CN113072832B

CN113072832B - Combined rheology modifier and preparation method and application thereof

Info

Publication number: CN113072832B
Application number: CN202010010742.8A
Authority: CN
Inventors: 冯聪聪; 纪学顺
Original assignee: Wanhua Chemical Group Co Ltd; Wanhua Chemical Ningbo Co Ltd
Current assignee: Wanhua Chemical Group Co Ltd; Wanhua Chemical Ningbo Co Ltd
Priority date: 2020-01-06
Filing date: 2020-01-06
Publication date: 2023-03-03
Anticipated expiration: 2040-01-06
Also published as: CN113072832A

Abstract

The invention discloses a combined rheology modifier and a preparation method and application thereof. The combined rheology modifier of the invention comprises the following components: 1) 40-80 wt% of water; 2) 5-20 wt% of polyurethane polymer containing ionic group; 3) 15 to 40wt% of an acrylic polymer, the percentages being based on the total weight of the modifier. The polyacrylate polymer with high molecular weight can effectively thicken a low solid content and high solvent system, and the synergistic effect of the polyurethane polymer ensures that the polyacrylate polymer has high thickening efficiency and better fluidity and leveling property; meanwhile, the combined rheology modifier disclosed by the invention has balance in hydrophilic and hydrophobic aspects, can be better stabilized in a water-based system, improves the overall resistance of the water-based paint system, and meets different requirements.

Description

Combined rheology modifier and preparation method and application thereof

Technical Field

The present invention relates to a combination type rheology modifier which has high thickening efficiency and resistance in an aqueous system. The invention also relates to a preparation method and application of the combined rheology modifier.

Background

With the gradual increase of the environmental protection requirements of people and the strict national requirements on environmental protection, the water-based paint system is widely applied at present. The water paint has the advantages of reducing environmental pollution, improving operation and construction environment, saving a large amount of organic solvent, and the like.

The preparation of the water-based paint to film formation comprises four processes of manufacturing, storing, constructing, leveling and film formation. The viscosity requirements of the coating system vary in different processes, for example during storage of the coating, the need to maintain a high low shear viscosity for long periods of time to prevent the dispersed particles from settling down due to gravity; moderate viscosity is desired in the construction process, so that smooth brushing can be ensured, and certain film forming thickness can be ensured to improve covering power; the viscosity should be recovered in a short time after construction to facilitate leveling of the coating film, and the viscosity should be rapidly recovered to be high after leveling to prevent sagging. For aqueous coating systems, the viscosity can be adjusted by adjusting the concentration of other solid substances, but the range of adjustment is very limited, and additives are usually added to adjust the viscosity and rheological properties of the system under different shear conditions, and such additives are usually called rheological additives. In addition to providing the desired viscosity of the system, such adjuvants can sometimes improve the flow properties of the system, the dispersion of the pigments and fillers in the system, the adhesion of the coating system, and the like.

The traditional thickener for aqueous systems is mainly water-soluble macromolecule, the molecular structure is completely hydrophilic, and the thickener does not contain hydrophobic structures, such as cellulose (HEC) and acrylic thickener (ASE), and the thickener achieves the purpose of thickening the aqueous phase by forming hydrogen bonds with water molecules in the system. The thickening agent can effectively improve the low shear viscosity of a system, but the viscosity is rapidly reduced when the shear is increased, and the defects of splashing, insufficient coating film, reduced coating film gloss and the like are easily generated in the coating process.

The polyurethane thickener is a thickener developed in the 80 th 20 th century and is a water-soluble oligomer containing hydrophobic groups. The main structure of the thickening agent is a hydrophilic main component, the hydrophilic main component is a hydrophilic polymer chain, and the hydrophilic polymer chain and the hydrophobic group are connected together through covalent bonds to form the associative thickening agent. In aqueous systems, the hydrophilic portion of such thickeners ensures the dissolution or dispersion of the thickener molecules in water by forming hydrogen bonds with water; in an aqueous system, a hydrophobic part on the thickening agent is bridged to emulsion, solid particles and micelles which can form hydrophobic association in an aqueous system to form a spatial three-dimensional network structure, so that the thickening of the aqueous system is realized. Such thickeners can be classified as hydrophobic alkali swellable thickeners (HASE) and polyurethane associative thickeners (HEUR) and other types of associative thickeners. The aqueous system added with HEUR has more excellent leveling property, excellent film fullness and high film-forming gloss, thereby being widely applied.

EP1765900 (Cognis) describes thickeners based on aqueous formulations of nonionic water-dispersible or water-soluble polyurethanes having a special structure. The specific structure of these polymers is achieved by the presence of allophanate bonds which are generated by the use of an excess of isocyanate. As component (a) hydrophilic polyols having at least 2 OH groups can be used, which may additionally contain ether groups.

WO 2006/002813 describes polyurethane thickeners for various applications in aqueous media. These thickeners are prepared from a hydrophilic polyol having at least two hydroxyl groups, one or more hydrophobic compounds such as long chain alcohols and at least 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).

CN 103403052 describes a radiation curable compound which can be used as a rheological aid in radiation curable coating materials. The rheology aid comprises at least one (meth) acrylate group and at least one group of the formula-NH- (CO) -NR attached thereto ¹ R ² The urea group can participate in the solidification in the later film forming process by introducing double bonds into the main chain. The thickener is a hydrophobic modified alkali swelling thickener, and the connecting group of the thickener is changed from a carboxylic ester bond to a carbamate bond.

CN 108299608 describes an alkali swelling associative thickener, which is prepared from the following components in percentage by mass: 10 to 15 percent of methacrylic acid, 15 to 20 percent of ethyl acrylate, 0.1 to 5 percent of polyurea crosslinking monomer, 0.1 to 3 percent of hydrophobic association monomer, 0.5 to 2 percent of anionic surfactant, 0.2 to 0.1 percent of nonionic surfactant and 0.1 to 1 percent of initiator. And is prepared by emulsion polymerization. The thickener is not easily affected by the amount of residual solvent, dispersant and other assistants in the water system and the ion concentration of the system, and has high stability.

CN 103788283 describes a hydrophobically modified associative thickener, which is prepared from 28.0-32.0% by weight of raw materials and 68.0-72.0% by weight of deionized water, wherein the raw materials are composed of the following components by weight: 10.0-75.5% of hydrophilic monomer, 15.0-85.0% of hydrophobic monomer, 0-3.0% of crosslinking monomer, 0-25.0% of hydrophobic modified monomer with surface activity, 1.0-14.0% of emulsifier and 0.1-1.0% of initiator. The hydrophobic modified associative thickener is synthesized by adopting a seed emulsion polymerization method, not only meets the standard of the daily chemical industry, but also has the advantages of stable application performance and long quality guarantee period.

CN 103204968 describes a high performance alkali swelling thickener which is characterized by comprising the following components in parts by weight: 1000-1010 parts of mixed acrylate monomer, 5-60 parts of emulsifier, 1-50 parts of initiator, 10-150 parts of protective colloid and 1600-1900 parts of deionized water; the mixed acrylate monomer is a mixture of a soft monomer, a hard monomer and a crosslinking functional monomer. The high-performance alkali swelling thickener disclosed by the invention has the advantages of high swelling, high viscosity and high light transmittance, can resist high temperature and low temperature, and is not only suitable for daily cosmetics, household care products and adhesives, but also suitable for the field of oil field drilling.

US20190002613 describes a hydrophobically modified alkali swellable emulsion polymer useful as a rheology modifier. More particularly, this invention relates to hydrophobically modified alkali-swellable emulsion polymers containing residues of polyunsaturated amphiphilic macromonomers. In one aspect, the disclosed polymers are useful for thickening aqueous surfactant-containing compositions while providing excellent rheological properties, clarity, and the ability to stably suspend insoluble and particulate materials for extended periods of time for compositions containing them.

The polyurethane thickener product, the hydrophobically modified alkali swelling thickener and the alkali swelling thickener product described in the above patents can be applied to aqueous systems, but have the problems of narrow applicability and low thickening efficiency.

Disclosure of Invention

The first purpose of the invention is to provide a rheological modifier which simultaneously has a polyurethane thickener and an acrylate combination, and the polymer can effectively increase the viscosity in an aqueous system and meet the requirements of the coating on the viscosity in different stages.

The combined rheology modifier of the invention comprises the following components:

1) 20 to 80wt%, such as 40 to 80wt%, preferably 50 to 60wt% water;

2) 5 to 20% by weight, for example 8 to 17% by weight, preferably 10 to 15% by weight, of an ionic group-containing polyurethane polymer;

3) 15 to 40wt%, such as 18 to 35wt%, preferably 20 to 30wt% of an acrylic polymer, said percentages being based on the total weight of the composition.

The ionic group is selected from one or more of sulfonate, sulfate, and carboxylate functional groups containing an anionic structure. The anionic functional group is derived from one or more of the group including, but not limited to, sodium dimethylolpropionate, sodium dimethylolbutyrate, 1,2-propanediol-3-sulfonate, 1,4-butanediol-3-sulfo (sodium) sulfonate, sodium ethylenediamine ethanesulfonate, sodium ethylenediamine ethanecarboxylate, sodium dimethylolbenzenesulfonate, and the like, preferably sodium dimethylolbenzenesulfonate.

The polyurethane polymer containing the ionic group is obtained by polymerizing polyether polyol and polyisocyanate, adding an ionic chain extender and a monofunctional end-capping substance after the reaction is completed, and carrying out chain extension and end-capping polymerization.

In the polyurethane polymer, the polyisocyanate is one or any combination of diisocyanate or/and triisocyanate; polyisocyanates are compounds having at least 2 up to 3 isocyanate groups per molecule. Suitable polyisocyanates preferably contain an average of from 2 (diisocyanates) to at most 3 NCO groups per molecule. For example, suitable isocyanates which may be mentioned are 1,5-naphthalene diisocyanate, 4,4' -diphenylmethane diisocyanate (MDI), xylylene Diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), 4,4' -diphenyldimethylmethane diisocyanate, di-and tetraalkyldiphenylmethane diisocyanates, 4,4-bibenzyl diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, isomers of Toluene Diisocyanate (TDI), 1-methyl-2,4-diisocyanate cyclohexane, 1,6-diisocyanate-2,2,4-trimethylhexane, 1-isocyanatomethyl-S-isocyanato-1-trimethylcyclohexane, 4924 zxft 49494924 ' -diisocyanatophenylperfluoroethane, tetramethoxybutane-42 zxft Diisocyanate, butane-8583 zxft 6243, isophorone diisocyanate (IPD 9843), isophorone diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, or mixtures thereof.

In a preferred embodiment, the polymers of the invention comprise polymerized isocyanate groups, particularly preferred aliphatic diisocyanate groups, for example those derived from 1,4-butylidene diisocyanate, 1,12-dodecamethylene diisocyanate, 1,10-decamethylene diisocyanate, 2-butyl-2-ethylpentamethylene diisocyanate, 2,4,4-or 2,2,4-trimethylhexamethylene diisocyanate and hexamethylene diisocyanate (hexane-1,6-diisocyanate, HDI). Also cycloaliphatic diisocyanates such as isophorone diisocyanate (IPDI), 2-isocyanatopropylcyclohexyl isocyanate, 4-methylcyclohexane-1,3-diisocyanate (H-TDI) and 1,3-bis (isocyanatomethyl) cyclohexane. Furthermore, diisocyanates of the "saturated MDI" type, such as 4,4 '-methylenebis (cyclohexyl isocyanate) (or also dicyclohexylmethane-4,4' -diisocyanate) or 2,4-methylenebis (cyclohexyl) diisocyanate, can also be present as monomers in the polyurethanes of the present invention. The isocyanate plays a role in connection in the polymer, and different units can be grafted to a main chain to generate a common effect, so that the performance requirements of the invention are met.

In the polyurethane polymer, the polyether polyol is a pure oxyalkylene group, and includes but is not limited to one or any combination of polyethylene glycol (PEG), polypropylene glycol (PPG), polyethylene-polypropylene glycol (PEG-PPG) and polytetramethylene glycol; polyethylene glycol (PEG) is preferred in this patent, wherein the polyethylene glycol has a molecular weight of 500-20000 daltons, preferably 2000-15000 daltons.

The molar ratio of polyether polyol to polyisocyanate is 1:1 to 1:5, preferably 1: 2-1.

The ionic chain extender is selected from one or more of a sulfonate, a sulfate and a carboxylate containing an anionic structure. The ion chain extender is preferably selected from one or more of sodium dimethylolpropionate, sodium dimethylolbutyrate, 1,2-propanediol-3-sodium sulfonate, 1,4-butanediol-3-sulfo (sodium) sulfonate, ethylenediamine sodium ethanesulfonate, ethylenediamine sodium ethanecarboxylate, sodium dimethylolbenzene sulfonate and the like, and is preferably selected from sodium dimethylolbenzene sulfonate. The amount of the ionic chain extender used is preferably 1.5 to 7%, preferably 2 to 5%, based on the mass of the polyurethane resin.

The monofunctional end-capping material is selected from one or more of dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, 1-dodecylalcohol, 1-tetradecanol, 1-hexadecanol, 2-butyloctanol, 2-hexyldecanol, octadecanol, and the isomeric eicosanol. The amount of monofunctional end-capping material used is 2 to 8%, preferably 3 to 6%, based on the mass of the polyurethane resin.

The polyurethane-based polymer in the present invention can be produced by various methods known for producing polyurethane, and the synthesis can be carried out in the absence of water, for example, azeotropic dehydration or vacuum heating dehydration; during reaction, nitrogen is used for protection to prevent water vapor from entering. Can be synthesized by a solution method or a bulk synthesis method. The solvent used for the solution method synthesis is an inert organic solvent capable of dissolving polyurethane, preferably benzene, toluene, xylene, cyclohexane, acetone, butanone, ethyl acetate, butyl acetate and the like, and the solvent can be added before or during the reaction; the synthesis in bulk without the addition of organic solvents is preferred. The polymerization reaction of the polyether polyol and the polyisocyanate may also be carried out in the presence of water, which is generally used in an amount of 1.5 to 5 times the total amount of the polyether polyol and the polyisocyanate.

The reaction temperature for the polymerization of the polyether polyol and the polyisocyanate is 40 to 130 ℃, preferably 50 to 110 ℃, more preferably 70 to 100 ℃, and the reaction time may be, for example, 0.5 to 5 hours. The polymerization is generally carried out under the condition of a catalyst, the catalyst is one or two or more of organic metal catalyst and/or amine catalyst, and the organic metal catalyst is one or more of dibutyltin dilaurate, stannous octoate, bismuth decanoate, bismuth octoate or silver catalyst; the amine catalyst is one or two of triethylamine and 1,4-diazabicyclo [2.2.2] octane, and the dosage of the catalyst is 0.005-0.2wt% of the total dosage of the polyisocyanate and the polyether polyol.

The polyurethane polymer is a linear chain or branched high molecular polymer containing ionic groups. The weight-average molecular weight of the polyurethane polymer is generally 2000 to 50000, preferably 5000 to 40000. In one embodiment, the polyurethane-based polymer has the following general structural formula:

wherein: r1 and R2 are the same or different and are alkyl with 12-26 carbon atoms;

n is any integer from 1 to 20;

m is any integer of 1-15;

y is any integer from 1 to 10;

a is a polyisocyanate residue;

b is a polyether polyol residue.

The polyurethane polymer disclosed by the invention preferably comprises an anionic group capable of reacting with an isocyanate bond on a polymer main chain, and the introduction of the anionic group can improve the stability of the polyurethane polymer in the acrylate polymerization reaction process and improve the polymerization efficiency.

The polyurethane polymer is a high molecular polymer, and the molecular mass of the polyurethane polymer is 2000-50000, preferably 5000-40000; the molecular weight is too high to be dispersed, and the stabilizing effect on the second step reaction is poor; the molecular weight is too low to function as a thickener.

Preferably, the polyurethane polymer of the present invention has a blocked hydrophobic structure at the end, and the number of functional groups capable of reacting with isocyanate bonds in the hydrophobic structure is 1 to 2, preferably 1; such functional groups include, but are not limited to, amino groups, including primary amino groups, and/or secondary amino groups; hydroxyl groups include primary, secondary, and tertiary hydroxyl groups; urea groups, etc.; primary and/or secondary hydroxyl groups are preferred, the reactivity of amino groups with isocyanate linkages is too fast to control and gel easily, and the reactivity of tertiary and ureido groups with isocyanate linkages is low, affecting the reaction efficiency.

In the polyurethane-based polymer of the present invention, the one or more monofunctional hydrophobic end-capping structures comprise from 8 carbon atoms to 30 carbon atoms, preferably from 12 carbon atoms to 26 carbon atoms, excluding the linking group carbon atoms; derived from, for example, one or more of dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, 1-dodecylalcohol, 1-tetradecanol, 1-hexadecanol, 2-butyloctanol, 2-hexyldecanol, octadecanol, the isomeric eicosanols, and the like. The hydrophobic end capping structure can effectively control the molecular weight, can form a single end capping on a main chain to terminate the growth of a molecular chain, can form an association structure between a coating system and a hydrophobic structure on latex particles or pigments and fillers, participates in the establishment of a three-dimensional network structure of the system, and plays a vital role in improving the viscosity of the whole system.

Further, the acrylic polymer is a polymer which adopts free radical polymerization and has a certain crosslinking structure, and is polymerized by the following monomers:

a) From 20% to 69.99% by weight, from about 25% to about 45% by weight in another aspect, and from about 27% to about 40% by weight in a further aspect, of a carboxylic acid monomer selected from one or more of acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, aconitic acid, or maleic acid and salts thereof;

b) 30% to 79.99% by weight, in another aspect about 40% to about 70% by weight, and in a further aspect about 45% to about 65% by weight of a C1-C5 alkyl ester and/or C1-C5 hydroxyalkyl ester of (meth) acrylic acid (i.e., acrylic acid and/or methacrylic acid);

c) 0.01wt% to 3wt%,0.05wt% to about 1wt%, and in a further aspect about 0.08wt% to about 0.8wt% of at least one crosslinking monomer;

wherein the total amount of monomers a), b) and c) is 100wt%.

Further, the acrylic polymer is obtained by emulsion-polymerizing a carboxylic acid monomer, a C1-C5 alkyl ester and/or a C1-C5 hydroxyalkyl ester of (meth) acrylic acid, and a crosslinking monomer in the presence of an initiator and a reducing agent.

The crosslinking agent (crosslinking monomer) selected for use is a monomer having at least two polymerizable ethylenically unsaturated double bonds, which may be selected from polyalkenyl polyethers (e.g. etherification products of allyl alcohol with linear or branched polyols having 2 to 15 carbon atoms) or (meth) acrylate compounds of linear or branched polyols having 2 to 20 carbon atoms, wherein the polyols are selected from one or more of sucrose, pentaerythritol, dipentaerythritol, trimethylolpropane and dimers thereof. The cross-linking agent in the composition of the invention can establish an effective three-dimensional network structure in use, so that the free water of the whole system is reduced, and the viscosity and the stability of the system are improved.

The crosslinking agent (meth) acrylate compound may be selected from, for example, one or more of ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,6-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate and tetramethylolmethane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, tetramethylolmethane tetra (meth) acrylate and pentaerythritol tetra (meth) acrylate, and the like.

The crosslinking monomeric polyalkenyl polyether includes polyallyl ethers having a functionality of 2-4 per molecule, such as one or more of pentaerythritol diallyl ether, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, trimethylolpropane diallyl ether, trimethylolpropane triallyl ether, and the like. Likewise, other types of crosslinking agents such as silicon crosslinking agents, zinc oxide crosslinking agents, divinyl benzene, methylene bisacrylamide, and the like are also within the scope of the present invention.

In the acrylate polymers of the present invention, the crosslinking agent is selected in an amount ranging from about 0.01% to about 3%, in another aspect from about 0.05% to about 1%, and in a further aspect from about 0.08% to about 0.8% by weight based on the total weight of the monomers.

In the acrylate polymer, the selected initiator is a free radical initiator which is at least one of organic peroxide compounds, azo compounds, inorganic persulfate compounds and hydrogen peroxide, or optional compositions thereof, and the free radical initiator comprises but is not limited to azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide, lauroyl peroxide, ammonium persulfate, sodium persulfate and hydrogen peroxide. The initiator may be used in an amount of 0.05 to 1wt%, preferably 0.1 to 0.4wt%, based on the total weight of monomers (total of carboxylic acid monomers, C1-C5 alkyl and/or C1-C5 hydroxyalkyl esters of (meth) acrylic acid and crosslinking monomers).

The reducing agent is one or more of sodium pyrosulfite, sodium hypophosphite, sodium bisulfite, sodium sulfite, sodium hydrosulfite and ferrous sulfate. The reducing agent may be used in an amount of 0.05 to 1wt%, preferably 0.1 to 0.4wt%, based on the total weight of the monomers (sum of carboxylic acid monomers, C1-C5 alkyl and/or C1-C5 hydroxyalkyl esters of (meth) acrylic acid and crosslinking monomers).

The reaction temperature of the emulsion polymerization of the acrylic polymer is generally 10 to 90 ℃, preferably 20 to 70 ℃, more preferably 25 to 60 ℃, and the reaction is generally carried out under an inert gas atmosphere such as nitrogen or argon. The reaction time for the emulsion polymerization can be from 3 to 10 hours, preferably from 4 to 6 hours.

The acrylate polymer of the invention generates free radicals through the combined action of the initiator and the reducing agent to carry out emulsion polymerization. The method can obtain the polyacrylate polymer with large molecular weight, effectively reduce the initiation temperature and save energy.

According to a second aspect of the present invention, there is provided a process for the preparation of the above combined rheology modifier, comprising the steps of:

a) Polymerizing polyether polyol and polyisocyanate, adding an ion-containing chain extender and a monofunctional end-capping substance after the reaction is completed, and performing chain extension and end-capping polymerization to obtain a polyurethane polymer;

b) Adding the polyurethane polymer in a) and a certain amount of carboxylic acid monomer, C1-C5 alkyl ester and/or C1-C5 hydroxyalkyl ester of (meth) acrylic acid and crosslinking monomer into a reactor, adding an oxidizing agent and a reducing agent for emulsion polymerization to obtain a white emulsion-like product, namely the combined rheology modifier.

In the polyurethane polymer, the polyisocyanate is one or any combination of diisocyanate or/and triisocyanate; polyisocyanates are compounds having at least 2 up to 3 isocyanate groups per molecule. Suitable polyisocyanates preferably contain an average of from 2 (diisocyanates) to at most 3 NCO groups per molecule. Suitable isocyanates which may be mentioned are, for example, 1,5-naphthylene diisocyanate, 4,4' -diphenylmethane diisocyanate (MDI), xylylene Diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), 4,4' -diphenyldimethylmethane diisocyanate, di-and tetraalkyldiphenylmethane diisocyanates, 4,4-bibenzyl diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, isomers of Toluene Diisocyanate (TDI), 1-methyl-2,4-diisocyanatocyclohexane, 1,6-diisocyanato-2,2,4-trimethylhexane, 1-isocyanatomethyl-S-isocyanato-1-trimethylcyclohexane, 4924 zxft 494924 ' -diisocyanatophenylperfluoroethane, tetramethoxybutane-42-diisocyanate, butane-8583-zxft 6242-diisocyanate, butane-8583-zxft 83-diisocyanate, IPD-diisocyanate, isophorone diisocyanate (HDIzod-359843), hexamethylene diisocyanate, isophorone diisocyanate (HDIzodi), and hexamethylene diisocyanate.

In a preferred embodiment, the polymers of the invention comprise polymerized isocyanate groups, particularly preferred aliphatic diisocyanate groups, for example those derived from 1,4-butylidene diisocyanate, 1,12-dodecamethylene diisocyanate, 1,10-decamethylene diisocyanate, 2-butyl-2-ethylpentamethylene diisocyanate, 2,4,4-or 2,2,4-trimethylhexamethylene diisocyanate and hexamethylene diisocyanate (hexane-1,6-diisocyanate, HDI). Also cycloaliphatic diisocyanates are isophorone diisocyanate (IPDI), 2-isocyanatopropylcyclohexyl isocyanate, 4-methylcyclohexane-1,3-diisocyanate (H-TDI) and 1,3-bis (isocyanatomethyl) cyclohexane. Furthermore, diisocyanates of the "saturated MDI" such as 4,4 '-methylenebis (cyclohexyl isocyanate) (or also known as dicyclohexylmethane-4,4' -diisocyanate) or 2,4-methylenebis (cyclohexyl) diisocyanate can also be present as radicals in the polyurethanes of the invention. The isocyanate plays a role in connection in the polymer, and different units can be grafted to a main chain to generate a common effect, so that the performance requirement of the invention is met.

In the polyurethane polymer, the polyether polyol is a pure oxyalkylene group, and includes but is not limited to one or any combination of polyethylene glycol (PEG), polypropylene glycol (PPG), polyethylene-polypropylene glycol (PEG-PPG) and polytetramethylene glycol; polyethylene glycol (PEG) is preferred in this patent, wherein the molecular weight of the PEG is between 500 and 20000 daltons, preferably between 2000 and 15000 daltons.

The molar ratio of polyether polyol to polyisocyanate is preferably 1:1 to 1:5, more preferably 1: 2-1.

The ionic chain extender is selected from one or more of sulfonate, sulfate and carboxylate containing an anionic structure. The ionic chain extender is preferably selected from one or more of sodium dimethylolpropionate, sodium dimethylolbutyrate, 1,2-propylene glycol-3-sodium sulfonate, 1,4-butanediol-3-sodium (sulfur) sulfonate, ethylenediamine ethanesulfonic acid sodium salt, ethylenediamine ethanecarboxylic acid sodium salt, sodium dimethylolbenzene sulfonate and the like, and is preferably sodium dimethylolbenzene sulfonate. The amount of the ionic chain extender may be 1.5 to 7%, preferably 2 to 5%, based on the mass of the polyurethane resin.

The monofunctional end-capping material is selected from one or more of dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, 1-dodecylalcohol, 1-tetradecanol, 1-hexadecanol, 2-butyloctanol, 2-hexyldecanol, octadecanol, and isomeric eicosanol. The monofunctional end-capping material may be used in an amount of 2 to 8%, preferably 3 to 6%, based on the mass of the polyurethane resin.

The reaction temperature for the polymerization of the polyether polyol and the polyisocyanate is 40 to 130 ℃, preferably 50 to 110 ℃, more preferably 70 to 100 ℃, and the reaction time may be, for example, 0.5 to 5 hours. The polymerization is generally carried out under the condition of a catalyst, the catalyst is one or two or more of organic metal catalyst and/or amine catalyst, and the organic metal catalyst is one or more of dibutyltin dilaurate, stannous octoate, bismuth decanoate, bismuth octoate or silver catalyst; the amine catalyst is one or two of triethylamine and 1,4-diazabicyclo [2.2.2] octane, and the using amount of the catalyst can be 0.005-0.2wt% of the total using amount of the polyisocyanate and the polyether polyol.

The acrylic ester polymer is a polymer which adopts free radical polymerization and has a certain crosslinking structure, and is polymerized by the following monomers:

a) At least one carboxylic acid monomer selected from one or more of acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, aconitic acid, or maleic acid and salts thereof;

b) C1-C5 alkyl esters and/or C1-C5 hydroxyalkyl esters of acrylic acid and/or methacrylic acid;

c) 0.01% to 3%, preferably 0.05% to about 1%, by weight of at least one crosslinking monomer;

wherein the total amount of monomers a), b) and c) is 100wt%.

In the acrylate polymer of the present invention, the ethylenically unsaturated monomer containing at least one carboxylic acid group in the carboxylic acid monomer is selected from (meth) acrylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, crotonic acid, aconitic acid, and mixtures thereof.

In the acrylic polymer of the present invention, the amount of carboxylic acid monomer ranges from 20% to 69.99% by weight, in another aspect from about 25% to about 45% by weight, and in a further aspect from about 27% to about 40% by weight, based on the total weight of the monomers.

In the acrylate polymer of the present invention, the at least one C1-C5 alkyl ester and/or at least one C1-C5 hydroxyalkyl ester of acrylic acid and/or methacrylic acid selected includes, but is not limited to, a (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, isoamyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate (butanediol mono (meth) acrylate), and a mixture of two or more thereof.

In the acrylate polymers of the present invention, at least one C1-C5 alkyl ester and/or at least one C1-C5 hydroxyalkyl ester of acrylic acid and/or methacrylic acid is selected in an amount ranging from 30% to 79.99% by weight, in another aspect from about 40% to about 70% by weight, and in a further aspect from about 45% to about 65% by weight, based on the total weight of the monomers.

In the acrylate polymer of the present invention, the selected crosslinking agent is a monomer having at least two polymerizable ethylenically unsaturated double bonds, which may be selected from (meth) acrylate compounds of polyalkenyl polyethers selected from the etherification products of allyl alcohol with linear or branched polyols having 2 to 15 carbon atoms or linear or branched polyols having 2 to 20 carbon atoms, wherein the polyols are selected from one or more of sucrose, pentaerythritol, dipentaerythritol, trimethylolpropane and dimers thereof. The cross-linking agent in the composition of the invention can establish an effective three-dimensional network structure in use, so that the free water of the whole system is reduced, and the viscosity and the stability of the system are improved.

In the acrylate polymer of the present invention, the selected crosslinking agent includes (meth) acrylate compounds, such as one or more of ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,6-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate and tetramethylolmethane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, and the like.

In the acrylate polymer of the present invention, the cross-linking agent selected may be polyallyl ether having a functionality of 2 to 4 per molecule, such as pentaerythritol diallyl ether, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, trimethylolpropane diallyl ether, trimethylolpropane triallyl ether, and the like. Likewise, other types of crosslinking agents such as silicon crosslinking agents, zinc oxide crosslinking agents, divinyl benzene, methylene bisacrylamide, and the like are also within the scope of the present invention.

In the acrylate polymer, the selected initiator is a free radical initiator, the initiator is at least one of an organic peroxide compound, an azo compound, an inorganic persulfate compound and hydrogen peroxide, or an optional composition thereof, and the free radical initiator comprises but is not limited to azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide, lauroyl peroxide, ammonium persulfate, sodium persulfate and hydrogen peroxide. The initiator may be used in an amount of 0.05 to 1wt%, preferably 0.1 to 0.4wt%, based on the total weight of the monomers (sum of carboxylic acid monomers, C1-C5 alkyl and/or C1-C5 hydroxyalkyl esters of (meth) acrylic acid and crosslinking monomers).

In the acrylate polymer, the selected reducing agent is one or a combination of more of sodium metabisulfite, sodium hypophosphite, sodium bisulfite, sodium sulfite, sodium hydrosulfite and ferrous sulfate. The reducing agent can be used in an amount of 0.05 to 1wt%, preferably 0.1 to 0.4wt%, based on the total weight of the monomers (carboxylic acid monomers, C1-C5 alkyl and/or C1-C5 hydroxyalkyl esters of (meth) acrylic acid and the sum of the crosslinking monomers).

The acrylate polymer of the invention generates free radicals through the combined action of the initiator and the reducing agent to carry out emulsion polymerization. The method can obtain polyacrylate polymer with large molecular weight, effectively reduce initiation temperature, and save energy.

The polyurethane polymer in the present invention can be produced by various methods for producing polyurethane, and the synthesis can be carried out in the absence of water, for example, azeotropic dehydration or vacuum heating dehydration can be used; during reaction, nitrogen is adopted for protection to prevent water vapor from entering. The synthesis can be carried out by a solution method or a bulk synthesis method. The solvent used for the solution method synthesis is an inert organic solvent capable of dissolving polyurethane, preferably benzene, toluene, xylene, cyclohexane, acetone, butanone, ethyl acetate, butyl acetate and the like, and the solvent can be added before or during the reaction; the synthesis in bulk without the addition of organic solvents is preferred. The polymerization of the polyether polyol and the polyisocyanate may also be carried out in the presence of water, the amount of water used being generally 1.5 to 5 times the total amount of polyether polyol and polyisocyanate.

Generally, the reaction temperature in step a) of the present invention is not strictly limited, and may be selected from 40 to 130 ℃, preferably from 50 to 110 ℃, and more preferably from 70 to 100 ℃, and the optimal reaction temperature may be selected to effectively reduce the formation of by-products and improve the quality of the product.

The reaction time of step a) according to the invention can be from 0.5 to 5h.

Step a) and step b) of the present invention are preferably protected with an inert gas, which is nitrogen or helium, preferably nitrogen.

In addition, the preparation step a) of the polyurethane polymer of the present invention is carried out under the condition of a catalyst, wherein the catalyst is one or two or more of an organometallic catalyst and/or an amine catalyst. Wherein the organic metal catalyst is one or two or more of dibutyltin dilaurate, stannous octoate, bismuth decanoate, bismuth octoate and silver catalysts; the amine catalyst is one or two of triethylamine and 1,4-diazabicyclo [2.2.2] octane. The amount of the catalyst is 0.005-0.2wt% of the total amount of the polyisocyanate and the polyether polyol.

The acrylic polymer is synthesized by one-pot emulsion polymerization, in the step b), the polyurethane polymer in the step a) and metered carboxylic acid monomer, C1-C5 alkyl ester monomer and/or C1-C5 hydroxyalkyl ester monomer of (methyl) acrylic acid and cross-linking agent are added into a reaction kettle together, and water is added simultaneously, wherein the dosage of the water can be 1-5 times, preferably 1.5-2 times of the total mass of the monomers, and the mixture is uniformly mixed. The polyurethane polymer in this case functions as an emulsion stabilizer in the reaction.

The polymerization temperature of the acrylic copolymer is 10 to 90 ℃, preferably 20 to 70 ℃, more preferably 25 to 60 ℃, and the reaction is preferably carried out under the protection of nitrogen.

When the initiator and the reducing agent are added in a certain amount in the step b) to initiate polymerization reaction, and the polymerization is kept for 3 to 10 hours, preferably 4 to 6 hours after the reaction is completely carried out. When the reaction is complete, the temperature is reduced and the material is discharged, thus obtaining the combined rheology modifier of the invention.

According to a third aspect of the present invention there is provided the use of the combined rheology modifier of the invention for thickening latex paints, varnishes, adhesives, leathers, paper, inks, cosmetics, or personal care products. The viscosity modulating compositions of the present invention are suitable for the thickening of aqueous or primarily aqueous systems, such as latex paints, varnishes, adhesives, leathers, paper, inks, cosmetics, personal care products, and the like.

The invention has the positive effects that:

the combined rheology modifier comprises a polyurethane polymer and an acrylate polymer, and the two polymers are polymerized by a special process. The polymerization mode can enable the product of the invention to have the advantages of both the polyurethane thickener and the acrylate thickener, and overcome the defects of the product. For example, the polyacrylate polymer with high molecular weight can effectively thicken a low solid content and high solvent system, and the synergistic effect of the polyurethane polymer ensures that the thickening efficiency of the invention is very high and the invention has better fluidity and leveling property; meanwhile, the combined rheology modifier disclosed by the invention has balance in the aspects of hydrophilicity and hydrophobicity, can better stabilize a water-based system, improves the overall tolerance of the water-based paint system, and meets different requirements.

Detailed Description

The present invention will be further described with reference to the following examples for better carrying out the invention, but the examples are not intended to limit the invention.

The commercial products polyurethane thickener B1, hydrophobically modified alkali swelling thickener B2, alkali swelling thickener B3 and sample B4 synthesized according to patent CN 103403052 were selected as comparative samples and compared with the products made in the following examples in different coating formulations.

In which the polyurethane thickener B1 is DOW-chemical

RM-8W, B1 are conventional linear thickeners, which are predominantlyIs prepared from polyether polyol, diisocyanate and blocked alkyl chain through polymerizing. The product has high market acceptance, and the main parameters are as follows:

appearance of the product	Turbid liquid
		Chemical type	Non-ionic
Density of	1.044g/cm ³
		Viscosity of the solution	3000cp
Non-volatile matter	21.5％
		Solvent(s)	Water (W)

Wherein the hydrophobically modified alkali swellable thickener B2 is DOW chemical

TT-935 and B2 are conventional hydrophobic modified alkali swelling thickeners, the main constituent monomer is at least one hydrophobic monomer of (methyl) acrylic ester, (methyl) acrylic acid and long-chain alkyl polyoxyethylene ether (methyl) acrylic ester or alkyl phenyl polyoxyethylene ether crotonate or triphenyl ethyl phenoxy ether methyl propylene. The polymerization process adopts an emulsion polymerization method. B2 is a post product in the market, which is mainlyThe parameters are as follows:

appearance of the product	Milky white liquid
		Chemical type	Anion(s)
Density of	1.06g/cm ³
		Viscosity of the solution	0-25cp
Non-volatile substance	30％
		Solvent(s)	Water (W)

Wherein the alkali swelling thickener B3 is DOW chemical

ASE-60, the main structure of the resin is (methyl) acrylate and (methyl) acrylic acid copolymer, and the ASE-60 is obtained by adopting an emulsion polymerization mode. B3 is a product with high market acceptance, and the main parameters are as follows:

appearance of the product	Milky white liquid
		Chemical type	Anion(s)
Density of	1.06g/cm ³
		Viscosity of the solution	0-25cp
Non-volatile matter	29％
		Solvent(s)	Water (W)

The radiation curable rheological agent B4 is a sample synthesized according to the patent CN 103403052, the product can be used for a photocuring system, the structure and the function of the product are similar to those of a B2 hydrophobic modified alkali swelling thickener, and the main parameters are as follows:

appearance of the product	Viscous light milky liquid
		Chemical type	Non-ionic
Density of	1.12g/cm ³
		Viscosity of the solution	About 25000cp
Non-volatile matter	30％
		Solvent(s)	Water/diethylene glycol monobutyl ether

The raw materials and components listed in the following table were used in the examples of the present invention.

Example 1

A combination rheology modifier having the synthetic formulation composition of Table 1:

TABLE 1

The combined rheological modifier synthesized by adopting the formula comprises the following steps:

1) Adding 100g polyethylene glycol 6000 (PEG 6000) into 500ml three-neck flask equipped with electromagnetic stirring and nitrogen inlet, and removing water at negative pressure (pressure less than 100 Pa) at 110 deg.C for 2 hr;

2) Cooling to 80 ℃, introducing nitrogen into the three-neck flask to release pressure, adding 3.56g of dimethylolbenzenesulfonic acid into the three-neck flask, and mechanically stirring until the mixture is uniformly stirred;

3) Under the protection of nitrogen, 0.05g of BICAT8018 and 10.4g of HMDI are added into a three-neck flask to start polymerization reaction for 1.5 hours, and then 4.55g of octadecanol is added to keep the temperature at80 ℃ for reaction for 2 hours to obtain a polyurethane polymer;

4) After the reaction is finished, 276g of water is added into the prepared polyurethane to prepare a solution with about 30 percent of solid content, so as to obtain polyurethane polymer PU1;

5) 380gPU is added into a 3L four-neck flask with a mechanical stirring and a nitrogen inlet, 200gEA, 100g MAA, 2.4g TMPDE and 350g deionized water are added into the four-neck flask, stirring is started, and the materials are uniformly mixed;

6) Heating to 40 deg.C, introducing nitrogen gas for bubbling, and removing oxygen completely;

7) Into a four-necked flask was charged 1g of APS (dissolved in 11g of water) and 0.8g of NaHSO ₃ (10 g of water is used for dissolving) to start the polymerization reaction, the reaction temperature is increased from 40 ℃ to 85 ℃, and the temperature is kept at 85 ℃ for 2h to ensure that the monomers are fully polymerized;

8) And after the heat preservation is finished, cooling and discharging to obtain the product C1.

Example 2

A combination rheology modifier having the synthetic formulation composition of Table 2:

TABLE 2

The synthesis procedure of example 2 is similar to that of example 1, and no further description is given here, and a combination rheology modifier C2 is obtained according to this formulation.

Example 3

A combination rheology modifier having the synthetic formulation composition of Table 3:

TABLE 3

The synthesis procedure of example 3 is similar to that of example 1, and no further description is given here, and a combination rheology modifier C3 is obtained according to this formulation.

Example 4

A combination rheology modifier having the synthetic formulation composition of Table 4:

TABLE 4

The synthesis procedure of example 4 is similar to that of example 1, and no further description is given here, and a combination type rheology modifier C4 is obtained according to this formulation.

Example 5

A combination rheology modifier having the synthetic formulation composition of Table 5:

TABLE 5

The synthesis procedure of example 5 is similar to that of example 1, and no further description is given here, and a combination rheology modifier C5 is obtained according to this formulation.

Examples 6 to 9

Examples 6 to 9 are application examples, and items and methods to be tested in the examples are as follows:

1) Adding the same amount of thickener into the system, and inspecting the KU viscosity of the system;

2) Gloss testing: carrying out three parallel tests at an angle of 60 degrees by using a gloss meter, and taking an average value;

3) And (3) permeability testing: visual inspection; and (3) judging standard: the permeability is 5 minutes, and the permeability is 1 minute;

4) The storage stability is that the prepared finished paint is put into a 50 ℃ oven and is placed for 14 days, and the performance of the finished paint is inspected; and (3) judging standard: the storage stability was good at 5 points, not good at 1 point;

5) And (3) testing the activation period: mixing the component A and the component B at the room temperature of 25 ℃ and the humidity of 50%, adding water to dilute the mixture to the construction viscosity, and tracking the viscosity change of the mixture;

6) And (3) weather resistance test: keeping the temperature in an UVB-313nm aging box at 60 ℃, illuminating for 4 hours by adopting the light intensity of 0.68w/m < 2 >, taking out a paint film and condensing for 4 hours at 50 ℃; the two are alternately circulated until 1000 hours, and the performance of the paint film is inspected; and (4) judging standard: the weather resistance is good by 5 minutes, and the weather resistance is bad by 1 minute;

7) And (3) testing water resistance: preparing a film with the thickness of 20 microns on a polished tinplate with the humidity of 50% at the room temperature of 25 ℃, putting the tinplate containing a paint film into water for 7 days, and observing the foaming condition of the foamed paint film; and (3) judging standard: the water resistance is good for 5 minutes, and the water resistance is poor for 1 minute;

8) And (3) baking varnish drying process: film preparation, namely drying the surface of a paint film for 20 minutes at room temperature, then putting the paint film into an oven at80 ℃ for baking for 5 to 10 minutes, then heating to 140 ℃ for baking for 30 minutes, and finishing drying;

9) Two-component drying process: and (3) preparing a film, drying the surface of the paint film for 20 minutes at room temperature, baking the paint film in an oven at80 ℃ for 30 minutes, and curing the paint film for 24 hours at room temperature to test the performance.

10 Scrub resistance test: manufacturing a plate according to the national standard GB/T9266-2009, and testing by adopting a BGD 526 architectural coating scrub resistance instrument;

11 Low temperature film formation test: the film was scraped off on a clean glass plate using a 400 μm wet film maker and immediately after completion was dried in a constant temperature and humidity cabinet at 3 ℃. Drying in a constant temperature and humidity cabinet for 4.5-5.5 hours until the paint film is dried;

12 Contrast ratio test: manufacturing a plate according to the national standard GB/T23981-2009, and testing by adopting a C84-III reflectivity instrument;

13 Transparency test): putting the sample into a sampling vessel, and measuring by using a DC420 spectrophotometer;

14 Suspension test: the sample and the suspended standard spheres were placed in a 50 ℃ oven and their settling rate was observed.

Example 6

The building coating is a branch of the largest amount of the water-based coating market, the maturity is high, and the application types of the thickening agent are more. This application example demonstrates the use of the combination rheology modifiers of the invention in architectural coatings and comparison to commercially available products.

Building interior wall formula: 44% PVC

TABLE 6

In this formulation, comparative examples were synthesized of combination rheology modifiers C1-C5 and commercial products B1, B2, B3, with the following table results:

TABLE 7

As can be seen from table 7, the combination rheology modifier of the invention of this patent has good thickening efficiency in building interior wall formulations of 44% PVC without negatively impacting scrub resistance, low temperature film formation, storage stability and contrast ratio.

Example 7

The combined rheological modifier also has a good performance effect in the formula of the water-borne wood paint. This application example demonstrates the use of the combination rheology modifiers of the invention in architectural coatings and comparison to commercially available products.

The formula of the woodware matte varnish is as follows:

TABLE 8

TABLE 9

It can be seen from table 9 that the combination type rheology modifier of the present invention has good thickening efficiency in this aqueous woodenware matte varnish without negatively affecting gloss, transparency, storage stability and high temperature stability.

Example 8

In a water-based two-component system, the paint has the performance similar to that of an oil-based paint and is environment-friendly, so the paint is developed quickly in recent years and is also an important application direction of the water-based paint. This application example demonstrates the use of the inventive combination rheology modifier in a two-component system and comparison to commercially available products. Before construction, the formula needs to be mixed with A and B, 10-15% of water is added for boiling and diluting to the construction viscosity.

The formula of the two components is as follows:

watch 10

TABLE 11

As can be seen from table 11, the combination rheology modifier of the invention of this patent has a good thickening efficiency in this dispersion stoving varnish without negatively affecting gloss, transparency, storage stability and high temperature stability.

Example 9

The combined rheology modifier of the invention also performs well in the personal care area. This application example demonstrates the use of the combination rheology modifiers of the invention in personal care shampoo formulations and comparison to commercial products.

TABLE 12

Number of	Raw materials	Mass/g
			1	TEXAPON N70	14
2	DEHYTON PK45	3.2
			3	JR400	0.3
4	PHCG	0.5
			5	ROSE	0.5
6	Rheology modifier	2.5
			7	Water (I)	79
	Total of	100

watch 13

As can be seen from table 13, the combination rheology modifier of the instant invention has better thickening efficiency in personal care shampoo formulations without negatively impacting the storage stability, clarity and suspensibility of the formulations.

The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, simplifications, substitutions and equivalents which do not depart from the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims

1. A combination rheology modifier comprising the following components:

1) 20-80 wt% of water;

2) 5-20 wt% of polyurethane polymer containing ionic group;

3) 15 to 40wt% of an acrylate polymer, the percentages being based on the total weight of the modifier;

the preparation method comprises the following steps:

a) Polymerizing polyether polyol and polyisocyanate, adding an ion-containing chain extender and a monofunctional end-capping substance after the reaction is completed to carry out chain extension and end-capping polymerization to obtain a polyurethane polymer, wherein the ion chain extender is selected from one or more of sulfonate, sulfate and carboxylate containing an anion structure;

b) Adding the polyurethane polymer in a) and a certain amount of carboxylic acid monomer, C1-C5 alkyl ester and/or C1-C5 hydroxyalkyl ester of (meth) acrylic acid and crosslinking monomer into a reactor together, adding an initiator and a reducing agent for emulsion polymerization to obtain a white emulsion product,

wherein, the polyurethane polymer has the following structural general formula:

wherein: r ₁ And R ₂ Alkyl of 12 to 26 carbon atoms, which may be the same or different;

n is any integer from 1 to 20;

m is any integer of 1-15;

y is any integer from 1 to 10;

a is a polyisocyanate residue;

b is a polyether polyol residue.

2. The combined rheology modifier of claim 1, wherein it comprises the following components:

1) 40 to 80wt% of water;

2) 8 to 17wt% of polyurethane polymer containing ionic groups;

3) 18 to 35 weight percent of an acrylic polymer, the percentages being based on the total weight of the composition.

3. The combined rheology modifier of claim 2, wherein it comprises the following components:

1) 50-60wt% water;

2) 10 to 15wt% of polyurethane polymer containing ionic group;

3) 20 to 30wt% of an acrylic polymer, said percentages being based on the total weight of the modifier.

4. The combined rheology modifier of any of claims 1-3, wherein the polyisocyanate is one or any combination of a diisocyanate or/and a triisocyanate; and/or

The polyether glycol is selected from one or any combination of polyethylene glycol (PEG), polypropylene glycol (PPG), polyethylene glycol-polypropylene glycol (PEG-PPG) and polytetramethylene glycol; and/or

The molar ratio of polyether polyol to polyisocyanate is 1:1 to 1; and/or

The dosage of the ionic chain extender is 1.5 to 7 percent based on the mass of the polyurethane resin; and/or

The monofunctional end-capping material is selected from one or more of dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, 1-dodecylalcohol, 1-tetradecanol, 1-hexadecanol, 2-butyloctanol, 2-hexyldecanol, octadecanol, and the isomeric eicosanol, and the monofunctional end-capping material is used in an amount of 2~8% based on the mass of the polyurethane resin.

5. The combined rheology modifier of claim 4 wherein the polyisocyanate is one or more of 1,5-naphthalene diisocyanate, 4,4' -diphenylmethane diisocyanate (MDI), xylylene Diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), 4,4' -diphenyldimethylmethane diisocyanate, di-and tetraalkyldiphenylmethane diisocyanates, 4,4-bibenzyl diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, isomers of Toluene Diisocyanate (TDI), 1-methyl-2,4-diisocyanate cyclohexane, 1,6-diisocyanato-24 zxft 3724-trimethylhexane, 1-isocyanatomethyl-S-isocyanato-1-trimethylcyclohexane, 4,4' -diisocyanatophenylethane, perfluorobutane-6242-dibutylene 6242, 1-isocyanato-358543, isophorone diisocyanate (HDIfI), isophorone diisocyanate (HDIfI-359843); and/or

The molar ratio of polyether polyol to polyisocyanate is 1:2 to 1; and/or

The ionic chain extender is selected from one or more of dimethylolpropionic acid sodium, dimethylolbutyric acid sodium, 1,2-propylene glycol-3-sodium sulfonate, 1,4-butanediol-3-sodium sulfo (sulfate), ethylenediamine ethanesulfonic acid sodium, ethylenediamine ethanecarboxylic acid sodium and dimethylolbenzene sulfonic acid sodium, and the dosage of the ionic chain extender is 2-5% of the mass of the polyurethane resin; and/or

The using amount of the monofunctional end-capping substance is 3-6% of the mass of the polyurethane resin.

6. The combination rheology modifier of claim 5, wherein the ionic chain extender is selected from sodium dimethylolbenzene sulfonate.

7. The combination rheology modifier of any of claims 1-3, wherein the reaction temperature of the polyether polyol and the polyisocyanate polymerization is from 40 to 130 ℃ and the reaction time is from 0.5 to 5 hours; and/or

The polyether polyol and the polyisocyanate are polymerized under the condition of a catalyst, wherein the catalyst is one or more of organic metal catalysts and/or amine catalysts, and the organic metal catalysts are one or more of dibutyltin dilaurate, stannous octoate, bismuth decanoate, bismuth octoate or silver catalysts; the amine catalyst is one or two of triethylamine and 1,4-diazabicyclo [2.2.2] octane, and the dosage of the catalyst is 0.005-0.2wt% of the total dosage of the polyisocyanate and the polyether polyol.

8. The combination rheology modifier of claim 7, wherein the reaction temperature for the polymerization of the polyether polyol and the polyisocyanate is from 50 to 110 ℃.

9. The combination rheology modifier of claim 8, wherein the reaction temperature for the polymerization of the polyether polyol and the polyisocyanate is from 70 to 100 ℃.

10. The combinatorial rheology modifier of any of claims 1 to 3, wherein the polyurethane-based polymers have a weight average molecular weight of 2000 to 50000.

11. The combinatorial rheology modifier of claim 10, wherein the polyurethane-based polymer has a weight average molecular weight of 5000 to 40000.

12. The combination rheology modifier of any of claims 1-3, wherein the acrylate polymer is polymerized from:

a) 20-69.99 wt% of a carboxylic acid monomer selected from one or more of acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, aconitic acid, or maleic acid and salts thereof;

b) 30-79.99 wt% of C1-C5 alkyl and/or C1-C5 hydroxyalkyl (meth) acrylates;

c) 0.01wt% to 3wt% of at least one crosslinking monomer;

wherein the total amount of the monomers a), b) and c) is 100wt%.

13. The combination rheology modifier of claim 12, wherein the acrylate polymer is polymerized from:

a) 25wt% -45wt% of carboxylic acid monomer selected from one or more of acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, aconitic acid, or maleic acid and salts thereof;

b) From 40% to 70% by weight of C1-C5 alkyl and/or C1-C5 hydroxyalkyl (meth) acrylates;

c) 0.05wt% to 1wt% of at least one crosslinking monomer;

wherein the total amount of the monomers a), b) and c) is 100wt%.

14. The combination rheology modifier of claim 13, wherein the acrylate polymer is polymerized from:

a) 27wt% to 40wt% of a carboxylic acid monomer;

b) 45wt% to 65wt% of a C1-C5 alkyl ester and/or a C1-C5 hydroxyalkyl ester of (meth) acrylic acid;

c) 0.08wt% to 0.8wt% of at least one crosslinking monomer;

wherein the total amount of monomers a), b) and c) is 100wt%.

15. The combined rheology modifier of any of claims 1-3, wherein,

the crosslinking monomer is a monomer having at least two polymerizable ethylenically unsaturated double bonds, and is selected from (meth) acrylate compounds of polyalkenyl polyethers or linear or branched polyols having 2 to 20 carbon atoms; polyalkenyl polyethers are the etherification products of allyl alcohols with linear or branched polyols having from 2 to 15 carbon atoms.

16. The combinatorial rheology modifier of claim 15, wherein the crosslinker (meth) acrylate compounds are selected from one or more of ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, and tetramethylolmethane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, and pentaerythritol tetra (meth) acrylate; and/or, the crosslinking monomeric polyalkenyl polyether comprises a polyallyl ether having a functionality of 2 to 4 per molecule.

17. The combined rheology modifier of claim 16, wherein the crosslinking monomer polyalkenyl polyether is selected from one or more of pentaerythritol diallyl ether, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, trimethylolpropane diallyl ether, trimethylolpropane triallyl ether.

18. A method of making the combination rheology modifier of any of claims 1-17 comprising the steps of:

a) Polymerizing polyether polyol and polyisocyanate, and adding an ion-containing chain extender and a monofunctional end-capping substance after the reaction is completed to perform chain extension and end-capping polymerization to obtain a polyurethane polymer;

b) Adding the polyurethane polymer in the a) and a certain amount of carboxylic acid monomer, C1-C5 alkyl ester and/or C1-C5 hydroxyalkyl ester of (methyl) acrylic acid and crosslinking monomer into a reactor together, and adding an initiator and a reducing agent for emulsion polymerization to obtain a white emulsion product.

19. The process according to claim 18, wherein the polymerization temperature of the polyether polyol and the polyisocyanate is 40 to 130 ℃ and the reaction time is 0.5 to 5 hours; and/or

The polymerization of polyether polyol and polyisocyanate is carried out under the condition of a catalyst, wherein the catalyst is one or two or more of organic metal catalyst and/or amine catalyst, and the organic metal catalyst is one or more of dibutyltin dilaurate, stannous octoate, bismuth decanoate, bismuth octoate or silver catalyst; the amine catalyst is one or two of triethylamine and 1,4-diazabicyclo [2.2.2] octane, and the using amount of the catalyst is 0.005-0.2wt% of the total using amount of the polyisocyanate and the polyether polyol.

20. The production method according to claim 19, wherein the polymerization reaction temperature of the polyether polyol and the polyisocyanate is 50 to 110 ℃.

21. The production method according to claim 20, wherein the polymerization reaction temperature of the polyether polyol and the polyisocyanate is 70 to 100 ℃.

22. The preparation method of claim 19, wherein the initiator is a radical initiator selected from one or more of organic peroxide compounds, azo compounds, inorganic persulfate compounds and hydrogen peroxide, the amount of the initiator is 0.05-1wt% of the total weight of the monomers, the reducing agent is one or more of sodium metabisulfite, sodium hypophosphite, sodium bisulfite, sodium sulfite, sodium hydrosulfite and ferrous sulfate, and the amount of the reducing agent is 0.05-1wt% of the total weight of the monomers; and/or

The synthesis mode of the acrylate polymer adopts emulsion polymerization by a one-pot method, in the step b), the polyurethane polymer in the step a) and metered carboxylic acid monomer, C1-C5 alkyl ester and/or C1-C5 hydroxyalkyl ester monomer of (methyl) acrylic acid and cross-linking agent are added into a reaction kettle together, and simultaneously water is added, the dosage of the water is 1-5 times of the total mass of the monomers, and the mixture is uniformly mixed; and/or

The polymerization reaction temperature of the acrylate copolymer is 10-90 ℃, and the reaction is carried out under the protection of nitrogen.

23. The method of claim 22, wherein the initiator is used in an amount of 0.1 to 0.4wt% based on the total weight of the monomers; the dosage of the reducing agent is 0.1 to 0.4 weight percent of the total weight of the monomers; and/or

The acrylic ester polymer is synthesized by emulsion polymerization by a one-pot method, and in the step b), the using amount of water is 1.5-2 times of the total mass of the monomers; and/or

The polymerization temperature of the acrylate copolymer is 20-70 ℃.

24. The method as claimed in claim 23, wherein the polymerization temperature of the acrylate-based copolymer is 25-60 ℃.

25. Use of the combined rheology modifier of any of claims 1 to 17 or obtained by the preparation process of any of claims 18 to 24 for a thickener for latex paints, varnishes, adhesives, leather, paper, inks, cosmetics, or personal care applications.