CN102101909A - Water soluble polyurethane associative thickener, and inverse polymerization method and use thereof - Google Patents
Water soluble polyurethane associative thickener, and inverse polymerization method and use thereof Download PDFInfo
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Abstract
The invention discloses a water soluble polyurethane associative thickener, and an inverse polymerization method and use thereof. The method comprises: dehydrating polyethylene glycol by using an organic solvent with a boiling point below 110 DEG C; adding diisocyanate in the protection of an inert gas to perform a reaction; adding fatty alcohol of which the chain is 8 to 22 carbon atoms long as a capping agent for further reaction; adding polyol containing at least three hydroxys as a chain extender to perform an reaction till there are no free isocyanate groups; and adding water, and removing the organic solvent by an azeotropic process to obtain the water soluble polyurethane associative thickener which is white, transparent and sticky fluid. The dehydration temperature of water soluble associative polyurethane is low, so the side reactions are inhibited effectively; and reaction is performed in the organic solvent and catalyst is not required, so cost is reduced and the hydrolysis side reaction of the product due to the catalyst is avoided. Because the polyol is used as a chain extender, the thickener of the invention has a branch structure and high thickening performance.
Description
Technical field
The present invention relates to a kind of thickening material, particularly a kind of water-soluble association type polyurethane thickener and reversed-phase polymerization method and application belong to the material field.
Background technology
Polyurethane associative thickener is a class thickening material that grows up the eighties in 20th century, is a kind of water-soluble oligomer that contains hydrophobic grouping.Traditional urethane associative thickening agent molecule is generally obtained by organic single-isocyanate and polyethers direct addition, or earlier by the polyethers of certain molecular weight and excessive di-isocyanate reaction, obtain by organic amine or alcohol end capping again, it is a linear structure, two ends are the oleophylic end group, and the centre is the long-chain hydrophilic radical.The thickening power principle of polyurethane associative thickener is: the oleophylic end group associates into micella, micellar associates and has formed reticulated structure, the water coupling in hydrophilic group and the system just, forming the micellar terminal group is adsorbed on the different micella particles by two hydrophobic ends, the thickening material molecule forms bridging between particle, with the polymer particle of emulsion and the granules of pigments that the has been adsorbed with dispersion agent formation reticulated structure that associates mutually, and interconnection winding and system viscosity is increased has formed the thickening phenomenon.
Because the isocyanate groups (NCO) of organic single-isocyanate or vulcabond is to the reactive behavior that has of water and reactive hydrogen, therefore, take place for fear of by product, before carrying out polyreaction, common in the prior art by the vacuum-drying dewatering, with the moisture removal in the raw material, carry out bulk polymerization, the product that obtains is generally waxy solid, it is very inconvenient when using, need dissolve with solvent and solubility promoter etc., it could be added to as emulsion paint etc. needs in the product of thickening.In addition, existing reversed-phase polymerization method, side reaction product is many, and the polyurethane associative thickener color that obtains is darker, and reaction viscosity is big, and the mass-and heat-transfer difficulty improves molecular weight and the branched structure difficulty that reaches effective thickening, and products production and storage stability are not high.
Summary of the invention
In order to overcome the shortcoming and defect part of prior art, primary and foremost purpose of the present invention is to provide a kind of reversed-phase polymerization method of water-soluble association type polyurethane thickener.The present invention is a branched structure by the water-soluble association type polyurethane thickener that the reversed-phase polymerization method obtains, and thickening capabilities is strong.
The water-soluble association type polyurethane thickener that provides described reversed-phase polymerization method to obtain is provided.
A further object of the present invention is to provide the application of described water-soluble association type polyurethane thickener.
Purpose of the present invention is achieved through the following technical solutions: a kind of reversed-phase polymerization method of water-soluble association type polyurethane thickener comprises following steps:
(1) organic solvent is mixed with polyoxyethylene glycol, dewatered 1～5 hour in 50～110 ℃ of reflux by water-and-oil separator;
(2) then under protection of inert gas, added di-isocyanate reaction 1～5 hour in 50～110 ℃ of products in the step (1), then add end-capping reagent reaction 2～10 hours, add chainextender at last and react, do not have free isocyanate groups group afterreaction to finish when the infrared colour spectrum detects;
(3) add entry in the product solution that then obtains toward step (2), azeotropic removes organic solvent and water, obtains water-soluble association type polyurethane thickener.
Described chainextender is the polyvalent alcohol that contains at least 3 hydroxyls.
Described end-capping reagent is that carbon chain lengths is C
8～C
22Fatty Alcohol(C12-C14 and C12-C18).
Wherein, the consumption of vulcabond is pressed oh group (OH) mol ratio 1 in its isocyano group (NCO) and polyoxyethylene glycol, chainextender and the end-capping reagent: calculate (1～1.1).Wherein the molar ratio of polyoxyethylene glycol and end-capping reagent is preferably 1: (0.1～1), the mol ratio of chainextender and end-capping reagent are 1: (3～4).
The described reflux temperature of step (1) is preferably 50～80 ℃.
The consumption of described organic solvent (quality) be equivalent to described polyoxyethylene glycol, end-capping reagent, vulcabond and chainextender consumption (quality) summation 50%～200%;
The preferred boiling point of described organic solvent is to be lower than 110 ℃ organic solvent, and preferred benzene class organic solvent, carbon chain lengths are C
2～C
7Organic solvent of ketone or ester class organic solvent at least a.
One or both of preferred acetone of described organic solvent of ketone or methylethylketone.
At least a in described ester class organic solvent preferable formic acid ethyl ester, ritalin, vinyl acetic monomer, propyl acetate or the acetic acid isopropyl ester.
Described preferred benzene of benzene class organic solvent or toluene.
Described rare gas element preferred nitrogen.
The molecular weight of the described polyoxyethylene glycol of step (1) is preferred 1000～10000, and preferred molecular weight is 4000～8000.
At least a in the preferred lauryl alcohol of the described end-capping reagent of step (2), tridecyl alcohol, palmityl alcohol or the stearyl alcohol.
At least a in the preferred TriMethylolPropane(TMP) of the described chainextender of step (2) (TMP), tetramethylolmethane or the glycerine.
The preferred isophorone diisocyanate of the described vulcabond of step (2) (IPDI), 1, hexamethylene-diisocyanate (HDI), 2,6-vulcabond methylhexanoic acid ester (LDI), tolylene diisocyanate (TDI), 4, at least a in 4 '-diphenylmethanediisocyanate (MDI), dicyclohexyl methane diisocyanate (HMDI), xylylene diisocyanate (XDI), naphthalene-1,5 vulcabond (NDI), Methylcyclohexyl diisocyanate (HTDI) or the tetramethylxylylene diisocyanate (TMXDI).
The consumption of the described water of step (3) adds according to the purpose concentration of described water-soluble association type polyurethane thickener.
The preferred deionized water of described water.
A kind of water-soluble association type polyurethane thickener is to be prepared by above-mentioned reverse polymerization method.
Described water-soluble association type polyurethane thickener is that solid content is 20～50%, number-average molecular weight 10000～150000, and rotary viscosity 10000～100000cps (20 ℃), the pH value is 5～7 white translucent viscous fluid.Add 0.1～5% described water-soluble association type polyurethane thickener in the water and milk system, emulsion viscosity has significant increase.
Described water-soluble association type polyurethane thickener hydrophilicity is good, is applicable to the system thickening of Aquo System, is particularly suitable for makeup or personal care product etc.
The present invention has following advantage and beneficial effect with respect to prior art:
(1) the present invention is good by the water-soluble association type polyurethane thickener outward appearance that the reversed-phase polymerization method obtains, and for the translucent thick liquid of white, can directly use; Good stability, in 5～30 ℃ of placements, internal state did not change in 1 year; Rotary viscosity is 10000～100000cps, and the pH value is 5～7, can promote levelling and spreadability effectively, prolongs to film the open hour.
(2) reversed-phase polymerization method of the present invention is simple, and cost is low, and the industrialization ratio is easier to realize.In this reversed-phase polymerization method,, produce polymkeric substance cladodification structure, more effectively must produce the associative thickening effect owing to use the polyvalent alcohol chainextender.The reaction efficiency height of reaction isocyano group and hydroxyl in organic solvent, the present invention need not use catalyzer, thereby reduces the hydrolysis of urethane in storage and the use, helps stability.And by water-and-oil separator product is separated with organic solvent, organic solvent thoroughly can be deleted, the product environmental protection that obtains is applied to the material that thickening and human body contact closely, safety, toxicological harmless.
(3) dehydration temperaturre of this reversed-phase polymerization method is than low 10～20 ℃ at least of existing vacuum dehydration technologies, under this temperature, polyoxyethylene glycol is difficult for oxygenolysis, thereby greatly reduces the generation of side reaction, helps obtaining the high water-soluble association type polyurethane thickener of purity.Employed organic solvent difference, dehydration temperaturre of the present invention can be lower, and is specifically as shown in table 1.
Table 1
| Organic solvent | Acetone | Butanone | Vinyl acetic monomer | Benzene | Toluene | Mibk | Dimethylbenzene | N-BUTYL ACETATE |
| Preparation minimum temperature ℃ | 57 | 80 | 78 | 80 | 110 | 118 | 140 | 126 |
Embodiment
The present invention is described in further detail below in conjunction with embodiment, but embodiments of the present invention are not limited thereto.
Embodiment 1
(1) add 60 mass parts PEG6000 and 30 mass parts vinyl acetic monomers in the flask of band whipping appts, mixing uses water-and-oil separator in 77 ℃ of dehydrations 1 hour.
(2) be cooled to 60 ℃ and charge into nitrogen, add 2.52 mass parts HDI, 60 ℃ of reactions 4.5 hours, add 0.93 mass parts lauryl alcohol then, 60 ℃ were reacted 5 hours, added 0.22 mass parts TMP at last and reacted, and had free isocyanate groups group afterreaction to finish when the infrared colour spectrum detects.
(3) adding 255 mass parts deionized waters in the product solution that then obtains toward step (2), be warming up to 98 ℃ of azeotropic, deviate from organic solvent, the moisture of replenish loss by water-and-oil separator, be cooled to room temperature, promptly obtain the aqurous ployurethane associative thickener of solid content 20%.
The mol ratio of NCO and OH is 1: 1 among this embodiment, and the mol ratio of PEG6000 and lauryl alcohol is 1: 0.5, and the mol ratio of TMP and lauryl alcohol is 1: 3.The aqurous ployurethane associative thickener outward appearance that makes is good, is the translucent thick liquid of white, and viscosity is 11200cps (GB/T10247-1988), and the pH value is 7.0, can directly use; Good stability, in 5～30 ℃ of placements, internal state did not change in 1 year.
Embodiment 2
(1) add 80 mass parts PEG8000 and 160 mass parts acetone in the flask of band whipping appts, mixing uses water-and-oil separator in 57 ℃ of dehydrations 5 hours.
(2) be cooled to 50 ℃ and charge into nitrogen, add 3.02 mass parts HDI, 60 ℃ of reactions 4.5 hours, add 1.49 mass parts lauryl alcohols then, 50 ℃ were reacted 5 hours, added 0.36 mass parts TMP at last and reacted, and had free isocyanate groups group afterreaction to finish when the infrared colour spectrum detects.
(3) adding 85 mass parts deionized waters in the product solution that then obtains toward step (2), be warming up to 98 ℃ of azeotropic, deviate from organic solvent by water-and-oil separator, the moisture of replenish loss is cooled to the aqurous ployurethane associative thickener that room temperature had both obtained solid content 50%.
The mol ratio of NCO and OH is 1: 1 among this embodiment, and the mol ratio of PEG8000 and lauryl alcohol is 1: 0.8, and the mol ratio of TMP and lauryl alcohol is 1: 3.The aqurous ployurethane associative thickener outward appearance that makes is good, is the translucent thick liquid of white, and viscosity is 99000cps (GB/T10247-1988), and the pH value is 5.0, can directly use; Good stability, in 5～30 ℃ of placements, internal state did not change in 1 year.
Embodiment 3
(1) in the flask of band whipping appts, adds 100 mass parts PEG10000,100 mass parts butanone mixings, use water-and-oil separator in 80 ℃ of dehydrations 5 hours.
(2) be cooled to 75 ℃ and charge into nitrogen, add 3.48 mass parts TDI, 75 ℃ of reactions 1 hour, add 2.7 mass parts stearyl alcohol then, 75 ℃ were reacted 1 hour, added 0.34 mass parts tetramethylolmethane at last and reacted, and had free isocyanate groups group afterreaction to finish when the infrared colour spectrum detects.
(3) adding 320 mass parts deionized waters in the product solution that then obtains toward step (2), be warming up to 95 ℃ of azeotropic, deviate from organic solvent, the moisture of replenish loss by water-and-oil separator, be cooled to room temperature, promptly obtain the aqurous ployurethane associative thickener of solid content 25%.
The mol ratio of NCO and OH is 1: 1 among this embodiment, and the mol ratio of PEG10000 and stearyl alcohol is 1: 1, and the mol ratio of tetramethylolmethane and stearyl alcohol is 1: 4.The aqurous ployurethane associative thickener outward appearance that makes is good, is the translucent thick liquid of white, and viscosity is 22100cps (GB/T10247-1988), and the pH value is 6.5, can directly use; Good stability, in 5～30 ℃ of placements, internal state did not change in 1 year.
Embodiment 4
(1) in the flask of band whipping appts, adds 100 mass parts PEG1000,100 mass parts acetone mixings, use water-and-oil separator in 57 ℃ of dehydrations 2 hours.
(2) be cooled to 50 ℃ and charge into nitrogen, add 18.48 mass parts HDI, 50 ℃ of reactions 4 hours, add 2.7 mass parts stearyl alcohol then, 50 ℃ were reacted 2 hours, added 0.45 mass parts TMP at last and reacted, and had free isocyanate groups group afterreaction to finish when the infrared colour spectrum detects.
(3) adding 365 mass parts deionized waters in the product solution that then obtains toward step (2), be warming up to 95 ℃ of azeotropic, deviate from organic solvent, the moisture of replenish loss by water-and-oil separator, be cooled to room temperature, promptly obtain the aqurous ployurethane associative thickener of solid content 25%.
The mol ratio of NCO and OH is 1: 1 among this embodiment, and the mol ratio of PEG1000 and stearyl alcohol is 1: 0.1, and the mol ratio of TMP and stearyl alcohol is 1: 3.The aqurous ployurethane associative thickener outward appearance that makes is good, is the translucent thick liquid of white, and viscosity is 28000cps (GB/T10247-1988), and the pH value is 6.5, can directly use; Good stability, in 5～30 ℃ of placements, internal state did not change in 1 year.
Embodiment 5
(1) in the flask of band whipping appts, adds 40 mass parts PEG4000,160 mass parts acetone mixings, use water-and-oil separator in 57 ℃ of dehydrations 5 hours.
(2) be cooled to 50 ℃ and charge into nitrogen, add 2.52 mass parts HDI, 60 ℃ of reactions 4.5 hours, add 0.93 mass parts lauryl alcohol then, 50 ℃ were reacted 5 hours, added 0.22 mass parts TMP at last and reacted, and had free isocyanate groups group afterreaction to finish when the infrared colour spectrum detects.
(3) adding 43.7 mass parts deionized waters in the product solution that then obtains toward step (2), be warming up to 98 ℃ of azeotropic, deviate from organic solvent by water-and-oil separator, the moisture of replenish loss is cooled to the aqurous ployurethane associative thickener that room temperature had both obtained solid content 50%.
The mol ratio of NCO and OH is 1: 1 among this embodiment, and the mol ratio of PEG4000 and lauryl alcohol is 1: 0.5, and the mol ratio of TMP and lauryl alcohol is 1: 3.The aqurous ployurethane associative thickener outward appearance that makes is good, is the translucent thick liquid of white, and viscosity is 69000cps (GB/T10247-1988), and the pH value is 5.0, can directly use; Good stability, in 5～30 ℃ of placements, internal state did not change in 1 year.
The thickening property test
Take by weighing benzene emulsion 200g, add deionized water 30g under stirring, mix the back and add associative thickener to be measured, stirred 20 minutes, leave standstill the rotary viscosity (6r/min and 60r/min) of test emulsion after 20 minutes.The amount of the thickening material that adds is 1% of emulsion and a water inventory.
Viscosity and thixotropy index under different the shearing
| Annotate | PU75 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Rotary viscosity | 6r/min (20 ℃)/4# rotor | 20000 | 27000 | 28500 | 22000 | 21000 | 26000 |
| Rotary viscosity | 60r/min (20 ℃)/4# rotor | 6000 | 10500 | 9800 | 7000 | 6400 | 10000 |
| Thixotropy index | 6r/60r (20 ℃)/4# rotor | 3.33 | 2.62 | 2.91 | 3.14 | 3.28 | 2.6 |
Annotate: PU75 is the famous product grade of certain import.
Can find out that according to above data the water-soluble association type polyurethane thickener that adds 1% the present invention preparation can obtain the viscosity higher than PU75, but thixotropy index is all little than PU75, better with PEG4000～8000 effects especially.This explanation benzene emulsion uses this thickening material not only to improve low-shear viscosity, also improves shear viscosity, and the system flow state more meets the state of Newtonian fuid, helps obtaining even curface.
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. the reversed-phase polymerization method of a water-soluble association type polyurethane thickener is characterized in that comprising following steps:
(1) organic solvent is mixed with polyoxyethylene glycol, dewatered 1～5 hour in 50～110 ℃ of reflux by water-and-oil separator;
(2) then under protection of inert gas, added di-isocyanate reaction 1～5 hour in 50～110 ℃ of products in the step (1), then add end-capping reagent reaction 2～10 hours, add chainextender at last and react, do not have free isocyanate groups group afterreaction to finish when the infrared colour spectrum detects;
(3) add entry in the product solution that obtains toward step (2), azeotropic removes organic solvent and water, obtains water-soluble association type polyurethane thickener;
Described organic solvent is that boiling point is to be lower than 110 ℃ organic solvent; Described end-capping reagent is that carbon chain lengths is C
8～C
22Fatty Alcohol(C12-C14 and C12-C18); Described chainextender is the polyvalent alcohol that contains at least 3 hydroxyls;
Wherein, the consumption of vulcabond is pressed the oh group mol ratio 1 in its isocyano group and polyoxyethylene glycol, chainextender and the end-capping reagent: calculate (1～1.1).
2. reversed-phase polymerization method according to claim 1 is characterized in that: the molar ratio of described polyoxyethylene glycol and described end-capping reagent is 1: (0.1～1); The mol ratio of described chainextender and described end-capping reagent is 1: (3～4).
3. reversed-phase polymerization method according to claim 1 is characterized in that: the reflux temperature described in the step (1) is 50～80 ℃.
4. reversed-phase polymerization method according to claim 1 is characterized in that: described chainextender is at least a in TriMethylolPropane(TMP), tetramethylolmethane or the glycerine.
5. reversed-phase polymerization method according to claim 1 is characterized in that: the consumption of described organic solvent be equivalent to described polyoxyethylene glycol, end-capping reagent, vulcabond and chainextender the consumption summation 50%～200%; Described organic solvent is benzene class organic solvent, carbon chain lengths C
2～C
7Organic solvent of ketone or ester class organic solvent at least a.
6. reversed-phase polymerization method according to claim 5 is characterized in that:
Described organic solvent of ketone is one or both of acetone or methylethylketone;
Described ester class organic solvent is at least a in ethyl formate, ritalin, vinyl acetic monomer, propyl acetate or the acetic acid isopropyl ester;
Described benzene class organic solvent is benzene or toluene.
7. reversed-phase polymerization method according to claim 1 is characterized in that: the molecular weight of described polyoxyethylene glycol is 4000～8000.
8. reversed-phase polymerization method according to claim 1, it is characterized in that: described vulcabond is an isophorone diisocyanate, 1, hexamethylene-diisocyanate, 2,6-vulcabond methylhexanoic acid ester, tolylene diisocyanate, 4, at least a in 4 '-diphenylmethanediisocyanate, dicyclohexyl methane diisocyanate, xylylene diisocyanate, naphthalene-1,5 vulcabond, Methylcyclohexyl diisocyanate or the tetramethylxylylene diisocyanate.
9. a water-soluble association type polyurethane thickener is to be prepared by each described reverse polymerization method of claim 1～8.
10. the described water-soluble association type polyurethane thickener of claim 9 is applied to the thickening of Aquo System.
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| CN102898612A (en) * | 2012-10-31 | 2013-01-30 | 丽水学院 | Preparation method of linear water-based polyurethane thickener containing hydrophobic side bases |
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| CN103396524A (en) * | 2013-07-19 | 2013-11-20 | 武汉科技大学 | Non-ionic branched-type waterborne polyurethane containing hydrophobic end group and preparation method thereof |
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| CN106380572A (en) * | 2016-09-28 | 2017-02-08 | 安徽大学 | Method for preparing star-like waterborne polyurethane associated type thickening agent |
| US11802213B2 (en) | 2017-05-11 | 2023-10-31 | Elementis Specialties, Inc. | ICI thickener composition and uses |
| CN107353392A (en) * | 2017-08-30 | 2017-11-17 | 瑞安市隆联新材料有限公司 | A kind of aqueous polyurethane thickener and the application in alcohol edition-0 moistening liquid is exempted from |
| CN107353392B (en) * | 2017-08-30 | 2020-11-20 | 瑞安市隆联新材料有限公司 | Water-based polyurethane thickener and application thereof in alcohol-free fountain solution |
| CN110591038B (en) * | 2019-08-29 | 2021-06-29 | 威尔（福建）生物有限公司 | Preparation method and application of thickening agent for aqueous emulsion |
| CN110591038A (en) * | 2019-08-29 | 2019-12-20 | 威尔（福建）生物有限公司 | Preparation method and application of thickening agent for aqueous emulsion |
| CN110965362A (en) * | 2019-12-21 | 2020-04-07 | 苏州大学 | Branched-chain polyurethane thickener and preparation method thereof |
| CN111393595A (en) * | 2020-05-06 | 2020-07-10 | 东莞市竤穗实业投资有限公司 | Bio-based polycarbodiimide crosslinking agent with temperature-sensitive characteristic and preparation method thereof |
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