in this application wantonly is with or without.
Embodiment
For better implement the present invention, below in conjunction with embodiment the present invention is done further explanation, but embodiment is not a limitation of the present invention.
The mixture of used abbreviation HMA representative
and
, wherein the content of
is 92wt%.
Utilize rich reining in to fly CAP2000+ type cone-plate viscosity apparatus, STM-IV stormer viscosity appearance, Bo Le and fly DV-prime (LV) viscosity apparatus and measure shear viscosity (ICI viscosity), middle shear viscosity (Ku viscosity), the low-shear viscosity that adds emulsion after the thickener preparation respectively.
Embodiment 1
With 50g polyoxyethylene glycol 8000 (PEG8000), join 250ml and be equipped with in the 250ml there-necked flask of induction stirring and nitrogen inlet, negative pressure (pressure is less than 100Pa) dewatered 1.5 hours for 110 ℃.Be cooled to 90 ℃, and use mechanical stirring instead, under the nitrogen protection, add 0.04g catalyst B ICAT8018 (the leading chemistry of the U.S.), 1.31g HDI, 90 ℃ of reaction 1h add 0.67g HMA afterwards, and 90 ℃ of reaction 2h obtain urethane.
Reaction finishes, and in the urethane that makes, adds 207.92g water and is configured to 20% aqueous solution that contains admittedly, obtains polyurethane thickener preparation (Thickener 1), and viscosity is 3.5Pa.s (Bo Le flies CAP2000+ type cone-plate viscosity apparatus).
Above-mentioned polyurethane thickener preparation is used for 300g ACRYLIC EMULSION (DOW chemistry Primal
TM-AC261 emulsion) thickening, wherein, Thickener 1 add-on accounts for 0%, 0.15%, 0.35%, 0.5%, 0.7%, 0.8%, 0.9% of ACRYLIC EMULSION weight respectively.Measure the adding thickening material high, medium and low shear viscosity of emulsion afterwards, experimental result is as shown in table 1.
Table 1 embodiment 1 experimental result
Can see that from table 1 adding of the polyurethane thickener among the embodiment 1 can effectively increase the various viscosity of emulsion, wherein in an amount of increasing, under the low viscous situation, can effectively improve the shear viscosity of emulsion.The emulsion flowability is fine, and it is plentiful to film, and glossiness is high.
Embodiment 2
Be similar to the implementation method of case 1, but that employing is 2.04g HMDI rather than embodiment 1 employed 1.31gHDI.
Reaction finishes, and uses 210.84g to contain water rather than the 207.92g water of 26.38g nonionogenic tenside ANTAROX BL-225 (Rhodia), is made into 20% and contains solution admittedly, obtains polyurethane thickener preparation (Thickener 2), and viscosity is 5Pa.s.
Employing is measured the thickening properties of thickener preparation to emulsion with embodiment 1 identical method.Wherein, the Thickener2 add-on accounts for 0%, 0.04%, 0.08%, 0.12%, 0.16%, 0.2%, 0.24% of ACRYLIC EMULSION weight respectively, and test result is seen table 2.
Table 2 embodiment 2 experimental results
Can see that from table 2 polyurethane thickener among the embodiment 2 has high thickening efficiency, when less addition, can effectively increase emulsion in, low-shear viscosity.
Embodiment 3
Be similar to the implementation method of case 1, employing be 1.77g IPDI rather than 1.31g HDI synthesis of polyurethane, reaction finishes, and uses 209.76g water to be made into 20% and contains solution admittedly, obtains polyurethane thickener preparation (Thickener 3), viscosity is 4.5Pa.s.
Employing is measured the thickening properties of thickening material to emulsion with embodiment 1 identical method, and wherein, the add-on of Thickener3 is identical with embodiment 1, and test result is seen table 3.
Table 3 embodiment 3 experimental results
Can see that from table 3 polyurethane thickener among the embodiment 3 has thickening efficiency preferably, can increase the high, medium and low shear viscosity of emulsion simultaneously, performance is comparatively balanced.
Comparative Examples
Aliphatic monoamine as a comparison and the end capped polyurethane thickener of fragrant monoamine, synthesis condition are with embodiment 1, and its difference only is to have adopted common aliphatic amide-NSC 9824, perhaps common aromatic amine-aniline.Concrete building-up process is following:
With 50g polyoxyethylene glycol 8000 (PEG8000), join 250ml and be equipped with in the 250ml there-necked flask of induction stirring and nitrogen inlet, negative pressure (pressure is less than 100Pa) dewatered 1.5 hours for 110 ℃.Be cooled to 90 ℃, and use mechanical stirring instead, nitrogen protection adds 0.04g catalyst B ICAT8018 (the leading chemistry of the U.S.), 1.31g HDI, 90 ℃ of reaction 1h down.
Add the 0.44g NSC 9824,90 ℃ of reaction 2h.Reaction finishes, and adds 207g water and is configured to 20% aqueous solution that contains admittedly, obtains polyurethane thickener preparation (Thickener 4).Gained thickening material viscosity is 1.5Pa.s, adopts the method for embodiment 1 to measure the thickening properties of thickening material to emulsion, and the result sees table 4.
Or add 0.32g aniline, 90 ℃ are reacted 2h.Reaction finishes, and adds 206.52g water and is configured to 20% aqueous solution that contains admittedly, obtains polyurethane thickener preparation (Thickener 5), and gained thickening material viscosity is 1.0Pa.s.
Adopt the method for embodiment 1 to measure the thickening properties of thickening material to emulsion, wherein, the add-on of Thickener4 and Thickener5 is identical with embodiment 1 respectively, and test result is seen table 5.
Table 4 Comparative Examples NSC 9824 end-blocking experimental result
Contrast table 4 can find out with the data among the table 1-3, with the thickening efficiency of comparatively hydrophobic and the end capped polyurethane thickener of inflexible HMA far above adopting the end capped thickening material of fatty amine-NSC 9824.
Table 5 Comparative Examples aniline end-blocking experimental result
Contrast table 5 can be found out with the data among the table 1-3, utilizes common aromatic series monoamine-aniline as end capped thickening material, its thickening efficiency a little less than.Far below adopting the comparatively hydrophobic and end capped polyurethane thickener of inflexible HMA.
Polyurethane associative thickener Thickener 3 of the present invention is used for the rubber-emulsion paint field.According to following general formulation configuration white latex paint, add synthetic polyurethane thickener Thickener 3 of the present invention, investigate the performance of rubber-emulsion paint.
Material |
Quality/g |
Water |
48 |
CF-10 |
0.384 |
731A |
5.36 |
Terepthaloyl moietie |
4 |
Tego825 |
0.8 |
NaOH |
0.4 |
White titanium pigment 902 |
66.04 |
Lime carbonate 1500 orders |
84.88 |
Kaolin 1500 orders |
40.88 |
Texonal |
1.2 |
ECO502 |
96.6 |
Tego825 |
0.6 |
Water |
44.8 |
TT-935 |
4 |
Thickener?3 |
2 |
The KU viscosity of gained rubber-emulsion paint is 115, and ICI viscosity is 135CP.Thickener 3 can effectively increase the middle and high shear viscosity of rubber-emulsion paint.
Get above-mentioned rubber-emulsion paint and last black and white plate and film (100 μ m wet film), the black and white part contrast ratio of gained paint film is 95.5% (C84-III reflectance test appearance).Explain that Thickener 3 and system consistency are fine, color stuffing disperses better, and filming has good opacifying power.
Get above-mentioned white paint 200g, add the phthalocyanine blue of 3%wt, dispose blue colored paint, KU viscosity becomes 108 by 115 behind the adding pigment, and ICI viscosity becomes 132CP by 135CP.Stable fine to mill base of the rubber-emulsion paint that adds Thickener 3 is described, adds the back system viscosity and change not quite.
Colored paint is filmed (100 μ m wet film), investigate aberration after referring to grind and change, be merely 0.3 through measuring the aberration that refers to the place of grinding and do not refer to the place of grinding (Japanese Konica ColorReader, CR10).The color developing that the rubber-emulsion paint that adds Thickener3 is described is good.
The stable storing property testing is got above-mentioned Virgin's milk shellac varnish, and in 55 ℃ of held 30 days, rubber-emulsion paint did not have phenomenons such as obvious minute water, caking.Explain that the rubber-emulsion paint that adds Thickener 3 has good stability.
According to the thickening material of the method for this patent preparation, in rubber-emulsion paint, show excellent performance such as high thickening efficiency, good color development performance, good system consistency and stability in storage etc.
The foregoing description is the preferable implementation method of the present invention; But the present invention does not receive the restriction of above-mentioned implementation method; Other are any not to deviate from the substitute mode that change, modification, simplification, the replacement done under spirit of the present invention and the principle all should be equivalence, is included within protection scope of the present invention.