Polyurea component A and preparation method thereof, and polyurea containing component A and preparation method thereof

Abstract

This invention discloses a polyurea component A and its preparation method, as well as a polyurea containing component A and its preparation method, belonging to the field of polyurea technology. The technical solution is as follows: S1: Using polycaprolactone diol, polyether polyol, and halogen-substituted phenol or phenolic alcohol derivatives as mixed initiators, a bimetallic catalyst is used to catalyze the ring-opening polymerization of epoxides to synthesize a polyether polyol / polyester ether polyol containing flame-retardant elements; S2: The polyether polyol / polyester ether polyol prepared in step S1 is reacted with isocyanate and polytetrahydrofuran ether diol to prepare component A. This invention utilizes the synthesized polyether polyol / polyester ether polyol to impart excellent flame-retardant and mechanical properties to polyurea materials.

Description

Technical Field

[0001] The present invention relates to the technical field of polyurea, and in particular to a polyurea A component and a preparation method thereof, and a polyurea containing the A component and a preparation method thereof. Background Art

[0002] Spray polyurea elastomer, a new type of spray coating component, has been widely used in construction, transportation, chemical storage tanks, and other fields due to its rapid molding, high reactivity, and environmentally friendly properties. In recent years, it has rapidly developed and is gradually moving into high-end applications. For example, a 2mm thick polyurea coating is sprayed as a protective layer during LNG tank construction. The Ministry of Housing and Urban-Rural Development is focusing on promoting building insulation components with high fire resistance and excellent thermal insulation properties. However, polyurea is still a typical organic polymer component and is flammable, making improving its flame retardancy a pressing issue. In CN 112592647A, carbon black is added to component A and a carbonizing agent is added to component B, enhancing the flame retardancy of polyurea through an intumescent flame retardant mechanism. In CN 111961327A, inorganic powders such as antimony dioxide, ammonium sulfate, and magnesium hydroxide are used to enhance flame retardancy. However, the use of these inorganic powders as additive flame retardants is complex and inevitably reduces mechanical properties. CN112794987A uses DOPO and 3-chloropropyltrimethoxysilane as flame retardant elements. The preparation process is complex (reduced pressure distillation) and uses low-boiling-point, highly toxic solvents such as dichloromethane. CN112592646A uses DOPO and its derivatives to react with epoxidized eleostearic acid to prepare phosphorus-containing polyols. Its flame retardancy can reach B2 level, but its preparation steps are numerous, which is not conducive to large-scale promotion. Summary of the Invention

[0003] The technical problems addressed by the present invention are: existing spray-coated polyurea materials inherently have poor flame retardancy, and added flame retardants significantly reduce mechanical properties. Polyurea materials synthesized from conventional polyether-modified polyurea components (A) generally have low mechanical properties. The present invention provides a polyurea component (A), a preparation method, and a polyurea containing this component, and a preparation method thereof. The synthesized polyether polyol / polyester ether polyol is used to impart excellent flame retardancy and mechanical properties to the polyurea material.

[0004] In a first aspect, the present invention provides a method for preparing a polyurea component A, comprising the following steps:

[0005] S1: Using polycaprolactone diol, polyether polyol and phenol or phenolic alcohol derivatives containing halogen substituents as mixed initiators, a bimetallic catalyst is used to catalyze the ring-opening polymerization of alkylene oxide to synthesize polyether polyol / polyester ether polyol containing flame retardant elements;

[0006] S2: Component A is prepared by reacting the polyether polyol / polyester ether polyol prepared in step S1 with isocyanate and polytetramethylene ether glycol.

[0007] Preferably, in the polyether polyol / polyester ether polyol containing flame retardant elements, the structural formula of the polyether polyol is as follows:

[0008] and / or ;

[0009] Among them, R b The structural formula is or or or , R is Br or Cl;

[0010] The structural formula of polyester ether polyol is shown below:

[0011] ;

[0012] Among them, R a represents the initiator used to synthesize polycaprolactone diol, n, m and n1 represent the degree of polymerization of polyester and polyether, 10≤n≤70, 2≤n1≤60, 3≤m≤20.

[0013] Preferably, in step S1, the molecular weight of the polycaprolactone diol is 500-1000 g / mol; the molecular weight of the polyether polyol in the mixed initiator is 300-2000 g / mol, and the functionality is 2-3; the hydroxyl value of the polyether polyol / polyester ether polyol is 28-170 mgKOH / g, the functionality is 1.5-3, and the viscosity is 800-15000 mPa·s.

[0014] Preferably, in step S1, the mass ratio of polycaprolactone diol, polyether polyol and phenol or phenolic alcohol derivative containing a halogen substituent is 1: 1-10: 1-10; the mass ratio of the mixed initiator to the alkylene oxide is 1:0.3-5, the amount of the bimetallic catalyst is 50-2000 ppm; and the reaction temperature is 125-145°C.

[0015] Preferably, in step S1, the phenol or phenolic alcohol derivative containing a halogen substituent is one or more of tribromophenol, tetrabromobisphenol A, tetrachlorobisphenol A, 2,3-dichlorophenol, 2,4-dichlorophenol, 2,6-dichlorophenol, 2,4,6-trichlorophenol and 3,4,5-trichlorophenol; and the alkylene oxide is one or more of propylene oxide, ethylene oxide and butylene oxide.

[0016] Preferably, in step S2, the isocyanate is one or more of toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), hexamethylene diisocyanate (HDI), and lysine diisocyanate (LDI).

[0017] Preferably, in step S2, the molecular weight of polytetramethylene ether glycol is 500-2000, and the moisture content is ≤0.5wt%. Too high a moisture content will affect the reaction activity; in component A, the NCO content is 12-18wt%.

[0018] In a second aspect, the present invention provides a polyurea comprising the polyurea A component.

[0019] In a third aspect, the present invention provides a method for preparing the above-mentioned polyurea, comprising mixing component A with component B comprising amino-terminated polyether, a chain extender, a coupling agent, and a color paste, and then spraying the mixture to obtain polyurea.

[0020] Preferably, the mass ratio of the terminal amino polyether, chain extender, coupling agent and color paste in component B is (40-70): (10-40): (0.5-3): (1-5).

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] The present invention introduces a halogen-containing initiator and polycaprolactone diol into a polyether initiator, and introduces polyester segments and halogens into the polyether backbone to synthesize a polyether polyol / polyester ether polyol that exhibits both reactive flame retardancy and excellent mechanical properties. This polyol is then used in component A of a polyurea material to prepare a semi-prepolymer. The preparation method is simple and easy to construct, and the resulting polyurea exhibits high flame retardancy and excellent mechanical properties. The present invention utilizes a bimetallic catalyst process for a one-step synthesis of flame-retardant polyether polyol / polyester ether polyol, eliminating the need for post-processing and resulting in high reaction yields. The preparation method is simple, environmentally friendly, and eliminates the three wastes. DETAILED DESCRIPTION

[0023] In order to enable those skilled in the art to better understand the technical solutions of the present invention, the technical solutions in the embodiments of the present invention are clearly and completely described below. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative work should fall within the scope of protection of the present invention.

[0024] The following is the raw material information in the embodiment of the present invention:

[0025] Polyether polyols:

[0026] INOVOL C204, Shandong Yinuowei New Materials Co., Ltd. (2 functionalities, 400 molecular weight);

[0027] INOVOL C210, Shandong Yinuowei New Materials Co., Ltd. (2 functionalities, 1000 molecular weight);

[0028] INOVOL C305, Shandong Yinuowei New Materials Co., Ltd. (3 functionalities, 500 molecular weight);

[0029] INOVOL C310, Shandong Yinuowei New Materials Co., Ltd. (3 functionalities, 1000 molecular weight).

[0030] Polycaprolactone diol, Japan Daicel, PLACCEL 205U, 210.

[0031] Polytetramethylenetetramethylene ether (PTMEG), BASF, polyTHF ® 1000.

[0032] Amino-terminated polyether, Huntsman, D230.

[0033] Example 1 Preparation of polyether polyol / polyester ether polyol ①

[0034] 80 g of INOVOL C204, 200 g of PLACCEL 210, 146 g of tetrachlorobisphenol A, 66 g of tribromophenol, and 0.12 g of DMC catalyst were added to a pressure vessel. The atmosphere was replaced with nitrogen three times, then the temperature was raised to 100°C for dehydration for 2 h. The temperature was raised to 130°C, and 35 g of propylene oxide was added dropwise to initiate the reaction. After the pressure dropped to -0.08 MPa, a mixture of 275 g of propylene oxide and 200 g of ethylene oxide was slowly introduced, controlling the pressure to less than 0.30 MPa during the reaction. The reaction was carried out under internal pressure for 2 h, and then stripping was performed for 0.5 h to obtain a reactive flame-retardant polyether polyol / polyester ether polyol ①.

[0035] The structural formula of the polyether polyol containing flame retardant elements is:

[0036]

[0037] ;

[0038] The structural formula of polyester ether polyol is:

[0039] .

[0040] The hydroxyl value of the tested polyether polyol / polyester ether polyol ① was 111.6 mg KOH / g, and the viscosity was 1946 mPa·s.

[0041] Example 2 Preparation of polyether polyol / polyester ether polyol ②

[0042] 100g of INOVOL C305, 106g of PLACCEL 205U, 164g of tetrabromobisphenol A, 81.5g of 2,6-dichlorophenol, 20g of 3,4,5-trichlorophenol, and 0.30g of DMC catalyst were added to a pressure vessel. The atmosphere was replaced with nitrogen three times and the temperature was raised to 100°C for dehydration for 2h. The temperature was raised to 135°C and 29g of propylene oxide was added dropwise as an initiator. After the pressure dropped to -0.08MPa, a mixture of 800g of propylene oxide and 200g of ethylene oxide was slowly introduced, controlling the pressure below 0.30MPa during the reaction. The reaction was carried out under internal pressure for 2h. The monomer removal was performed for 0.5h to obtain a reactive flame-retardant polyether polyol / polyester ether polyol ②.

[0043] The structural formula of the polyether polyol containing flame retardant elements is:

[0044]

[0045]

[0046] The structural formula of polyester ether polyol is:

[0047] .

[0048] The hydroxyl value of the tested polyether polyol / polyester ether polyol ② was 71 mg KOH / g, and the viscosity was 2674 mPa·s.

[0049] Example 3 Preparation of polyether polyol / polyester ether polyol ③

[0050] 110 g of INOVOL C310, 100 g of PLACCEL 205U, 20 g of 2,3-dichlorophenol, 20 g of 2,4-dichlorophenol, 39 g of 2,4,6-trichlorophenol, 163 g of tetrabromobisphenol A, and 0.46 g of DMC catalyst were added to a pressure vessel. The atmosphere was replaced with nitrogen three times and the temperature was raised to 100°C for dehydration for 2 h. The temperature was raised to 135°C and 42 g of propylene oxide was added dropwise to initiate the reaction. After the pressure dropped to -0.08 MPa, a mixture of 750 g of propylene oxide and 750 g of butylene oxide was slowly introduced, controlling the pressure to less than 0.30 MPa during the reaction. The reaction was carried out under internal pressure for 3 h. The reaction was then stripped for 0.5 h to obtain a reactive flame-retardant polyether polyol / polyester ether polyol ③.

[0051] The structural formula of the polyether polyol containing flame retardant elements is:

[0052]

[0053]

[0054]

[0055] The structural formula of polyester ether polyol is:

[0056] .

[0057] The hydroxyl value of the tested polyether polyol / polyester ether polyol ③ was 59 mg KOH / g, and the viscosity was 1536 mPa·s.

[0058] Example 4 Preparation of polyurea ①

[0059] Component A: 100g polyether polyol / polyester ether polyol ①, 100g PTMEG, and 162g MDI-50. Heat to 80°C and react for 2 hours. The NCO content of the product is 14.8wt%. Component B: Mix 60 parts amino-terminated polyether, 34 parts chain extender diethyltoluenediamine (DETDA), 2 parts coupling agent KH-550, and 4 parts colorant. Components A and B are evenly mixed in a 1:1 volume ratio using a sprayer and applied to the sample surface to a thickness of (1.5±0.2) mm. Cured at 25±1°C for 7 days before testing performance.

[0060] Example 5 Preparation of polyurea ②

[0061] Component A: 100g polyether polyol / polyester ether polyol ②, 100g PTMEG, and 154g MDI. Heat to 80°C and react for 2 hours. The NCO content of the product is 15.2wt%. Component B: Mix 65 parts amino-terminated polyether, 29 parts chain extender diethyltoluenediamine (DETDA), 2 parts coupling agent KH-550, and 4 parts colorant. Components A and B are evenly mixed in a 1:1 volume ratio using a sprayer and applied to the sample surface to a thickness of (1.5±0.2) mm. Cured at 25±1°C for 7 days before testing performance.

[0062] Example 6 Preparation of polyurea ③

[0063] Component A: 100g polyether polyol / polyester ether polyol ③, 100g PTMEG, and 145g MDI-50. Heat to 80°C and react for 2 hours. The NCO content of the product is 15.1wt%. Component B: Mix 62 parts amino-terminated polyether, 31 parts chain extender diethyltoluenediamine (DETDA), 2 parts coupling agent KH-550, and 5 parts colorant. Components A and B are evenly mixed in a 1:1 volume ratio using a sprayer and applied to the sample surface to a thickness of (1.5±0.2) mm. Cured at 25±1°C for 7 days before testing performance.

[0064] Comparative Example 1

[0065] The difference from Example 4 is that INOVOL C210 is used in component A of Comparative Example 1 instead of polyether polyol / polyester ether polyol ①, and the NCO content of the component A product is 14.9 wt%.

[0066] Comparative Example 2

[0067] 80 g of INOVOL C204, 220 g of tetrachlorobisphenol A, 66 g of tribromophenol, and 0.12 g of DMC catalyst were placed in a pressure vessel. The atmosphere was purged with nitrogen three times, then the temperature was raised to 100°C for dehydration for 2 hours. The temperature was then raised to 130°C, and 35 g of propylene oxide was added dropwise to initiate the reaction. After the pressure dropped to -0.08 MPa, a mixture of 230 g of propylene oxide and 100 g of ethylene oxide was slowly introduced, maintaining the pressure below 0.30 MPa. The reaction was continued for 2 hours, followed by stripping for 0.5 hours to obtain a reactive flame-retardant polyether polyol. The polyether polyol had a hydroxyl value of 101.2 mg KOH / g and a viscosity of 2866 mPa·s.

[0068] Comparative Example 2 Preparation of polyurea: The difference from Example 4 is that the polyether polyol prepared above is used in Component A of Comparative Example 2 instead of polyether polyol / polyester ether polyol ①, and the NCO content of the product of Component A is 15.3 wt%.

[0069] Performance Testing

[0070] The performance of the sprayed polyurea was evaluated according to the national standard GB / T23446-2009: dumbbell-shaped and uncut rectangular strips were prepared according to GB / T528 and GB / T529-2008. Tensile testing was performed according to GB / T16777-2008 at a tensile speed of (500±50) mm, with no fewer than six samples tested. Tear testing was performed according to GB / T529-2008 at a tensile speed of (500±50) mm, with no fewer than six samples tested. Flame retardancy was evaluated according to GB / 8624-2012. The mechanical and flame retardant test results for the polyureas of Examples 4-6 and Comparative Example 1 are shown in Table 1.

[0071] Table 1

[0072]

[0073] As shown in Table 1, the spray polyurea made from the polyether polyol / polyester ether polyol prepared by the present invention has the best comprehensive performance of tensile strength and elongation at break, the spray polyurea made from ordinary polyether has low tensile strength (Comparative Example 1) and poor flame retardancy, and the polyurea made from a single flame retardant polyether has low elongation at break (Comparative Example 2).

[0074] Although the present invention has been described in detail with reference to preferred embodiments, the present invention is not limited thereto. Without departing from the spirit and essence of the present invention, a person of ordinary skill in the art may make various equivalent modifications or substitutions to the embodiments of the present invention, and such modifications or substitutions shall be within the scope of the present invention. Any person skilled in the art who can easily conceive of changes or substitutions within the technical scope disclosed in the present invention shall be included in the scope of protection of the present invention. Therefore, the scope of protection of the present invention shall be subject to the scope of protection of the claims.

Claims

1. A method for preparing a polyurea component A, characterized in that: The following steps are involved: S1: Using polycaprolactone diol, polyether polyol and phenol or phenolic alcohol derivatives containing halogen substituents as mixed initiators, using a bimetallic catalyst to catalyze the ring-opening polymerization of alkylene oxide to synthesize polyether polyol / polyester ether polyol containing flame retardant elements; S2: reacting the polyether polyol / polyester ether polyol prepared in step S1 with isocyanate and polytetramethylene ether diol to prepare component A; Among the polyether polyols / polyester ether polyols containing flame retardant elements, the structural formula of the polyether polyol is as follows: and / or ; Among them, R b The structural formula is or or or , R is Br or Cl; The structural formula of polyester ether polyol is as follows: ； Among them, R a It represents the initiator used to synthesize polycaprolactone diol, n, m and n1 represent the degree of polymerization of polyester and polyether, 10≤n≤70, 2≤n1≤60, 3≤m≤20.

2. The method for preparing the polyurea A component according to claim 1, characterized in that: In step S1, the molecular weight of polycaprolactone diol is 500-1000 g / mol; the molecular weight of polyether polyol in the mixed initiator is 300-2000 g / mol, and the functionality is 2-3; the hydroxyl value of polyether polyol / polyester ether polyol is 28-170 mgKOH / g, the functionality is 1.5-3, and the viscosity is 800-15000 mPa·s.

3. The method for preparing the polyurea A component according to claim 1, characterized in that: In step S1, the mass ratio of polycaprolactone diol, polyether polyol and phenol or phenolic alcohol derivative containing halogen substituents is 1: 1-10: 1-10; the mass ratio of mixed initiator to alkylene oxide is 1: 0.3-5, the amount of bimetallic catalyst is 50-2000 ppm; and the reaction temperature is 125-145°C.

4. The method for preparing the polyurea A component according to claim 1, characterized in that: In step S1, the phenol or phenolic alcohol derivative containing a halogen substituent is one or more of tribromophenol, tetrabromobisphenol A, tetrachlorobisphenol A, 2,4-dichlorophenol and 2,4,6-trichlorophenol; the alkylene oxide is propylene oxide; in step S2, the isocyanate is one or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and lysine diisocyanate.

5. The method for preparing the polyurea A component according to claim 1, characterized in that: In step S2, the molecular weight of polytetramethylene ether glycol is 500-2000, and the water content is ≤0.5wt%; in component A, the NCO content is 12-18wt%.

6. The polyurea component A prepared by the method for preparing the polyurea component A according to any one of claims 1 to 5.

7. A polyurea comprising the polyurea A component of claim 6.

8. The method for preparing polyurea according to claim 7, characterized in that: The component A is mixed with the component B containing the amino-terminated polyether, the chain extender, the coupling agent and the color paste, and then sprayed to obtain the polyurea.

9. The method for preparing polyurea according to claim 8, characterized in that: The mass ratio of the terminal amino polyether, chain extender, coupling agent and color paste in component B is (40-70): (10-40): (0.5-3): (1-5).

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