Hyperbranched polyurea materials, their preparation methods and applications

Abstract

The present invention relates to the technical field of chemical materials, and discloses a hyperbranched polyurea material, a preparation method and an application thereof. The hyperbranched polyurea material comprises a hyperbranched polyester polyol structural unit shown in formula (1) and an isocyanate structural unit shown in formula (2) provided by isocyanate; R1, R2 and R3 are the same or different, and each is one or more of C1-C9 alkylene group, olefin group, ester group and oxygen atom; X is an integer of 10-40, Y is an integer of 3-20, and Z is an integer of 5-80; R4 is an aromatic or aliphatic residue; the hyperbranched polyurea material has both excellent processing performance and mechanical properties; #imgabs0#

Description

Technical Field

[0001] The present invention relates to the technical field of chemical materials, and particularly relates to a hyperbranched polyurea material, a preparation method thereof and an application thereof. Background Art

[0002] Polyurea is an elastomer obtained by reacting an isocyanate component with an amino compound component. Since the reaction principle of polyurea is similar to that of polyurethane, and the application forms and fields are also basically the same, therefore, in a broad sense, polyurethane often includes polyurea and is collectively referred to as polyurethane. Structurally, polyurethane and polyurea also have similarities. Because common two-component polyurea often uses the reaction of hydroxyl group and isocyanate group for prepolymer modification, resulting in the presence of urethane group structure in the molecule. Generally speaking, materials in which the final curing reaction is completed by the reaction of isocyanate group and amino group are collectively referred to as polyurea materials, while materials in which the final curing reaction is the reaction of isocyanate group and hydroxyl group become polyurethane materials.

[0003] One of the major characteristics of polyurea is its fast curing reaction rate. In practical applications, the curing time of fast-reacting spray polyurea is often in seconds, making its construction efficiency extremely high, and it is less affected by environmental humidity. Construction in humid environments (such as tunnels, underground projects, etc.) has more advantages and is basically not affected by the side reaction of the reaction of isocyanate with water to generate carbon dioxide and produce foaming phenomena.

[0004] As is well known, the molecular weight of a polymer has an important influence on its physical and mechanical properties. For example, the tensile strength of a polymer increases with the increase of molecular weight. This is because the increase in molecular weight increases the chain entanglement between crystals, thereby enhancing the connection of longitudinal and transverse microfibers. When a tensile test is carried out, the chain entanglement inhibits the relative sliding of microfibers, thus increasing the tensile strength. However, the larger the molecular weight of a polymer, the corresponding increase in its shear viscosity, the worse the fluidity, and the sharp increase in apparent viscosity, making the processing performance of the polymer worse.

[0005] Although the performance of spray polyurea is widely praised, its fast curing characteristic also limits its application to a certain extent. Due to the fast curing speed, the molecular weight of polyurea should not be too large. Excessive molecular weight will lead to poor fluidity of the material, and curing will occur before the two components are completely mixed. In the prior art, the fluidity of the material is often improved by reducing the molecular weight, but this will also sacrifice the mechanical properties of the material.

[0006] Therefore, it is of great significance to research and develop a polyurea material that takes into account both mechanical properties and processing performance. Summary of the Invention

[0007] The object of the present invention is to overcome the defect problem existing in the prior art that the polyurea elastomer cannot balance the mechanical properties and processing properties, and to provide a hyperbranched polyurea material, a preparation method and an application thereof. The hyperbranched polyurea material balances excellent processing properties and mechanical properties.

[0008] To achieve the above object, in the first aspect of the present invention, a hyperbranched polyurea material is provided, wherein the hyperbranched polyurea material comprises a hyperbranched polyester polyol structural unit represented by formula (1) and an isocyanate structural unit represented by formula (2) provided by an isocyanate;

[0009]

[0010] wherein, R1, R2 and R3 are the same or different, and each is one or more of an alkylene group, an olefin group, an ester group and an oxygen atom having 1 to 9 carbon atoms; X is an integer from 10 to 40, Y is an integer from 3 to 20, and Z is an integer from 5 to 80; R4 is an aromatic or aliphatic residue.

[0011] In the second aspect of the present invention, a preparation method of a hyperbranched polyurea material is provided, wherein the preparation method comprises:

[0012] (1) Contacting an isocyanate, an organosilane, a hyperbranched polyester polyol, an optional polyether polyol and an optional diluent to carry out a prepolymerization reaction to obtain component A;

[0013] (2) Mixing an amino-terminated polyether, a chain extender, a filler and an auxiliary agent to obtain component B;

[0014] (3) Contacting component A with component B to carry out a reaction to obtain a hyperbranched polyurea material.

[0015] In the third aspect of the present invention, an application of the aforementioned hyperbranched polyurea material in the field of building coatings is provided.

[0016] Through the above technical solutions, by introducing a large number of branched structures, the present invention improves the fluidity of the prepolymer, improves the processing properties of the polyurea elastomer, and at the same time enhances the mechanical properties of the elastomer, enabling it to balance excellent processing properties and mechanical properties and expanding the scope of use. Description of the Drawings

[0017] Figure 1 is the GPC curve of the hyperbranched polyester polyol prepared in Example 1;

[0018] Figure 2 is the infrared spectrum of the hyperbranched polyester polyol prepared in Example 1;

[0019] Figure 3 is the digital photo of the hyperbranched polyurea material prepared in Example 1;

[0020] Figure 4 is the viscosity curve of Component A prepared in Examples 1-3;

[0021] Figure 5 is the tensile curve of the hyperbranched polyurea material prepared in Examples 1-3. Detailed Embodiments

[0022] The endpoints and any values in the ranges disclosed herein are not limited to the exact ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed herein.

[0023] In a first aspect of the present invention, a hyperbranched polyurea material is provided, wherein the hyperbranched polyurea material comprises a hyperbranched polyester polyol structural unit represented by formula (1) and an isocyanate structural unit represented by formula (2) provided by an isocyanate;

[0024]

[0025] wherein, R1, R2 and R3 are the same or different, and each is one or more of C1-C9 alkylene, alkenyl, ester group and oxygen atom; X is an integer from 10 to 40, Y is an integer from 3 to 20, Z is an integer from 5 to 80; R4 is an aromatic or aliphatic residue.

[0026] According to the present invention, preferably, the hyperbranched polyester polyol comprises any one of the structural units represented by formulas (3)-(5);

[0027]

[0028] wherein, in formula (3), x1 is from 10 to 40, y1 is from 3 to 20, z1 is from 5 to 80; in formula (4), x2 is from 10 to 40, y2 is from 3 to 20, z2 is from 5 to 80; in formula (5), x3 is from 10 to 40, y3 is from 3 to 20, z3 is from 5 to 80.

[0029] According to the present invention, preferably, in formula (3), x1 is from 15 to 40, y1 is from 3 to 20, z1 is from 8 to 75; in formula (4), x2 is from 15 to 40, y2 is from 3 to 20, z2 is from 8 to 75; in formula (5), x3 is from 15 to 40, y3 is from 3 to 20, z3 is from 8 to 75.

[0030] The inventors of the present invention have found that: when a hyperbranched polyester polyol reacts with an isocyanate by prepolymerization, due to the hyperbranched structure contained in the polyol mixture, in addition, the polyol also contains ester groups, has a relatively high molecular weight and a relatively low viscosity, thus making the viscosity of the prepared hyperbranched polyester polyol system relatively low and the mechanical properties of the material relatively high.

[0031] According to the present invention, the hyperbranched polyester polyol includes one or more of hyperbranched polycaprolactone polyol, hyperbranched polyvalerolactone polyol and hyperbranched polylactide polyol.

[0032] According to the present invention, the number-average molecular weight of the hyperbranched polyester polyol is 50,000 - 200,000, preferably 55,000 - 100,000; the hydroxyl value is 5 - 100 mgKOH / g, preferably 7 - 55 mgKOH / g.

[0033] According to the present invention, the preparation method of the hyperbranched polyester polyol includes:

[0034] (1-1) Preparation of star-shaped polybutadiene

[0035] Under an inert atmosphere, in the presence of a n-butyllithium initiator, a cyclohexane solution of butadiene is contacted with a SiCl4 coupling agent for a coupling reaction to obtain star-shaped polybutadiene SPB;

[0036] (1-2) Preparation of star-shaped epoxidized polybutadiene

[0037] The SPB, toluene, HCOOH and H2O2 are contacted for a second reaction to obtain star-shaped epoxidized polybutadiene EPB;

[0038] (1-3) Preparation of star-shaped hydroxylated polybutadiene

[0039] The EPB, THF, trifluoromethanesulfonic acid and deionized water are contacted for a third reaction to obtain star-shaped hydroxylated polybutadiene S-HPB;

[0040] (1-4) Refinement of star-shaped hydroxylated polybutadiene

[0041] The S-HPB is refined to remove water to obtain refined S-HPB;

[0042] (1-5) Preparation of hyperbranched polycaprolactone polyol

[0043] Under an inert gas environment, in the presence of the refined S-HPB, 1,5,7-triazabicyclo[4.4.0]dec-5-ene is contacted with an inner lactone for a fifth reaction, wherein the inner lactone is selected from one or more of ε-caprolactone, δ-valerolactone and lactide, to obtain a hyperbranched polyester polyol.

[0044] According to the present invention, in step (1-1), the conditions for the coupling reaction include: the temperature is 10-80 °C and the time is 5-10 h; preferably, the molar ratio of butadiene, the initiator and the coupling agent is 80-200:4:1; in the present invention, the coupling agent is selected from KH550, KH560, KH570, etc.

[0045] According to the present invention, in step (1-1), the coupling reaction further includes adding isopropanol to terminate the reaction, washing with water, removing the solvent, and drying to obtain star-shaped polybutadiene.

[0046] Preferably, in step (1-2), the conditions for the second reaction include: the temperature is 10-60 °C and the time is 3-6 h; preferably, the mass ratio of the SPB, HCOOH and H2O2 is 40:1:5-10;

[0047] Preferably, in step (1-3), the conditions for the third reaction include: the temperature is 10-60 °C and the time is 3-6 h; preferably, the mass ratio of the EPB, trifluoromethanesulfonic acid and deionized water is 6:5:6;

[0048] Preferably, in step (1-4), the conditions for the refining and water removal include: the temperature is 10-30 °C and the time is 2-3 h; under preferred conditions, it is carried out under vacuum conditions.

[0049] Preferably, in step (1-5), the conditions for the contact include: the temperature is 10-40 °C and the time is 8-16 h; preferably, the mass ratio of 1,5,7-triazabicyclo[4.4.0]dec-5-ene, S-HPB and the cyclic ester is 1:3:15-150;

[0050] According to a preferred specific embodiment of the present invention, the method for preparing the hyperbranched polyester polyol includes:

[0051] (1-1) Prepare star-shaped polybutadiene

[0052] Under an inert atmosphere, a cyclohexane solution of butadiene is prepared, preheated in a 50 °C constant temperature water bath for 10 min, n-BuLi is added to initiate the polymerization reaction, and after 3 h, the SiCl4 coupling agent is added for the coupling reaction. The molar ratio of butadiene, the initiator and the coupling agent is 80-200:4:1; after 5 h, isopropanol is added to terminate the reaction, washed with water, the solvent is removed, and dried to obtain star-shaped polybutadiene (SPB);

[0053]

[0054] (1-2) Prepare star-shaped epoxidized polybutadiene

[0055] Dissolve the SPB obtained in step (1-1) in toluene, add HCOOH, and slowly dropwise add H2O2. The mass ratio of the SPB, HCOOH, and H2O2 is 40:1:5-10; continue the reaction at 40 °C for 1.5 h. After the reaction, wash with water, remove the solvent, and dry to obtain star-shaped epoxidized polybutadiene (EPB);

[0056]

[0057] In the present invention, the schematic diagram of the above product is as follows:

[0058] (1-3) Preparation of star-shaped hydroxylated polybutadiene

[0059] Dissolve the EPB obtained in step (1-2) in THF, add trifluoromethanesulfonic acid (TfOH) and deionized water. The mass ratio of the EPB, the trifluoromethanesulfonic acid, and the deionized water is 6:5:6; react at 25 °C for 3.5 h. After the reaction, extract, wash with water, remove the solvent, and dry to obtain star-shaped hydroxylated polybutadiene (S-HPB);

[0060]

[0061] In the present invention, the schematic diagram of the above product is as follows:

[0062] (1-4) Refinement of star-shaped hydroxylated polybutadiene

[0063] Use the method of azeotropic water removal with THF multiple times for the S-HPB obtained in step (1-3). Further, under vacuum conditions, refine and remove water at 20 °C for 3 h. After refinement, prepare it into a solution and seal it with wax for standby;

[0064] (1-5) Preparation of hyperbranched polycaprolactone polyol

[0065] Under an inert gas environment, add 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) to a round-bottom flask, then add a macromolecular initiator (S-HPB) and a solvent. After the TBD is completely dissolved, add ε-caprolactone (ε-CL). The mass ratio of the 1,5,7-triazabicyclo[4.4.0]dec-5-ene, S-HPB, and ε-caprolactone is 1:3:15-150; react for 10 h. After the reaction, terminate the polymerization with benzoic acid, precipitate with methanol, wash, and dry to obtain hyperbranched polycaprolactone polyol.

[0066]

[0067] In the present invention, the schematic diagram of the above product is as follows:

[0068] According to the present invention, the preparation method of the hyperbranched polyvalerolactone polyol is the same as that of the hyperbranched polycaprolactone polyol, except that the raw material ε-caprolactone is replaced by δ-valerolactone.

[0069] According to the present invention, the preparation method of the hyperbranched polylactide polyol is the same as that of the hyperbranched polycaprolactone polyol, except that the raw material ε-caprolactone is replaced by lactide.

[0070] According to the present invention, the isocyanate is selected from one or more of toluene diisocyanate, diphenylmethane-4,4'-diisocyanate, polymethylene polyphenyl polyisocyanate, liquefied diphenylmethane diisocyanate, xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, cyclohexane dimethylene diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate.

[0071] According to the present invention, the hyperbranched polyurea material further comprises structural units provided by organosilane, optional polyether polyol, optional diluent, amino-terminated polyether, and chain extender.

[0072] According to the present invention, the organosilane is selected from one or more of polydimethylsiloxane, polydiphenylsiloxane, polyphenylmethylsiloxane, polydiethylsiloxane, divinylpolysiloxane, and vinylmethylpolysiloxane; preferably, the organosilane is polydimethylsiloxane and / or polydiphenylsiloxane; more preferably, the organosilane is polydimethylsiloxane.

[0073] According to the present invention, the polyether(ester) polyol is selected from one or more of polytetrahydrofuran diol, polyoxypropylene ether polyol, polyoxyethylene ether polyol, hydroxyl-terminated polybutadiene, polypropylene glycol, polyethylene glycol, triglyceride fatty acid, polycaprolactone polyol, polycarbonate diol, and 1,4-butanediol. In the present invention, the role of the polyether(ester) polyol is to adjust the strength and toughness of the polyurea material.

[0074] According to the present invention, the amino-terminated polyether is selected from one or more of amino-terminated polyether T5000, T3000, T403, D4000, D2000, D400, and D230; preferably, the amino-terminated polyether is selected from one or more of T5000, T3000, T403, D2000, and D400.

[0075] According to the present invention, the chain extender is selected from one or more of N-methyldiethanolamine, isophoronediamine (IPDA), polytetramethylene ether glycol bis(p-aminobenzoate), diethyltoluenediamine, dimethylthiotoluenediamine, N,N'-dialkyldiamine, N,N'-dialkylmethyldiamine, 1,4-bis(sec-butylamino)benzene, 4,4'-bis(sec-amino)diphenylmethane, 4,4'-methylenebis(3-chloro-2,6-diethylaniline) (M-CDEA), 4,4'-methylenebis(2,6-diethylaniline) (M-DEA), N,N'-bis(sec-pentyl)cyclohexanediamine; preferably, the chain extender is selected from one or more of N-methyldiethanolamine, isophoronediamine (IPDA), polytetramethylene ether glycol bis(p-aminobenzoate), diethyltoluenediamine, and 4,4'-methylenebis(3-chloro-2,6-diethylaniline) (M-CDEA).

[0076] According to the present invention, based on the total weight of the isocyanate, organosilane, hyperbranched polyester polyol, and optional polyether polyol, the dosage of the isocyanate is 20-70% by weight, the content of the organosilane is 1-20% by weight, the content of the hyperbranched polyester polyol is 5-30% by weight, and the content of the polyether polyol is 0-50% by weight; preferably, based on the total weight of the isocyanate, organosilane, hyperbranched polyester polyol, optional polyether polyol, and optional diluent, the content of the isocyanate is 30-50% by weight, the content of the organosilane is 2-8% by weight, the content of the hyperbranched polyester polyol is 5-30% by weight, and the content of the polyether(ester) polyol is 15-43% by weight.

[0077] Preferably, based on the total weight of the amino-terminated polyether and the chain extender, the content of the amino-terminated polyether is 40-70% by weight, and the content of the chain extender is 10-50% by weight; preferably, based on the total weight of component B, the content of the amino-terminated polyether is 45-60% by weight, and the content of the chain extender is 25-50% by weight.

[0078] Preferably, in terms of the isocyanate index, the ratio of the total weight of the isocyanate, organosilane, hyperbranched polyester polyol, and optional polyether polyol to the total weight of the amino-terminated polyether and the chain extender is (1-1.2):1.

[0079] According to the present invention, the hyperbranched polyurea material has a tensile strength of 18-31 MPa, an elongation at break of 200-400%, and a tear strength of 100-170 N / mm; preferably, the polyurea material has a tensile strength of 20-31 MPa, an elongation at break of 200-390%, and a tear strength of 102-166 N / mm.

[0080] The second aspect of the present invention provides a method for preparing a hyperbranched polyurea material, wherein the preparation method includes:

[0081] (1) Contacting an isocyanate, an organosilane, a hyperbranched polyester polyol, an optional polyether polyol, and an optional diluent to carry out a prepolymerization reaction to obtain Component A;

[0082] (2) Mixing an amino-terminated polyether, a chain extender, a filler, and an auxiliary agent to obtain Component B;

[0083] (3) Contacting Component A with Component B to carry out a reaction to obtain a hyperbranched polyurea material.

[0084] According to the present invention, based on the total weight of Component A, the dosage of the isocyanate is 20-70% by weight, the dosage of the organosilane is 1-20% by weight, the dosage of the hyperbranched polyester polyol is 5-30% by weight, the dosage of the polyether polyol is 0-50% by weight, and the dosage of the diluent is 0-15% by weight; preferably, based on the total weight of Component A, the dosage of the isocyanate is 30-50% by weight, the dosage of the organosilane is 2-8% by weight, the dosage of the hyperbranched polyester polyol is 5-30% by weight, the dosage of the polyether (ester) polyol is 15-43% by weight, and the dosage of the diluent is 5-12% by weight. In the present invention, limiting the dosages of the respective components within the foregoing ranges has the advantage of maintaining a relatively low viscosity of Component A and relatively high mechanical properties of the material. Additionally, in the present invention, the organosilane has the effect of reducing the kinematic viscosity.

[0085] According to the present invention, the content of NCO in Component A is 10-20% by weight, preferably 12-17% by weight.

[0086] According to the present invention, the viscosity of Component A is 80-150 mPa·s, preferably, the viscosity of Component A is 100-120 mPa·s.

[0087] According to the present invention, the diluent is selected from one or more of tolylene diphenyl phosphate, 2-ethylhexyl diphenyl carbonate, propylene carbonate, ethyl carbonate, dibutyl phthalate, 2-chloroethyl ester, and acetone.

[0088] According to the present invention, the filler is selected from one or more of magnesium hydroxide, aluminum hydroxide, silicon dioxide, carbon black, graphene, and carbon nanotubes; preferably, the filler is selected from one or more of aluminum hydroxide, silicon dioxide, and carbon nanotubes. In the present invention, the role of the filler is to improve the mechanical properties of the material.

[0089] According to the present invention, the auxiliary agent includes a color paste, an antifoaming agent, and an antibacterial agent.

[0090] According to the present invention, preferably, based on the total weight of component B, the dosage of the amino-terminated polyether is 40-70% by weight, the dosage of the chain extender is 10-50% by weight, the dosage of the filler is 1-10% by weight, and the dosage of the auxiliary is 1-10% by weight; preferably, based on the total weight of component B, the dosage of the amino-terminated polyether is 45-60% by weight, the dosage of the chain extender is 25-50% by weight, the dosage of the filler is 2-6% by weight, and the dosage of the auxiliary is 2-7% by weight. In the present invention, limiting the dosages of the respective components within the aforementioned ranges has the advantage of maintaining relatively high mechanical properties of the material.

[0091] According to the present invention, preferably, in terms of the isocyanate index, the ratio of component A to component B is (1-1.2):1, preferably (1-1.05):1.

[0092] According to the present invention, it should be noted that the "isocyanate index" refers to the molar ratio of the isocyanate group component to the amino group component.

[0093] According to the present invention, the isocyanate, organosilane, hyperbranched polyester polyol, optional polyether polyol, optional diluent, amino-terminated polyether, and chain extender are the same as those described above and will not be elaborated here.

[0094] According to the present invention, in step (1), the conditions for the prepolymerization reaction include: the temperature is 60-100°C and the time is 1-2 h; preferably, the temperature is 70-80°C and the time is 1-1.5 h. In the present invention, after the prepolymerization reaction is completed, a cooling treatment is carried out.

[0095] According to the present invention, preferably, the polyol is pre-dehydrated under vacuum conditions at 60-120°C for 0.5-1.5 h, and then cooled to 40-60°C for subsequent prepolymerization reaction with the isocyanate and organosilane.

[0096] Preferably, in step (2), the conditions for the mixing include: the stirring rate is 800-1500 rpm, the temperature is 20-60°C, and the time is 30-120 min; preferably, the stirring rate is 1000-1200 rpm, the temperature is 30-40°C, and the time is 40-60 min.

[0097] According to the present invention, in step (3), the conditions for the contact reaction are such that component A and component B are sufficiently mixed; that is, mixing and polymerization reaction are carried out simultaneously; preferably, the conditions for the contact reaction include: the temperature is 60-75°C. In the present invention, a two-component spray gun is used for spraying. The amino-terminated polyether participates in the mixing and curing reaction of component A and component B. After component A and component B are mixed, they cure, similar to AB glue.

[0098] According to a preferred specific embodiment of the present invention, the preparation method of the hyperbranched polyurea material comprises:

[0099] (1) Preparation of Component A:

[0100] Add the polyol mixture composed of hyperbranched polyester polyol and polyether (ester) polyol into a reaction kettle, dehydrate under vacuum conditions at 60 - 120 °C for 0.5 - 1.5 h, then cool down to 40 - 60 °C, add the corresponding proportion of the isocyanate and organosilane into the reaction kettle, heat up to 70 - 80 °C, keep the temperature for reaction for 1 - 1.5 h, cool down after the prepolymerization reaction is completed to obtain Component A, wherein the NCO% content is 12 - 17%; based on the total weight of Component A, the dosage of the isocyanate is 30 - 50% by weight, the dosage of the organosilane is 2 - 8% by weight, the dosage of the hyperbranched polyester polyol is 5 - 30% by weight, and the dosage of the polyether (ester) polyol is 15 - 43% by weight;

[0101] (2) Preparation of Component B:

[0102] Add the following raw materials into the reaction kettle according to the formula amount: based on the total weight of Component B, the content of the amino - terminated polyether is 45 - 60% by weight, the content of the chain extender is 25 - 50% by weight, the content of the filler is 2 - 6% by weight, and the content of the auxiliary agent is 2 - 7% by weight; heat up to 30 - 40 °C, under nitrogen conditions, the stirring rate is 1000 - 1200 rpm, stir for 40 - 60 min to obtain Component B;

[0103] (3) Preparation of the polyurea material

[0104] Fully mix Component A and Component B according to the R value (1.0 - 1.05):1 to obtain the hyperbranched polyurea material.

[0105] The fourth aspect of the present invention provides an application of the aforementioned hyperbranched polyurea material in the field of building coatings.

[0106] According to the present invention, the field of building coatings includes building waterproof coatings and building reinforcing coatings.

[0107] The present invention will be described in detail below through examples.

[0108] In the following examples and comparative examples:

[0109] Test the tensile strength, elongation at break and tear strength after being placed for 7 days under the conditions specified in GB / T528 - 2009 and GB / T 529 - 2008;

[0110] Testing conditions for the molecular weight of hyperbranched polyester polyol: Malvern OMNISEC multi-detector GPC / SEC system, chloroform mobile phase, flow rate 1 ml / min, polystyrene standard sample;

[0111] Testing conditions for the viscosity of Component A: Brookfield DV2T viscometer, temperature 60 °C.

[0112] The following raw material sources are for illustrative purposes:

[0113] ε-Caprolactone, δ-valerolactone, lactide, 1,5,7-triazabicyclo[4.4.0]dec-5-ene were purchased from Sigma-Aldrich;

[0114] Polyoxypropylene ether polyol, polytetrahydrofuran diol, polydimethylsiloxane, polydiphenylsiloxane, polydivinylsiloxane, polytetramethylene ether glycol bis(p-aminobenzoate) were purchased from Aladdin Chemical Reagents;

[0115] Amino-terminated polyether was purchased from Chaoxu Chemical Co., Ltd.;

[0116] Polycarbonate diol was purchased from The Dow Chemical Company;

[0117] Polycaprolactone polyol was purchased from Daicel Corporation.

[0118] Example 1

[0119] This example is to illustrate the polyurea material prepared by the method of the present invention.

[0120] (1) Preparation of Component A:

[0121] 12 g of hyperbranched polycaprolactone polyol, 38 g of polytetrahydrofuran diol and 4 g of polydimethylsiloxane were added to a reaction kettle, dehydrated under vacuum at 80 °C for 1 h, then cooled to 40 °C, 37 g of toluene diisocyanate and 9 g of propylene carbonate were added, heated to 80 °C, and kept at this temperature for reaction for 1.5 h. After the prepolymerization reaction was completed, it was cooled to obtain Component A, in which the NCO% content was 17%;

[0122] Among them, the hyperbranched polycaprolactone polyol was prepared by the following method:

[0123] (1-1) Preparation of star-shaped polybutadiene

[0124] Under an argon atmosphere, the butadiene pretreated with n-BuLi was vaporized and introduced into cyclohexane to prepare a cyclohexane solution of butadiene (monomer: solvent = 1:8, w / w = 1:8). It was preheated in a constant temperature water bath at 50 °C for 10 min, and a measured amount of n-BuLi was quickly added to initiate the polymerization reaction. After 3 h, a SiCl4 coupling agent was added for the coupling reaction. The molar ratio of butadiene, initiator, and coupling agent was 200:4:1. The reaction continued at 50 °C for 5 h, and then isopropanol was added to terminate the reaction. After washing with water, removing the solvent, and drying, star-shaped polybutadiene (SPB) was obtained.

[0125]

[0126] (1-2) Preparation of star-shaped epoxidized polybutadiene

[0127] The dried SPB obtained in step (1-1) was weighed and dissolved in toluene. It was placed in a water bath at 40 °C, and HCOOH was added. H2O2 was slowly added dropwise. The mass ratio of SPB, HCOOH, and H2O2 was 40:1:5. The reaction continued for 1.5 h. After the reaction, it was washed with water, the solvent was removed, and it was dried to obtain star-shaped epoxidized polybutadiene (EPB).

[0128]

[0129] (1-3) Preparation of star-shaped hydroxylated polybutadiene

[0130] The dried EPB obtained in step (1-2) was weighed and dissolved in THF. Trifluoromethanesulfonic acid (TfOH) and deionized water were added. The mass ratio of the amounts of EPB, trifluoromethanesulfonic acid, and deionized water was 6:5:6. The reaction was carried out at 25 °C for 3.5 h. After the reaction, it was extracted with chloroform, washed with water, the solvent was removed, and it was dried to obtain star-shaped hydroxylated polybutadiene (S-HPB).

[0131]

[0132] (1-4) Purification of star-shaped hydroxylated polybutadiene

[0133] The S-HPB obtained in step (1-3) was further purified by azeotropic water removal with THF multiple times. A certain amount of S-HPB was added into a two-necked flask after being evacuated, baked, and filled with argon three times under high-purity argon. After sealing, it was successively connected to a three-way stopcock, a cold trap, and a vacuum pump. Under the protection of high-purity argon, refined THF was added to the device to fully dissolve S-HPB. Under reduced pressure, THF was pumped into the cold trap, and then THF was added again to dissolve it. The above operations were repeated 3-4 times. S-HPB was dried to a constant weight, and a certain amount of refined toluene was added to dissolve it, and it was prepared into a solution and sealed with wax for standby.

[0134] (1-5) Preparation of hyperbranched polycaprolactone polyol

[0135] Under an argon atmosphere, 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) was added to a round-bottom flask, and then a macromolecular initiator (S-HPB) and refined toluene were added. After TBD was completely dissolved, ε-caprolactone (ε-CL) was added. The mass ratio of 1,5,7-triazabicyclo[4.4.0]dec-5-ene, the S-HPB, and the cyclic lactone was 1:3:15. The reaction was carried out at 25 °C for 10 h. After the reaction was completed, the polymerization was terminated with benzoic acid, precipitated with methanol, washed, and dried to obtain hyperbranched polycaprolactone polyol.

[0136]

[0137] After testing, the number-average molecular weight of the obtained hyperbranched polycaprolactone polyol was 57,000, and the hydroxyl value was 28 mg KOH / g.

[0138] Structural formula:

[0139] Among them, x1 is 40, y1 is 7, and z1 is 15.

[0140] Figure 1 is the GPC curve of the hyperbranched polyester polyol prepared in Example 1; from Figure 1 it can be seen that the molecular weight distribution of this hyperbranched polyester polyol shows a single-peak distribution, and the molecular weight of the polyol is uniform.

[0141] Figure 2 is the infrared spectrum of the hyperbranched polyester polyol prepared in Example 1; from Figure 2 it can be seen that this hyperbranched polyester polyol contains obvious polyester absorption peaks (1750 cm -1 ).

[0142] Figure 3 is the digital photo of the hyperbranched polyurea material prepared in Example 1; this hyperbranched polyurea material product is a coating, which was sprayed on a flat plate for convenient testing and made into a sheet; from Figure 3 it can be seen that the surface of this hyperbranched polyurea material is smooth and flat, and the material is well spray-formed.

[0143] (2) Preparation of Component B:

[0144] The following raw materials were poured into a reaction kettle: 38.5 g of T5000 amino-terminated polyether, 13 g of 4,4'-methylenebis(3-chloro-2,6-diethylaniline), 6.4 g of N-methyldiethanolamine, 3.3 g of a filler (aluminum hydroxide, silica), and 3.85 g of other additives (specifically color paste, defoamer, antibacterial agent). The temperature was raised to 40 °C, and under nitrogen conditions, it was stirred for 60 min to obtain Component B;

[0145] (3) Preparation of polyurea material

[0146] The component A and component B are sprayed with a two-component spray gun at a temperature of 70°C according to an R value of 1.05:1 to obtain a hyperbranched polyurea material S1.

[0147] Example 2

[0148] This example is to illustrate the polyurea material prepared by the method of the present invention.

[0149] (1) Preparation of component A:

[0150] 10 g of hyperbranched polyvalerolactone polyol, 22 g of polycarbonate diol, 12 g of polyoxypropylene ether polyol, and 3 g of polydiphenylsiloxane are added to a reaction kettle, dehydrated under vacuum at 100°C for 1 h, then cooled to 45°C, and 46 g of diphenylmethane-4,4'-diisocyanate and 7 g of dibutyl phthalate are added. The temperature is raised to 90°C and the reaction is carried out for 1.5 h under insulation. After defoaming, it is cooled to obtain component A, in which the NCO% content is 15%;

[0151] Among them, the preparation method of the hyperbranched polyvalerolactone polyol is the same as that of the hyperbranched polycaprolactone polyol in Example 1, the difference is that: "ε-caprolactone" is replaced by "δ-valerolactone"; the number-average molecular weight of the obtained hyperbranched polyvalerolactone polyol is 98000, and the hydroxyl value is 7 mgKOH / g.

[0152] Structural formula:

[0153] Among them, x2 is 15, y2 is 3, and z2 is 75.

[0154] (2) Preparation of component B:

[0155] The following raw materials are poured into a reaction kettle: 50 g of amino-terminated polyether, 18 g of polytetramethylene ether glycol bis(p-aminobenzoate), 22 g of isophorone diamine, 5 g of filler (carbon black, graphene), and 5 g of other additives (specifically defoamer, antibacterial agent). The temperature is raised to 30°C and stirred for 60 min under nitrogen to obtain component B;

[0156] (3) Preparation of polyurea material

[0157] The component A and component B are sprayed with a two-component spray gun at a temperature of 65°C according to an R value of 1.04:1 to obtain a hyperbranched polyurea material S2.

[0158] Example 3

[0159] This example is to illustrate the polyurea material prepared by the method of the present invention.

[0160] The polyurea material was prepared in the same manner as in Example 1, except that:

[0161] (1) Preparation of Component A:

[0162] 15 g of hyperbranched polycaprolactone polyol, 10 g of polypropylene glycol, 20 g of polypropylene oxide ether diol, and 5 g of polydimethylsiloxane were added to a reaction kettle, and 45 g of dicyclohexylmethane diisocyanate and 5 g of 2-ethylhexyl diphenyl ester were added to obtain Component A, wherein the NCO% content was 16%;

[0163] Among them, the preparation method of the hyperbranched polycaprolactone polyol was the same as that of the hyperbranched polycaprolactone polyol in Example 1, except that: the number average molecular weight of the hyperbranched polycaprolactone polyol was 85000, and the hydroxyl value was 55 mgKOH / g.

[0164] Structural formula:

[0165] Among them, x1 was 30, y1 was 20, and z1 was 8.

[0166] (2) Preparation of Component B:

[0167] The following raw materials were poured into a reaction kettle: 60 g of amino-terminated polyether, 15 g of polytetramethylene ether glycol bis(p-aminobenzoate), 15 g of isophorone diamine, 5 g of filler (aluminum hydroxide, silicon dioxide), and 5 g of other additives to obtain Component B;

[0168] (3) Preparation of the polyurea material

[0169] The Component A and Component B were sprayed with a two-component spray gun at a temperature of 60 °C according to an R value of 1.11:1 to obtain the hyperbranched polyurea material S3.

[0170] Figure 4 is the viscosity curve of Component A prepared in Examples 1-3; from Figure 4 it can be seen that: the viscosity of Component A decreases rapidly with the change of temperature, and the viscosity is relatively low at 60 °C.

[0171] Figure 5 is the tensile curve of the hyperbranched polyurea material prepared in Examples 1-3; from Figure 5 it can be seen that: the hyperbranched polyurea material has good tensile properties, and the tensile stress is all greater than 20 MPa.

[0172] Example 4

[0173] This example is to illustrate the polyurea material prepared by the method of the present invention.

[0174] (1) Preparation of Component A:

[0175] 30 g of hyperbranched poly(lactide) polyol, 2 g of polycaprolactone polyol, 15 g of poly(propylene oxide) glycol, and 4 g of polyphenylmethylsiloxane were added to a reaction kettle, and dehydrated under vacuum at 80 °C for 1 h. Then the temperature was lowered to 40 °C, 37 g of isophorone diisocyanate and 12 g of 2-ethylhexyl diphenyl phosphate were added, and the temperature was raised to 80 °C and kept for reaction for 1.5 h. After defoaming, the temperature was lowered to obtain Component A, in which the NCO% content was 13%;

[0176] Among them, the preparation method of the hyperbranched poly(lactide) polyol was the same as that of the hyperbranched polycaprolactone polyol in Example 1, the difference was that: "ε-caprolactone" was replaced by "lactide"; the number-average molecular weight of the obtained hyperbranched poly(lactide) polyol was 155,000, and the hydroxyl value was 12 mgKOH / g.

[0177] Structural formula:

[0178] Among them, x3 was 40, y3 was 8, and z3 was 30.

[0179] (2) Preparation of Component B:

[0180] The following raw materials were poured into a reaction kettle: 24.5 g of T403 amino-terminated polyether, 6.6 g of diethyltoluenediamine, 8.8 g of 4,4'-methylenebis(3-chloro-2,6-diethylaniline), 1.3 g of filler (aluminum hydroxide, silica, carbon black, graphene), and 3.1 g of other additives (specifically color paste, defoaming agent, antibacterial agent). The temperature was raised to 30 °C, and stirred for 60 min under nitrogen to obtain Component B;

[0181] (3) Preparation of polyurea material

[0182] The Component A and Component B were sprayed with a two-component spray gun at a temperature of 70 °C according to an R value of 1.05:1 to obtain hyperbranched polyurea material S4.

[0183] Example 5

[0184] This example is to illustrate the polyurea material prepared by the method of the present invention.

[0185] The polyurea material was prepared in the same manner as in Example 1, the difference was that:

[0186] (1) Preparation of Component A:

[0187] 5 g of hyperbranched polycaprolactone polyol, 43 g of poly(propylene oxide) polyol, and 2 g of polydimethylvinylsiloxane were added to a reaction kettle, 45 g of toluene diisocyanate and 5 g of propylene carbonate were added to obtain Component A, in which the NCO% content was 19%;

[0188] Among them, the preparation method of the hyperbranched polycaprolactone polyol is the same as that of the hyperbranched polycaprolactone polyol in Example 1, the difference is that: the number-average molecular weight of the hyperbranched polycaprolactone polyol in Example 5 is 196,000, and the hydroxyl value is 15 mg KOH / g.

[0189] Structural formula:

[0190] Among them, x1 is 35, y1 is 13, and z1 is 30.

[0191] (2) Preparation of Component B:

[0192] Pour the following raw materials into the reaction kettle: 45 g of D400 amino-terminated polyether, 38 g of polytetramethylene ether glycol bis(p-aminobenzoate), 10 g of N-methyldiethanolamine, 5 g of filler (aluminum hydroxide, silicon dioxide), and 2 g of other additives to obtain Component B;

[0193] (3) Preparation of the polyurea material

[0194] Spray the Component A and Component B with a two-component spray gun at a temperature of 70°C according to an R value of 1.17:1 to obtain the hyperbranched polyurea material S5.

[0195] Comparative Example 1

[0196] Prepare the polyurea material according to the same method as in Example 1, the difference is that: in the preparation process of (1) Component A, the amounts of each component are changed, specifically: 1 g of hyperbranched polycaprolactone polyol, 49 g of polytetrahydrofuran diol, 5 g of polydimethylsiloxane, and 45 g of toluene diisocyanate.

[0197] As a result, the polyurea material DS1 is obtained.

[0198] Comparative Example 2

[0199] Prepare the polyurea material according to the same method as in Example 1, the difference is that: in the preparation process of (1) Component A, the amounts of each component are changed, specifically: 10 g of hyperbranched polycaprolactone polyol, 15 g of polytetrahydrofuran polyol, 30 g of polydimethylsiloxane, and 45 g of toluene diisocyanate.

[0200] As a result, the polyurea material DS2 is obtained.

[0201] Comparative Example 3

[0202] Prepare the polyurea material according to the same method as in Example 1, the difference is that: in the preparation process of (1) Component A, the amounts of each component are changed, specifically: 40 g of hyperbranched polycaprolactone polyol, 10 g of polytetrahydrofuran polyol, 5 g of polydimethylsiloxane, and 45 g of toluene diisocyanate.

[0203] As a result, the polyurea material DS3 was obtained.

[0204] Comparative Example 4

[0205] The polyurea material was prepared in the same manner as in Example 1, except that: in the preparation process of component A (1), "hyperbranched polycaprolactone polyol" was replaced with "polycaprolactone polyol".

[0206] As a result, the polyurea material DS4 was obtained.

[0207] Comparative Example 5

[0208] The polyurea material was prepared in the same manner as in Example 1, except that:

[0209] (2) Preparation of component B:

[0210] The following raw materials were poured into a reaction kettle: 30 g of amino-terminated polyether, 50 g of polytetramethylene ether glycol bis(p-aminobenzoate), 10 g of isophorone diamine, 5 g of filler (aluminum hydroxide, silica), and 5 g of other additives, to obtain component B;

[0211] (3) Preparation of the polyurea material

[0212] The component A and component B were thoroughly mixed at an R value of 1.05:1 to obtain the polyurea material DS5.

[0213] Test Example

[0214] The polyurea materials prepared in Examples 1-5 and Comparative Examples 1-5 were subjected to performance tests. Specifically, component A and component B were sprayed using a high-pressure spraying machine. The two-component materials of component A and component B were transported to the main machine by a feeding pump, mixed evenly in a dynamic mixing chamber after being heated, pressurized, and accurately metered, and then sprayed onto the surface and quickly cured and formed. The results are shown in Table 1.

[0215] Table 1

[0216]

[0217] It can be seen from the results in Table 1 that the tensile strength of Examples 1-5 using the polyurea material of the present invention is 28-38 MPa, all ≥ 28 MPa, indicating good mechanical properties and low viscosity. Among them, in Example 4, more hyperbranched polyester polyol was used, and the viscosity also increased.

[0218] In Comparative Example 1, due to the too low amount of hyperbranched polyester polyol, the mechanical properties of the polyurea material were poor, the tensile strength decreased significantly, the tear strength was low, and the material became soft.

[0219] In Comparative Example 2, due to the excessive amount of polydimethylsiloxane component, the mechanical properties of the polyurea material are poor, the tensile strength decreases significantly, the elongation at break increases, the tear strength decreases, and the material is too soft.

[0220] In Comparative Example 3, due to the excessive amount of hyperbranched polyester polyol, the viscosity of Component A is too high, making it difficult to mold the material. The viscosity is too large to be sprayed, and the mechanical properties are not tested.

[0221] In Comparative Example 4, due to the use of high molecular weight linear polyester polyol, Component A has a high viscosity and the tear strength decreases.

[0222] In Comparative Example 5, due to the too low amount of amino-terminated polyether, the mechanical properties of the polyurea material are poor, it is difficult to mold, and the tear strength decreases.

[0223] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention, including any other suitable combination of each technical feature. These simple modifications and combinations should also be regarded as the content disclosed by the present invention and fall within the protection scope of the present invention.

Claims

1. A highly branched polyurea material, characterized in that, The hyperbranched polyurea material includes a hyperbranched polyester polyol structural unit represented by formula (1) or a hyperbranched polyester polyol structural unit represented by formula (5), and an isocyanate structural unit represented by formula (2) provided by an isocyanate; , formula (1); , formula (2); , formula (5); Wherein, in formula (1): R1, R2 and R3 are the same or different, and each is one or more of C1-C9 alkylene groups; x is an integer from 10 to 40, y is an integer from 3 to 20, and z is an integer from 5 to 80; In formula (2): R4 is an aromatic or aliphatic residue; In formula (5): x3 is from 10 to 40, y3 is from 3 to 20, and z3 is from 5 to 80; The hyperbranched polyurea material further includes structural units provided by an organosilane, an optional polyether polyol, an amino-terminated polyether and a chain extender; and based on the total weight of the isocyanate, organosilane, hyperbranched polyester polyol, and optional polyether polyol, the dosage of the isocyanate is 20-70% by weight, the content of the organosilane is 1-20% by weight, the content of the hyperbranched polyester polyol is 5-30% by weight, and the content of the polyether polyol is 0-50% by weight.

2. The hyperbranched polyurea material according to claim 1, wherein The hyperbranched polyester polyol includes any one of the structural units represented by formula (3)-(4); , formula (3); , formula (4); Wherein, in formula (3), x1 is from 10 to 40, y1 is from 3 to 20, and z1 is from 5 to 80; In formula (4), x2 is from 10 to 40, y2 is from 3 to 20, and z2 is from 5 to 80.

3. The hyperbranched polyurea material according to claim 1, wherein The number average molecular weight of the hyperbranched polyester polyol is 50,000-200,000; the hydroxyl value is 5-100 mgKOH / g.

4. The hyperbranched polyurea material according to claim 3, wherein, The number average molecular weight of the hyperbranched polyester polyol is 55,000-100,000; the hydroxyl value is 7-55 mgKOH / g.

5. The hyperbranched polyurea material according to claim 1, wherein, The isocyanate is selected from one or more of toluene diisocyanate, diphenylmethane-4,4'-diisocyanate, polymethylene polyphenyl polyisocyanate, liquefied diphenylmethane diisocyanate, xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, cyclohexane dimethylene diisocyanate and 4,4'-dicyclohexylmethane diisocyanate.

6. The hyperbranched polyurea material according to claim 1, wherein, The polyether polyol is selected from one or more of polytetrahydrofuran diol, polypropylene oxide polyether polyol, polyethylene oxide polyether polyol, polypropylene glycol, and polyethylene glycol.

7. The hyperbranched polyurea material according to claim 1, wherein Based on the total weight of the amino-terminated polyether and the chain extender, the content of the amino-terminated polyether is 40-70% by weight, and the content of the chain extender is 10-50% by weight.

8. The hyperbranched polyurea material according to claim 1, wherein Calculated by the isocyanate index, the ratio of the total weight of the isocyanate, organosilane, hyperbranched polyester polyol, and optional polyether polyol to the total weight of the amino-terminated polyether and the chain extender is (1-1.2):

1.

9. The hyperbranched polyurea material according to any one of claims 1-8, wherein, The tensile strength of the hyperbranched polyurea material is 28-38 MPa, the elongation at break is 200-400%, and the tear strength is 100-170 N / mm.

10. A preparation method of a hyperbranched polyurea material, characterized in that, The preparation method described above includes: (1) Contacting an isocyanate, an organosilane, a hyperbranched polyester polyol, an optional polyether polyol and an optional diluent to carry out a prepolymerization reaction to obtain component A; Among them, the hyperbranched polyester polyol includes the hyperbranched polyester polyol structural unit shown in formula (1) or the hyperbranched polyester polyol structural unit shown in formula (5), and the isocyanate structural unit shown in formula (2) provided by the isocyanate; , formula (1); , formula (2); , formula (5); Among them, in formula (1): R1, R2 and R3 are the same or different, and each is one or more of C1-C9 alkylene groups; x is an integer from 10 to 40, y is an integer from 3 to 20, and z is an integer from 5 to 80; In formula (2): R4 is an aromatic or aliphatic residue; In formula (5): x3 is from 10 to 40, y3 is from 3 to 20, and z3 is from 5 to 80; And based on the total weight of component A, the dosage of the isocyanate is 20-70% by weight, the dosage of the organosilane is 1-20% by weight, the dosage of the hyperbranched polyester polyol is 5-30% by weight, the dosage of the polyether polyol is 0-50% by weight, and the dosage of the diluent is 0-15% by weight; (2) Mix the amino-terminated polyether, chain extender, filler and auxiliary agent to obtain component B; (3) Contact component A with component B for reaction to obtain a hyperbranched polyurea material.

11. The preparation method according to claim 10, wherein Based on the total weight of component B, the dosage of the amino-terminated polyether is 40-70% by weight, the dosage of the chain extender is 10-50% by weight, the dosage of the filler is 1-10% by weight, and the dosage of the auxiliary agent is 1-10% by weight.

12. The preparation method according to claim 10, wherein, The content of NCO in component A is 10-20% by weight.

13. The preparation method according to claim 12, wherein, The content of NCO in component A is 12-17% by weight.

14. The preparation method according to claim 10, wherein Calculated by the isocyanate index, the ratio of component A to component B is (1-1.2):

1.

15. The preparation method according to claim 10, wherein, In step (1), the conditions of the prepolymerization reaction include: the temperature is 60-100 °C, and the time is 1-2 h.

16. The preparation method according to claim 10, wherein, In step (2), the conditions of the mixing include: the stirring rate is 800-150 rpm, the temperature is 20-60 °C, and the time is 30-120 min.

17. The preparation method according to claim 10, wherein In step (3), the conditions of the contact reaction include: the temperature is 60-75 °C.

18. The preparation method according to claim 17, wherein The contact is implemented by spraying with a two-component spray gun.

19. Application of the hyperbranched polyurea material according to any one of claims 1-9 in the field of building coatings.

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