CN116355169A

CN116355169A - Polymer, preparation method and application thereof

Info

Publication number: CN116355169A
Application number: CN202310222443.4A
Authority: CN
Inventors: 陆晓晶; 魏东初
Original assignee: Apexene Technology Shanghai Co ltd
Current assignee: Apexene Technology Shanghai Co ltd
Priority date: 2023-03-09
Filing date: 2023-03-09
Publication date: 2023-06-30

Abstract

The invention provides a polymer, a preparation method and application thereof, wherein the polymer is formed by polymerizing the following components: 1) At least one monohydric alcohol comprising formula V ₁ Compounds of formula V ₂ One or two of the compounds: 2) At least one polyether polyol; 3) At least one diisocyanate. The polymer provided by the invention is used as a thickening agent in a film forming system containing the aqueous resin, can form a denser hydrophobic association network, can improve thickening efficiency, and can also improve the permeability of a wet film and the water resistance of a dry film of the aqueous resin system.

Description

Polymer, preparation method and application thereof

Technical Field

The invention relates to the technical field of fine chemical engineering, in particular to a polymer and a preparation method and application thereof.

Background

With the increasing awareness of human environmental protection, strict laws and regulations are formulated in each country to limit the emission of VOCs, and it is a great trend to perform "oil-to-water" in the field of resin application. In recent years, the aqueous resin has been rapidly developed due to the advantages of low toxicity, safety, environmental protection, convenient construction and the like. In order to make aqueous resins suitable for a wide variety of application modes (e.g., spraying, rolling, brushing, etc.) and thus for wide application in the fields of paints, inks, and adhesives, additional thickening agents are often required to adjust rheology. Among them, polyurethane associative thickeners (HEUR) are used for thickening aqueous resin systems because of their advantages of high thickening efficiency, good leveling property and storage stability, high glossiness after film formation, and the like.

The conventional polymer has a very simple structure, and a linear polymer is prepared by reacting an excessive amount of isocyanate with polyethylene glycol to prepare a prepolymer, and reacting a long-chain alkanol with the rest of isocyanate to terminate the prepolymer. The two ends of the linear polymer are provided with hydrophobic group structures of long-chain alkane, and the thickening effect in the aqueous solution is realized through two-point association between the hydrophobic groups, and the thickening effect is general.

Patent CN101633718A, CN109439056a discloses that long chain alkyl groups are introduced as hydrophobic groups in a linear polyurethane thickener by using a chain extender, thereby improving the thickening effect thereof, but the method of introducing hydrophobic groups in the middle of a molecular main chain by using a chain extender causes lower reactivity due to steric hindrance effect, and the polyurethane thickener after chain extension has excessive molecular weight, is difficult to disperse in an aqueous solution, thereby influencing the thickening effect thereof.

CN113061224a firstly carries out ring opening reaction on long-chain alkyl acid and acrylic glycidyl ester, and finally grafts to the tail end of a conventional linear polyurethane thickener, thereby realizing that a photocuring reactive group c=c is introduced into polyurethane thickener molecules, but the method can only introduce a hydrophobic long chain at the tail end of polyurethane molecules, the density of hydrophobic association network formed between hydrophobic groups is insufficient, and the photocuring polyurethane thickener with high thickening efficiency is difficult to obtain.

In addition, polyurethane thickeners are often applied to various aqueous resin systems, thickener molecules are dissociated in a cured coating after the polyurethane thickeners are cured to form films, chain segments with extremely strong hydrophilicity such as polyethylene glycol exist in the molecules, migration and exudation are easy to occur if hydrophobic association among the thickener molecules is not compact, the phenomenon of whitening is generated on the surface of the coating before film formation, permeability is reduced, and a series of problems such as mechanical performance reduction, whitening appearance and the like are caused when the coating after film formation is washed by rainwater and solvents.

Disclosure of Invention

In view of the above-mentioned drawbacks of the prior art, it is an object of the present invention to provide a novel polymer, a process for its preparation and its use. The invention provides a method for preparing the polymer by carrying out ring opening reaction on epoxidized polyalphaolefin and long-chain fatty acid or fatty acid with photo-curing reaction active group C=C, and then respectively preparing the polymer through grafting reaction, wherein the polymer contains a plurality of hydrophobic side chains, and can realize multipoint association while retaining the photo-curing groups to form a denser hydrophobic association network, so that the thickening efficiency is improved.

To achieve the above and other related objects, the present invention is achieved by the following technical means.

The invention discloses a polymer formed by polymerization of components,

1) At least one monohydric alcohol comprising formula V ₁ Compounds of formula V ₂ One or two of the compounds:

wherein R is ₁ Is a straight-chain alkyl group or a branched-chain alkyl group having 1 to 30 carbon atoms; n is an integer greater than or equal to 1;

R ₂ is a straight-chain hydrocarbon group, a branched-chain hydrocarbon group, a cyclic hydrocarbon group with a side chain or without a side chain of C1-C30, a benzene ring, an aromatic condensed ring or an aromatic heterocyclic ring of C1-C30;

2) At least one polyether polyol;

3) At least one diisocyanate.

Preferably, R ₁ Is a straight-chain alkyl group having 1 to 30 carbon atoms. For example R ₁ The number of carbon atoms of (c) may be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30. More preferably, R ₁ Is a straight-chain alkyl group having 1 to 14 carbon atoms.

Preferably, n is 1 or 2.

Preferably, R ₂ Is a C1-C30 straight-chain hydrocarbon group or a branched-chain hydrocarbon group.

Preferably, the monohydric alcohol is the ring-opening reaction product of an epoxidized polyalphaolefin and a carboxylic acid compound.

Preferably, the structural formula of the epoxidized polyalphaolefin is shown in formula III:

wherein R is ₁ Is a straight-chain alkyl group or a branched-chain alkyl group having 1 to 30 carbon atoms; n is an integer not less than 1.

Preferably, the carboxylic acid compound has the structural formula R ₂ -COOH, wherein R ₂ Is a straight-chain hydrocarbon group, a branched-chain hydrocarbon group, a cyclic hydrocarbon group with a side chain or without a side chain of C1-C30, a benzene ring, an aromatic condensed ring or an aromatic heterocyclic ring of C1-C30.

More preferably, the carboxylic acid compound includes: h ₂₃ C ₁₁ -COOH、H ₁₁ C ₆ -COOH、

H ₃₁ C ₁₅ -COOH/>

Preferably, the monohydric alcohol is synthesized as follows,

and/or +.>

More preferably, in order to prevent oxidation or other side reactions of the c=c double bond in the monohydric alcohol or carboxylic acid compound prepared by the reaction, an inert gas (in this application, inert gas refers to elemental gases and nitrogen gases corresponding to all group 0 elements of the periodic table) may be introduced during the reaction, and the inert gas is preferably nitrogen.

More preferably, in order to prevent the c=c double bond in the monohydric alcohol or carboxylic acid compound prepared by the reaction from polymerizing in advance, a polymerization inhibitor may be added to the reaction.

Further preferably, the polymerization inhibitor is one or more selected from 2, 6-di-tert-butyl-p-cresol (BHT), p-hydroxyanisole or methyl hydroquinone.

Further preferably, the polymerization inhibitor is used in an amount of 0.05 to 0.5wt% of the monomer having a c=c double bond.

More preferably, the molar ratio of the carboxylic acid compound to the epoxidized polyalphaolefin is (1 to 1.2): 1. as can be 1: 1. 1.1:1 or 1.2:1.

more preferably, the reaction temperature is from 90 to 140 ℃, and still more preferably from 110 to 140 ℃. As an example, 90℃at 100℃at 110℃at 120℃at 130℃or 140℃may be mentioned. The temperature is too high, and byproducts are easy to generate; too low a temperature may affect the reaction.

More preferably, the reaction system includes a first catalyst; the first catalyst is a quaternary ammonium salt compound.

More preferably, the quaternary ammonium salt compound is one or more selected from benzyl trimethyl ammonium chloride, tetrabutylammonium bromide, dodecyl trimethyl ammonium chloride, dodecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium chloride or hexadecyl trimethyl ammonium chloride.

More preferably, the first catalyst is present in an amount of from 0.05 to 0.5wt% of the epoxidized polyalphaolefin. Excessive catalyst usage can result in waste of raw materials; too small an amount may affect the conversion of the epoxidized polyalphaolefin prepolymer.

More preferably, the reaction end point is controlled at an acid value of the product below 30mgKOH/g.

Further preferably, the reaction end point is controlled so that the acid value of the product is less than 5 to 25mgKOH/g.

Still more preferably, the reaction end point is controlled so that the acid value of the product is less than 16 to 22mgKOH/g.

Preferably, the polyether polyol comprises polyethylene glycol having a molecular weight of 400 to 20000 g/mol.

More preferably, the polyether polyol comprises polyethylene glycol having a molecular weight of 6000 to 10000 g/mol.

Preferably, the diisocyanate is a C1-C20 linear alkyl, branched or unbranched cyclic alkyl, a C1-C20 benzene ring, or an aromatic fused ring diisocyanate.

More preferably, the diisocyanate is isophorone diisocyanate (IPDI), hexamethylene Diisocyanate (HDI), 4 '-dicyclohexylmethane diisocyanate (HMDI), diphenylmethane-4, 4' -diisocyanate or toluene-2, 4-diisocyanate.

The invention also provides a preparation method of the polymer, which comprises the following steps:

1) Polyether polyol and diisocyanate are contacted and reacted to generate prepolymer;

2) The prepolymer is contacted with the monohydric alcohol to produce the polymer.

Preferably, the molar ratio of hydroxyl groups in the monohydric alcohol to isocyanate groups in the prepolymer is (1 to 1.2): 1. as can be 1: 1. 1.05: 1. 1.0: 1. 1.1: 1. 1.15: 1. 1.18: 1. or 1.2:1.

preferably, the reaction system comprises a second catalyst; the second catalyst is one or more selected from dibutyl tin dilaurate, stannous octoate or organic bismuth catalysts.

More preferably, the organobismuth based catalyst is one or both selected from bismuth neodecanoate or bismuth 2-ethylhexanoate.

Preferably, the reaction system further comprises an organic solvent; the organic solvent is ketone.

More preferably, the organic solvent is one or more selected from acetone, methyl ethyl ketone, ethyl pyrrolidone.

Preferably, the reaction temperature is 60 to 100 ℃, preferably 75 to 95 ℃.

Preferably, step 2) further comprises a post-treatment step comprising distillation, wherein the organic solvent and unreacted reactants in the reaction solution are removed by distillation under reduced pressure.

Preferably, the degree of polymerization of the prepolymer formed from the polyether polyol and the diisocyanate is from 2 to 20.

Preferably, in order to prevent oxidation or other side reactions of the c=c double bond in the monohydric alcohol, an inert gas (in this application, inert gas refers to elemental gases and nitrogen corresponding to all group 0 elements of the periodic table) may be introduced during the reaction, and the inert gas is preferably nitrogen.

Preferably, in order to prevent the c=c double bond in the monohydric alcohol from polymerizing in advance, a polymerization inhibitor may be added to the reaction.

More preferably, the polymerization inhibitor is one or more selected from 2, 6-di-tert-butyl-p-cresol (BHT), p-hydroxyanisole or methyl hydroquinone.

More preferably, the polymerization inhibitor is used in an amount of 0.05 to 0.5wt% of the monomer containing c=c double bonds.

The invention also discloses application of the polymer as a thickening agent in a film forming system containing aqueous resin.

Preferably, the aqueous resin is an aqueous acrylic resin, an aqueous polyurethane-acrylate resin, an aqueous photo-curable acrylic resin, an aqueous photo-curable polyurethane resin or an aqueous photo-curable polyurethane-acrylate resin.

Preferably, the film-forming system comprising the aqueous resin comprises one or more of an aqueous coating, an aqueous ink or an aqueous binder.

Preferably, the polymer is used in an amount of 0.1 to 1.0wt% based on the mass of the aqueous resin. Such as 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1.0wt%, and the like.

As described above, the present invention provides a novel polymer and a method for preparing the same, wherein an unsaturated double bond-containing poly alpha olefin oligomer is directly peroxidized, thereby preparing an epoxidized poly alpha olefin, which can be prepared by a ring opening reaction with a long chain fatty acid or a fatty acid having a photo-curing reactive group C=C, and then by a grafting reaction, respectively. The polymer is used as a thickener in a film forming system containing water-based resin, and belongs to a conventional polyurethane thickener and a photocuring polyurethane thickener, wherein the photocuring polyurethane thickener contains a plurality of hydrophobic side chains, the photocuring groups are reserved, meanwhile, multipoint association can be realized, the thickening efficiency is improved, the terminal of the molecule of the conventional polyurethane thickener is introduced with a plurality of hydrophobic side chains, the multipoint association is facilitated to form a more compact hydrophobic association network, the phenomenon of whitening caused by the fact that the polyurethane thickener is released to the surface of a paint film after paint preparation is avoided, and the length and the branching degree of the hydrophobic side chains can be freely adjusted according to the length of hydrophilic polyethylene glycol chain segments, so that the polyurethane thickener with high thickening efficiency is obtained. Compared with the prior art, the preparation method is simple, the hydrophobic chain segment is directly synthesized in place by one step through polymerization reaction, the photo-curing reactive group C=C or other hydrophobic side chains are introduced through ring opening reaction, the molecular structure of the polyurethane thickener is designed and adjusted, and the conventional or photo-curing polyurethane thickener with different branching degrees and hydrophobic side chain lengths can be conveniently synthesized.

When the thickener is applied to a film forming system containing water-based resin, the wet film permeability can be obviously improved, the phenomenon of whitening on the surface of a paint film after spraying is avoided, the color comparison and color matching in practical application are facilitated, and the paint film has excellent water resistance after being completely dried.

Drawings

FIG. 1 is an infrared spectrum of the polymer prepared in example 7.

FIG. 2 is an infrared spectrum of the polymer prepared in example 8.

FIG. 3 is an infrared spectrum of the polymer prepared in example 9.

FIG. 4 is a graph of rheological measurements of the polymer prepared in example 7 at various concentrations.

FIG. 5 is a graph of rheological measurements of the polymer prepared in example 8 at various concentrations.

FIG. 6 is a graph of rheological measurements of the polymer prepared in example 9 at various concentrations.

FIG. 7 is a graph of rheological measurements of the polymer prepared in example 10 at various concentrations.

FIG. 8 is a graph of rheological measurements of the polymer prepared in example 11 at various concentrations.

Fig. 9 is a graph of rheological measurements of the polymers prepared in the comparative examples at different concentrations.

FIG. 10 is a graph of a rheology test of a polymer at an add-on level of 0.25wt% for JF1025 emulsion systems.

Detailed Description

Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention.

It should be understood that the process equipment or devices not specifically identified in the examples below are all conventional in the art.

Furthermore, it is to be understood that the reference to one or more method steps in this disclosure does not exclude the presence of other method steps before or after the combination step or the insertion of other method steps between these explicitly mentioned steps, unless otherwise indicated. Moreover, unless otherwise indicated, the numbering of the method steps is merely a convenient tool for identifying the method steps and is not intended to limit the order of arrangement of the method steps or to limit the scope of the invention in which the invention may be practiced, as such changes or modifications in their relative relationships may be regarded as within the scope of the invention without substantial modification to the technical matter.

In a specific embodiment of the present application, a method for preparing a specific polymer is provided:

(1) The epoxidised poly alpha olefin and carboxylic acid compound undergo ring opening reaction to generate monohydric alcohol, and the preparation method is as follows:

placing the epoxidized polyalphaolefin and the carboxylic acid compound into a reaction bottle, adding a first catalyst, heating to a certain temperature, keeping the temperature for 2 hours for reaction, continuing heating, keeping the temperature for reaction until the sampling test acid value is lower than 30mg KOH/g, and obtaining the product monohydric alcohol.

(2) The method for preparing the polymer from the monol, the polyether polyol and the diisocyanate comprises the following steps:

polyethylene glycol with the molecular weight of 400-20000 g/mol is added into a reaction vessel, and is heated and melted under the vacuum condition of 0.1MPa, and then stirring is started, the temperature is continuously increased to 120-130 ℃ and dehydration is carried out for 2h. Adding dehydrated polyethylene glycol and an organic solvent into a reaction bottle, starting stirring, uniformly mixing diisocyanate and a second catalyst, adding a dropping device, starting a condenser, starting heating under the protection of inert gas, starting to drop when the temperature rises to a certain temperature, continuously heating up after the drop is completed within 0.5h, carrying out heat preservation reaction, continuously heating up again, carrying out heat preservation reaction, and generating a prepolymer;

and (2) adding the monohydric alcohol prepared in the step (1), continuously introducing inert gas, continuously heating, and carrying out heat preservation reaction. The reaction temperature is 60-100 ℃, and the molar ratio of hydroxyl groups in the monohydric alcohol to isocyanate groups in the diisocyanate is (1-1.2): 1.

After the reaction is completed, the reaction solution is distilled under reduced pressure to remove the solvent, and the obtained product is the polymer.

And (3) carrying out infrared structural characterization on the product by adopting a liquid film method.

In a specific embodiment, the structural formula of the epoxidized polyalphaolefin is shown in formula III:

Specifically, R is ₁ Is a straight-chain alkyl group having 1 to 30 carbon atoms. For example R ₁ The number of carbon atoms of (c) may be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30. Further preferably, R ₁ Is a straight-chain alkyl group having 1 to 14 carbon atoms.

Specifically, n is 1 or 2.

More specific examples of epoxidized polyalphaolefins used in the following examples include:

in specific examples, the synthetic route for the epoxidized polyalphaolefin III is shown below:

1) The alpha olefin monomer is polymerized to obtain poly alpha olefin, and the synthetic route is as follows:

2) The polyalphaolefin is oxidized to form an epoxidized polyalphaolefin, which is synthesized as follows:

in specific examples, the preparation method of the epoxidized polyalphaolefin is as follows:

1) Refining of alpha olefins: the alpha olefin is distilled under reduced pressure, and then the distilled product is eluted through a glass column filled with activated neutral alumina, so that impurities which have influence on the activity of the catalyst in the alpha olefin, particularly oxygen-containing impurities such as water, long-chain fatty alcohol, long-chain fatty ether and the like which are mixed in the alpha olefin are removed, the elution process is carried out in a nitrogen glove box or under the protection of nitrogen by a Schlenk technology, and the activation method of the neutral alumina is that the neutral alumina is baked for 4 hours at 600 ℃ in a muffle furnace.

2) Preparation of polyalphaolefins: firstly, heating the polymerization reaction kettle to above 100 ℃, vacuumizing and baking for 1-2 hours, and replacing the reaction kettle with high-purity nitrogen for multiple times to remove water and oxygen impurities in the reaction kettle. And then, circularly regulating the temperature of the reaction kettle to 40-120 ℃ through jacket cooling water, adding refined alpha olefin and partial cocatalyst, stirring for 10-60 min, adding a metallocene compound dissolved by inert solvents such as toluene and the like and the residual cocatalyst into the polymerization reaction kettle, wherein the concentration of the metallocene compound in a reaction system is 0.01-1 mmol/L (calculated by transition metal), the molar ratio of metal ions in the cocatalyst to transition metal contained in the metallocene compound is 1-1000:1, and opening a nitrogen valve to charge nitrogen to 0.1-1.0 MPa for reaction. In the reaction process, the pressure in the reactor is kept constant by supplementing nitrogen, and the reaction temperature is controlled in a coordinated manner by the jacket heat conduction oil and coil cooling water in the reactor. After the polymerization reaction is finished, opening a blow-down pipe for decompression, discharging a crude product from a polymerization reaction kettle, adding acidified ethanol into the crude product for stopping the reaction, adding 3wt% of activated clay into the obtained product for adsorbing and removing catalyst residues, then performing pressure filtration to obtain filtrate, performing reduced pressure distillation on the obtained filtrate to remove solvent and unreacted monomers, and collecting corresponding dimer and trimer fractions under a certain vacuum degree and different temperatures, thereby obtaining the poly-alpha-olefin containing unsaturated double bonds.

3) Preparation of epoxidized polyalphaolefins: the dimer or trimer of the poly alpha olefin prepared by the preparation method is placed in a reaction bottle, water, sodium bicarbonate and solvent are added, then the mixture is strongly stirred, the temperature of the ice water bath is reduced to below 0 ℃, oxidant is slowly added into the reaction bottle in batches for stirring reaction (at the moment, the temperature of the reaction liquid is controlled below 0 ℃), and the mixture is naturally heated to room temperature after the oxidant is added, and the stirring reaction is continued for 1-7 d.

After the reaction is finished, the reaction solution is filtered and distilled (40 ℃ and the vacuum degree is 10 KPa) to remove the solvent, and then the solvent is purified by a chromatographic column, wherein the volume ratio of the eluent is 10:1 in petroleum ether/ethyl acetate, and finally obtaining the epoxidized polyalphaolefin.

Example 1

This example provides a more specific process for the preparation of polyalphaolefins.

In the preparation method, the main catalyst is a metallocene compound, and the structural formula is as follows:

alpha olefin is 1-decene, cocatalyst is methylaluminoxane, and solvent isToluene, the concentration of the metallocene compound in the reaction system was 0.3mmol/L (calculated as Zr), the concentration of methylaluminoxane in the reaction system was 60mmol/L, the addition amount of 1-decene was 600mL, the addition amount of toluene was 200mL, the reaction temperature was 60℃and the reaction pressure was 0.1MPa. After 1h of reaction, the reaction is finished, the obtained filtrate is collected into a dimer fraction C with the temperature of 110-135 ℃ under the vacuum degree of 0.8torr ₂₀ H ₄₀ Collecting trimer fraction C at 150-170 deg.C ₃₀ H ₆₀ 。

Example 2

In the preparation method, alpha olefin is 1-octene, a main catalyst is a metallocene compound, the structural formula of the metallocene compound is the same as that of the embodiment 1, a cocatalyst is methylaluminoxane, a solvent is toluene, the concentration of the metallocene compound in a reaction system is 0.3mmol/L (calculated by Zr), the concentration of the methylaluminoxane in the reaction system is 60mmol/L, the adding amount of 1-octene is 600mL, the adding amount of toluene is 200mL, the reaction temperature is 60 ℃, and the reaction pressure is 0.1MPa. After 1h of reaction, the reaction is finished, the obtained filtrate is collected to obtain dimer fraction C with the temperature of 100-125 ℃ under the vacuum degree of 0.8torr ₁₆ H ₃₂ Collecting trimer fraction C at 135-155 deg.C ₂₄ H ₄₈ 。

Example 3

The embodiment provides a more specific preparation method of epoxidized polyalphaolefin III-1, wherein the structural formula of the epoxidized polyalphaolefin is as follows:

wherein the polyalphaolefin of formula II is a polyalphaolefin dimer C prepared in example 1 ₂₀ H ₄₀ The solvent adopts acetone, the oxidant is potassium peroxomonosulphonate, the poly alpha olefin is 60g, the potassium peroxomonosulphonate is 263g, the sodium bicarbonate is 110g, the water is 240g, the acetone is 150g, the reaction temperature is normal temperature, and the reaction time is 6d. After working up, epoxidized polyalphaolefins C are obtained ₂₀ H ₄₀ O 52g, the yield was 86.7%.

¹ H-NMR (400 MHz, deuterated toluene): delta 3.05 (2 h, d, j=4.1 Hz), 1.45-1.54 (8 h, m), 1.19-1.33 (24 h, m), 0.83-0.89 (6 h, m). From the resonance absorption peak at δ3.05, the presence of epoxy groups in the epoxide molecular structure leads to a shift of the surrounding 2H to the lower field, and an increase in chemical shift.

Example 4

The embodiment provides a more specific preparation method of epoxidized polyalphaolefin III-2, wherein the structural formula of the epoxidized polyalphaolefin is as follows:

wherein the polyalphaolefin of formula II is a polyalphaolefin trimer C prepared in example 1 ₃₀ H ₆₀ The solvent adopts acetone, the oxidant is potassium peroxomonosulphonate, the poly alpha olefin is 66g, the potassium peroxomonosulphonate is 250g, the sodium bicarbonate is 125g, the water is 300g, the acetone is 200g, the reaction temperature is normal temperature, and the reaction time is 6d. After working up, epoxidized polyalphaolefins C are obtained ₃₀ H ₆₀ O53.5g, yield 81.1%.

¹ H-NMR (400 MHz, deuterated toluene): delta 3.08 (2h, d, j=4.1 Hz), 1.61 (2h, d, j=8.3 Hz), 1.52 (2h, t, j=6.7 Hz), 1.48 (2h, tt, j=7.1, 6.7 Hz), 1.18 to 1.31 (39 h, m), 0.83 to 0.90 (9 h, m), 0.80 (4 h, q, j=7.2 Hz). From the resonance absorption peak at δ3.08, the presence of epoxy groups in the epoxide molecular structure results in a shift of the surrounding 2H to the lower field, and an increase in chemical shift.

Example 5

The embodiment provides a more specific preparation method of epoxidized polyalphaolefin III-3, wherein the structural formula of the epoxidized polyalphaolefin is as follows:

wherein the polyalphaolefin of formula II is an unsaturated polyalphaolefin prepared as in example 2Dimer C ₁₆ H ₃₂ The solvent adopts acetone and acetonitrile, the oxidant is potassium peroxomonosulphonate, the polyalphaolefin is 135g, the potassium peroxomonosulphonate is 500g, the sodium bicarbonate is 225g, the water is 600g, the acetone is 200g, the acetonitrile is 200g, the reaction temperature is normal temperature, and the reaction time is 6d. After working up, epoxidized polyalphaolefins C are obtained ₁₆ H ₃₂ O119 g, yield 88.1%.

¹ H-NMR (400 MHz, deuterated toluene) delta 3.05 (2H, d, j=4.1 Hz), 1.45-1.51 (8H, m), 1.17-1.32 (16H, m), 0.87 (6H, t, j=7.0 Hz). From the resonance absorption peak at δ3.05, the presence of epoxy groups in the epoxide molecular structure leads to a shift of the surrounding 2H to the lower field, and an increase in chemical shift.

Example 6

The embodiment provides a more specific preparation method of epoxidized polyalphaolefin III-4, wherein the structural formula of the epoxidized polyalphaolefin is as follows:

wherein the polyalphaolefin of formula II is a polyalphaolefin trimer C prepared in example 2 ₂₄ H ₄₈ The solvent adopts acetone and acetonitrile, the oxidant is potassium peroxomonosulphonate, the polyalphaolefin is 120g, the potassium peroxomonosulphonate is 465g, the sodium bicarbonate is 205g, the water is 600g, the acetone is 200g, the acetonitrile is 200g, the reaction temperature is normal temperature, and the reaction time is 6d. After working up, epoxidized polyalphaolefins C are obtained ₂₄ H ₄₈ 104.5g of O and the yield thereof was found to be 87.1%.

¹ H-NMR (400 MHz, deuterated toluene) delta 3.07 (2H, d, j=4.1 Hz), 1.60 (2H, d, j=8.3 Hz), 1.52 (2H, t, j=6.7 Hz), 1.48 (2H, tt, j=7.1, 6.7 Hz), 1.16-1.33 (27H, m), 0.87 (9H, t, j=7.0 Hz), 0.80 (4H, q, j=7.2 Hz). From the resonance absorption peak at δ3.07, the presence of epoxy groups in the epoxide molecular structure leads to a shift of the surrounding 2H to the lower field, and an increase in chemical shift.

Example 7

This example provides a more specific method of preparing a polymer.

Wherein, in the step (1), the epoxidized polyalphaolefin III-1 is prepared by the preparation method in the example 3, the dosage is 42g (0.142 mol), the carboxylic acid compound is lauric acid (dodecanoic acid), the dosage is 31g (0.155 mol), the first catalyst is cetyltrimethylammonium chloride, the dosage is 0.05g, the reaction temperature is firstly increased to 120 ℃, the temperature is kept for 2 hours, the temperature is increased to 140 ℃, and the reaction end point is lower than the acid value of 16mg KOH/g.

In the step (2), the molecular weight of polyethylene glycol is 10000, the dosage of polyethylene glycol after dehydration is 400g (0.04 mol), the dosage of organic solvent is 20g and 5g respectively, the dosage of diisocyanate is isophorone diisocyanate (IPDI), the dosage is 22.5g (0.10 mol), the second catalyst is dibutyl tin Dilaurate (DBLT), the dosage is 0.02g, the dropwise adding temperature of isophorone diisocyanate (IPDI) and dibutyl tin dilaurate is 70 ℃, the reaction temperature is 80 ℃ first, the heat preservation reaction is carried out for 3 hours, the temperature is continuously raised to 85 ℃, the heat preservation reaction is carried out for 3 hours, and finally 73g of monohydric alcohol prepared in the step (1) is added, the temperature is raised to 90 ℃, the heat preservation reaction is carried out for 2 hours, and the inert gas is nitrogen.

The polymer sample prepared in this example was subjected to infrared analysis by using a Bruker Tensor27 type Fourier infrared spectrometer by using a liquid film method, and an infrared spectrum of the sample was obtained, as shown in FIG. 1.

FTIR:3342cm ^-1 (v _s N-H),2881cm ^-1 (v _s -CH ₂ -),1717cm ^-1 (v _s C＝O),1462cm ^-1 (δ-CH ₂ -),

1284cm ^-1 (v _as C-O),1099cm ^-1 (v _s C-O),844cm ^-1 (γ-CH ₂ -,-CH ₃ ). It can be seen that between 2200 and 2300cm ^-1 No significant absorption peaks were present in the range of (C), indicating that the-NCO groups had been completely reacted by grafting.

Example 8

This example provides a more specific method of preparing a polymer.

Wherein, in the step (1), the epoxidized poly alpha olefin III-1 is prepared by adopting the preparation method in the example 3, the dosage is 42g (0.142 mol), the carboxylic acid compound adopts 6-heptene-1-acid, the dosage is 20g (0.156 mol), the first catalyst adopts hexadecyl trimethyl ammonium chloride, the dosage is 0.05g, the reaction temperature is firstly increased to 120 ℃, the heat preservation reaction is carried out for 2 hours, the temperature is then increased to 140 ℃, and the reaction end point is lower than the acid value of 18mg KOH/g.

In the step (2), the molecular weight of polyethylene glycol is 10000, the dosage of polyethylene glycol after dehydration is 400g (0.04 mol), the dosage of organic solvent is 25g, the dosage of diisocyanate is isophorone diisocyanate (IPDI), the dosage is 22.5g (0.10 mol), the second catalyst is dibutyl tin Dilaurate (DBLT), the dosage is 0.02g, the dropping temperature of isophorone diisocyanate (IPDI) and dibutyl tin dilaurate is 70 ℃, the reaction temperature is 80 ℃ first, the heat preservation reaction is carried out for 3 hours, the temperature is continuously raised to 85 ℃, the heat preservation reaction is carried out for 3 hours, and finally 73g of monohydric alcohol prepared in the step (1) is added, the temperature is raised to 90 ℃, the heat preservation reaction is carried out for 2 hours, and the inert gas is nitrogen.

The polymer sample prepared in this example was subjected to infrared analysis by using a Bruker Tensor27 type Fourier infrared spectrometer by using a liquid film method, and an infrared spectrum of the sample was obtained, as shown in FIG. 2.

FTIR:3522cm ^-1 (v _s N-H),2875cm ^-1 (v _s -CH ₂ -),1718cm ^-1 (v _s C＝O),1645cm ^-1 (v _s C＝C),1470

cm ^-1 (δ-CH ₂ -),1245cm ^-1 (v _as C-O),1112cm ^-1 (v _s C-O),841cm ^-1 (γ-CH2-,-CH3)。

It can be seen that between 2200 and 2300cm ^-1 No significant absorption peak in the range of (2) indicates that the-NCO group has been completely grafted, at 1645cm ^-1 The marked absorption peak with c=c indicates that the double bond has been grafted onto the polymer.

Example 9

This example provides a more specific method of preparing a polymer.

Wherein, in the step (1), the epoxidized poly alpha olefin III-2 is prepared by adopting the preparation method in the example 4, the dosage is 62g (0.142 mol), the carboxylic acid compound adopts beta-carboxyethyl acrylate (beta-CEA), the dosage is 24.5g (0.170 mol), the first catalyst adopts cetyltrimethylammonium chloride, the dosage is 0.05g, the polymerization inhibitor p-hydroxyanisole is added, the dosage is 50mg, the reaction temperature is firstly increased to 110 ℃, the temperature is kept for 2 hours, the temperature is then increased to 120 ℃, and the reaction end point is lower than the acid value of 22mg KOH/g.

In the step (2), the molecular weight of polyethylene glycol is 10000, the dosage of polyethylene glycol after dehydration is 400g (0.04 mol), the dosage of organic solvent is 20g and 5g of methyl ethyl ketone and acetone respectively, the dosage of diisocyanate is isophorone diisocyanate (IPDI), the dosage of diisocyanate is 22.5g (0.10 mol), the second catalyst is dibutyl tin Dilaurate (DBLT), the dosage of the second catalyst is 0.02g, the dropwise adding temperature of isophorone diisocyanate (IPDI) and dibutyl tin dilaurate is 70 ℃, the reaction temperature is 80 ℃ first, the heat preservation reaction is carried out for 3 hours, the temperature is continuously raised to 85 ℃, the heat preservation reaction is carried out for 3 hours, 86.5g of monohydric alcohol prepared in the step (1) is added, the temperature is raised to 90 ℃, the heat preservation reaction is carried out for 2 hours, and the inert gas is nitrogen.

The polymer sample prepared in this example was subjected to infrared analysis by using a Bruker Tensor27 type Fourier infrared spectrometer by using a liquid film method, and an infrared spectrum of the sample was obtained, as shown in FIG. 3.

FTIR:3439cm ^-1 (v _s N-H),2889cm ^-1 (v _s -CH ₂ -),1728cm ^-1 (v _s C＝O),1640cm ^-1 (v _s C＝C),1470

cm ^-1 (δ-CH ₂ -),1285cm ^-1 (v _as C-O),1108cm ^-1 (v _s C-O),836cm ^-1 (γ-CH ₂ -,-CH ₃ )。

It can be seen that between 2200 and 2300cm ^-1 No significant absorption peak in the range of (2) indicates that the-NCO group has been completely grafted, at 1640cm ^-1 The marked absorption peak with c=c indicates that the double bond has been grafted onto the polymer.

Example 10

This example provides a more specific method of preparing a polymer.

Wherein, in the step (1), the epoxidized poly alpha olefin III-3 is prepared by adopting the preparation method in the example 5, the dosage is 34g (0.142 mol), the carboxylic acid compound is palmitic acid (hexadecanoic acid), the dosage is 40g (0.156 mol), the first catalyst is cetyltrimethylammonium chloride, the dosage is 0.05g, the reaction temperature is firstly increased to 120 ℃, the temperature is kept for 2 hours, the temperature is increased to 140 ℃, and the reaction end point is lower than the acid value of 16mg KOH/g.

In the step (2), the molecular weight of polyethylene glycol is 6000, the dosage of dehydrated polyethylene glycol is 240g (0.04 mol), the dosage of organic solvent adopts methyl ethyl ketone and acetone, the dosage of organic solvent adopts Hexamethylene Diisocyanate (HDI) and 17g (0.10 mol), the dosage of second catalyst adopts dibutyl tin Dilaurate (DBLT), the dropping temperature of Hexamethylene Diisocyanate (HDI) and dibutyl tin dilaurate is 70 ℃, the reaction temperature is 80 ℃ firstly, the heat preservation reaction is carried out for 2 hours, the temperature is continuously raised to 85 ℃, the heat preservation reaction is carried out for 2 hours, 74g of monohydric alcohol prepared in the step (1) is added, the temperature is raised to 90 ℃, the heat preservation reaction is carried out for 2 hours, and the inert gas is nitrogen.

The polymer sample prepared in this example was subjected to infrared analysis by Bruker Tensor27 type Fourier infrared spectrometer using a liquid film method, and subjected to spectrogram analysis, 3369cm ^-1 (v _s N-H),2878cm ^-1 (v _s -CH ₂ -),1725cm ^-1 (v _s C＝O),1466cm ^-1 (δ-CH ₂ -),1258cm ^-1 (v _as C-O),1111cm ^-1 (v _s C-O),845cm ^-1 (γ-CH ₂ -,-CH ₃ ). It can be seen that between 2200 and 2300cm ^-1 No significant absorption peaks were present in the range of (C), indicating that the-NCO groups had been completely reacted by grafting.

Example 11

This example provides a more specific method of preparing a polymer.

Wherein, in the step (1), the epoxidized poly alpha olefin III-4 is prepared by adopting the preparation method in the example 6, the dosage is 50g (0.142 mol), the carboxylic acid compound is 2-isooctanoic acid, the dosage is 22g (0.153 mol), the first catalyst is cetyltrimethylammonium chloride, the dosage is 0.05g, the reaction temperature is firstly increased to 120 ℃, the temperature is kept for 2 hours, the temperature is increased to 140 ℃, and the reaction end point is lower than the acid value of 16mg KOH/g.

In the step (2), the molecular weight of polyethylene glycol is 6000, the dosage of polyethylene glycol after dehydration is 240g (0.04 mol), the dosage of organic solvent is 10g of methyl ethyl ketone, the dosage of diisocyanate is 4,4 '-dicyclohexylmethane diisocyanate (HMDI), the dosage of diisocyanate is 26.5g (0.10 mol), the second catalyst is dibutyl tin Dilaurate (DBLT), the dripping temperature of 0.02g, 4' -dicyclohexylmethane diisocyanate (HMDI) and dibutyl tin dilaurate is 70 ℃, the reaction temperature is 80 ℃ first, the heat preservation reaction is carried out for 2 hours, the temperature is continuously raised to 85 ℃, the heat preservation reaction is carried out for 2 hours, 72g of monohydric alcohol prepared in the step (1) is added, the temperature is raised to 90 ℃, and the heat preservation reaction is carried out for 2 hours.

The polymer sample prepared in this example was subjected to infrared analysis by Bruker Tensor27 type Fourier infrared spectrometer using a liquid film method, and the analysis spectrum was 3456cm ^-1 (v _s N-H),2883cm ^-1 (v _s -CH ₂ -),1714cm ^-1 (v _s C＝O),1459cm ^-1 (δ-CH ₂ -),1276cm ^-1 (v _as C-O),1119cm ^-1 (v _s C-O),838cm ^-1 (γ-CH ₂ -,-CH ₃ ). It can be seen that there is no significant absorption peak in the range 2200-2300cm-1, indicating that the-NCO groups have been completely reacted by grafting.

Comparative example

This comparative example is the comparative example of example 8.

Except that 1-stearyl alcohol was used as the monohydric alcohol in an amount of 36.5g.

Samples of the polymers prepared in the comparative examples were subjected to infrared analysis using a Bruker Tensor27 type Fourier infrared spectrometer using a liquid film method, and the analysis spectrum, FTIR:3321cm ^-1 (v _s N-H),2888cm ^-1 (v _s -CH ₂ -),1723cm ^-1 (v _s C＝O),1467cm ^-1 (δ-CH ₂ -),1249cm ^-1 (v _as C-O),1105cm ^-1 (v _s C-O),847cm ^-1 (γ-CH ₂ -,-CH ₃ )。

At 2200-2300cm ^-1 No significant absorption peaks were present in the range of (C), indicating that the-NCO groups had been completely reacted by grafting.

The following performance tests were performed on the polymers prepared in examples 7 to 11 and comparative examples: rheology determination, thickening performance testing, and other performance testing. The results of the measurements are shown in FIGS. 4 to 10 and tables 2 to 3.

The test criteria or methods are as follows:

(1) Rheological property measurement: the application adopts a rotor rheometer to control different shear rates (0.01-100 s) at room temperature (25+/-1℃) ^-1 ) The shear viscosity of the polymers prepared in examples 7 to 11 and comparative examples was measured at concentrations of 0.5wt%, 1.0wt%, 2.0wt% and 3.0wt%, respectively.

The preparation method was that the mixed solutions (mass ratio 4:1) of water and diethylene glycol monobutyl ether for the polymers prepared in examples 7 to 11 and comparative example were prepared as aqueous solutions having concentrations of 0.5wt%, 1.0wt%, 2.0wt% and 3.0wt%, respectively.

In the testing process, the solution of the sample to be tested is prepared and then is kept still for 30min until the solution reaches an equilibrium state, and meanwhile, a silicone oil liquid seal is used at the edge of the sample to prevent the concentration of the sample solution from changing due to water evaporation.

Measurement results:

the shear viscosity and shear rate of the polymers prepared in examples 7 to 11 and comparative examples with different concentrations are plotted in the same logarithmic coordinate system, and the test results are shown in fig. 4 to 9;

at low shear rate (0.01 s ^-1 And 0.1s ^-1 ) The results of the shear viscosity test of the polymers prepared in examples 7 to 11 and comparative examples at different concentrations are shown in Table 2.

TABLE 2

Typically, the viscosity of the aqueous polymer solution is reduced by shear and once the external shear is removed, the solution viscosity quickly returns to near the initial viscosity, which rheology imparts good thixotropic properties to the aqueous polymer solution. The polymers prepared in examples 7 to 11 of the present invention form an association network by means of association between a plurality of hydrophobic chains at the ends in a solution, and this force is a reversible weak force, when the solution system is subjected to a large external force shearing action, the hydrophobic force at the ends of polyurethane molecules is broken, which is manifested as a decrease in viscosity, and when the external force is withdrawn, the hydrophobic chains at the ends of polyurethane molecules are automatically inserted into the hydrophobic cores of adjacent micelles to form micelle aggregates, which is manifested as a restoration of viscosity, so that the aqueous polymer solution system has good thixotropic properties.

From fig. 4 to 9, the shear viscosity of the aqueous polymer solution increases with increasing concentration, wherein the viscosity of examples 7 to 11 at low shear rate changes little with the shear rate, i.e., the shear stress is linear with the shear rate, approaching a typical newtonian fluid state in which the shear rate cannot break the dynamic balance of the association network formed between the hydrophobic segments, i.e., the association network cannot be broken by the shear force, and thus the aqueous polymer solution assumes a newtonian fluid state at low shear rate, the shear force increases the disassociation rate with increasing shear rate, the dynamic balance of the association network is broken, and the structure is broken, thus causing the aqueous polymer solution to undergo shear thinning at high shear rate. As is clear from examples 7 to 11 and comparative examples, the comparative examples are prepared by grafting 1-octadecanol onto polyurethane, and the polyurethane has only one hydrophobic chain at the molecular end, so that a dense hydrophobic association network is difficult to form and is easily damaged by shearing force, so that the corresponding aqueous solution shows shear thinning behavior at a low shearing rate, while examples 7 to 11 are prepared by carrying out ring opening reaction on epoxidized polyalphaolefin and other carboxylic acids and then grafting with polyurethane, and the obtained polyurethane has at least 3 hydrophobic chains at the molecular end, so that the hydrophobic association effect in the aqueous solution is stronger, and a more perfect hydrophobic association network can be formed.

In addition, from the viewpoint of thickening efficiency, the data in Table 2 show that the aqueous polymer solutions of examples 7 to 11 have significantly higher shear viscosity than the comparative examples under the same thickener concentration and shear rate, which indicates that the hydrophobic association between the plurality of hydrophobic chains at the molecular terminals of the polyurethane thickener is greater, and that the formed association network has a high density which is advantageous for improving thickening efficiency, and examples 7 to 11 achieve the same thickening effect at a lower amount than comparative examples, in which the hydrophobic association is significantly inferior to examples 7 to 11 because the polyurethane molecules have only one hydrophobic side chain on both sides, and a higher amount is required to achieve the same thickening effect.

(2) Thickening performance test:

the test object is JF1025 aqueous acrylic resin emulsion, the JF1025 aqueous acrylic resin emulsion is prepared by emulsion polymerization of acrylic ester monomers, the appearance is milky semitransparent liquid, the solid content is 42+/-1%, and the JF1025 aqueous acrylic resin emulsion is applied to film-forming resin of quick-drying wood coating and is provided by the Zibojiafeng chemical engineering development Co.

The test method was to add the polymers prepared in examples 7 to 11 and comparative example to JF1025 aqueous acrylic resin emulsion at high dispersion as a thickener in a fixed addition amount of 0.25wt% and then to control different shear rates at room temperature (25.+ -. 1 ℃ C.) according to the above method to determine the shear viscosity of JF1025 aqueous acrylic resin emulsion without adding a thickener and with adding a different thickener, respectively.

Measurement results: the shear viscosity and shear rate of JF1025 aqueous acrylic resin emulsion without the addition of the thickener and with the addition of 0.25wt% of the polymer prepared in examples 7 to 11 and comparative example as the thickener were plotted on the same logarithmic coordinate system, and the test results are shown in FIG. 10, at a low shear rate (0.01 s ^-1 And 0.1s ^-1 ) The shear viscosity is shown in Table 3 below.

TABLE 3 Table 3

From the rheological test of fig. 10, the JF1025 emulsion without any thickener added exhibited a significant shear thinning characteristic, with a significant decrease in viscosity with increasing shear rate. The JF1025 emulsion was maintained at 0.1s after the addition of the polymer of the comparative example ^-1 The viscosity decreases slowly before the shear rate and then increases further to break the hydrophobically associating network, with the viscosity of the emulsion system also beginning to decrease significantly. The JF10258 emulsion viscosity decreased slowly with increasing shear rate after addition of the polymers of examples 7-11, especially at lower previous shear rates, the corresponding JF1025 emulsion viscosity changed very little with shear rate, and the shear stress and shear rate were approximately linear and nearly newtonian. The reason is that the embodiment 7-11 introduces a plurality of hydrophobic side chains at the tail end of polyurethane molecules, which is favorable for forming a denser hydrophobic association network by multipoint association, can obviously reduce the shear thinning amplitude when being used for an acrylic ester emulsion system, and is favorable for maintaining the viscosity at a high shear rate and avoiding splashing caused by too thin viscosity during construction. The more the number of hydrophobic side chains at the tail end of the molecule and the higher the number of carbon atoms of the side chains, the stronger the strength of the formed hydrophobic association network, and the stronger the resistance to shearing force, the higher the shearing viscosity is maintained under the condition of high shearing strength in rheological property.

In addition, from the viewpoint of thickening efficiency, the data in Table 3 shows that JF1025 emulsion added with 0.25wt% of the polymers of examples 7 to 11 has higher viscosity under the same thickener concentration and shear rate, and thus it is considered that the polymers prepared in examples 7 to 11 have higher thickening efficiency than the comparative examples, and the same thickening effect can be achieved at lower use amount.

(3) Varnish formulation and other Performance testing

The polymer prepared in example 7 was compared with a commercially available polyurethane thickener RM-8W formulated waterborne wood lacquer varnish, the formulation of which is shown in Table 1:

TABLE 1

Component (A)	Dosage/g
		JF1025 aqueous acrylic resin emulsion	66
Film forming aid (DPM DPnB=1:1)	7.5
		Wetting agent BYK-346	0.5
Defoaming agent BYK-028	0.1
		Thickening agent	0.2
Water and its preparation method	25.7

The first varnish as shown in the above table was sprayed on wood, dried at room temperature for 24 hours, polished, sprayed with a second varnish, dried at room temperature for 7 days, and the water resistance on the paint film was tested separately, using the normal temperature water immersion method (GB/T23999-2009). And meanwhile, observing and recording the state of a paint film in the spraying process. The polymer prepared in example 7 was sprayed in the same amount as the commercial polyurethane thickener RM-8W formulated aqueous wood lacquer varnish for spraying.

The polymer of example 7 is compared with the wet film appearance of the water-based wood lacquer varnish prepared by the commercial polyurethane thickener RM-8W after spraying, the varnish film added with the polymer of example 7 is transparent and has no milky white after spraying, and the surface of the coating sprayed by the varnish added with the RM-8W thickener is milky white, which indicates that the wet film permeability of the water-based wood lacquer varnish prepared by the polymer of example 7 is better. When the spraying template is constructed, if the wet film is opaque, the difficulty in observing and controlling the color is greatly increased, the color mixing of the water-based paint is not facilitated, and the same color mixing effect as that of the solvent-based paint cannot be achieved. The water-based varnish paint film added with the polymer prepared in the example 7 has slight blushing phenomenon for the water resistance test after 7d, the varnish paint film added with the polymer prepared in the example 7 is recovered faster, the varnish paint film added with the RM-8W thickener is recovered completely within 10min, and the recovery of 30min is required, which indicates that the water resistance can be improved when the polymer prepared in the example 7 is used as the thickener for the water-based wood paint.

The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.

Claims

1. A polymer formed by polymerization comprising the following components, characterized in that:

2) At least one polyether polyol;

3) At least one diisocyanate.

2. The polymer of claim 1, wherein the monohydric alcohol is the ring-opening reaction product of an epoxidized polyalphaolefin and a carboxylic acid compound.

3. The polymer of claim 2, wherein the molar ratio of the carboxylic acid compound to the epoxidized polyalphaolefin is (1 to 1.2): 1, a step of;

and/or the reaction temperature is 90-140 ℃;

and/or, the reaction system comprises a first catalyst; the first catalyst is a quaternary ammonium salt compound.

4. The polymer according to claim 1, wherein the polyether polyol comprises polyethylene glycol having a molecular weight of 400 to 20000 g/mol.

5. The polymer according to claim 1, wherein the diisocyanate is a C1-C20 linear alkyl, branched or unbranched cyclic alkyl, a C1-C20 benzene ring or aromatic fused ring diisocyanate.

6. A process for the preparation of a polymer as claimed in any one of claims 1 to 5, comprising the steps of:

7. The process according to claim 6, wherein the molar ratio of the monohydric alcohol to the isocyanate groups in the prepolymer is (1 to 1.2): 1, a step of;

and/or, a second catalyst is included in the reaction system; the second catalyst is one or more selected from dibutyl tin dilaurate, stannous octoate or organic bismuth catalysts;

and/or, the reaction system also comprises an organic solvent; the organic solvent is ketone;

and/or the reaction temperature is 60-100 ℃.

8. The process according to claim 6, wherein the prepolymer of the polyether polyol and the diisocyanate has a degree of polymerization of 2 to 20.

9. Use of a polymer according to any one of claims 1 to 5 or a polymer prepared by a method according to any one of claims 6 to 8 as a thickener in a film-forming system comprising an aqueous resin.

10. The use according to claim 9, wherein the aqueous resin is an aqueous acrylic resin, an aqueous polyurethane-acrylate resin, an aqueous photo-curable acrylic resin, an aqueous photo-curable polyurethane resin or an aqueous photo-curable polyurethane-acrylate resin;

and/or the film-forming system containing the aqueous resin comprises one or more of an aqueous coating, an aqueous ink or an aqueous binder;

and/or the polymer is used in an amount of 0.1 to 1.0wt% based on the mass of the aqueous resin.