Hydrogenated castor oil branched polyurethane associative thickener and preparation method and application thereof
阅读说明：本技术 一种氢化蓖麻油支化聚氨酯缔合增稠剂及其制备方法和应用 (Hydrogenated castor oil branched polyurethane associative thickener and preparation method and application thereof ) 是由 宋春梅 陆曼 万波 林雅婷 周新栋 于 2021-05-24 设计创作，主要内容包括：本发明公开了一种氢化蓖麻油支化聚氨酯缔合增稠剂,所述增稠剂具有分子结构简单,氢化蓖麻油支化端基中可通过形成氨酯键引入烷基、芳香官能团,及多官能团物质,增稠效率高、储存稳定性好,所述聚氨酯增稠剂可以增稠水,水性聚氨酯乳液、水性苯丙乳液、水性丙烯酸酯乳液、水性环氧树脂。本发明还公开了所述氢化蓖麻油支化缔合聚氨酯增稠剂的制备方法,以聚乙二醇、二异氰酸酯、氢化蓖麻油、封端剂醇为原料,在催化剂下,反应制备得到所述氢化蓖麻油支化缔合聚氨酯增稠剂。本发明的制备方法具有操作简单,收率高；原料价廉易得；绿色环保,无毒无污染的特点。(The invention discloses a hydrogenated castor oil branched polyurethane associative thickener which has a simple molecular structure, alkyl, aromatic functional groups and polyfunctional substances can be introduced into a branched end group of hydrogenated castor oil through formation of urethane bonds, the thickening efficiency is high, the storage stability is good, and the polyurethane thickener can thicken water, aqueous polyurethane emulsion, aqueous styrene-acrylic emulsion, aqueous acrylic emulsion and aqueous epoxy resin. The invention also discloses a preparation method of the hydrogenated castor oil branched associated polyurethane thickener, which comprises the step of reacting polyethylene glycol, diisocyanate, hydrogenated castor oil and end capping reagent alcohol serving as raw materials in the presence of a catalyst to prepare the hydrogenated castor oil branched associated polyurethane thickener. The preparation method has the advantages of simple operation and high yield; the raw materials are cheap and easy to obtain; green and environment-friendly, and has no toxicity and pollution.)
1. A hydrogenated castor oil branched polyurethane associative thickener is characterized by having a structure shown in formula (III) and formula (IV) or a mixture of the two:
wherein:
n＝90～681；
r is a residual functional group except isocyanate and is selected from one of isophorone isocyanate IPDI, hexamethylene diisocyanate HDI, methyl phenyl diisocyanate TDI and dicyclohexyl methane diisocyanate HMDI except isocyanate;
r' is a residual functional group other than hydroxyl and is selected from CnH2n+1OH branched monoalcohols and linear CH3-(CH2)nResidual functional groups of-OH, other than hydroxyl groups, said CnH2n+1OH is isotridecyl alcohol, isohexadecyl alcohol, isooctadecyl alcohol; the CH3-(CH2)nthe-OH is dodecyl alcohol, tetradecyl alcohol, hexadecyl alcohol and octadecyl alcohol, wherein n is 11-28.
2. A preparation method of a hydrogenated castor oil branched polyurethane associative thickener is characterized in that polyethylene glycol (PEG), diisocyanate, hydrogenated castor oil, blocking agent alcohol or blocked monoamine are used as reaction raw materials and react in the presence of a catalyst to obtain the hydrogenated castor oil branched polyurethane associative thickener, and the method is shown as a scheme (1):
wherein:
n＝90～681；
r is a residual functional group except isocyanate and is selected from one of isophorone isocyanate IPDI, hexamethylene diisocyanate HDI, methyl phenyl diisocyanate TDI and dicyclohexyl methane diisocyanate HMDI except isocyanate;
r' is a residual functional group other than hydroxyl and is selected from CnH2n+1OH branched monoalcohols and linear CH3-(CH2)nResidual functional groups of-OH, other than hydroxyl groups, said CnH2n+1OH is isotridecyl alcohol, isohexadecyl alcohol, isooctadecyl alcohol; the CH3-(CH2)nthe-OH is dodecyl alcohol, tetradecyl alcohol, hexadecyl alcohol and octadecyl alcohol, wherein n is 11-28.
3. The method according to claim 2, characterized in that it comprises in particular the steps of:
(1) adding polyethylene glycol (PEG) and diisocyanate into a reactor, and carrying out polyurethane reaction under the action of a catalyst 1 to obtain a prepolymer;
(2) adding hydrogenated castor oil into the prepolymer generated in the step (1), and reacting in the presence of a catalyst 2 to obtain a hydrogenated castor oil branched PU prepolymer;
(3) adding end capping reagent alcohol or end capping monoamine and a catalyst 3 into the product generated in the step (2), and reacting to obtain a hydrogenated castor oil branched polyurethane associative thickener;
or, the method specifically comprises the following steps:
(1') adding polyethylene glycol (PEG), diisocyanate and end-capping reagent alcohol or end-capping monoamine into a reactor, and reacting under the action of a catalyst 1 to obtain a prepolymer;
(2') adding hydrogenated castor oil into the prepolymer generated in the step (1), and reacting under the action of a catalyst 2 to obtain the hydrogenated castor oil branched polyurethane associative thickener.
4. The method of claim 3, wherein in step (1), the mass ratio of PEG to diisocyanate to catalyst 1 is 1: 0.00108-0.264: 0.00012-0.0024; and/or the catalyst 1 is selected from one or more of dibutyltin dilaurate DBTDL, stannous octoate, organic bismuth and a tin-bismuth mixed catalyst; and/or the PEG is selected from one of molecular weights of 2000-30000; and/or the isocyanate is selected from one or more of isophorone isocyanate IPDI, hexamethylene diisocyanate HDI, methyl phenyl diisocyanate TDI and dicyclohexyl methane diisocyanate HMDI; and/or the reaction temperature is 50-130 ℃; the reaction time is 0.5-5 hours.
5. The method of claim 3, wherein in the step (2), the mass ratio of the prepolymer to the hydrogenated castor oil to the catalyst 2 is 1: 0.0015 to 0.0291: 0.00001 to 0.0012; and/or the catalyst 2 is selected from one or more of dibutyltin dilaurate DBTDL, stannous octoate, organic bismuth and a tin-bismuth mixed catalyst; and/or the reaction temperature is 50-130 ℃; and/or the reaction time is 0.5-5 hours.
6. The method of claim 3, wherein in step (3), the hydrogenated castor oil branched PU prepolymer, the blocking agent alcohol or the blocked monoamine, and the catalyst 3 are present in a mass ratio of: 1: 0.0016-0.14: 0.00020-0.0018; and/or the catalyst 3 is selected from one or more of DBTDL, stannous octoate, organic bismuth and a tin-bismuth mixed catalyst; and/or the end-capping reagent alcohol is selected from isotridecyl alcohol, isohexadecyl alcohol, isooctadecyl alcohol CnH2n+1OH branched monoalcohols and linear dodecanol, tetradecanol, hexadecanol, octadecanol CH3-(CH2)n-OH, n is 11-28; and/or the reaction temperature is 50-130 ℃; and/or the reaction time is 0.5-5 hours.
7. The method of claim 3, wherein in step (1'), the PEG, capping agent alcohol or capping agentThe mass ratio of the terminal monoamine to the diisocyanate to the catalyst 1 is as follows: 1: 0.0016-0.14: 0.00108-0.264: 0.00012-0.0024; and/or the end-capping reagent alcohol is selected from isotridecyl alcohol, isohexadecyl alcohol, isooctadecyl alcohol CnH2n+ 1OH branched monoalcohols and linear dodecanol, tetradecanol, hexadecanol, octadecanol CH3-(CH2)n-OH, n is 11-28; and/or the catalyst 1 is selected from one or more of dibutyltin dilaurate DBTDL, stannous octoate, organic bismuth and a tin-bismuth mixed catalyst; and/or the PEG is selected from one of molecular weights of 2000-30000; and/or the isocyanate is selected from one or more of isophorone isocyanate IPDI, hexamethylene diisocyanate HDI, methyl phenyl diisocyanate TDI and dicyclohexyl methane diisocyanate HMDI; and/or the reaction temperature is 50-130 ℃; and/or the reaction time is 0.5-5 hours.
8. The method of claim 3, wherein in the step (2'), the mass ratio of the prepolymer to the hydrogenated castor oil to the catalyst 2 is 1: (0.0015 to 0.0291): (0.00001 to 0.0012); and/or the catalyst 2 is selected from one or more of dibutyltin dilaurate DBTDL, stannous octoate, organic bismuth and a tin-bismuth mixed catalyst; and/or the reaction temperature is 50-130 ℃; and/or the reaction time is 0.5-5 hours.
9. Use of the hydrogenated castor oil branched polyurethane associative thickener of claim 1 in wood paints, wall paints, metal paints, anticorrosion coatings, leather coatings, paper coatings, stone paint, wood grain paper, adhesives.
Technical Field
The invention belongs to the technical field of chemistry and coatings and adhesives thereof, and particularly relates to a hydrogenated castor oil branched polyurethane associative thickener, and a preparation method and application thereof.
Background
The water paint has the advantages of no environmental pollution, no organic solvent, etc. However, the water-based paint is low in viscosity (1-10 mPa.s), is easy to sag, and cannot be directly coated. The thickening agent can endow adhesive or emulsion paint with stable physical and chemical properties and excellent mechanical properties (increased storage stability, suitability for blade coating, spray coating, roller coating and other constructions). Thickeners are widely used in the fields of cosmetics, foods, medicines, emulsion paints, dyes, adhesives, leathers, paper making, etc.
Four thickeners are currently common:
(1) inorganic thickeners, such as bentonite, have low price and strong corrosion resistance, and have the defects of poor leveling property and poor compatibility: (2) cellulose, such as carboxymethyl cellulose, and the thickening agent is easy to be corroded and degraded by bacteria and has poor corrosion resistance; (3) polyacrylates, which are susceptible to pH and electrolytes, and have poor thixotropy and poor hydrolysis resistance; (4) waterborne polyurethanes, environmentally friendly thickeners with a special thickening mechanism, also known as third generation thickeners. Such thickeners are predominantly linear; it is not easy to prepare polymers with high molecular weight; therefore, the dosage is large during thickening, and the cost is increased.
The existing polyurethane thickener prepared by taking glycerol, pentaerythritol and sorbitol as cores has short hydrophobic chain, more hydroxyl functional groups, high activity and easy crosslinking.
The polyurethane thickener is prepared by using hydrogenated castor oil as a core, and has the advantages of large molecular weight of products, long branched chain of the core and difficult crosslinking. The branching degree is low, and a space three-dimensional network structure is formed on the emulsion, the solid particles and the micelle which have the hydrophobic association effect, so that the thickening of an aqueous system is realized.
Hydrogenated Castor Oil (HCO) is a saturated derivative of castor oil and has a molecular formula of a mixture of formula (I) and formula (II):
the hydroxyl group on hydrogenated castor oil (OH functionality ═ 2.7) can react with NCO, so hydrogenated castor oil can be incorporated into the HEUR design to make a hydrogenated castor oil branched polyurethane associative thickener. The castor oil-containing paint has long service life, is not easy to yellow, and has good fullness and glossiness. Hydrogenated castor oil is natural renewable vegetable oil, is cheap and rich in source, has excellent industrial application value, and is widely applied to the fields of coatings, adhesives, cosmetics, lubricants and the like.
HEUR has the effects of thickening and leveling, can effectively adjust the rheological property of the fluid and improve the application defects. The HEUR thickener has high efficiency, and can remarkably improve the emulsion system at low content with less use amountThe viscosity of the product is high, and the product has excellent thickening effect. In addition, HEUR thickener can also improve system heightThe viscosity of the oil is reduced byThe possibility of spattering arises when, for example, a roll coating is used. In general, the viscosity of HEUR thickened emulsion systems recoversSome time is needed after the disappearance, which is beneficial to leveling; unlike the thickening characteristic of cellulose thickener, the viscosity is recovered instantly, and the leveling property is higherAnd (4) poor. Meanwhile, the HEUR thickening agent can also endow the paint with very good glossiness, so that the paint is water-resistant, washing-resistant, not easy to mildew and strong in antimicrobial erosion capability.
Small amounts of HEUR can improve the rheological properties of emulsions, mostly by assessing viscosity (. eta.) versus shear rateTo study the rheological characteristics of HEUR thickened emulsions; the time dependence of viscosity in the construction process, namely thixotropy, is also important. Thixotropy is directly related to the rate of viscosity recovery after the paint is applied, and plays a decisive role in some of the problems common in painting processes, such as leveling and sagging. The HEUR thickened emulsion has thixotropy and is high in viscosityThe high viscosity of the oil can be kept,after removal, time is needed for viscosity recovery, and the system leveling is facilitated.
WO 2006/002813 describes polyurethane thickeners for various applications in aqueous media. These thickeners are prepared from a hydrophilic polyol having two hydroxyl groups, one or more hydrophobic compounds such as long chain alcohols and difunctional isocyanates; in this case, an excess of NCO groups is used; the catalyst used was 1, 8-diazabicyclo [5-4-0] undec-7-ene (DABCO).
The polyurethane thickener products described in the above patents are predominantly linear; it is not easy to prepare polymers with high molecular weight; therefore, the dosage is large during thickening, and the cost is increased. The existing polyurethane thickener prepared by taking glycerol, pentaerythritol and sorbitol as cores has short hydrophobic chain, more hydroxyl functional groups, high activity and easy crosslinking.
The polyurethane thickener prepared from the long-branched polyol with the functionality of 3 and 4 is easy to crosslink; when the functionality is 4, the thickener itself tends to be a spherical micelle, and cannot associate with the emulsion, the solid particles, and the micelle to form a spatial network structure, thereby reducing the thickening effect.
The above information disclosed in this background section is only for enhancement of understanding of the background of the disclosure and therefore it may contain information that does not constitute prior art that is already known to a person of ordinary skill in the art.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a hydrogenated castor oil branched polyurethane associative thickener which is a nonionic thickener, the molecular structure of the thickener takes polyethylene glycol as a core, isocyanate is connected to two ends of the polyethylene glycol, natural high-molecular hydrogenated castor oil is selected as a chain extender to end a part of prepolymer, and then the end capping is completed by using monohydric alcohol or monoamine, and the structure of the thickener is one or a mixture of two as shown in formula (III) and formula (IV):
wherein:
n＝90～681；
r is a residual functional group except isocyanate, such as one of the residual functional groups except isocyanate in raw materials of isophorone isocyanate IPDI, hexamethylene diisocyanate HDI, methyl phenyl diisocyanate TDI, dicyclohexyl methane diisocyanate HMDI and the like.
R' is a residual functional group other than hydroxy, e.g. CnH2n+1OH branched monoalcohols and linear CH3-(CH2)n-OH residual functional groups other than hydroxyl, said CnH2n+1OH is isotridecyl alcohol, isohexadecyl alcohol, isooctadecyl alcohol, etc.; the CH3-(CH2)nthe-OH is dodecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, octadecyl alcohol and the like, wherein n is 11-28.
The invention also provides a preparation method of the hydrogenated castor oil branched polyurethane associative thickener, which comprises the following steps of taking polyethylene glycol (PEG), diisocyanate, hydrogenated castor oil and end capping reagent alcohol as reaction raw materials, and reacting in the presence of a catalyst to obtain the hydrogenated castor oil branched polyurethane associative thickener, wherein the method is shown as a scheme (1):
wherein:
n＝90～681；
r is a residual functional group except isocyanate, such as one of the residual functional groups except isocyanate in raw materials of isophorone isocyanate IPDI, hexamethylene diisocyanate HDI, methyl phenyl diisocyanate TDI, dicyclohexyl methane diisocyanate HMDI and the like.
R' is a residual functional group other than hydroxy, e.g. CnH2n+1OH branched monoalcohols and linear CH3-(CH2)n-OH residual functional groups other than hydroxyl, said CnH2n+1OH is isotridecyl alcohol, isohexadecyl alcohol, isooctadecyl alcohol, etc.; the CH3-(CH2)nthe-OH is dodecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, octadecyl alcohol and the like, wherein n is 11-28.
The method specifically comprises the following steps:
(1) adding polyethylene glycol (PEG) and diisocyanate into a reactor, and carrying out polyurethane reaction under the action of a catalyst 1 to obtain a prepolymer;
(2) adding hydrogenated castor oil into the prepolymer generated in the step (1), and reacting in the presence of a catalyst 2 to obtain a hydrogenated castor oil branched PU prepolymer;
(3) and (3) adding a blocking agent alcohol or a blocking monoamine and a catalyst 3 into the product generated in the step (2), and reacting to obtain the hydrogenated castor oil branched polyurethane associative thickener.
In the step (1), the mass ratio of the PEG to the diisocyanate to the catalyst 1 is as follows: 1: 0.00108-0.264: 0.00012-0.0024; preferably, the ratio is 1: (0.0073-0.0291): (0.0007-0.0012).
In the step (1), the molar ratio of PEG to diisocyanate is as follows: 1: 1.01-4; preferably, the ratio is 1 to (1.1-2.5).
In the step (1), the catalyst 1 is one or more selected from dibutyltin dilaurate DBTDL, stannous octoate, organic bismuth and tin-bismuth mixed catalysts; preferably, DBTDL.
In the step (1), the PEG may have one of molecular weights of 2000 to 30000.
In the step (1), the isocyanate is selected from one or more of isophorone isocyanate IPDI, hexamethylene diisocyanate HDI, methyl phenyl diisocyanate TDI, dicyclohexyl methane diisocyanate HMDI and the like; preferably, IPDI and HDI.
In the step (1), the reaction temperature is 50-130 ℃; preferably, the temperature is 80-100 ℃.
In the step (1), the reaction time is 0.5-5 hours; preferably, it is 1 to 3 hours.
In the step (2), the mass ratio of the prepolymer, the hydrogenated castor oil and the catalyst 2 is as follows: 1: 0.0015-0.0291: 0.00001-0.0012; preferably, the ratio is 1: (0.0073-0.0291): (0.0007-0.0012).
In the step (2), the catalyst 2 is selected from one or more of dibutyltin dilaurate DBTDL, stannous octoate, organic bismuth and a tin-bismuth mixed catalyst; preferably, DBTDL.
In the step (2), the reaction temperature is 50-130 ℃; preferably, the temperature is 80-100 ℃.
In the step (2), the reaction time is 0.5-5 hours; preferably, it is 1 to 3 hours.
In the step (3), the hydrogenated castor oil branched PU prepolymer, the end capping reagent alcohol or the end capping monoamine and the catalyst 3 are in the following mass ratio: 1: 0.0016-0.14: 0.00020-0.0018.
In the step (3), the end capping reagent alcohol is selected from CnH2n+1OH branched monoalcohols and linear CH3-(CH2)n-OH; wherein, the CnH2n+1OH is isotridecyl alcohol, isohexadecyl alcohol, isooctadecyl alcohol, etc.; the CH3-(CH2)n-OH is dodecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, octadecyl alcohol, etc., and n is 11-28.
In the step (3), the catalyst 3 is selected from one or more of dibutyltin dilaurate DBTDL, stannous octoate, organic bismuth and a tin-bismuth mixed catalyst; preferably, DBTDL.
In the step (3), the reaction temperature is 50-130 ℃; preferably, the temperature is 80-100 ℃.
In the step (3), the reaction time is 0.5-5 hours; preferably, it is 1 to 3 hours.
Or the like, or, alternatively,
the method specifically comprises the following steps:
(1') adding polyethylene glycol (PEG), diisocyanate and end-capping reagent alcohol or end-capping monoamine into a reactor, and reacting under the action of a catalyst 1 to obtain a prepolymer;
(2') adding hydrogenated castor oil into the prepolymer generated in the step (1), and reacting under the action of a catalyst 2 to obtain the hydrogenated castor oil branched polyurethane associative thickener.
In the step (1'), the mass ratio of the PEG, the blocking agent alcohol or the blocking monoamine, the diisocyanate and the catalyst 1 is as follows: 1: 0.0016-0.14: 0.00108-0.264: 0.00012-0.0024; preferably, the ratio of the total weight of the components is 1 to (0.035-0.076) to (0.055-0.085) to (0.0013-0.0020).
In step (1'), the blocking agent alcohol is selected from CnH2n+1OH branched monoalcohols and linear CH3-(CH2)n-OH; wherein, the CnH2n+1OH is isotridecyl alcohol, isohexadecyl alcohol, isooctadecyl alcohol, etc.; the CH3-(CH2)n-OH is dodecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, octadecyl alcohol, etc., and n is 11-28.
In the step (1'), the catalyst 1 is selected from one or more of dibutyltin dilaurate DBTDL, stannous octoate, organic bismuth and tin-bismuth mixed catalysts; preferably, DBTDL.
In the step (1'), the PEG may have one of molecular weights of 2000 to 30000.
In the step (1'), the isocyanate is selected from one or more of isophorone isocyanate IPDI, hexamethylene diisocyanate HDI, methyl phenyl diisocyanate TDI, dicyclohexyl methane diisocyanate HMDI and the like; preferably IPDI and HDI.
In the step (1'), the reaction temperature is 50-130 ℃; preferably, the temperature is 80-100 ℃.
In the step (1'), the reaction time is 0.5-5 hours; preferably, it is 1 to 3 hours.
In the step (2'), the mass ratio of the prepolymer to the hydrogenated castor oil to the catalyst 2 is 1 to (0.0015-0.0291) to (0.00001-0.0012); preferably, the ratio is 1: (0.0073-0.0291): (0.0007-0.0012).
In the step (2'), the catalyst 2 is selected from one or more of dibutyltin dilaurate DBTDL, stannous octoate, organic bismuth and tin-bismuth mixed catalyst; preferably, DBTDL.
In the step (2'), the reaction temperature is 50-130 ℃; preferably, the temperature is 80-100 ℃.
In the step (2'), the reaction time is 0.5-5 hours; preferably, it is 1 to 3 hours.
Or the like, or, alternatively,
the method specifically comprises the following steps:
(1') adding polyethylene glycol (PEG), hydrogenated castor oil, diisocyanate and end-capping reagent alcohol or end-capping monoamine into a reactor, and reacting under the action of a catalyst 1 to obtain a prepolymer; obtaining the hydrogenated castor oil branched polyurethane associative thickener.
In the step (1'), the mass ratio of the PEG, the hydrogenated castor oil, the blocking agent alcohol or the blocking monoamine, the diisocyanate and the catalyst 1 is as follows: 1: 0.0015-0.0291: 0.0016-0.14: 0.00108-0.264: 0.00012-0.0024; preferably, the ratio of the total weight of the components is 1 to (0.0073-0.0291) to (0.0035-0.076) to (0.055-0.085) to (0.0013-0.002).
In step (1'), the blocking agent alcohol is selected from CnH2n+1OH side chain onePolyhydric alcohol and straight-chain CH3-(CH2)n-OH; wherein, the CnH2n+1OH is isotridecyl alcohol, isohexadecyl alcohol, isooctadecyl alcohol, etc.; the CH3-(CH2)n-OH is dodecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, octadecyl alcohol, etc., and n is 11-28.
In the step (1'), the catalyst 1 is selected from one or more of dibutyltin dilaurate DBTDL, stannous octoate, organic bismuth and tin-bismuth mixed catalysts; preferably, DBTDL.
In the step (1'), the PEG may have one of molecular weights of 2000 to 30000.
In the step (1'), the isocyanate is selected from one or more of isophorone isocyanate IPDI, hexamethylene diisocyanate HDI, methyl phenyl diisocyanate TDI, dicyclohexyl methane diisocyanate HMDI and the like; preferably IPDI and HDI.
In the step (1'), the reaction temperature is 50-130 ℃; preferably, the temperature is 80-100 ℃.
In the step (1'), the reaction time is 0.5-5 hours; preferably, it is 1 to 3 hours.
In one embodiment, the preparation method of the hydrogenated castor oil branched polyurethane associative thickener (HCO-HEUR thickener) comprises the following steps:
the first step is as follows: prepolymerization reaction: adding polyethylene glycol (PEG) into a four-neck flask, heating until materials are completely melted, heating and vacuumizing, cooling after 0-5 hours, stopping vacuumizing, adding diisocyanate, stirring and mixing, adding a polyurethane reaction catalyst 1 (such as DBTDL), reacting at the constant temperature of 50-130 ℃ for 0.5-5 hours, sampling to determine the NCO value of a prepolymer, and carrying out the next reaction after the NCO content reaches 1.20% -1.32%;
the second step is that: branching reaction (addition of hydrogenated castor oil): adding hydrogenated castor oil to react with NCO in the prepolymer generated in the first step under the action of a catalyst 2 (such as DBTDL) at a constant temperature of 50-130 ℃, sampling and determining an NCO value after reacting for 0.5-5 hours, and obtaining a hydrogenated castor oil branched PU prepolymer after the NCO content reaches 0.8% -1.20%;
the third step: end capping reaction: adding end capping reagent alcohol, stirring and mixing, adding a catalyst 3 (such as DBTDL), reacting at the constant temperature of 50-130 ℃ for 0.5-5 hours, and sampling to determine the residual value of NCO in the product; and after the NCO content reaches a preset value of 0-0.03%, terminating the reaction to obtain the hydrogenated castor oil branched polyurethane associated thickener.
After the third reaction step, when using a hydrogenated castor oil branched polyurethane associative thickener, a mixing step is required: adding a solvent (such as ethylene glycol monobutyl ether and the like) and deionized water into the hydrogenated castor oil branched polyurethane associative thickener, uniformly stirring, and cooling to obtain the HCO-HEUR6(bY) -M containing the hydrogenated castor oil branched polyurethane associative thickener with the solid content of about 20-70%.
The hydrogenated castor oil branched polyurethane associative thickener comprises the following components in percentage by mass: 1: 0-4.0.
Wherein, the solvent can be one of ethylene glycol butyl ether, diethylene glycol butyl ether or ethylene glycol dibutyl ether.
The invention also provides the hydrogenated castor oil branched polyurethane associative thickener prepared by the method.
The invention also provides application of the hydrogenated castor oil branched polyurethane associative thickener in the fields of wood paint, wall paint, metal paint, anticorrosive paint, leather paint, paper coating, stone paint, wood grain paper, adhesive and the like.
The hydrogenated castor oil branched polyurethane associative thickener takes polyethylene glycol as a core in structure, firstly isocyanate is connected to two ends of the polyurethane associative thickener, secondly hydrogenated castor oil branching is introduced, and finally hydrophobic end groups are connected, so that the polyurethane associative thickener is more beneficial to the design of hydrophilic and hydrophobic molecules and has the following advantages in structure:
the molecular structure is simple, and polyethylene glycol with different lengths can be adopted, so that different hydrophilicities are realized. The isocyanate has diverse choices, and can be introduced into various kinds of phenylene diisocyanate and the like, thereby realizing different associative thickening effects. By adopting hydrogenated castor oil for branching, the branching degree can be controlled by the addition amount of the castor oil. The hydrogenated castor oil has rich source, low price, no toxicity or pollution and environmental protection. The end capping agent has diversity, and any compound with hydroxyl or amine can be introduced to realize different associative thickening effects. The thickening agent can thicken waterborne polyurethane, waterborne polyacrylate, waterborne epoxy resin, waterborne styrene-acrylic emulsion and the like. The thickening agent can be used for thickening wood paint, wall paint, metal paint, anticorrosive paint, leather paint, paper coating, real stone paint, wood grain paper and various adhesives. When the amount of the thickening water of the high molecular polyurethane thickener is 2.8 percent, the viscosity of the water is increased from 0.8mPa.S at room temperature to 5000mPa.S, the thickening is 6250 times, and the effect is obvious. The viscosity of the thickened water-based paint is 3mPa.S, when the using amount of the thickener is 1.5%, the thickened water-based paint is 36000mPa.S, the thickened water-based paint is 12000 times, and the effect is obvious.
The preparation method has the advantages that organic bismuth can be used for replacing organotin catalysis, and green and environment-friendly effects can be further realized. The water-based thickener is nontoxic, pollution-free and green. The hydrophobic end-capping structure with single functionality is derived from one or more of dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, 1-dodecylalcohol, 1-tetradecanol, 1-hexadecanol, 2-butyloctanol, 2-hexyldecanol, octadecanol, octacosanol and isomeric eicosanol.
Drawings
FIG. 1 nuclear magnetism of hydrogenated Castor oil branched polyurethane associative thickener of example 1 (P6-IP-20% -C16)1H NMR spectrum.
FIG. 2 is an IR spectrum of a hydrogenated castor oil branched polyurethane associative thickener of example 1 (P6-IP-20% -C16).
FIG. 3 is a gel chromatography GPC chart of the hydrogenated castor oil branched polyurethane associative thickener of example 1 (P6-IP-20% -C16).
FIG. 4 is a graph of the emulsion dynamic shear of the hydrogenated castor oil branched polyurethane associative thickener of example 1 (P6-IP-20% -C16).
FIG. 5 is a leveling test of the hydrogenated castor oil branched polyurethane associative thickener of example 1 (P6-IP-20% -C16).
FIG. 6 is nuclear magnetic spectrum of castor oil branched polyurethane associative thickener synthesized by different examples.
FIG. 7 is an infrared spectrum of a castor oil branched polyurethane associative thickener synthesized according to various examples.
FIG. 8 is a GPC chart of castor oil branched polyurethane associative thickeners synthesized in various examples.
FIG. 9 is a rheological profile of the thickening water of the castor oil branched polyurethane associative thickeners synthesized in the various examples.
Different hydrogenated castor oil branching percentages (a) bC 13; (b) bC 16; (c) bC18 capped HEUR in water (a) 4%; (b)2.2 percent; (c) rheological hysteresis curves at 1.6% concentration.
FIG. 10 is a rheological profile of a thickened emulsion of a castor oil branched polyurethane associative thickener synthesized in various examples.
In the emulsion system, the hydrophobic ends with different branching percentages are (a) bC 13; (b) bC 16; (c) bC 18L/H6 (bY) -M at (a) 3%; (b)2.5 percent; (c) the rheological hysteresis curves at 1.5% concentration and the rheological hysteresis curves at different concentrations of the aqueous solution of a nuclear thickener of hydrogenated castor oil branched polyurethane with a degree of branching of 20% (note: the rheological curves of L/H6(b16) and L/H6(b18) at the same concentration are shown in figures (b ') and (c'), respectively).
FIG. 11 is a horizontal flow chart of a thickened emulsion of a castor oil branched polyurethane associative thickener synthesized in different examples.
The hydrophobic ends for percent branching are (a') bC 13; (b') bC 16; (c') L/H6(bY) -M of bC18 at 3% of (a); (b)2.5 percent; (c) leveling test results at 1.5% concentration. The results show that the formula of the synthesized polyurethane thickener can be selected according to the application, and the dosage can be adjusted to achieve the coating with leveling and sagging balance.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples and the accompanying drawings. The procedures, conditions, experimental methods and the like for carrying out the present invention are general knowledge and common general knowledge in the art except for the contents specifically mentioned below, and the present invention is not particularly limited.
Example 1 preparation of P6-IP-20% -C16
The invention provides a preparation method of a hydrogenated castor oil branched polyurethane associative thickener P6-IP-20% -C16, which specifically comprises the following operation steps:
(1) prepolymerization reaction: adding 200g of PEG6000 into a four-neck flask with a mechanical stirring device, a thermometer, a vacuumizing port and a charging port, heating to 50-60 ℃, heating to 120 ℃ after materials are completely melted, vacuumizing, keeping the vacuum degree below 0.095MPa, and cooling to 90 ℃ after 2 hours (keeping vacuum); stopping vacuumizing, adding 15g of IPDI, stirring and mixing for 15min, adding 0.28g of DBTDL, reacting for 2h at constant temperature, and sampling to determine the NCO value of the prepolymer; when the NCO content is below 1.32 percent to obtain a prepolymer, carrying out the next reaction;
the mass ratio of PEG6000 to IPDI to DBTDL is as follows: 1: 0.075: 0.0014.
(2) Branching reaction (addition of hydrogenated castor oil): adding 6.27g of hydrogenated castor oil and a part (20%) of the total NCO amount in the prepolymer to react under the action of 0.25g of catalyst DBTDL, sampling and determining the NCO value after reacting for 0.5-1h, and carrying out the next reaction when the NCO content is below 1.20% to obtain a hydrogenated castor oil branched PU prepolymer;
the mass ratio of the prepolymer to the hydrogenated castor oil to the DBTDL is as follows: 1: 0.0291: 0.0012.
(3) End capping reaction: after the preset value is reached, adding 10.05g of end-capping reagent alcohol (bC16), stirring for 15min, adding 0.34g of DBTDL, reacting for 2h at constant temperature, and sampling to determine the NCO residual value in the product; when the NCO content is below 0.03 percent, the reaction is terminated to obtain the hydrogenated castor oil branched polyurethane thickener;
the mass ratio of the hydrogenated castor oil branched PU prepolymer to the end capping reagent alcohol to the DBTDL is as follows: 1: 0.0453: 0.0015.
(4) Mixing: adding 165g of ethylene glycol butyl ether into the hydrogenated castor oil branched polyurethane associative thickener, adding 165g of deionized water, uniformly stirring, and cooling to below 40 ℃ to obtain HCO-HEUR6(bY) -M containing the hydrogenated castor oil branched polyurethane associative thickener, wherein Y is 16 and represents bC16, and the solid content is measured to be 39.17%. M is 20% and represents the calculated percentage of NCO participating in the branching reaction.
The mass ratio of the hydrogenated castor oil polyurethane associative thickener to the ethylene glycol monobutyl ether to the deionized water is as follows: 1: 0.711.
Example 2 preparation of P6-IP-5% -C16
The invention provides a preparation method of a hydrogenated castor oil branched polyurethane associative thickener P6-IP-5% -C16, which specifically comprises the following operation steps:
(1) prepolymerization reaction: adding 200g of PEG6000 into a four-neck flask with a mechanical stirring device, a thermometer, a vacuumizing port and a charging port, heating to 50-60 ℃, heating to 120 ℃ after materials are completely melted, vacuumizing, keeping the vacuum degree below 0.095MPa, and cooling to 90 ℃ after 2 hours (keeping vacuum); stopping vacuumizing, adding 15g of IPDI, stirring and mixing for 15min, adding 0.26g of DBTDL, reacting for 2h at constant temperature, and sampling to determine the NCO value of the prepolymer; when the NCO content is below 1.32%, carrying out the next reaction;
the mass ratio of PEG6000 to IPDI to DBTDL is as follows: 1: 0.075: 0.0013.
(2) Branching reaction (addition of hydrogenated castor oil): adding 1.58g of hydrogenated castor oil and a part (5%) of NCO total amount in the prepolymer to react under the action of 0.18g of catalyst DBTDL, sampling and determining an NCO value after reacting for 0.5-1h, and obtaining hydrogenated castor oil branched PU prepolymer to carry out the next reaction when the NCO content is below 1.20%;
the mass ratio of the prepolymer to the hydrogenated castor oil to the DBTDL is as follows: 1: 0.0073: 0.0008.
(3) End capping reaction: after the preset value is reached, adding 14.92g of end-capping reagent alcohol (bC16), stirring for 15min, adding 0.32g of DBTDL, reacting for 2h at constant temperature, and sampling to determine the NCO residual value in the product; when the NCO content is below 0.03 percent, the reaction is terminated to obtain the hydrogenated castor oil branched polyurethane associative thickener;
the mass ratio of the hydrogenated castor oil branched PU prepolymer to the end capping reagent alcohol to the DBTDL is as follows: 1: 0.0687: 0.0014
(4) Mixing: adding 165g of ethylene glycol butyl ether into the hydrogenated castor oil branched polyurethane associative thickener, adding 165g of deionized water, uniformly stirring, and cooling to below 40 ℃ to obtain HCO-HEUR6(bY) -M containing the castor oil branched polyurethane associative thickener with the measured solid content of 39.09%, wherein Y is 16 and respectively represents bC 16. M is 5% and represents the calculated percentage of NCO participating in the branching reaction.
The hydrogenated castor oil branched polyurethane associative thickener, the ethylene glycol butyl ether and the deionized water have the mass ratio of: 1: 0.710
Example 3 preparation of P6-IP-5% -C13
The invention provides a preparation method of a hydrogenated castor oil branched polyurethane associative thickener P6-IP-5% -C13, which specifically comprises the following operation steps:
(1) prepolymerization reaction: adding 200g of PEG6000 into a four-neck flask with a mechanical stirring device, a thermometer, a vacuumizing port and a charging port, heating to 50-60 ℃, heating to 120 ℃ after materials are completely melted, vacuumizing, keeping the vacuum degree below 0.095MPa, and cooling to 90 ℃ after 2 hours (keeping vacuum); stopping vacuumizing, adding 15g of IPDI, stirring and mixing for 15min, adding 0.39g of DBTDL, reacting for 2h at constant temperature, and sampling to determine the NCO value of the prepolymer; when the NCO content is below 1.32 percent to obtain a prepolymer, carrying out the next reaction;
the mass ratio of PEG6000 to IPDI to DBTDL is as follows: 1: 0.075: 0.0020.
(2) Branching reaction (addition of hydrogenated castor oil): adding 1.58g of hydrogenated castor oil and a part (5%) of NCO total amount in the prepolymer to react under the action of 0.24g of catalyst DBTDL, sampling and determining an NCO value after reacting for 0.5-1h, and obtaining hydrogenated castor oil branched PU prepolymer to carry out the next reaction when the NCO content is below 1.20%;
the mass ratio of the prepolymer to the hydrogenated castor oil to the DBTDL is as follows: 1: 0.0073: 0.0011.
(3) End capping reaction: after the preset value is reached, adding 10.54g of end-capping reagent alcohol (bC13), stirring for 15min, adding 0.30g of DBTDL, reacting for 2h at constant temperature, and sampling to determine the NCO residual value in the product; hydrogenated castor oil branched polyurethane associative thickeners terminating the reaction when the NCO content is below 0.03%;
the mass ratio of the hydrogenated castor oil branched PU prepolymer to the end capping reagent alcohol to the DBTDL is as follows: 1: 0.048: 0.0013.
(4) Mixing: adding 165g of ethylene glycol butyl ether into the hydrogenated castor oil branched polyurethane associative thickener, adding 165g of deionized water, uniformly stirring, and cooling to below 40 ℃ to obtain HCO-HEUR6(bY) -M containing the castor oil branched polyurethane associative thickener, wherein the measured solid content is 38.98%, and Y is 13 and respectively represents bC 13. M is 5% and represents the calculated percentage of NCO participating in the branching reaction.
The mass ratio of the hydrogenated castor oil polyurethane associative thickener to the ethylene glycol monobutyl ether to the deionized water is as follows: 1: 0.722.
Example 4 preparation of P6-IP-10% -C16
The invention provides a preparation method of a hydrogenated castor oil branched polyurethane associative thickener P6-IP-10% -C16, which specifically comprises the following operation steps:
(1) prepolymerization reaction: adding 200g of PEG6000 into a four-neck flask with a mechanical stirring device, a thermometer, a vacuumizing port and a charging port, heating to 50-60 ℃, heating to 120 ℃ after materials are completely melted, vacuumizing, keeping the vacuum degree below 0.095MPa, and cooling to 90 ℃ after 2 hours (keeping vacuum); stopping vacuumizing, adding 15g of IPDI, stirring and mixing for 15min, adding 0.35g of DBTDL, reacting for 2h at constant temperature, and sampling to determine the NCO value of the prepolymer; when the NCO content is below 1.32 percent to obtain a prepolymer, carrying out the next reaction;
the mass ratio of PEG6000 to IPD1 to DBTDL is as follows: 1: 0.075: 0.0018.
(2) Branching reaction (addition of hydrogenated castor oil): adding 3.2g of hydrogenated castor oil and a part (10%) of the total NCO amount in the prepolymer to react under the action of 0.20g of catalyst DBTDL, sampling and determining the NCO value after reacting for 0.5-1h, and obtaining hydrogenated castor oil branched PU prepolymer to carry out the next reaction when the NCO content is below 1.20%;
the mass ratio of the prepolymer to the hydrogenated castor oil to the DBTDL is as follows: 1: 0.1486: 0.0009.
(3) End capping reaction: after the preset value is reached, adding 12.3g of end-capping reagent alcohol (bC16), stirring for 15min, adding 0.30g of DBTDL, reacting for 2h at constant temperature, and sampling to determine the NCO residual value in the product; when the NCO content is below 0.03 percent, the reaction is terminated to obtain the hydrogenated castor oil branched polyurethane associative thickener;
the mass ratio of the hydrogenated castor oil branched PU prepolymer to the end capping reagent alcohol to the DBTDL is as follows: 1: 0.0562: 0.0014.
(4) Mixing: adding 165g of ethylene glycol butyl ether into the hydrogenated castor oil branched polyurethane associative thickener, adding 165g of deionized water, uniformly stirring, and cooling to below 40 ℃ to obtain HCO-HEUR6(bY) -M containing the hydrogenated castor oil branched polyurethane associative thickener, wherein the measured solid content is 38.8%, and Y is 16 and respectively represents bC 16. M is 10% and represents the calculated percentage of NCO participating in the branching reaction.
The mass ratio of the hydrogenated castor oil polyurethane associative thickener to the ethylene glycol monobutyl ether to the deionized water is as follows: 1: 0.713.
Example 5 preparation of P6-IP-10% -C13
The invention provides a preparation method of a hydrogenated castor oil branched polyurethane associative thickener P6-IP-10% -C13, which specifically comprises the following operation steps:
(1) prepolymerization reaction: adding 200g of PEG6000 into a four-neck flask with a mechanical stirring device, a thermometer, a vacuumizing port and a charging port, heating to 50-60 ℃, heating to 120 ℃ after materials are completely melted, vacuumizing, keeping the vacuum degree below 0.095MPa, and cooling to 90 ℃ after 2 hours (keeping vacuum); stopping vacuumizing, adding 15g of IPDI, stirring and mixing for 15min, adding 0.32g of DBTDL, reacting for 2h at constant temperature, and sampling to determine the NCO value of the prepolymer; when the NCO content is below 1.32 percent to obtain a prepolymer, carrying out the next reaction;
the mass ratio of PEG6000 to IPDI to DBTDL is as follows: 1: 0.075: 0.0016.
(2) Branching reaction (addition of hydrogenated castor oil): adding 3.2g of hydrogenated castor oil and a part (10%) of the total NCO amount in the prepolymer to react under the action of 0.21g of catalyst DBTDL, sampling and determining the NCO value after reacting for 0.5-1h, and obtaining hydrogenated castor oil PU prepolymer to carry out the next reaction when the NCO content is less than 1.20%;
the mass ratio of the prepolymer to the hydrogenated castor oil to the DBTDL is as follows: 1: 0.1486: 0.0010.
(3) End capping reaction: after the preset value is reached, adding 11.33g of end-capping reagent alcohol (bC13), stirring for 15min, adding 0.26g of DBTDL, reacting for 2h at constant temperature, and sampling to determine the NCO residual value in the product; when the NCO content is below 0.03 percent, the reaction is terminated to obtain the hydrogenated castor oil branched polyurethane associative thickener;
the mass ratio of the hydrogenated castor oil branched PU prepolymer to the end capping reagent alcohol to the DBTDL is as follows: 1: 0.0518: 0.0012.
(4) Mixing: adding 165g of ethylene glycol butyl ether into the hydrogenated castor oil branched polyurethane associative thickener, adding 165g of deionized water, uniformly stirring, and cooling to below 40 ℃ to obtain HCO-HEUR6(bY) -M containing the castor oil branched polyurethane associative thickener, wherein the measured solid content is 38.84%, and Y is 13 and respectively represents bC 13. M is 10% and represents the calculated percentage of NCO participating in the branching reaction.
The mass ratio of the hydrogenated castor oil polyurethane associative thickener to the ethylene glycol monobutyl ether to the deionized water is as follows: 1: 0.716.
Example 6 preparation of P6-IP-15% -C13
The invention provides a preparation method of a castor oil branched polyurethane associative thickener P6-IP-15% -C13, which specifically comprises the following operation steps:
(1) prepolymerization reaction: adding 200g of PEG6000 into a four-neck flask with a mechanical stirring device, a thermometer, a vacuumizing port and a charging port, heating to 50-60 ℃, heating to 120 ℃ after materials are completely melted, vacuumizing, keeping the vacuum degree below 0.095MPa, and cooling to 90 ℃ after 2 hours (keeping vacuum); stopping vacuumizing, adding 15g of IPDI, stirring and mixing for 15min, adding 0.34g of DBTDL, reacting for 2h at constant temperature, and sampling to determine the NCO value of the prepolymer; when the NCO content is below 1.32 percent to obtain a prepolymer, carrying out the next reaction;
the mass ratio of PEG6000 to IPDI to DBTDL is as follows: 1: 0.075: 0.0017.
(2) Branching reaction (addition of hydrogenated castor oil): adding 4.7g of hydrogenated castor oil and a part (15%) of the total NCO amount in the prepolymer to react under the action of 0.21g of catalyst DBTDL, sampling and determining the NCO value after reacting for 0.5-1h, and obtaining hydrogenated castor oil branched PU prepolymer to carry out the next reaction when the NCO content is below 1.20%;
the mass ratio of the prepolymer to the hydrogenated castor oil to the DBTDL is as follows: 1: 0.0218: 0.0010.
(3) End capping reaction: after the preset value is reached, adding 9.48g of end-capping reagent alcohol (bC13), stirring for 15min, adding 0.35g of DBTDL, reacting for 2h at constant temperature, and sampling to determine the residual value of NCO in the product; when the NCO content is below 0.03 percent, the reaction is terminated to obtain the hydrogenated castor oil branched polyurethane associative thickener;
the mass ratio of the hydrogenated castor oil branched PU prepolymer to the end capping reagent alcohol to the DBTDL is as follows: 1: 0.0430: 0.0016.
(4) Mixing: adding 165g of ethylene glycol butyl ether into the hydrogenated castor oil branched polyurethane associative thickener, adding 165g of deionized water, uniformly stirring, and cooling to below 40 ℃ to obtain HCO-HEUR6(bY) -M containing the hydrogenated castor oil branched polyurethane associative thickener, wherein the measured solid content is 38.92%, and Y is 13 and respectively represents bC 13. M is 15% and represents the calculated percentage of NCO participating in the branching reaction.
The mass ratio of the hydrogenated castor oil polyurethane associative thickener to the ethylene glycol monobutyl ether to the deionized water is as follows: 1: 0.717.
Example 7 preparation of P6-IP-15% -C18
The invention provides a preparation method of a hydrogenated castor oil branched polyurethane associative thickener P6-IP-15% -C18, which specifically comprises the following operation steps:
(1) prepolymerization reaction: adding 200g of PEG6000 into a four-neck flask with a mechanical stirring device, a thermometer, a vacuumizing port and a charging port, heating to 50-60 ℃, heating to 120 ℃ after materials are completely melted, vacuumizing, keeping the vacuum degree below 0.095MPa, and cooling to 90 ℃ after 2 hours (keeping vacuum); stopping vacuumizing, adding 15g of IPDI, stirring and mixing for 15min, adding 0.34g of DBTDL, reacting for 2h at constant temperature, and sampling to determine the NCO value of the prepolymer; when the NCO content is below 1.32 percent to obtain a prepolymer, carrying out the next reaction;
the mass ratio of PEG6000 to IPDI to DBTDL is as follows: 1: 0.075: 0.0017.
(2) Branching reaction (addition of hydrogenated castor oil): adding 4.7g of hydrogenated castor oil and a part (15%) of the total NCO amount in the prepolymer to react under the action of 0.16g of catalyst DBTDL, sampling and determining the NCO value after reacting for 0.5-1h, and obtaining hydrogenated castor oil branched PU prepolymer to carry out the next reaction when the NCO content is below 1.20%;
the mass ratio of the prepolymer to the hydrogenated castor oil to the DBTDL is as follows: 1: 0.0218: 0.0007.
(3) End capping reaction: after the preset value is reached, adding 11.42g of end-capping reagent alcohol (bC18), stirring for 15min, adding 0.39g of DBTDL, reacting for 2h at constant temperature, and sampling to determine the NCO residual value in the product; when the NCO content is below 0.03 percent, the reaction is terminated to obtain the hydrogenated castor oil branched polyurethane associative thickener;
the mass ratio of the hydrogenated castor branched PU prepolymer to the end capping reagent alcohol to the DBTDL is as follows: 1: 0.0519: 0.0018.
(4) Mixing: adding 165g of ethylene glycol butyl ether into the hydrogenated castor oil branched polyurethane associative thickener, adding 165g of deionized water, stirring uniformly, cooling to below 40 ℃, and obtaining HCO-HEUR6(bY) -M containing the hydrogenated castor oil branched polyurethane associative thickener with the measured solid content of 39.07%, wherein Y is 18 and respectively represents bC 18. M is 15% and represents the calculated percentage of NCO participating in the branching reaction.
The mass ratio of the hydrogenated castor oil polyurethane associative thickener to the ethylene glycol monobutyl ether to the deionized water is as follows: 1: 0.711.
Example 8 preparation of P6-IP-5% -C18
The invention provides a preparation method of a hydrogenated castor oil branched polyurethane associative thickener P6-IP-5% -C18, which specifically comprises the following operation steps:
(1) prepolymerization reaction: adding 200g of PEG6000 into a four-neck flask with a mechanical stirring device, a thermometer, a vacuumizing port and a charging port, heating to 50-60 ℃, heating to 120 ℃ after materials are completely melted, vacuumizing, keeping the vacuum degree below 0.095MPa, and cooling to 90 ℃ after 2 hours (keeping vacuum); stopping vacuumizing, adding 15g of IPDI, stirring and mixing for 15min, adding 0.32g of DBTDL, reacting for 2h at constant temperature, sampling to determine the NCO value of the prepolymer, obtaining the prepolymer when the NCO content is below 1.32%, and carrying out the next reaction;
the mass ratio of PEG6000 to IPDI to DBTDL is 1: 0.075: 0.0016.
(2) Branching reaction (addition of hydrogenated castor oil): adding 1.57g of hydrogenated castor oil and a part (5%) of NCO total amount in the prepolymer to react under the action of 0.15g of catalyst stannous zincate, sampling and determining an NCO value after reacting for 0.5-1h, and obtaining hydrogenated castor oil branched PU prepolymer to carry out the next reaction when the NCO content is below 1.20%;
the mass ratio of the prepolymer to the hydrogenated castor oil to the stannous zincate is as follows: 1: 0.0073: 0.0007.
(3) End capping reaction: after the preset value is reached, 16.65g of end-capping reagent alcohol (bC18) is added, the mixture is stirred for 15min, 0.21g of DBTDL is added, the mixture is reacted for 2h at constant temperature, and the residual value of NCO in the product is measured by sampling; when the NCO content is below 0.03 percent, the reaction is terminated to obtain the hydrogenated castor oil branched polyurethane associative thickener;
the mass ratio of the hydrogenated castor oil branched PU prepolymer to the end capping reagent alcohol to the DBTDL is as follows: 1: 0.0767: 0.0010.
(4) Mixing: 170g of ethylene glycol butyl ether is added into the hydrogenated castor oil branched polyurethane associative thickener, 170g of deionized water is added, the mixture is stirred uniformly and cooled to below 40 ℃, and the HCO-HEUR6(bY) -M containing the hydrogenated castor oil branched polyurethane associative thickener with the measured solid content of 37.75 percent is obtained, wherein Y is 18 and represents bC 18. M is 5% and represents the calculated percentage of NCO participating in the branching reaction.
The mass ratio of the hydrogenated castor oil polyurethane associative thickener to the ethylene glycol monobutyl ether to the deionized water is as follows: 1: 0.727.
Example 9 preparation of P12-HDI-20% -C28
The invention provides a preparation method of a hydrogenated castor oil branched polyurethane associative thickener P12-HDI-20% -C28, which comprises the following steps:
(1) prepolymerization reaction: adding 400g of PEG12000 into a four-neck flask with a mechanical stirrer, a thermometer, a vacuumizing port and a charging port, heating to 50-60 ℃, heating to 120 ℃ after materials are completely melted, vacuumizing, keeping the vacuum degree below 0.095MPa, and cooling to 80 ℃ after 2 hours (keeping vacuum); stopping vacuumizing, adding 11g of HDI, stirring and mixing for 15min, adding 0.27g of stannous octoate, reacting for 1h at constant temperature, and sampling to determine the NCO value of the prepolymer; when the NCO content is below 1.32 percent to obtain a prepolymer, carrying out the next reaction;
the mass ratio of PEG12000 to HDI to stannous octoate is as follows: 1: 0.0275: 0.00068.
(2) Branching reaction (addition of hydrogenated castor oil): adding 6.27g of hydrogenated castor oil and a part (20%) of NCO total amount in the prepolymer to react under the action of 0.09g of catalyst stannous octoate, sampling and determining an NCO value after reacting for 0.5-1h, and obtaining hydrogenated castor oil branched PU prepolymer to carry out the next reaction when the NCO content is less than 1.20%;
the mass ratio of the prepolymer to the hydrogenated castor oil to the stannous octoate is as follows: 1: 0.0153: 0.00021.
(3) End capping reaction: after the preset value is reached, adding 13.21g of blocking agent alcohol (bC28), stirring for 15min, adding 0.16g of stannous octoate, reacting for 2h at constant temperature, and sampling to determine the NCO residual value in the product; when the NCO content is below 0.03 percent, the reaction is terminated to obtain the hydrogenated castor oil branched polyurethane associative thickener;
the hydrogenated castor oil branched PU prepolymer, the end capping agent alcohol and the stannous octoate are prepared from the following components in percentage by mass: 1: 0.0316: 0.00038.
(4) Mixing: adding 120g of diethylene glycol butyl ether into the hydrogenated castor oil branched polyurethane associative thickener, adding 165g of deionized water, uniformly stirring, and cooling to below 40 ℃ to obtain HCO-HEUR6(bY) -M containing the hydrogenated castor oil branched polyurethane associative thickener with the measured solid content of 58.4%, wherein Y is 28 and represents bC28 respectively. M is 20% and represents the calculated percentage of NCO participating in the branching reaction.
The mass ratio of the hydrogenated castor oil branched polyurethane associative thickener to the diethylene glycol monobutyl ether to the deionized water is as follows: 1: 0.30: 0.413.
Example 10 preparation of P30-TD-5% -C18
The invention provides a preparation method of a hydrogenated castor oil branched polyurethane associative thickener P30-TD-5% -C18, which specifically comprises the following operation steps:
(1) prepolymerization reaction: adding 1000g of PEG30000 into a four-neck flask with a mechanical stirrer, a thermometer, a vacuumizing port and a charging port, heating to 50-60 ℃, heating to 120 ℃ after materials are completely melted, vacuumizing, keeping the vacuum degree below 0.095MPa, and cooling to 50 ℃ (keeping the vacuum) after 2 hours; stopping vacuumizing, adding 10.8g of TDI, stirring and mixing for 15min, adding 0.12g of organic bismuth, reacting at constant temperature for 2h, sampling to determine the NCO value of the prepolymer, obtaining the prepolymer when the NCO content is below 1.32%, and carrying out the next reaction;
the mass ratio of PEG6000 to TDI to organic bismuth is 1: 0.00108: 0.00012.
(2) Branching reaction (addition of hydrogenated castor oil): adding 1.57g of hydrogenated castor oil and a part (5%) of NCO total amount in the prepolymer to react under the action of 0.01g of catalyst organic bismuth, sampling and determining an NCO value after reacting for 0.5-1h, and obtaining hydrogenated castor oil branched PU prepolymer to carry out the next reaction when the NCO content is below 1.20%;
the mass ratio of the prepolymer to the hydrogenated castor oil to the organic bismuth is as follows: 1: 0.0015: 0.00001.
(3) End capping reaction: after the preset value is reached, 16.65g of end-capping reagent alcohol (bC18) is added, the mixture is stirred for 15min, 0.02g of organic bismuth is added, the mixture is reacted for 2h at constant temperature, and the residual value of NCO in the product is measured by sampling; when the NCO content is below 0.03 percent, the reaction is terminated to obtain the hydrogenated castor oil branched polyurethane associative thickener;
the mass ratio of the hydrogenated castor oil branched PU prepolymer to the end capping reagent alcohol to the organic bismuth is as follows: 1: 0.0016: 0.0002.
(4) Mixing: adding 500g of ethylene glycol butyl ether into the hydrogenated castor oil branched polyurethane associative thickener, adding 1000g of deionized water, stirring uniformly, cooling to below 40 ℃, and obtaining HCO-HEUR6(bY) -M containing the hydrogenated castor oil branched polyurethane associative thickener with the measured solid content of 40%, wherein Y is 18 and represents bC 18. M is 5% and represents the calculated percentage of NCO participating in the branching reaction.
The mass ratio of the hydrogenated castor oil polyurethane associative thickener to the ethylene glycol monobutyl ether to the deionized water is as follows: 1: 0.5: 0.97.
Example 11 preparation of P2-HMDI-5% -C12
The invention provides a preparation method of a hydrogenated castor oil branched polyurethane associative thickener P2-HMDI-5% -C12, which specifically comprises the following operation steps:
(1) prepolymerization reaction: adding 67g of PEG2000 into a four-neck flask with a mechanical stirring device, a thermometer, a vacuumizing port and a charging port, heating to 50-60 ℃, heating to 120 ℃ after materials are completely melted, vacuumizing, keeping the vacuum degree below 0.095MPa, and cooling to 80 ℃ after 2 hours (keeping vacuum); stopping vacuumizing, adding 17.7g of HMDI, stirring and mixing for 15min, adding 0.16g of organic bismuth, reacting for 2h at constant temperature, sampling to determine the NCO value of the prepolymer, obtaining the prepolymer when the NCO content is below 1.32%, and carrying out the next reaction;
the mass ratio of PEG2000 to HMDI to organic bismuth is 1: 0.264: 0.0024.
(2) Branching reaction (addition of hydrogenated castor oil): adding 1.57g of hydrogenated castor oil and a part (5%) of NCO total amount in the prepolymer to react under the action of 0.08g of catalyst organic bismuth, sampling and determining an NCO value after reacting for 0.5-1h, and obtaining hydrogenated castor oil branched PU prepolymer to carry out the next reaction when the NCO content is below 1.20%;
the mass ratio of the prepolymer to the hydrogenated castor oil to the organic bismuth is as follows: 1: 0.0196: 0.001.
(3) End capping reaction: after the preset value is reached, adding 11.5g of end-capping reagent alcohol (C12), stirring for 15min, adding 0.11g of organic bismuth, reacting for 2h at constant temperature, and sampling to determine the NCO residual value in the product; when the NCO content is below 0.03 percent, the reaction is terminated to obtain the hydrogenated castor oil branched polyurethane associative thickener;
the mass ratio of the hydrogenated castor oil branched PU prepolymer to the end capping reagent alcohol to the organic bismuth is as follows: 1: 0.14: 0.0014.
(4) Mixing: adding 25g of ethylene glycol butyl ether into the hydrogenated castor oil branched polyurethane associative thickener, adding 50g of deionized water, stirring uniformly, and cooling to below 40 ℃ to obtain HCO-HEUR6(bY) -M containing the hydrogenated castor oil branched polyurethane associative thickener, wherein Y is 18 and represents bC18, and the measured solid content of the HCO-HEUR6(bY) -M is 49.75%. M is 5% and represents the calculated percentage of NCO participating in the branching reaction.
The mass ratio of the hydrogenated castor oil polyurethane associative thickener to the ethylene glycol monobutyl ether to the deionized water is as follows: 1: 0.31: 0.625.
Example 12 one-pot preparation of P6-IP-20% -C16
The invention provides a preparation method of a hydrogenated castor oil branched polyurethane associative thickener P6-IP-20% -C16, which specifically comprises the following operation steps:
in order to further shorten the experimental steps, a one-pot method is adopted to prepare the hydrogenated castor oil branched polyurethane associative thickener
(1) Adding 200g of PEG6000 into a four-neck flask with a mechanical stirring device, a thermometer, a vacuumizing port and a charging port, heating to 50-60 ℃, heating to 120 ℃ after materials are completely melted, vacuumizing, keeping the vacuum degree below 0.095MPa, and cooling to 90 ℃ after 2 hours (keeping vacuum); the vacuum was stopped and 6.27g of hydrogenated castor oil, 10.05g of blocking agent alcohol (bC16) were added and stirred well. Adding 15g of IPDI, stirring and mixing for 15min, adding 0.28g of DBTDL, reacting for 2h at constant temperature, sampling and determining NCO value; stopping the reaction when the NCO content is below 0.03 percent to obtain the hydrogenated castor oil branched polyurethane associative thickener;
the mass ratio of PEG6000 to hydrogenated castor oil to end capping reagent alcohol to IPDI to DBTDL is as follows: 1: 0.03135: 0.05025: 0.075: 0.0014.
(2) Mixing: adding 165g of ethylene glycol butyl ether into the hydrogenated castor oil branched polyurethane associative thickener, adding 165g of deionized water, uniformly stirring, and cooling to below 40 ℃ to obtain HCO-HEUR6(bY) -M containing the hydrogenated castor oil branched polyurethane associative thickener, wherein Y is 16 and represents bC16, and the solid content is measured to be 39.17%. The degree of branching M was 20%, representing the calculated percentage of NCO participating in the branching reaction.
Example 13 two-step preparation of P6-IP-20% -C16
The invention provides a preparation method of a hydrogenated castor oil branched polyurethane associative thickener P6-IP-20% -C16, which specifically comprises the following operation steps:
in order to further shorten the experimental steps, a two-step method is adopted to prepare the hydrogenated castor oil branched polyurethane associative thickener
(1) Prepolymerization reaction: adding 200g of PEG6000 into a four-neck flask with a mechanical stirring device, a thermometer, a vacuumizing port and a charging port, heating to 50-60 ℃, heating to 120 ℃ after materials are completely melted, vacuumizing, keeping the vacuum degree below 0.095MPa, and cooling to 90 ℃ after 2 hours (keeping vacuum); the vacuum was stopped and 10.05g of the blocking agent alcohol (bC16) was stirred well.
Adding 15g of IPDI, stirring and mixing for 15min, adding 0.28g of tin-bismuth mixed catalyst, reacting for 2h at constant temperature, and sampling to determine the NCO value of the prepolymer; when the NCO content is below 0.12 percent to obtain a prepolymer, carrying out the next reaction;
the mass ratio of PEG6000 to the end capping reagent alcohol to the IPDI to the tin bismuth mixed catalyst is as follows: 1: 0.05025: 0.075: 0.0014.
(2) Branching reaction (addition of hydrogenated castor oil): adding 6.27g of hydrogenated castor oil and a part (20%) of the total NCO amount in the prepolymer to react under the action of 0.25g of a tin-bismuth mixed catalyst, sampling and determining the NCO value after reacting for 0.5-1h, wherein the NCO content is less than 0.020%, and obtaining the hydrogenated castor oil branched polyurethane associative thickener;
the mass ratio of the prepolymer to the hydrogenated castor oil to the tin bismuth mixed catalyst is as follows: 1: 0.0291: 0.0012.
(3) Mixing: adding 165g of ethylene glycol butyl ether into the hydrogenated castor oil branched polyurethane associative thickener, adding 165g of deionized water, uniformly stirring, and cooling to below 40 ℃ to obtain HCO-HEUR6(bY) -M containing the hydrogenated castor oil branched polyurethane associative thickener, wherein Y is 16 and represents bC16, and the solid content is measured to be 39.17%. M is 20% and represents the calculated percentage of NCO participating in the branching reaction.
The mass ratio of the hydrogenated castor oil polyurethane associative thickener to the ethylene glycol monobutyl ether to the deionized water is as follows: 1: 0.711.
It should be noted that, since the invention cannot exhaust all experiments, when the preparation method of the invention is implemented, the hydrogenated castor oil branched polyurethane associative thickener with high thickening efficiency and good storage stability can be obtained as long as the raw materials, the catalyst 1-5, the blocking agent alcohol, the reaction temperature, the reaction time, the material ratio and the like are within the scope of the protection of the claims of the invention.
Polymer label english abbreviation description: HCO-HEUR6(bY) -M, where Y is 13, 16 and 18, representing bC13, bC16 and bC18 isomeric alcohols, respectively. M is 5%, 10%, 15% and 20%, representing the percentage of NCO that participates in the branching reaction of hydrogenated castor oil. HEUR6 represents polyurethane synthesized from PEG 6000. HCO stands for hydrogenated castor oil.
P6-IP-20% -bC16 represents the starting materials PEG6000, IPDI, bC16, 20% represents the percentage of NCO used up with the hydrogenated castor oil which participates in the branching reaction and the percentage of NCO used up with the monoalcohol capping agent.
Application example 1 application of the hydrogenated castor oil branched polyurethane associative thickener synthesized in example 1 of the present invention:
preparation of HCO-HEUR6(bY) -M thickening aqueous solution
Adding calculated amount of HCO-HEUR6(bY) -M into deionized water (viscosity of 0.8mPa.S), stirring at room temperature for 20min or more to disperse HCO-HEUR6(bY) -M in water solution uniformly to obtain mass fraction
HCO-HEUR6(bY) -M aqueous solutions in various ratios (0.5%, 1%, 1.6%, 2.2%, 4%).
TABLE 1 thickener solids content and Water number
The thickened water curve is shown in figure 9: the viscosity of water is 0.8mpa.s and is newtonian fluid. In FIG. 9(b), the% in the graph represents the% NCO content of the hydrogenated castor oil reaction. HCO-HEUR6(b16) -M aqueous solution with the thickener dosage of 2.2 percent shows shear thinning behavior and obvious thixotropy. In thatIs 4s-1The viscosity values of 1600mPa.S of HCO-HEUR6(b16) -10% (example 4) are still the highest, but the thixotropy is also the greatest. In thatIs 4s-1HCO-HEUR6(b16) -20% viscosity value of 980 mPa.S; in thatIs 200s-1When the viscosity value of HCO-HEUR6(b16) -20% (example 1) with the branching degree is maximum, the high shear viscosity of 600mPa.S can be maintained. HCO-HEUR6(b16) -5% (example 2) inIs 4s-1The viscosity was 970 mpa.s.
Similarly, in FIG. 9(c), a 1.6% HCO-HEUR6(b18) aqueous solution exhibited shear thinning behavior with marked thixotropy. In thatIs 4s-1When the viscosity value is highest, the thixotropy is also highest when HCO-HEUR6(b18) -20 percent is highest; in thatIs 200s-1The viscosity of HCO-HEUR6(b18) -M of different degrees of branching is substantially equal in magnitude. HCO-HEUR6(b18) -5% (example 8) and HCO-HEUR6(b18) -15% (example 7) all have viscosities much higher than that of water and are thixotropic fluids which aid in storage after thickening, and shear thinning and leveling when rolling, spreading and brushing.
In FIG. 9(a), HCO-HEUR6(b13) -5% (example 3), HCO-HEUR6(b13) -10% (example 5), and HCO-HEUR6(b13) -20% all had viscosities greater than the viscosity of water.
The overall viscosity was 500 to 1700mpa.s, a 625-fold increase 2125-fold over water.
Formulation of HCO-HEUR6(bY) -M thickened emulsions
Adding 300g of emulsion (viscosity of 3mPa.S) into a beaker, adding calculated amount of HCO-HEUR6(bY) -M, stirring at room temperature for 20min to uniformly disperse HCO-HEUR6(bY) -M in the emulsion to obtain HCO-HEUR6(bY) -M mass fraction
Different proportions (0.5%, 1%, 1.5%, 2.5%, 3%) of the thickened emulsion Latex/HCO-HEUR6(bY) -M, abbreviated to L/H6(bY) -M.
TABLE 2 thickener solids content and emulsion fraction
The rheological curves of the thickened emulsions are shown in FIG. 4 and FIG. 10.
FIG. 10: L/H6(bY) -M thickened emulsion rheology curves at different hydrogenated castor oil reaction NCO branching percentages (5%, 10%, 15%, 20%) in emulsion systems
(b) L/H6(b C16) -M, rheological hysteresis curve at 2.5% strength;
(c) rheological hysteresis curves at 1.5% concentration of L/H6(b C18) -M;
(a) L/H6(b C13) -M, using amount is 3%; rheological hysteresis curve at concentration
(Note: FIGS. (b ') and (c') are the rheological curves of L/H6(b16) and L/H6(b18), respectively, at the same concentration)
The viscosity of the emulsion is 3mPa.S, and the viscosity of the paint thickened by the thickener is 2600 to 36000mPa.S, which is 867-12000 times increased.
The protection of the present invention is not limited to the above embodiments. Variations and advantages that may occur to those skilled in the art may be incorporated into the invention without departing from the spirit and scope of the inventive concept, and the scope of the appended claims is intended to be protected.
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