CN112961320B - Polyethylene glycol bridged star-linked structure polyurethane thickener and preparation method thereof - Google Patents
Polyethylene glycol bridged star-linked structure polyurethane thickener and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an associated polyurethane thickener used in the processing fields of water-based paint, textile printing, water-based resin coating and the like, and discloses a polyethylene glycol bridged star-linked structure polyurethane thickener and a preparation method thereof. The method comprises the following steps: preparing raw materials; active prepolymerization; active end capping; grafting and bridging; and (5) finishing. In the invention, the thickening agent molecule has a central branch structure taking short-chain polyether as a framework, secondary branching is carried out at the tail end of each central branch, and a plurality of long-chain polyether chain links and hydrophobic association alkyl long chains are grafted to form a complex star structure; and a small amount of bifunctional long-chain polyether is used for partially bridging the complex star structure to form a bridged star structure of the polyurethane thickener. The thickening capacity is improved by the larger framework structure and the higher content of polyether chain links, and the using amount is less; the 'remote claw type' hydrophobic association structure effectively inhibits intramolecular association of the thickener, strengthens the intermolecular association effect of the thickener and has stronger thickening capability on dilute solution.
Description
Technical Field
The invention relates to an associated polyurethane thickener used in the processing fields of water-based paint, textile printing, water-based resin coating and the like, in particular to a polyethylene glycol bridged star-linked structure polyurethane thickener and a preparation method thereof.
Background
The associative polyurethane thickener has the advantages of good leveling property, stable viscosity, good comprehensive hand feeling and the like, and can be widely applied to the fields of water-based paint, textile printing, water-based resin coating and the like. However, the linear chain link structure of the common associative polyurethane thickener is small, and although the rheological property is good, the thickening capability is poor; in addition, the linear polyurethane thickener is easy to prepare and has good rheological property, but has poor intermolecular association capacity and low viscosity; the star-shaped polyurethane thickener has stronger intermolecular association and better thickening performance, but has poorer rheological property. Therefore, the method can moderately improve the branching degree of star-shaped polyurethane thickener molecules and introduce long-chain polyether bridging into the molecular structure of the star-shaped polyurethane thickener molecules to form a star-linked structure, so that the advantages of fully exerting and combining the linear structure and the star-shaped structure can be a research hotspot in the related research field in the future. The associative polyurethane thickener based on the prior art and the related technical characteristics thereof are mainly as follows: adopting aliphatic dihydric alcohol with different structures to carry out chain extension on the polyurethane prepolymer and using higher aliphatic monohydric alcohol to carry out end capping on the polyurethane prepolymer so as to obtain a linear structure with double association tail groups; adopting monohydric alcohols with different alkyl chain numbers to carry out end capping on the polyurethane prepolymer so as to obtain a branched structure with multiple association tail groups; and (3) chain extension is carried out on the polyurethane semi-terminated prepolymer by adopting micromolecule trihydric alcohol to prepare the star-shaped aqueous polyurethane associative thickener and the like.
At present, the preparation method of the associative polyurethane thickener comprises the following steps:
1. the preparation method of the side long-chain alkyl modified comb-shaped associative polyurethane thickener comprises the following raw materials of a polymerization monomer, an auxiliary agent and a solvent, wherein: the polymerization monomer comprises isophorone diisocyanate, polyethylene glycol 2000-8000, glycerol monooleate and n-hexadecanol; the auxiliary agent is a polymerization catalyst dibutyltin dilaurate; the solvent was ethyl acetate.
For example, according to a preparation method of a hydrophobic side chain type aqueous polyurethane associative thickener disclosed by "preparation and characterization of a hydrophobic side chain type aqueous polyurethane associative thickener" issued by cailing, zhang soldier, pall et al (No. 1 of 2016, volume 46 of paint industry) ", glycerol monooleate is used as a chain extender, polyethylene glycol is used as a hydrophilic chain segment, isophorone diisocyanate is used as a connection point, and the hydrophobic side chain type aqueous polyurethane associative thickener is synthesized by blocking cetyl alcohol.
The aqueous polyurethane associative thickener prepared by the method has lower critical micelle concentration and less consumption; meanwhile, the self-thickening effect of the thickener can be conveniently adjusted by the length of the hydrophilic segment and the content of the hydrophobic side chain moiety in the molecule thereof. However, due to the lack of strongly hydrophilic ionizable groups in the thickener molecule, the latex particles may be large, the thickening speed is slow and the thickening ability is relatively poor; meanwhile, for the same reason, the hydrophilicity of the thickening agent needs a polyethylene glycol structure with a longer chain link to ensure, so that the molecular weight of the product is higher, the viscosity of a reaction system is higher, and the reaction system is difficult to control; of course, since the thickener is non-ionic, it is structurally disadvantageous to adjust the acid and alkali resistance of the thickener.
2. The preparation method of the end long chain alkyl modified 'branched' associative polyurethane thickener comprises the following raw materials of polymeric monomer, adjuvant and solvent, wherein: the polymeric monomer comprises isophorone diisocyanate, polyethylene glycol 6000, and a monohydric alcohol end capping agent with a plurality of long-chain alkyl groups (C10); the auxiliary agent is a polymerization catalyst dibutyltin laurate; the solvent was toluene.
For example, Pengjun, Lixin, Zhengyanqing and the like, a preparation method of a dendrimer hydrophobically modified polyurethane associative thickener, which is disclosed as the synthesis of the dendrimer hydrophobically modified polyurethane associative thickener and the rheological behavior in emulsion (2016 coating industry, volume 46, 11 th of 2016), adopts end-capping agents with different numbers of hydrophobic tail chains at the tail ends to end-cap a polyurethane prepolymer, and prepares a polyurethane associative thickener with short and more hydrophobic tail groups.
The product has more short and more hydrophobic chains, which is beneficial to increasing the effective network chain density and forming a stronger hydrophobic network structure, so the thickening effect is obviously better than that of the common single hydrophobic tail chain end-capped product. However, because the hydrophobic structures in the product molecules are short and concentrated and of the same length, their "accessibility" to the association of the coating particles is limited; meanwhile, the difference of the main chain structure and the difference of the molecular weight of the thickener molecules are small, so that the association density among the molecules is not uniform enough, namely, the defects of the association structure are relatively concentrated. Therefore, the association structure between the molecules of the thickener is formed at a low speed, and the local association density is relatively high, so that the association is difficult and the application is limited. In addition, the multi-tailed capping agents in this preparation method are difficult to prepare, expensive and difficult to obtain.
3. The preparation method of the end long chain alkyl modified star-shaped associated polyurethane thickener comprises the following raw materials of a polymerization monomer, an auxiliary agent and a solvent, wherein: the polymeric monomer comprises isophorone diisocyanate, polyethylene glycol 6000, hexadecanol, glycerol and trimethylolpropane; the auxiliary agent is a polymerization catalyst dibutyltin dilaurate; the solvent is acetone.
For example, the synthesis and performance of star-shaped aqueous polyurethane associative thickeners, as described in sonzhou, yangjianji, wuqingyun et al (the "fine chemical industry" 34 vol.2017, No. 1), a preparation method of star-shaped aqueous polyurethane associative thickeners is disclosed, wherein isophorone diisocyanate and polyethylene glycol 6000 are reacted to prepare a prepolymer, glycerol or trimethylolpropane is used as a chain extender, and hexadecanol is used as an end-capping agent, so that the star-shaped aqueous polyurethane associative thickeners are prepared.
The viscosity of the star-shaped associative polyurethane thickener prepared by the method is maintained at a higher level during low shear, and the shear thinning phenomenon occurs during higher shear rate, so that the star-shaped associative polyurethane thickener has good thixotropy. However, this "star" associative polyurethane thickener requires the preparation of a semi-blocked monofunctional (monoisocyanate group) monomer in advance. In the preparation of semi-terminated monofunctional monomers, control of the product structure is difficult due to lack of selectivity of the reaction between the groups. Meanwhile, a certain amount of cetyl alcohol double-end-capped structures are inevitably generated in the product structure and accompanied by free cetyl alcohol, so that the thickening agent cannot be fully dissolved or dispersed in a thickening system, and the product quality and the using effect are influenced. In addition, the preparation method has the disadvantages of high viscosity of a reaction system, difficult control of reaction and inconvenience for organizing large-scale production in the middle and later stages of the reaction.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: provides a polyethylene glycol bridged star-linked structure polyurethane thickener and a preparation method thereof. The polyurethane thickener with the star-linked structure and bridged by the polyethylene glycol prepared by the method can be used for waterborne coatings, textile printing, waterborne resin coatings and the like. In the invention, the thickening agent molecule has a central branch structure taking short-chain polyether as a framework, secondary branching is carried out at the tail end of each central branch, and then a plurality of long-chain polyether chain links and hydrophobic association alkyl long chains are grafted sequentially to form a complex star structure of the polyurethane thickening agent; meanwhile, a small amount of bifunctional long-chain polyether is used for partially bridging the complex star structure to form a bridged star structure of the polyurethane thickener. The thickening agent has stronger thickening capability and saves more using amount due to the larger framework structure and the higher content of polyether chain links; the 'remote claw type' hydrophobic association structures on the plurality of branched chains effectively inhibit intramolecular association of the thickener, strengthen intermolecular association of the thickener and have stronger thickening capability on dilute solution.
In order to achieve the above object, the present invention provides a method for preparing a polyethylene glycol-bridged star-linked polyurethane thickener, comprising the steps of:
(1) preparing raw materials: the raw materials contain polymerization monomers, organic solvents, polymerization catalysts and emulsifiers; wherein the polymerization monomer comprises a multifunctional initiator, polyethylene glycol, an active end capping agent, an association end capping agent and a polyether bridging agent;
the multifunctional initiator is 1, 6-hexamethylene diisocyanate trimer;
the polyethylene glycol has a water content not higher than 2 per mill and a molecular weight of 1000-2000;
the active blocking agent is 1, 6-hexamethylene diisocyanate trimer;
the association blocking agent is one of polyethylene glycol monoalkyl esters with water content not higher than 2 ‰, and the polyethylene glycol monoalkyl ester has a chemical formula of HO (C)2H4O)nOCCmH2m+1Wherein n is 100 to 150, m is16～18；
The polyether bridging agent is one of polyethylene glycol with the water content not higher than 2 per thousand and the molecular weight of 2000-3000;
the polymerized monomer comprises the following components in parts by mole: 1 multifunctional initiator, 3 polyethylene glycol, 3.00-3.10 active end capping agent, 4.5-5.5 association end capping agent and 0.3-0.8 polyether bridging agent, wherein (the mole fraction of the association end capping agent plus the mole fraction of the polyether bridging agent multiplied by 2) is 6.0-6.5;
the dosage of the polymerization catalyst is 0.04-0.06 wt% of the total weight of the polymerization monomers;
the using amount of the emulsifier is 1-2 wt% of the total weight of the polymerized monomers;
(2) active prepolymerization: carrying out active prepolymerization reaction on a multifunctional initiator, polyethylene glycol, part of organic solvent and part of polymerization catalyst to prepare a polyethylene glycol-bridged star-linked polyurethane thickener prepolymer;
(3) active end capping: performing active end capping reaction on the polyethylene glycol bridged star-linked structure polyurethane thickener prepolymer, an active end capping agent, a part of organic solvent and a part of polymerization catalyst to prepare a polyethylene glycol bridged star-linked structure polyurethane thickener intermediate;
(4) grafting and bridging: grafting and bridging the intermediate of the polyethylene glycol-bridged star-linked structure polyurethane thickener with an associated end-capping agent, a polyether bridging agent, residual organic solvent and residual polymerization catalyst to prepare polyethylene glycol-bridged star-linked structure polyurethane thickener molecules;
(5) and (3) finishing: fully mixing polyethylene glycol-bridged star-linked structure polyurethane thickener molecules with an emulsifier, and removing an organic solvent under vacuum to prepare the polyethylene glycol-bridged star-linked structure polyurethane thickener.
Preferably, the step (2) is specifically:
(2.1) putting polyethylene glycol into a reactor, stirring and heating to 65-75 ℃;
(2.2) controlling the reaction temperature to be 70-80 ℃, and adding a multifunctional initiator dissolved in 20-30 wt% of organic solvent in total within 40-50 min;
(2.3) maintaining the reaction temperature at 70-80 ℃, adding a polymerization catalyst accounting for 30-40% of the total amount in 10-20 min, and carrying out heat preservation reaction for 10-20 min;
and (2.4) heating, controlling the reaction temperature to be 75-85 ℃, and carrying out heat preservation reaction for 60-90 min to obtain the polyethylene glycol bridged star-linked structure polyurethane thickener prepolymer.
Preferably, the step (3) is specifically:
(3.1) maintaining the reaction temperature at 75-85 ℃, and adding the material obtained in the step (2) into an active end-capping agent dissolved in an organic solvent accounting for 30-40% of the total amount within 50-60 min;
(3.2) maintaining the reaction temperature at 75-85 ℃, adding a polymerization catalyst accounting for 20-30% of the total amount in 10-20 min, and carrying out heat preservation reaction for 20-30 min;
and (3.3) heating, controlling the reaction temperature to be 80-90 ℃, and carrying out heat preservation reaction for 60-90 min to obtain the polyethylene glycol bridged star-linked structure polyurethane thickener intermediate.
Preferably, the step (4) is specifically:
(4.1) maintaining the reaction temperature at 80-90 ℃, adding an associated end-capping agent and the residual polymerization catalyst dissolved in the residual organic solvent into the material obtained in the step (3), and carrying out heat preservation reaction for 30-40 min;
and (4.2) maintaining the reaction temperature at 85-95 ℃, adding a polyether bridging agent, and carrying out heat preservation reaction for 60-90 min to obtain the polyethylene glycol bridged star-linked structure polyurethane thickener molecules.
Preferably, the step (5) is specifically:
(5.1) adding an emulsifier into the material obtained in the step (4), fully stirring, and carrying out vacuum drying at the temperature of not higher than 100 ℃ until the solid content is not lower than 90%;
and (5.2) cooling and crushing the dried product to prepare the polyethylene glycol-bridged star-linked structure polyurethane thickener.
Preferably, the organic solvent is methyl ethyl ketone or ethyl pyrrolidone.
Preferably, the polymerization catalyst is stannous octoate or dibutyltin dilaurate.
Preferably, the emulsifier is one of nonionic surfactants with HLB value of 8-10.
Preferably, the emulsifier is used in an amount of 1.2 to 1.8 wt% based on the total weight of the polymerized monomers.
In a second aspect, the invention provides a polyethylene glycol-bridged star-linked polyurethane thickener prepared by the above method.
Compared with the prior art, the invention has the following advantages and characteristics:
1. the thickening agent molecule has a central branch structure taking short-chain polyether as a framework, secondary branching is carried out at the tail end of each central branch, and then a plurality of long-chain polyether chain links and hydrophobic association alkyl long chains are grafted sequentially to form a complex star-shaped structure of the polyurethane thickening agent. Therefore, the intermolecular association capacity of the thickener is stronger, and the thickening performance is improved.
2. The invention uses a small amount of bifunctional long-chain polyether to perform partial bridging on the complex star structure to form a bridging star structure of the polyurethane thickener. Therefore, the thickening agent has certain application performance of a linear thickening agent, and the rheological property of the thickening agent with the complex star structure can be well adjusted.
3. The invention properly improves the branching degree of the high star-shaped polyurethane thickener molecules and introduces a small amount of long-chain polyether bridges between the star-shaped structures of the thickener to form a star-linked structure, thereby fully playing and combining the advantages of two associated polyurethane thickener structures of linear and star.
4. The thickening agent has a larger framework structure and higher content of polyether chain links, and the 'remote claw type' hydrophobic association structures on a plurality of branched chains of the thickening agent effectively inhibit intramolecular association of the thickening agent and strengthen intermolecular association of the thickening agent. Therefore, the thickening agent has stronger thickening capacity, less using amount and stronger thickening capacity to dilute solution.
5. The thickening agent has a larger skeleton structure and higher content of polyether chain links, so that the selection of polyethylene glycol with smaller molecular weight becomes possible, the viscosity of a reaction system is smaller, and the reaction reliability is better.
6. According to the invention, a small amount of weak hydrophilic nonionic emulsifier is compounded into the thickener product, so that the emulsifying and dispersing performances of the thickener are improved, and the thickening capability of the thickener is not negatively influenced.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a preparation method of a polyethylene glycol bridged star-linked structure polyurethane thickener, which comprises the following steps:
(1) preparing raw materials: the raw materials contain polymerization monomers, organic solvents, polymerization catalysts and emulsifiers; wherein the polymerization monomer comprises a multifunctional initiator, polyethylene glycol, an active end capping agent, an association end capping agent and a polyether bridging agent;
the multifunctional initiator is 1, 6-hexamethylene diisocyanate trimer;
the polyethylene glycol has a water content not higher than 2 per mill and a molecular weight of 1000-2000;
the active blocking agent is 1, 6-hexamethylene diisocyanate trimer;
the association blocking agent is one of polyethylene glycol monoalkyl esters with water content not higher than 2 ‰, and the polyethylene glycol monoalkyl ester has a chemical formula of HO (C)2H4O)nOCCmH2m+1Wherein n is 100-150, and m is 16-18;
the polyether bridging agent is one of polyethylene glycol with the water content not higher than 2 per mill and the molecular weight of 2000-3000;
the polymerized monomer comprises the following components in parts by mole: 1 part of multifunctional initiator, 3 parts of polyethylene glycol, 3.00-3.10 parts of active end capping agent, 4.5-5.5 parts of association end capping agent and 0.3-0.8 part of polyether bridging agent, wherein (the mole fraction of the association end capping agent plus the mole fraction multiplied by 2 of the polyether bridging agent) is 6.0-6.5 parts;
the dosage of the polymerization catalyst is 0.04-0.06 wt% of the total weight of the polymerization monomers;
the using amount of the emulsifier is 1-2 wt% of the total weight of the polymerized monomers;
(2) active prepolymerization: carrying out active prepolymerization reaction on a multifunctional initiator, polyethylene glycol, part of organic solvent and part of polymerization catalyst to prepare a polyethylene glycol-bridged star-linked polyurethane thickener prepolymer;
(3) active end capping: performing active end capping reaction on the polyethylene glycol bridged star-linked structure polyurethane thickener prepolymer, an active end capping agent, a part of organic solvent and a part of polymerization catalyst to prepare a polyethylene glycol bridged star-linked structure polyurethane thickener intermediate;
(4) grafting and bridging: grafting and bridging the intermediate of the polyethylene glycol-bridged star-linked structure polyurethane thickener with an association end-capping agent, a polyether bridging agent, residual organic solvent and residual polymerization catalyst to prepare polyethylene glycol-bridged star-linked structure polyurethane thickener molecules;
(5) and (3) finishing: fully mixing polyethylene glycol-bridged star-linked structure polyurethane thickener molecules with an emulsifier, and removing an organic solvent under vacuum to prepare the polyethylene glycol-bridged star-linked structure polyurethane thickener.
In a preferred embodiment, the amount of the organic solvent used is not particularly limited, and may be selected conventionally in the art as long as the polymerization reaction can be normally carried out.
In particular embodiments, the polymerization catalyst may be used in an amount of 0.04 wt%, 0.042 wt%, 0.044 wt%, 0.046 wt%, 0.048 wt%, 0.05 wt% based on the total weight of the polymerized monomers. 0.05 wt%, 0.054 wt%, 0.056 wt%, 0.058 wt%, or 0.06 wt%.
In a preferred embodiment, the step (2) is specifically:
(2.1) putting polyethylene glycol into a reactor, stirring and heating to 65-75 ℃;
(2.2) controlling the reaction temperature to be 70-80 ℃, and uniformly adding a multifunctional initiator dissolved in 20-30 wt% of the total amount of organic solvent within 40-50 min;
(2.3) maintaining the reaction temperature at 70-80 ℃, uniformly adding a polymerization catalyst accounting for 30-40% of the total amount in 10-20 min, and carrying out heat preservation reaction for 10-20 min;
and (2.4) heating, controlling the reaction temperature to be 75-85 ℃, and carrying out heat preservation reaction for 60-90 min to obtain the polyethylene glycol bridged star-linked structure polyurethane thickener prepolymer.
In specific embodiments, in step (2.4), the reaction temperature may be 75 ℃, 76 ℃, 77 ℃, 78 ℃, 79 ℃, 80 ℃, 81 ℃, 82 ℃, 83 ℃, 84 ℃ or 85 ℃; the reaction time may be 60min, 65min, 70min, 75min, 80min, 85min or 90 min.
In a preferred embodiment, the step (3) is specifically:
(3.1) maintaining the reaction temperature at 75-85 ℃, and adding the material obtained in the step (2) into an active end-capping agent dissolved in 30-40 wt% of the total amount of organic solvent within 50-60 min;
(3.2) maintaining the reaction temperature at 75-85 ℃, uniformly adding 20-30 wt% of polymerization catalyst in 10-20 min, and reacting for 20-30 min under heat preservation;
and (3.3) heating, controlling the reaction temperature to be 80-90 ℃, and carrying out heat preservation reaction for 60-90 min to obtain the polyethylene glycol bridged star-linked structure polyurethane thickener intermediate.
In a specific embodiment, in step (3.3), the reaction temperature may be 80 ℃, 81 ℃, 82 ℃, 83 ℃, 84 ℃, 85 ℃, 86 ℃, 87 ℃, 88 ℃, 89 ℃ or 90 ℃; the reaction time may be 60min, 65min, 70min, 75min, 80min, 85min or 90 min.
In a preferred embodiment, the step (4) is specifically:
(4.1) maintaining the reaction temperature at 80-90 ℃, adding an associated end-capping agent and the residual polymerization catalyst dissolved in the residual organic solvent into the material obtained in the step (3), and carrying out heat preservation reaction for 30-40 min;
and (4.2) maintaining the reaction temperature at 85-95 ℃, adding a polyether bridging agent, and carrying out heat preservation reaction for 60-90 min to obtain the polyethylene glycol bridged star-linked structure polyurethane thickener molecule.
In a preferred embodiment, the step (5) is specifically:
(5.1) adding an emulsifier into the material obtained in the step (4), fully stirring, and carrying out vacuum drying at the temperature of not higher than 100 ℃ until the solid content is not lower than 90%;
and (5.2) cooling and crushing the dried product to prepare the polyethylene glycol-bridged star-linked structure polyurethane thickener.
In a preferred embodiment, the organic solvent is methyl ethyl ketone or ethyl pyrrolidone.
In a preferred embodiment, the polymerization catalyst is stannous octoate or dibutyltin dilaurate.
In a preferred embodiment, the emulsifier is one of nonionic surfactants having an HLB value of 8 to 10.
In a preferred embodiment, the emulsifier is used in an amount of 1.2 to 1.8 wt% based on the total weight of the polymerized monomers.
In particular embodiments, the emulsifier may be used in an amount of 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 2 weight percent based on the total weight of the polymerized monomers.
In a second aspect, the invention provides a polyethylene glycol-bridged star-linked polyurethane thickener prepared by the above method.
The polyethylene glycol bridged star-linked structure polyurethane thickener prepared by the method can be widely applied to the fields of water-based paint, textile printing, water-based resin coating and the like, and has the advantages of strong thickening capability, good rheological property, high elution rate and the like. The finished product should be stored in a shady, cool and dry place in a sealed way.
The present invention will be described in detail below by way of examples, but the scope of the present invention is not limited thereto.
TABLE 1
Example 1
(1) Preparing raw materials, wherein the specific selection and the dosage of the raw materials are shown in table 1;
(2) active prepolymerization: carrying out active prepolymerization reaction on a multifunctional initiator, polyethylene glycol, part of organic solvent and part of polymerization catalyst to prepare a polyethylene glycol-bridged star-linked polyurethane thickener prepolymer;
(2.1) putting polyethylene glycol into a reactor, stirring and heating to 67 ℃;
(2.2) controlling the reaction temperature to be 72 ℃, and uniformly adding a multifunctional initiator dissolved in 22 percent of the total amount of organic solvent within 42 min;
(2.3) maintaining the reaction temperature at 72 ℃, uniformly adding 32 percent of polymerization catalyst in total amount within 12.5min, and keeping the temperature for reaction for 12 min;
(2.4) heating, controlling the reaction temperature to be 77 ℃, and carrying out heat preservation reaction for 85min to obtain a polyethylene glycol bridged star-linked structure polyurethane thickener prepolymer;
(3) active end capping: performing active end capping reaction on the polyethylene glycol bridged star-linked structure polyurethane thickener prepolymer, an active end capping agent, a part of organic solvent and a part of polymerization catalyst to prepare a polyethylene glycol bridged star-linked structure polyurethane thickener intermediate;
(3.1) maintaining the reaction temperature at 77 ℃, and adding the material obtained in the step (2.4) into an active end-capping agent dissolved in 32 percent of the total amount of organic solvent within 52 min;
(3.2) maintaining the reaction temperature at 77 ℃, uniformly adding a polymerization catalyst accounting for 22 percent of the total amount within 12min, and carrying out heat preservation reaction for 22 min;
(3.3) heating and controlling the reaction temperature to be 82 ℃, and carrying out heat preservation reaction for 77min to obtain a polyethylene glycol bridged star-linked structure polyurethane thickener intermediate;
(4) grafting and bridging: grafting and bridging the intermediate of the polyethylene glycol-bridged star-linked structure polyurethane thickener with an association end-capping agent, a polyether bridging agent, residual organic solvent and residual polymerization catalyst to prepare polyethylene glycol-bridged star-linked structure polyurethane thickener molecules;
(4.1) maintaining the reaction temperature at 82 ℃, adding the association end-capping reagent and the residual polymerization catalyst dissolved in the residual organic solvent into the material obtained in the step (3.3), and carrying out heat preservation reaction for 32 min;
(4.2) maintaining the reaction temperature at 87 ℃, adding a polyether bridging agent, and carrying out heat preservation reaction for 85min to obtain a polyethylene glycol bridged star-linked structure polyurethane thickener molecule;
(5) and (3) finishing: fully mixing polyethylene glycol bridged star-linked structure polyurethane thickener molecules with an emulsifier, and removing an organic solvent under vacuum to prepare the polyethylene glycol bridged star-linked structure polyurethane thickener;
(5.1) adding an emulsifier into the material obtained in the step (4.2), fully stirring, and drying in vacuum at 85 ℃ until the solid content is 92%;
(5.2) cooling and crushing the dried product to obtain a polyethylene glycol-bridged star-linked structure polyurethane thickener product S1.
Example 2
(1) Preparing raw materials, wherein the specific selection and the dosage of the raw materials are shown in table 1;
(2) active prepolymerization: carrying out active prepolymerization reaction on a multifunctional initiator, polyethylene glycol, part of organic solvent and part of polymerization catalyst to prepare a polyethylene glycol bridged star-linked structure polyurethane thickener prepolymer;
(2.1) putting polyethylene glycol into a reactor, stirring and heating to 70 ℃;
(2.2) controlling the reaction temperature to be 75 ℃, and uniformly adding a multifunctional initiator dissolved in 25 percent of the total amount of organic solvent within 42 min;
(2.3) maintaining the reaction temperature at 75 ℃, uniformly adding a polymerization catalyst accounting for 35 percent of the total amount in 12min, and carrying out heat preservation reaction for 12 min;
(2.4) heating and controlling the reaction temperature to be 80 ℃, and carrying out heat preservation reaction for 77min to obtain a polyethylene glycol bridged star-linked structure polyurethane thickener prepolymer;
(3) active end capping: carrying out active end capping reaction on the prepolymer of the polyethylene glycol bridged star-linked structure polyurethane thickener, an active end capping agent, part of organic solvent and part of polymerization catalyst to prepare an intermediate of the polyethylene glycol bridged star-linked structure polyurethane thickener;
(3.1) maintaining the reaction temperature at 80 ℃, and adding the material obtained in the step (2.4) into an active end-capping agent dissolved in 35% of the total amount of organic solvent within 52 min;
(3.2) maintaining the reaction temperature at 80 ℃, uniformly adding a polymerization catalyst accounting for 25 percent of the total amount in 12min, and carrying out heat preservation reaction for 22 min;
(3.3) heating and controlling the reaction temperature to be 85 ℃, and carrying out heat preservation reaction for 80min to obtain a polyethylene glycol bridged star-linked structure polyurethane thickener intermediate;
(4) grafting and bridging: grafting and bridging the intermediate of the polyethylene glycol-bridged star-linked structure polyurethane thickener with an association end-capping agent, a polyether bridging agent, residual organic solvent and residual polymerization catalyst to prepare polyethylene glycol-bridged star-linked structure polyurethane thickener molecules;
(4.1) maintaining the reaction temperature at 85 ℃, adding the association end-capping reagent and the residual polymerization catalyst dissolved in the residual organic solvent into the material obtained in the step (3.3), and carrying out heat preservation reaction for 32 min;
(4.2) maintaining the reaction temperature at 90 ℃, adding a polyether bridging agent, and carrying out heat preservation reaction for 77min to obtain a polyethylene glycol bridged star-linked structure polyurethane thickener molecule;
(5) and (3) finishing: fully mixing polyethylene glycol-bridged star-linked structure polyurethane thickener molecules with an emulsifier, and removing an organic solvent under vacuum to prepare the polyethylene glycol-bridged star-linked structure polyurethane thickener;
(5.1) adding an emulsifier into the material obtained in the step (4.2), fully stirring, and drying in vacuum at 90 ℃ until the solid content is 94%;
(5.2) cooling and crushing the dried product to obtain a polyethylene glycol-bridged star-linked structure polyurethane thickener product S2.
Example 3
(1) Preparing raw materials, wherein the specific selection and the dosage of the raw materials are shown in table 1;
(2) active prepolymerization: carrying out active prepolymerization reaction on a multifunctional initiator, polyethylene glycol, part of organic solvent and part of polymerization catalyst to prepare a polyethylene glycol-bridged star-linked polyurethane thickener prepolymer;
(2.1) putting polyethylene glycol into a reactor, stirring and heating to 73 ℃;
(2.2) controlling the reaction temperature to be 78 ℃, and uniformly adding a multifunctional initiator dissolved in 28 percent of the total amount of organic solvent within 48 min;
(2.3) maintaining the reaction temperature at 78 ℃, uniformly adding a polymerization catalyst accounting for 38 percent of the total amount in 18min, and carrying out heat preservation reaction for 18 min;
(2.4) heating, controlling the reaction temperature to be 83 ℃, and carrying out heat preservation reaction for 78min to obtain a polyethylene glycol bridged star-linked structure polyurethane thickener prepolymer;
(3) active end capping: performing active end capping reaction on the polyethylene glycol bridged star-linked structure polyurethane thickener prepolymer, an active end capping agent, a part of organic solvent and a part of polymerization catalyst to prepare a polyethylene glycol bridged star-linked structure polyurethane thickener intermediate;
(3.1) maintaining the reaction temperature at 83 ℃, and adding the material obtained in the step (2.4) into an active end-capping agent dissolved in 38 percent of the total amount of organic solvent within 58 min;
(3.2) maintaining the reaction temperature at 83 ℃, uniformly adding a polymerization catalyst accounting for 28 percent of the total amount in 18min, and carrying out heat preservation reaction for 28 min;
(3.3) heating and controlling the reaction temperature to 88 ℃, and carrying out heat preservation reaction for 78min to obtain a polyethylene glycol bridged star-coupled structure polyurethane thickener intermediate;
(4) grafting and bridging: grafting and bridging the intermediate of the polyethylene glycol-bridged star-linked structure polyurethane thickener with an association end-capping agent, a polyether bridging agent, residual organic solvent and residual polymerization catalyst to prepare polyethylene glycol-bridged star-linked structure polyurethane thickener molecules;
(4.1) maintaining the reaction temperature at 88 ℃, adding the association end-capping reagent and the residual polymerization catalyst dissolved in the residual organic solvent into the material obtained in the step (3.3), and carrying out heat preservation reaction for 38 min;
(4.2) maintaining the reaction temperature at 93 ℃, adding a polyether bridging agent, and carrying out heat preservation reaction for 78min to obtain a polyethylene glycol bridged star-linked structure polyurethane thickener molecule;
(5) and (3) finishing: fully mixing polyethylene glycol-bridged star-linked structure polyurethane thickener molecules with an emulsifier, and removing an organic solvent under vacuum to prepare the polyethylene glycol-bridged star-linked structure polyurethane thickener;
(5.1) adding an emulsifier into the material obtained in the step (4.2), fully stirring, and drying in vacuum at 88 ℃ until the solid content is 96%;
(5.2) cooling and crushing the dried product to obtain a polyethylene glycol bridged star-linked structure polyurethane thickener product S3.
Test example
1. The thickening ability of the thickeners obtained in examples was evaluated by the paste formation rate of a white paste having a viscosity of 50000 to 55000 mPas, and the results are shown in Table 2.
TABLE 2
| Example 1 | Example 2 | Example 3 |
| 1.25％ | 1.10％ | 1.20％ |
2. The leveling of the thickeners obtained in the examples was evaluated using the surface tension of 0.1% white paste, and the results are shown in table 3.
TABLE 3
| Example 1 | Example 2 | Example 3 |
| 42.0mN/m | 41.5mN/m | 39.5mN/m |
3. The elution rate of the thickener obtained in the example was evaluated by the removal rate of the paste from a cotton cloth having a weight gain of 5% after printing the thickener after washing at 80 ℃ for 5 minutes (bath ratio 1:50), and the results are shown in Table 4.
TABLE 4
| Example 1 | Example 2 | Example 3 |
| 94.0％ | 93.5％ | 93.0％ |
The results in tables 2-4 show that the polyethylene glycol-bridged star-linked polyurethane thickener prepared by the method has the characteristics of strong thickening capability, good leveling property and high elution rate.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A preparation method of a polyethylene glycol bridged star-linked structure polyurethane thickener is characterized by comprising the following steps:
(1) preparing raw materials: the raw materials contain polymerization monomers, organic solvents, polymerization catalysts and emulsifiers; wherein the polymerization monomer comprises a multifunctional initiator, polyethylene glycol, an active end capping agent, an association end capping agent and a polyether bridging agent;
the multifunctional initiator is 1, 6-hexamethylene diisocyanate trimer;
the polyethylene glycol has a water content not higher than 2 per mill and a molecular weight of 1000-2000;
the active blocking agent is 1, 6-hexamethylene diisocyanate trimer;
the association blocking agent is one of polyethylene glycol monoalkyl esters with water content not higher than 2 ‰, and the polyethylene glycol monoalkyl ester has a chemical formula of HO (C)2H4O)nOCCmH2m+1Wherein n is 100-150, and m is 16-18;
the polyether bridging agent is one of polyethylene glycol with the water content not higher than 2 per mill and the molecular weight of 2000-3000;
the polymerized monomer comprises the following components in parts by mole: 1 part of multifunctional initiator, 3 parts of polyethylene glycol, 3.00-3.10 parts of active end capping agent, 4.5-5.5 parts of association end capping agent and 0.3-0.8 part of polyether bridging agent, wherein (the mole fraction of the association end capping agent plus the mole fraction multiplied by 2 of the polyether bridging agent) is 6.0-6.5 parts;
the dosage of the polymerization catalyst is 0.04-0.06 wt% of the total weight of the polymerization monomers;
the using amount of the emulsifier is 1-2 wt% of the total weight of the polymerized monomers;
(2) active prepolymerization: carrying out active prepolymerization reaction on a multifunctional initiator, polyethylene glycol, part of organic solvent and part of polymerization catalyst to prepare a polyethylene glycol-bridged star-linked polyurethane thickener prepolymer;
(3) active end capping: performing active end capping reaction on the polyethylene glycol bridged star-linked structure polyurethane thickener prepolymer, an active end capping agent, a part of organic solvent and a part of polymerization catalyst to prepare a polyethylene glycol bridged star-linked structure polyurethane thickener intermediate;
(4) grafting and bridging: grafting and bridging the intermediate of the polyethylene glycol-bridged star-linked structure polyurethane thickener with an association end-capping agent, a polyether bridging agent, residual organic solvent and residual polymerization catalyst to prepare polyethylene glycol-bridged star-linked structure polyurethane thickener molecules;
(5) and (3) finishing: fully mixing polyethylene glycol-bridged star-linked structure polyurethane thickener molecules with an emulsifier, and removing an organic solvent under vacuum to prepare the polyethylene glycol-bridged star-linked structure polyurethane thickener.
2. The preparation method of the polyethylene glycol-bridged star-linked polyurethane thickener according to claim 1, wherein the step (2) is specifically as follows:
(2.1) putting polyethylene glycol into a reactor, stirring and heating to 65-75 ℃;
(2.2) controlling the reaction temperature to be 70-80 ℃, and adding a multifunctional initiator dissolved in 20-30 wt% of organic solvent in total within 40-50 min;
(2.3) maintaining the reaction temperature at 70-80 ℃, adding a polymerization catalyst accounting for 30-40% of the total amount in 10-20 min, and carrying out heat preservation reaction for 10-20 min;
and (2.4) heating, controlling the reaction temperature to be 75-85 ℃, and carrying out heat preservation reaction for 60-90 min to obtain the polyethylene glycol bridged star-linked structure polyurethane thickener prepolymer.
3. The preparation method of the polyethylene glycol-bridged star-linked polyurethane thickener according to claim 1 or 2, wherein the step (3) is specifically:
(3.1) maintaining the reaction temperature at 75-85 ℃, and adding the material obtained in the step (2) into an active end-capping agent dissolved in an organic solvent accounting for 30-40 wt% of the total amount within 50-60 min;
(3.2) maintaining the reaction temperature at 75-85 ℃, adding a polymerization catalyst accounting for 20-30% of the total amount in 10-20 min, and carrying out heat preservation reaction for 20-30 min;
and (3.3) heating, controlling the reaction temperature to be 80-90 ℃, and carrying out heat preservation reaction for 60-90 min to obtain the polyethylene glycol bridged star-linked structure polyurethane thickener intermediate.
4. The preparation method of the polyethylene glycol-bridged starburst structure polyurethane thickener according to claim 1 or 2, wherein the step (4) is specifically:
(4.1) maintaining the reaction temperature at 80-90 ℃, adding an associated end-capping agent and the residual polymerization catalyst dissolved in the residual organic solvent into the material obtained in the step (3), and carrying out heat preservation reaction for 30-40 min;
and (4.2) maintaining the reaction temperature at 85-95 ℃, adding a polyether bridging agent, and carrying out heat preservation reaction for 60-90 min to obtain the polyethylene glycol bridged star-linked structure polyurethane thickener molecules.
5. The preparation method of the polyethylene glycol-bridged star-linked polyurethane thickener according to claim 1 or 2, wherein the step (5) is specifically:
(5.1) adding an emulsifier into the material obtained in the step (4), fully stirring, and carrying out vacuum drying at the temperature of not higher than 100 ℃ until the solid content is not lower than 90%;
and (5.2) cooling and crushing the dried product to prepare the polyethylene glycol-bridged star-linked structure polyurethane thickener.
6. The method for preparing the polyethylene glycol-bridged star-linked polyurethane thickener according to claim 1, wherein the organic solvent is methyl ethyl ketone or ethyl pyrrolidone.
7. The method for preparing the polyethylene glycol-bridged star-linked polyurethane thickener according to claim 1 or 6, wherein the polymerization catalyst is stannous octoate or dibutyltin dilaurate.
8. The method for preparing the polyethylene glycol-bridged star-linked polyurethane thickener according to claim 1 or 6, wherein the emulsifier is one of nonionic surfactants with HLB value of 8-10.
9. The method for preparing the polyethylene glycol-bridged star-linked polyurethane thickener according to claim 1, wherein the amount of the emulsifier is 1.2-1.8 wt% of the total weight of the polymerized monomers.
10. Polyethylene glycol bridged star-linked structured polyurethane thickeners prepared by the process according to any one of claims 1 to 9.
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