Rigid polyurethane material for bonsai rockery and preparation method thereof

Abstract

The present invention belongs to the technical field of polyurethane, and specifically relates to a hard polyurethane material for bonsai rockery and a preparation method thereof, wherein the material is composed of component A and component B, and component A is composed of the following raw materials in parts by mass: polyether polyol a: 10-20 parts, polyester polyol b: 20-30 parts, hydrophobic castor oil polyester polyol c: 20-40 parts, polyether polyol d: 5-10 parts, chain extender: 2-5 parts, foam stabilizer: 1.5-2.5 parts, water: 2.5-3.0 parts, catalyst one: 2.0-3.0 parts, viscosity reducer: 10-15 parts; component B is composed of the following raw materials in parts by mass: isocyanate: 90-100 parts, polyether polyol d: 0-10 parts, and the mixing mass ratio of component A to component B is 1.0: (1.0-1.2). The foam of the present invention is fine, dimensionally stable, high in open porosity, good in water absorption and resistant to water corrosion. The present invention also provides its preparation method.

Description

Technical Field

[0001] The invention belongs to the technical field of polyurethane, and in particular relates to a hard polyurethane material for bonsai rockery and a preparation method thereof. Background Art

[0002] There are two common rockery materials on the market. One is natural rock material, which only needs to be built with concrete as the foundation and cement as the bonding material when it is artificially stacked. The other is cement mixed mortar, wire mesh or GRC (low-alkali glass fiber cement) as the material, and the artificial plastic molded rockery is also called "plastic stone". In order to meet the needs of family site area, bonsai rockery miniaturizes traditional large rockery and places it at home. Traditional bonsai rockery stones are made of natural rock materials or "plastic stones". Not only is the shaping construction of rockery shape more cumbersome, but it also requires high technical and artistic levels of construction workers. The construction carving technology will affect the beauty and stability of the rockery. Because decorative materials such as bonsai rockery occupy a small area and have high requirements for details and beauty, they are more suitable for mold making, which can greatly improve production efficiency and reduce production costs. Summary of the invention

[0003] In order to solve the above technical problems, the present invention provides a hard polyurethane material for bonsai rockery, which is suitable for integral molding using a mold, has fine foam, good dimensional stability, high open porosity, good water absorption and water corrosion resistance. The present invention also provides a preparation method thereof.

[0004] The hard polyurethane material for bonsai rockery of the present invention is composed of component A and component B, wherein component A is composed of the following raw materials in parts by weight:

[0005] Polyether polyol a: 10-20 parts,

[0006] Polyester polyol b: 20-30 parts,

[0007] Hydrophobic castor oil polyester polyol c: 20-40 parts,

[0008] Polyether polyol d: 5-10 parts,

[0009] Chain extender: 2-5 parts,

[0010] Foam stabilizer: 1.5-2.5 parts,

[0011] Water: 2.5-3.0 parts,

[0012] Catalyst 1: 2.0-3.0 parts,

[0013] Viscosity reducer: 10-15 parts;

[0014] Component B is composed of the following raw materials in parts by weight:

[0015] Isocyanate: 90-100 parts,

[0016] Polyether polyol d: 0-10 parts,

[0017] The mixing mass ratio of component A to component B is 1.0:(1.0-1.2);

[0018] The functionality of the polyether polyol a is 4, and the hydroxyl value is 730-770 mgKOH / g; preferably, it is INOVOL R403 produced by Shandong INOVOL New Materials Co., Ltd.

[0019] The polyester polyol b has a hydroxyl value of 220-240 mgKOH / g and a viscosity of 2000-2500 mPa•s at 25° C.; preferably, it is INOVOL PE-D245 produced by Shandong INOVOL Polyurethane Co., Ltd.

[0020] The hydrophobic castor oil polyester polyol has a c functionality of 2 and a hydroxyl value of 179.7-183 mgKOH / g;

[0021] The polyether polyol has a functionality of 3 and a hydroxyl value of 32-36 mgKOH / g. Preferably, it is INOVOL 350T produced by Shandong INOVOL New Materials Co., Ltd.

[0022] Preferably, the hydrophobic castor oil polyester polyol c is prepared from diol, dibasic acid, catalyst 2, and castor oil;

[0023] The diol is diethylene glycol and polydimethylphenol diol compounded in a molar ratio of 1:1; the dibasic acid is phthalic acid, the molar ratio of the diol and the dibasic acid is 2:1, the catalyst 2 is an organic transition metal catalyst, the catalyst 2 is preferably stannous octoate, and the addition amount of the catalyst 2 is 0.04% of the sum of the mass of the diol and the dibasic acid; the addition amount of castor oil is 2%-3.8% of the sum of the mass of the diol, the dibasic acid and the catalyst 2.

[0024] Preferably, the polydimethylphenol diol has a number average molecular weight of 364 and a functionality of 2.

[0025] Preferably, the preparation method of hydrophobic castor oil polyester polyol C comprises the following steps:

[0026] S1, put diethylene glycol, polydimethylphenol diol and phthalic acid into a reaction kettle, under nitrogen atmosphere and stirring conditions, heat the system to 180°C to discharge water, carry out esterification reaction, and after discharge of water, heat to 210°C to continue reaction;

[0027] S2. The reaction is carried out until the acid value of the system reaches 41-44 mgKOH / g, castor oil is added to the reactor, and then catalyst 2 is added. The temperature is raised to 230°C and kept warm for 3-4 hours, then the temperature is lowered to 60°C and vacuumized to -0.06 MPa for 1 hour to obtain the product.

[0028] Preferably, the chain extender is a mixture of glycerol and triethanolamine.

[0029] Preferably, the foam stabilizer is one or more of B8870 (Evonik Industries, Germany), L580 (Momentive High-Tech Materials Group), and DS11 (Jiangsu Meside Chemical Co., Ltd.), and more preferably DS11.

[0030] Preferably, the catalyst one is a mixture of A-1, PC8, delayed quaternary ammonium salt catalyst TMR-2, and formic acid.

[0031] Preferably, the viscosity reducing agent is one or both of 2,2,4-trimethyl-1,3-pentanediol diisobutyrate (TXIB, Eastman Chemical Company, USA) and propylene carbonate, and more preferably 2,2,4-trimethyl-1,3-pentanediol diisobutyrate.

[0032] Preferably, the isocyanate is polyphenylpolymethylene isocyanate.

[0033] The method for preparing the rigid polyurethane material for bonsai rockery of the present invention comprises the following steps:

[0034] (1) Add weighed polyether polyol a, polyester polyol b, hydrophobic castor oil polyester polyol c, polyether polyol d, chain extender, foam stabilizer, water, catalyst 1, and viscosity reducer into a reaction kettle, and stir the reaction at room temperature for 1-2 hours to obtain component A;

[0035] (2) Add isocyanate and polyether polyol d into the reaction kettle, stir at room temperature for 1-2 hours, and fill into barrels after the moisture content is detected to be less than 0.02%. After the barrels are filled with nitrogen, the barrels are sealed to obtain component B;

[0036] (3) When using, mix component A and component B evenly.

[0037] Compared with the prior art, the present invention has the following beneficial effects:

[0038] 1. By selecting amine-catalyzed high-hydroxyl polyether polyol a, and matching it with a chain extender, and coordinating with a 2-functional polyester system, compared with traditional polyethers, the cross-linking degree of 2-functional polyester foam can be significantly improved, and the foam dimensional stability can be improved;

[0039] 2. Through the design of hydrophobic castor oil polyester structure, polydimethylphenol diol is introduced. Compared with traditional small molecule alcohol castor oil polyester, the proportion of benzene ring structure is increased, the hydrophobicity of foam is improved, and the foam fineness and open porosity are improved. At the same time, the water corrosion resistance of foam after water absorption or long-term immersion in water can be improved;

[0040] 3. By using high molecular weight polyether polyol d and a foam stabilizer with a cell-opening effect, better dimensional stability and cell-opening effects in downstream applications are ensured, avoiding the destructive effect of traditional cell-opening systems on foam;

[0041] 4. Improve the combination of high-rise and fast-ripening catalysts through the selection of catalysts. At the same time, improve the balance of rise and gel during the foaming process through the adjustment of formic acid to ensure the foam opening effect and dimensional stability;

[0042] 5. The rigid polyurethane foam material prepared by the present invention is suitable for integral molding using a mold, and has the advantages of fine foam, good dimensional stability, high open porosity, good water absorption and water corrosion resistance, which solves the supply of water and nutrients for the green plants at the bottom, improves the preservation effect of the green plants while decorating the rockery, and can also adjust the density and color. The preparation method thereof is scientific and reasonable and easy to implement. DETAILED DESCRIPTION

[0043] The technical solution of the present invention will be clearly and completely described below in conjunction with embodiments.

[0044] Unless otherwise specified, all raw materials used in the examples are commercially available.

[0045] Among them, polyether polyol a, INOVOL R403, Shandong Yinuowei New Materials Co., Ltd.;

[0046] Polyester polyol b, INOVOL PE-D245, Shandong INOVOL Polyurethane Co., Ltd.;

[0047] Polyether polyol d, INOVOL 350T, Shandong INOVOL New Materials Co., Ltd.;

[0048] Example 1

[0049] The hard polyurethane material for bonsai rockery is composed of component A and component B, wherein component A is composed of the following raw materials:

[0050] Polyether polyol a (INOVOL R403): 15kg,

[0051] Polyester polyol b (INOVOL PE-D245): 26kg,

[0052] Hydrophobic castor oil polyester polyol c: 32kg,

[0053] Polyether polyol d (INOVOL 350T): 5kg,

[0054] Chain extender glycerol: 2kg,

[0055] Chain extender triethanolamine: 2kg,

[0056] Foam stabilizer DS11: 1.5kg,

[0057] Water: 2.8kg,

[0058] A-1: 0.2kg,

[0059] PC8: 0.3kg,

[0060] TMR-2: 1.0kg,

[0061] Formic acid: 0.5kg,

[0062] Viscosity reducer propylene carbonate: 13kg;

[0063] Component B is composed of the following raw materials in parts by weight:

[0064] Isocyanate (PM200): 90kg,

[0065] Polyether polyol d (INOVOL 350T): 10kg,

[0066] The mixing mass ratio of component A to component B is 1.0:1.1;

[0067] Wherein, the preparation method of hydrophobic castor oil polyester polyol C comprises the following steps:

[0068] S1. 106.12 kg (1000 mol) of diethylene glycol, 364 kg (1000 mol) of polydimethylphenol diol (number average molecular weight of 364, functionality of 2), and 166.13 kg (1000 mol) of phthalic acid are put into a reaction kettle. Under nitrogen atmosphere and stirring conditions, the system is heated to 180°C to discharge water for esterification reaction. After the water is discharged, the temperature is raised to 210°C to continue the reaction.

[0069] S2. The reaction is carried out until the acid value of the system reaches 42 mgKOH / g. 24.1 kg of castor oil is added to the reactor, and then 0.2545 kg of stannous dioctoate catalyst is added. The temperature is raised to 230°C and kept warm for 3 hours. The temperature is then lowered to 60°C and vacuumized to -0.06 MPa for 1 hour to obtain hydrophobic castor oil polyester polyol c with a functionality of 2 and a hydroxyl value of 179.7 mgKOH / g.

[0070] The method for preparing the rigid polyurethane material for bonsai rockery comprises the following steps:

[0071] (1) Add weighed polyether polyol a (INOVOL R403), polyester polyol b (INOVOL PE-D245), hydrophobic castor oil polyester polyol c, polyether polyol d (INOVOL 350T), chain extender (glycerol, triethanolamine), foam stabilizer DS11, water, catalyst 1 (A-1, PC8, TMR-2, formic acid), and viscosity reducer propylene carbonate into a reactor, stir and react at room temperature for 1 hour to obtain component A;

[0072] (2) Add isocyanate (PM200) and polyether polyol d (INOVOL 350T) into the reactor, stir at room temperature for 1 hour, and fill into barrels after the moisture content is detected to be less than 0.02%. After filling into barrels, replace with nitrogen and seal the barrels to obtain component B;

[0073] (3) When using, mix component A and component B evenly.

[0074] Example 2

[0075] The hard polyurethane material for bonsai rockery is composed of component A and component B, wherein component A is composed of the following raw materials:

[0076] Polyether polyol a (INOVOL R403): 20kg,

[0077] Polyester polyol b (INOVOL PE-D245): 30kg,

[0078] Hydrophobic castor oil polyester polyol c: 20kg,

[0079] Polyether polyol d (INOVOL 350T): 8kg,

[0080] Chain extender glycerol: 1kg,

[0081] Chain extender triethanolamine: 1kg,

[0082] Foam stabilizer B8870: 2kg,

[0083] Water: 2.5kg,

[0084] A-1: 0.3kg,

[0085] PC8: 0.2kg,

[0086] TMR-2: 1.0kg,

[0087] Formic acid: 1.0kg,

[0088] Viscosity reducer propylene carbonate: 15kg;

[0089] Component B is composed of the following raw materials in parts by weight:

[0090] Isocyanate (PM200): 95kg,

[0091] Polyether polyol d (INOVOL 350T): 5kg,

[0092] The mixing mass ratio of component A to component B is 1.0:1.0;

[0093] Wherein, the preparation method of hydrophobic castor oil polyester polyol C comprises the following steps:

[0094] S1. 106.12 kg (1000 mol) of diethylene glycol, 364 kg (1000 mol) of polydimethylphenol diol (number average molecular weight of 364, functionality of 2), and 166.13 kg (1000 mol) of phthalic acid are put into a reaction kettle. Under nitrogen atmosphere and stirring conditions, the system is heated to 180°C to discharge water for esterification reaction. After the water is discharged, the temperature is raised to 210°C to continue the reaction.

[0095] S2. The reaction is carried out until the acid value of the system reaches 41 mgKOH / g. 12.732 kg of castor oil is added to the reactor, and then 0.2545 kg of stannous dioctoate catalyst is added. The temperature is raised to 230°C and kept warm for 3 hours. The temperature is then lowered to 60°C and vacuumized to -0.06 MPa for 1 hour to obtain hydrophobic castor oil polyester polyol c with a functionality of 2 and a hydroxyl value of 183 mgKOH / g.

[0096] The method for preparing the rigid polyurethane material for bonsai rockery comprises the following steps:

[0097] (1) Add weighed polyether polyol a (INOVOL R403), polyester polyol b (INOVOL PE-D245), hydrophobic castor oil polyester polyol c, polyether polyol d (INOVOL 350T), chain extender (glycerol, triethanolamine), foam stabilizer B8870, water, catalyst 1 (A-1, PC8, TMR-2, formic acid), and viscosity reducer propylene carbonate into a reactor, stir and react at room temperature for 2 hours to obtain component A;

[0098] (2) Add isocyanate (PM200) and polyether polyol d (INOVOL 350T) into the reactor, stir at room temperature for 2 hours, and fill into barrels after the moisture content is detected to be less than 0.02%. After filling into barrels, replace with nitrogen and seal the barrels to obtain component B;

[0099] (3) When using, mix component A and component B evenly.

[0100] Example 3

[0101] The hard polyurethane material for bonsai rockery is composed of component A and component B, wherein component A is composed of the following raw materials:

[0102] Polyether polyol a (INOVOL R403): 10kg,

[0103] Polyester polyol b (INOVOL PE-D245): 20kg,

[0104] Hydrophobic castor oil polyester polyol c: 40kg,

[0105] Polyether polyol d (INOVOL 350T): 10kg,

[0106] Chain extender glycerol: 2kg,

[0107] Chain extender triethanolamine: 3kg,

[0108] Foam stabilizer L580: 2.5kg,

[0109] Water: 3kg,

[0110] A-1: 0.1kg,

[0111] PC8: 0.7kg,

[0112] TMR-2: 1.0kg,

[0113] Formic acid: 1.2kg,

[0114] Viscosity reducer 2,2,4-trimethyl-1,3-pentanediol diisobutyrate: 10kg;

[0115] Component B is composed of the following raw materials in parts by weight:

[0116] Isocyanate (PM200): 100kg,

[0117] The mixing mass ratio of component A to component B is 1.0:1.2;

[0118] Wherein, the preparation method of hydrophobic castor oil polyester polyol C comprises the following steps:

[0119] S1. 106.12 kg (1000 mol) of diethylene glycol, 364 kg (1000 mol) of polydimethylphenol diol (number average molecular weight of 364, functionality of 2), and 166.13 kg (1000 mol) of phthalic acid are put into a reaction kettle. Under nitrogen atmosphere and stirring conditions, the system is heated to 180°C to discharge water for esterification reaction. After the water is discharged, the temperature is raised to 210°C to continue the reaction.

[0120] S2. The reaction is carried out until the acid value of the system reaches 44 mgKOH / g. 19.1 kg of castor oil is added to the reactor, and then 0.2545 kg of stannous dioctoate catalyst is added. The temperature is raised to 230°C and kept warm for 4 hours. The temperature is then lowered to 60°C and vacuumized to -0.06 MPa for 1 hour to obtain hydrophobic castor oil polyester polyol c with a functionality of 2 and a hydroxyl value of 181.2 mgKOH / g.

[0121] The method for preparing the rigid polyurethane material for bonsai rockery comprises the following steps:

[0122] (1) Add weighed polyether polyol a (INOVOL R403), polyester polyol b (INOVOL PE-D245), hydrophobic castor oil polyester polyol c, polyether polyol d (INOVOL 350T), chain extender (glycerol, triethanolamine), foam stabilizer L580, water, catalyst 1 (A-1, PC8, TMR-2, formic acid), and viscosity reducer 2,2,4-trimethyl-1,3-pentanediol diisobutyrate into a reactor, stir and react at room temperature for 1 hour to obtain component A;

[0123] (2) Add isocyanate (PM200) into the reactor, stir at room temperature for 1 hour, and fill into barrels after the moisture content is detected to be less than 0.02%. After filling into barrels, replace with nitrogen and seal the barrels to obtain component B;

[0124] (3) When using, mix component A and component B evenly.

[0125] Comparative Example 1

[0126] The difference between this comparative example 1 and example 1 is that in component A, INOVOL R403 is replaced by polyether polyol R4110 of equal mass, R4110 is produced by Shandong Yinuowei New Materials Co., Ltd., has a hydroxyl value of 420-460 mgKOH / g, and a viscosity of 3000-4500 mPa•s, and no chain extender is used in component A.

[0127] Comparative Example 2

[0128] The difference between this comparative example 2 and example 2 is that in component A, the hydrophobic castor oil polyester polyol c is replaced with polyester polyol B503 of equal mass, B503 is produced by Shandong Yinuowei Polyurethane Co., Ltd., and has a hydroxyl value of 300-340 mgKOH / g.

[0129] Comparative Example 3

[0130] The difference between this comparative example 3 and example 3 is that in component A, INOVOL 350T is replaced by polyether polyol F330N of equal quality, F330N is produced by Shandong Yinuowei New Materials Co., Ltd., and has a hydroxyl value of 420-460 mgKOH / g; L580 is replaced by foam stabilizer JC7750 of equal quality, and JC7750 is produced by Cangzhou Lingang Junchi Chemical Co., Ltd.

[0131] Comparative Example 4

[0132] The difference between Comparative Example 4 and Example 1 is that no formic acid is used in the A component.

[0133] Performance Testing

[0134] The rigid polyurethane materials obtained in Examples 1-3 and Comparative Examples 1-4 were subjected to performance tests, and the results are shown in Table 1.

[0135] Table 1 Performance test table of rigid polyurethane materials of Examples 1-3 and Comparative Examples 1-4

[0136]

[0137] As can be seen from Table 1, the hard polyurethane material for bonsai rockery prepared by the present invention has fine polyurethane foam, good dimensional stability, high open porosity, good water absorption and water corrosion resistance through the reasonable matching of each component raw material. Compared with Example 1, Comparative Example 1 does not contain high hydroxyl value polyether R403 and chain extender, the foam crosslinking degree is weak, the molding is slow, and the dimensional stability is poor; Compared with Example 2, Comparative Example 2 does not contain hydrophobic polyester, although the pore fineness and open porosity have no obvious effect, but the foam is severely corroded after long-term immersion; Compared with Example 3, Comparative Example 3 does not have high molecular weight open-cell polyether polyol and open-cell foam stabilizer, the foam is not open-cell, the dimensional stability is poor, and there is shrinkage after placement; Compared with Example 1, Comparative Example 4 uses conventional catalysts and does not reasonably match a certain amount of formic acid, resulting in poor balance in the foaming process and shrinkage of the foam.

Claims

1. A rigid polyurethane material for bonsai rockery, characterized in that: It is composed of component A and component B. Component A is composed of the following raw materials in parts by weight: Polyether polyol a: 10-20 parts, Polyester polyol b: 20-30 parts, Hydrophobic castor oil polyester polyol c: 20-40 parts, Polyether polyol d: 5-10 parts, Chain extender: 2-5 parts, Foam stabilizer: 1.5-2.5 parts, Water: 2.5-3.0 parts, Catalyst 1: 2.0-3.0 parts, Viscosity reducer: 10-15 parts; Component B is composed of the following raw materials in parts by weight: Isocyanate: 90-100 parts, Polyether polyol d: 0-10 parts, The mixing mass ratio of component A to component B is 1.0:(1.0-1.2); The functionality of polyether polyol a is 4, and the hydroxyl value is 730-770 mgKOH / g; The hydroxyl value of polyester polyol b is 220-240 mgKOH / g, and the viscosity is 2000-2500 mPa•s at 25°C; The hydrophobic castor oil polyester polyol has a c functionality of 2 and a hydroxyl value of 179.7-183 mgKOH / g; The functionality of the polyether polyol is 3 and the hydroxyl value is 32-36 mgKOH / g; The hydrophobic castor oil polyester polyol C is prepared from a diol, a dibasic acid, a catalyst II and castor oil; wherein the diol is a compound of diethylene glycol and polydimethylphenol diol in a molar ratio of 1:1; the dibasic acid is phthalic acid, the molar ratio of the diol to the dibasic acid is 2:1, and the amount of castor oil added is 2%-3.8% of the sum of the mass of the diol, the dibasic acid and the catalyst II; The chain extender is a mixture of glycerol and triethanolamine; The foam stabilizer is one or more of B8870, L580 and DS11; Catalyst 1 is a mixture of A-1, PC8, TMR-2 and formic acid.

2. The hard polyurethane material for bonsai rockery according to claim 1, characterized in that: Catalyst 2 is an organic transition metal catalyst, and the addition amount of catalyst 2 is 0.04% of the sum of the mass of diol and dibasic acid.

3. The hard polyurethane material for bonsai rockery according to claim 1, characterized in that: The number average molecular weight of polydimethylphenol diol is 364 and the functionality is 2.

4. The hard polyurethane material for bonsai rockery according to claim 1, characterized in that: The preparation method of hydrophobic castor oil polyester polyol C comprises the following steps: S1, put diethylene glycol, polydimethylphenol diol and phthalic acid into a reaction kettle, under nitrogen atmosphere and stirring conditions, heat the system to 180°C to discharge water, carry out esterification reaction, and after discharge of water, heat to 210°C to continue reaction; S2. The reaction is carried out until the acid value of the system reaches 41-44 mgKOH / g, castor oil is added to the reactor, and then catalyst 2 is added. The temperature is raised to 230°C and kept warm for 3-4 hours, then the temperature is lowered to 60°C and vacuumized to -0.06 MPa for 1 hour to obtain the product.

5. The hard polyurethane material for bonsai rockery according to claim 1, characterized in that: The viscosity reducing agent is one or both of 2,2,4-trimethyl-1,3-pentanediol diisobutyrate and propylene carbonate.

6. The hard polyurethane material for bonsai rockery according to claim 1, characterized in that: The isocyanate is polyphenyl polymethylene isocyanate.

7. A method for preparing a rigid polyurethane material for bonsai rockery according to any one of claims 1 to 6, characterized in that: The following steps are involved: (1) Add weighed polyether polyol a, polyester polyol b, hydrophobic castor oil polyester polyol c, polyether polyol d, chain extender, foam stabilizer, water, catalyst 1, and viscosity reducer into a reaction kettle, and stir the reaction at room temperature for 1-2 hours to obtain component A; (2) Add isocyanate and polyether polyol d into a reaction kettle and stir at room temperature for 1-2 hours to obtain component B; (3) When using, mix component A and component B evenly.

Images