Polyether polyol and preparation method thereof, and rigid polyurethane foam and preparation method thereof

Abstract

The invention relates to the field of polyurethane materials, in particular to polyether polyol and a preparation method thereof as well as polyurethane rigid foam and a preparation method of the polyurethane rigid foam. Polyether polyol with a structure as shown in a formula (II), which is formed by taking a compound with a structure as shown in a formula (I) as an initiator, has a non-planar and rigid large annular hollow structure; a multi-benzene-ring structure can be formed in a polyurethane rigid foam skeleton, so that the strength of the foam skeleton is improved; the volatilized physical foaming agent is adsorbed in the reaction process, especially in the early stage of the reaction, the volatilization rate of the physical foaming agent is reduced, and exchange between the foaming agent in foam holes and air after foam is formed is reduced, so that foam heat conduction and foam heat conduction attenuation are reduced; the polyurethane rigid foam has the advantages of low density, low heat conductivity coefficient, high foam strength and excellent aging resistance.

Description

Technical Field

[0001] The invention relates to the field of polyurethane materials, and in particular to a polyether polyol and a preparation method thereof, and a polyurethane rigid foam and a preparation method thereof. Background Art

[0002] As a polymer insulation material, polyurethane rigid foam has the advantages of low density, low thermal conductivity and high strength. It can fill various spaces well and play a supporting role. It is widely used in the shells of refrigerators, freezers, electric water heaters and other electrical appliances. At present, the mainstream of the development of polyurethane rigid foam insulation materials such as refrigerators, freezers and electric water heaters is to reduce the injection volume to reduce costs and improve market competitiveness. However, low injection volume leads to low pressure density, which puts higher requirements on the strength of polyurethane rigid foam. At the same time, in order to ensure the stability of product quality, provide customers with high-quality products and reduce after-sales service, and create a good market reputation, the requirements for the long-term stability of products are getting higher and higher.

[0003] As a thermal insulation material, polyurethane rigid foam itself has received more attention from both the environmental protection perspective and the energy saving and low carbon perspective, as its thermal conductivity is closely related to energy consumption. In polyurethane rigid foam, the gas phase physical foaming agent component accounts for 60-70% of the thermal conductivity, and the polyurethane solid phase skeleton accounts for 20-30% of the thermal conductivity. This means that the gas phase physical foaming agent with a lower thermal conductivity will greatly reduce the thermal conductivity of polyurethane rigid foam. However, the use of a physical foaming agent with a low thermal conductivity will result in low foam strength and easy aging during the preparation process.

[0004] In summary, while ensuring the low density of polyurethane rigid foam, the market has an urgent demand for polyether polyols to have lower thermal conductivity, higher foam strength and better anti-aging ability. Summary of the invention

[0005] Therefore, the object of the present invention is to provide a polyether polyol and a preparation method thereof and a polyurethane rigid foam and a preparation method thereof. The polyether polyol of the structure (II) formed by the compound of the structure (I) as an initiator has a non-planar and rigid large circular hollow structure, which can form a multi-benzene ring structure in the polyurethane rigid foam skeleton, thereby improving the strength of the foam skeleton; and in the reaction process, especially in the early stage of the reaction, it adsorbs the volatilized physical foaming agent, reduces the volatility of the physical foaming agent and reduces the exchange between the foaming agent and the air in the foam cells after the foam is formed, thereby reducing the thermal conductivity of the foam and reducing the thermal conductivity attenuation of the foam, so that the polyurethane rigid foam has low density, low thermal conductivity, high foam strength and excellent anti-aging ability.

[0006] In order to achieve the above invention object, the technical solution provided by the present invention is as follows:

[0007] A compound, the structural formula of which is shown in formula (I):

[0008]

[0009] The compound represented by formula (I) of the present invention is a double-bound dibenzotetraaza

[14] cycloolefin dimer, referred to as "DIT-tmtaa".

[0010] On the other hand, the present invention provides a polyether polyol, the structural formula of which is shown in formula (II):

[0011]

[0012] Wherein, n1, n2, n3 and n4 are each independently any integer from 0 to 4, m1, m2, m3 and m4 are each independently any integer from 0 to 7, and n1, n2, n3, n4, m1, m2, m3 and m4 are not 0 at the same time.

[0013] The polyether polyol represented by formula (II) in the present invention is referred to as "DIT-tmtaa polyether polyol".

[0014] Furthermore, n1, n2, n3 and n4 are each independently any integer from 1 to 3; and / or m1, m2, m3 and m4 are each independently any integer from 1 to 5.

[0015] Furthermore, the polyether polyol has a hydroxyl value of 100 to 260 mg KOH / g, preferably 135 to 145 mg KOH / g, and a functionality of 2.0 to 4.0, preferably 2.5 to 3.5.

[0016] On the other hand, the present invention provides a method for preparing the above-mentioned compound, comprising reacting a dibenzotetraaza

[14] cycloolefin represented by formula (III) with m-toluene dichloride in the presence of a solvent to obtain;

[0017]

[0018] Optionally, the organic solvent is one or more of acetonitrile, methanol, and acetone;

[0019] Optionally, the mass ratio of the dibenzotetraaza

[14] cycloolefin represented by formula (III) to m-toluene dichloride is 3:1 to 1:1.

[0020] Furthermore, dibenzotetraaza

[14] cycloolefin can be purchased commercially or prepared by conventional methods in the art, for example, by reacting o-phenylenediamine with acetylacetone in the presence of nickel acetate tetrahydrate to prepare an annulene complex, and then dissolving the annulene complex and introducing hydrogen chloride gas to react.

[0021] On the other hand, the present invention provides a method for preparing a polyether polyol, comprising the following steps: subjecting a compound represented by formula (I) to addition polymerization with ethylene oxide and / or propylene oxide to obtain;

[0022]

[0023] Optionally, the reaction temperature of the addition polymerization is 90 to 140°C;

[0024] Optionally, the addition polymerization occurs under a protective atmosphere;

[0025] Optionally, the mass ratio of ethylene oxide to propylene oxide is 1:1.6 to 2.5 (preferably 1:2.0);

[0026] Optionally, the solvent is water;

[0027] Optionally, the addition polymerization further includes filtering and drying steps.

[0028] Wherein, the protective atmosphere in the present invention can be nitrogen.

[0029] Furthermore, the preparation method of the polyether polyol comprises the following steps: dissolving the compound represented by formula (I) in water, replacing the water with nitrogen, adding ethylene oxide, reacting at 90 to 140° C., stopping the reaction when the pressure remains constant, and obtaining a crude polyether; the crude polyether is filtered and dried to obtain a product.

[0030] The present invention also provides a polyurethane rigid foam, the raw materials for its preparation include any of the above-mentioned polyether polyols or the polyether polyols prepared by the above-mentioned preparation method; preferably, the raw materials for the preparation of the polyurethane rigid foam include the following components in parts by weight:

[0031] (1) Composition: 90-100 parts, preferably 95-100 parts;

[0032] (2) physical foaming agent: 5 to 25 parts, preferably 10 to 18 parts;

[0033] (3) 130 to 160 parts, preferably 130 to 150 parts, of a polyisocyanate; wherein the composition comprises a combined polyether, a surfactant, a catalyst and water in a mass ratio of 88 to 96.6:1.0 to 4.0:1.0 to 5.0:1.5 to 3, and the combined polyether comprises the polyether polyol described above or the polyether polyol obtained by the preparation method.

[0034] In the present invention, the polyisocyanate comprises at least one of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, p-phenylene diisocyanate, naphthalene diisocyanate, 1,4-cyclohexane diisocyanate, xylylene diisocyanate, and polymeric MDI, preferably polymeric MDI, with an NCO content of 30 to 32%. The polymeric MDI that can be used includes one or more of PM-200, PM-400, and PM-700 of Wanhua Chemical Group Co., Ltd.

[0035] The surfactant used in the present invention is a silicon surfactant, including but not limited to at least one of silicone oil AK8805 and silicone oil AK8830 produced by Nanjing Demei Shichuang Chemical Co., Ltd. and silicone oil B8525 and silicone oil B8545 produced by Evonik Degussa.

[0036] The catalyst used in the present invention is at least one of an amine catalyst and an organotin catalyst, preferably at least two of pentamethyldiethylenetriamine, dimethylcyclohexylamine, potassium acetate and stannous octoate.

[0037] More preferably, the catalyst contains, by weight, 0.1-2.0 parts of pentamethyldiethylenetriamine, 0.4-1.5 parts of dimethylcyclohexylamine and 0.1-0.5 parts of potassium acetate.

[0038] The physical foaming agent used in the present invention is at least one of pentane foaming agents, preferably cyclopentane.

[0039] Further, the composite polyether comprises the following components in parts by weight:

[0040] (a) polyether polyol A, 20 to 55 parts, preferably 20 to 30 parts, of any of the above polyether polyols or a polyether polyol prepared by the above preparation method;

[0041] (b) polyether polyol B, 15 to 40 parts, preferably 30 to 35 parts, of polyether polyol B prepared by addition reaction of sucrose as an initiator with propylene oxide;

[0042] (c) polyether polyol C, prepared by addition reaction of propylene oxide with sorbitol as an initiator to obtain 20 to 30 parts, preferably 25 to 30 parts, of polyether polyol C;

[0043] (d) polyether polyol D, prepared by addition reaction of diethylene glycol as an initiator with propylene oxide to obtain 5 to 15 parts, preferably 5 to 10 parts, of polyether polyol D;

[0044] Preferably, the hydroxyl value of the polyether polyol B is 350-430 mgKOH / g, and the functionality is 5.7-6.4; the hydroxyl value of the polyether polyol C is 410-485 mgKOH / g, and the functionality is 5.0-7.0; the hydroxyl value of the polyether polyol D is 180-275 mgKOH / g, and the functionality is 1.8-2.5.

[0045] On the other hand, the present invention provides a method for preparing the polyurethane rigid foam, comprising the following steps: mixing raw materials except polyisocyanate, then mixing with polyisocyanate, and foaming to obtain polyurethane rigid foam.

[0046] During the foaming process, the material temperature is 18-22°C and the pressure is 110-150MPa.

[0047] The polyurethane rigid foam involved in the present invention is mainly used for the heat preservation layer of refrigerators and freezers.

[0048] The technical solution of the present invention has the following advantages:

[0049] 1. Pentane physical foaming agents easily absorb the heat released by the polyurethane reaction in the early stage of foaming, and easily break the uncured polyurethane rigid foam skeleton during the foaming process and escape into the atmosphere. This will lead to a reduction in the amount of pentane foaming agents with low thermal conductivity, and the general volatility is 3-5%; it will also destroy the foam cell structure, causing the foam to be combined or the cell orientation to change. Both of these will increase the foam thermal conductivity and deteriorate the foam strength. The compound of formula (I) structure provided by the present invention, the polyether polyol of formula (II) structure formed by the compound of formula (I) structure as the initiator has a non-planar and rigid large circular hollow structure, which can form a multi-benzene ring structure in the polyurethane rigid foam skeleton, thereby improving the foam skeleton strength; and in the reaction process, especially in the early stage of the reaction, it absorbs the volatilized physical foaming agent, reduces the volatility of the physical foaming agent and reduces the exchange between the foaming agent and the air in the pores after the foam is formed, thereby reducing the foam thermal conductivity and reducing the foam thermal conductivity attenuation, so that the polyurethane rigid foam has low density, low thermal conductivity, high foam strength and excellent anti-aging ability.

[0050] 2. The polyether polyol provided by the present invention, the polyether polyol of the structure of formula (II), the compound of the initiator structure of formula (I) has four active hydrogens. After reacting with ethylene oxide and / or propylene oxide, the steric hindrance around the active hydrogen becomes larger; at the same time, the structure itself is a large ring, and the active sites are spaced farther apart. This makes the active hydrogen activity carried by the polyether polyol itself weaker than that of the traditional o-toluenediamine (OTDA) polyether after being made, the foam flows more gently, the fluidity is improved, the filling property of the box will be better, the strength of the foam in the box will be better, and the dimensional stability of the foam aging will also be better. On the whole, the comprehensive performance of the polyether polyol of the present invention is better than that of the OTDA polyether.

[0051] 3. The preparation method of the polyether polyol provided by the present invention is simple, easy to operate, and suitable for industrial production.

[0052] 4. The polyurethane rigid foam of the present invention, by using DIT-TMTAA polyether polyol and pentane foaming agent, can adsorb the pentane foaming agent volatilized during the reaction process, especially in the early stage of the reaction, reduce the volatility of the pentane foaming agent and reduce the exchange between the foaming agent and the air in the foam cells after the foam is formed, so that the foam cell size is reduced and the size distribution is uniform, thereby reducing the foam thermal conductivity and reducing the foam thermal conductivity attenuation. Due to the non-planar rigid large circular hollow structure of the amine polyether polyol of the present invention, the active sites are far apart and the steric hindrance is large, and the catalyst activity is low, so the fluidity is better than that of traditional polyether polyols, the strength of the foam in the box will be better, and the foam aging dimensional stability will also be better. BRIEF DESCRIPTION OF THE DRAWINGS

[0053] In order to more clearly illustrate the specific implementation methods of the present invention or the technical solutions in the prior art, the drawings required for use in the specific implementation methods or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some implementation methods of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0054] Figure 1 The dibenzotetraaza

[14] cycloolefin synthesized in Example 1 1 HNMR spectrum;

[0055] Figure 2 The DIT-tmtaa synthesized in Example 1 1 HNMR spectrum. DETAILED DESCRIPTION

[0056] The technical solution of the present invention is described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0057] If no specific experimental steps or conditions are specified in the examples, the conventional experimental steps or conditions described in the literature in the art can be used. If no manufacturer is specified for the reagents or instruments used, they are all conventional reagent products that can be obtained commercially. Raw materials for producing polyether polyols, such as o-phenylenediamine, acetylacetone, and nickel acetate tetrahydrate, can be directly purchased, for example, Aladdin.

[0058] The polyether polyol A is prepared according to the embodiment of the present invention, using DIT-tmtaa as a raw material and undergoing addition polymerization of ethylene oxide and / or propylene oxide, with a hydroxyl value of 100 to 260 mg KOH / g and a functionality of 2.5 to 4.0.

[0059] Polyether polyol B is prepared by addition reaction of sucrose as initiator with propylene oxide, with a hydroxyl value of 415 mgKOH / g and a functionality of 6.4. Manufacturer: Wanhua Chemical (Ningbo) Rongwei Polyurethane Co., Ltd.

[0060] Polyether polyol C is prepared by addition reaction of propylene oxide with sorbitol as initiator, with hydroxyl value of 455 mgKOH / g and functionality of 5.5. Manufacturer: Wanhua Chemical (Ningbo) Rongwei Polyurethane Co., Ltd.

[0061] Polyether polyol D is prepared by addition reaction of diethylene glycol as initiator with propylene oxide, with a hydroxyl value of 190 mgKOH / g and a functionality of 2.2. Manufacturer: Wanhua Chemical (Ningbo) Rongwei Polyurethane Co., Ltd.

[0062] Surfactant: B8525 (Evonik).

[0063] Physical foaming agent: cyclopentane (CP), Meilong Company.

[0064] Polyisocyanate: Wanhua PM-200 (polymeric MDI).

[0065] The following tests the hydroxyl value and functionality of polyether polyols according to standard GB / T 12008.3-1989.

[0066] Example 1

[0067] This embodiment provides a method for preparing a polyether polyol, and the process flow and preparation method are as follows:

[0068]

[0069]

[0070] (1) Synthesis of dibenzotetraaza

[14] cycloolefin: 0.2 mol o-phenylenediamine, 0.2 mol acetylacetone and 0.1 mol nickel acetate tetrahydrate were added to 250 mL ethanol as solvent, heated under reflux for 50 h under N2 protection, cooled to room temperature, filtered, then washed twice with ethanol and twice with water, and the filter cake was dried to obtain annulene complex. The complex was dissolved in 500 mL ether, hydrogen chloride (HCl) gas was introduced at a flow rate of 20 mL / min for half an hour, filtered, dried, dissolved in pyridine, poured into water to precipitate solid, filtered, and dried to obtain dibenzotetraaza

[14] cycloolefin.

[0071] Dibenzotetraaza

[14] cycloolefin 1 H NMR spectrum Figure 1 As shown. ESI m / z: 686.5 [M + ]. 1 H NMR (300 MHz, CDCl3): δ = 7.42 (m, 4H), 7.33 (m, 2H), 7.22 (m, 2H), 6.93 (m, 2H), 6.84 (m, 2H), 2.37 (s, 2H), 2.26 (s, 2H), 1.31 (s, 12H), proving that dibenzotetraaza

[14] cycloolefin was successfully synthesized.

[0072] (2) Dibenzotetraaza

[14] cycloolefin (290 mg, 0.843 mmol) was dissolved in anhydrous acetonitrile CH3CN (250 mL), and m-toluoyl chloride (160 mg, 0.788 mmol) dissolved in anhydrous acetonitrile CH3CN (250 mL) was added under N2 atmosphere within 40 minutes. After completion, the reaction was continued at 100-120°C for 3 hours. The reaction mixture was filtered while hot, and the solid particles were stored at 4°C for 12 hours after the filtrate was removed. The resulting solid precipitate was collected by filtration and washed with cold CH3CN several times to obtain DIT-tmtaa.

[0073] DIT-TMTAA 1 H NMR spectrum Figure 2 As shown. ESI m / z: 686.5 [M + ]. 1 H NMR (300 MHz, CDCl3): δ = 7.69 (m, 4H), 7.42 (m, 2H), 7.22 (m, 2H), 6.93 (m, 2H), 6.84 (m, 2H), 2.26 (s, 2H), 2.07 (s, 2H), proving that DIT-tmtaa was successfully synthesized.

[0074] (3) Water (5098 g, 283.2 mol) and DIT-tmtaa (498.2 g, 0.53 mol) were added to the reactor. After nitrogen replacement, the reaction mixture was slowly heated to 50°C. After 1 hour, stirring was started. The reaction mixture was then slowly heated and the stirring speed was slowly increased. After 6 hours, the reaction mixture was heated to 120°C and maintained for 2 hours. Ethylene oxide (58.3 g, 1.325 mol) was added at a flow rate of 40 g / h, and the pressure was controlled to be ≤0.6 MPa. After the pressure in the reactor remained constant, propylene oxide (153.7 g, 2.65 mol) was added at a flow rate of 80 g / h to continue the autocatalytic reaction. After the pressure in the reactor remained constant, the reaction was stopped to obtain a crude polyether. The crude polyether was filtered and dried to obtain a product, which was recorded as DIT-tmtaa polyether polyol A1. The hydroxyl value of the obtained DIT-tmtaa polyether polyol A1 was 110KOH / g and the functionality was 2.5.

[0075] Example 2

[0076] This embodiment provides a method for preparing a polyether polyol, comprising the following steps:

[0077] Water (5098g, 283.2mol) and DIT-tmtaa (498.2g, 0.53mol) were added to the reactor. After nitrogen replacement, it was slowly heated to 50°C. After 1h, stirring was started. Then it was slowly heated and the stirring speed was slowly increased. After 6h, it was heated to 120°C and maintained for 2h. Ethylene oxide (69.96g, 1.58mol) was added at a flow rate of 40g / h, and the pressure was controlled to be ≤0.6MPa during the period. After the pressure in the reactor remained unchanged, propylene oxide (184.44g, 3.18mol) was added at a flow rate of 80g / h to continue the autocatalytic reaction. After the pressure in the reactor remained unchanged, the reaction was stopped to obtain a crude polyether; the crude polyether was filtered and dried to obtain a product, which was recorded as DIT-tmtaa polyether polyol A2. The hydroxyl value of the obtained DIT-tmtaa polyether polyol A2 was 140KOH / g and the functionality was 3.0.

[0078] Example 3

[0079] This embodiment provides a method for preparing a polyether polyol, comprising the following steps:

[0080] Water (5098g, 283.2mol) and DIT-tmtaa (498.2g, 0.53mol) were added to the reactor. After nitrogen replacement, it was slowly heated to 50°C. After 1h, stirring was started. Then it was slowly heated and the stirring speed was slowly increased. After 6h, it was heated to 120°C and maintained for 2h. Ethylene oxide (81.84g, 1.86mol) was added at a flow rate of 40g / h, and the pressure was controlled to be ≤0.6MPa during the period. After the pressure in the reactor remained unchanged, propylene oxide (215.76g, 3.72mol) was added at a flow rate of 80g / h to continue the autocatalytic reaction. After the pressure in the reactor remained unchanged, the reaction was stopped to obtain a crude polyether; the crude polyether was filtered and dried to obtain a product, which was recorded as DIT-tmtaa polyether polyol A3. The hydroxyl value of the obtained DIT-tmtaa polyether polyol A3 was 135KOH / g and the functionality was 3.5.

[0081] Example 4

[0082] This embodiment provides a polyurethane rigid foam using DIT-tmtaa polyether polyol, and its raw material composition is as follows:

[0083] The mass ratio of the composition to cyclopentane (CP) and polyisocyanate (Wanhua PM-200) is 100:16:148.48; wherein, in terms of weight, the composition is composed of 93.2 parts of a combined polyether, 253.0 parts of a surfactant B85, 1.7 parts of a catalyst and 2.1 parts of distilled water. In terms of weight, the combined polyether is composed of 25 parts of polyether polyol A1 (prepared in Example 1), 31.2 parts of polyether polyol B, 25 parts of polyether polyol C and 12 parts of polyether polyol D. The catalyst is composed of pentamethyldiethylenetriamine, dimethylcyclohexylamine and potassium acetate, wherein pentamethyldiethylenetriamine: dimethylcyclohexylamine: potassium acetate = 1:4:2 (mass ratio).

[0084] The preparation method is as follows: 1) Mix polyether polyol A1, polyether polyol B, polyether polyol C and polyether polyol D to obtain a combined polyether; mix pentamethyldiethylenetriamine, dimethylcyclohexylamine and potassium acetate evenly to obtain a catalyst. Mix the combined polyether, surfactant, catalyst and water evenly to obtain a composition; 2) Mix the composition evenly with the physical foaming agent cyclopentane; 3) Mix the product of step 2) with polyisocyanate through a high-pressure foaming machine to obtain a polyurethane rigid foam. The operating parameters of the high-pressure foaming machine are: material temperature: 18-22°C, pressure 110-130MPa. The overfilling rate of the mixture in the mold is 115%, the curing time is 200s, and then the mold is opened to take out the finished polyurethane rigid foam.

[0085] Example 5

[0086] This embodiment provides a polyurethane rigid foam using DIT-tmtaa polyether polyol, and its raw material composition is as follows:

[0087] The mass ratio of the composition to cyclopentane (CP) and polyisocyanate (Wanhua PM-200) is 100:16:148.48; wherein, in terms of weight, the composition is composed of 92.4 parts of a combined polyether, 85253.0 parts of a surfactant B, 2.5 parts of a catalyst and 2.1 parts of distilled water. In terms of weight, the combined polyether is composed of 15 parts of polyether polyol A2 (prepared in Example 2), 40.4 parts of polyether polyol B, 25 parts of polyether polyol C and 12 parts of polyether polyol D. The catalyst is composed of pentamethyldiethylenetriamine, dimethylcyclohexylamine and potassium acetate, wherein pentamethyldiethylenetriamine: dimethylcyclohexylamine: potassium acetate = 1:5:2 (mass ratio).

[0088] The preparation method is as follows: 1) Mix polyether polyol A2, polyether polyol B, polyether polyol C and polyether polyol D to obtain a combined polyether; mix pentamethyldiethylenetriamine, dimethylcyclohexylamine and potassium acetate evenly to obtain a catalyst. Mix the combined polyether, surfactant, catalyst and water evenly to obtain a composition; 2) Mix the composition evenly with the physical foaming agent cyclopentane; 3) Mix the product of step 2) with polyisocyanate through a high-pressure foaming machine to obtain a polyurethane rigid foam. The operating parameters of the high-pressure foaming machine are: material temperature: 18-22°C, pressure 110-130MPa. The overfilling rate of the mixture in the mold is 115%, the curing time is 200s, and then the mold is opened to take out the finished polyurethane rigid foam.

[0089] Example 6

[0090] This embodiment provides a polyurethane rigid foam using DIT-tmtaa polyether polyol, and its raw material composition is as follows:

[0091] The mass ratio of the composition to cyclopentane (CP) and polyisocyanate (Wanhua PM-200) is 100:16:148.48; wherein, by weight, the composition is composed of 92.9 parts of a combined polyether, 253.0 parts of a surfactant B85, 2.0 parts of a catalyst and 2.1 parts of distilled water. By weight, the combined polyether is composed of 25 parts of polyether polyol A2 (prepared in Example 2), 34.9 parts of polyether polyol B, 25 parts of polyether polyol C and 8 parts of polyether polyol D. The catalyst is composed of pentamethyldiethylenetriamine, dimethylcyclohexylamine and potassium acetate, wherein pentamethyldiethylenetriamine: dimethylcyclohexylamine: potassium acetate = 1:4:2 (mass ratio).

[0092] The preparation method is as follows: 1) Mix polyether polyol A2, polyether polyol B, polyether polyol C and polyether polyol D to obtain a combined polyether; mix pentamethyldiethylenetriamine, dimethylcyclohexylamine and potassium acetate evenly to obtain a catalyst. Mix the combined polyether, surfactant, catalyst and water evenly to obtain a composition; 2) Mix the composition evenly with the physical foaming agent cyclopentane; 3) Mix the product of step 2) with polyisocyanate through a high-pressure foaming machine to obtain a polyurethane rigid foam. The operating parameters of the high-pressure foaming machine are: material temperature: 18-22°C, pressure 110-130MPa. The overfilling rate of the mixture in the mold is 115%, the curing time is 200s, and then the mold is opened to take out the finished polyurethane rigid foam.

[0093] Example 7

[0094] This embodiment provides a polyurethane rigid foam using DIT-tmtaa polyether polyol, and its raw material composition is as follows:

[0095] The mass ratio of the composition to cyclopentane (CP) and polyisocyanate (Wanhua PM-200) is 100:16:148.48; wherein, by weight, the composition is composed of 93.2 parts of a combined polyether, 53.0 parts of a surfactant B852, 1.7 parts of a catalyst and 2.1 parts of distilled water. By weight, the combined polyether is composed of 35 parts of polyether polyol A2 (prepared in Example 2), 28.2 parts of polyether polyol B, 25 parts of polyether polyol C and 5 parts of polyether polyol D. The catalyst is composed of pentamethyldiethylenetriamine, dimethylcyclohexylamine and potassium acetate, wherein pentamethyldiethylenetriamine: dimethylcyclohexylamine: potassium acetate = 1:3:2 (mass ratio).

[0096] The preparation method is as follows: 1) Mix polyether polyol A2, polyether polyol B, polyether polyol C and polyether polyol D to obtain a combined polyether; mix pentamethyldiethylenetriamine, dimethylcyclohexylamine and potassium acetate evenly to obtain a catalyst. Mix the combined polyether, surfactant, catalyst and water evenly to obtain a composition; 2) Mix the composition evenly with the physical foaming agent cyclopentane; 3) Mix the product of step 2) with polyisocyanate through a high-pressure foaming machine to obtain a polyurethane rigid foam. The operating parameters of the high-pressure foaming machine are: material temperature: 18-22°C, pressure 110-130MPa. The overfilling rate of the mixture in the mold is 115%, the curing time is 200s, and then the mold is opened to take out the finished polyurethane rigid foam.

[0097] Example 8

[0098] This embodiment provides a polyurethane rigid foam using DIT-tmtaa polyether polyol, and its raw material composition is as follows:

[0099] The mass ratio of the composition to cyclopentane (CP) and polyisocyanate (Wanhua PM-200) is 100:16:148.48; wherein, by weight, the composition is composed of 92.5 parts of a combined polyether, 253.0 parts of a surfactant B85, 2.4 parts of a catalyst and 2.1 parts of distilled water. By weight, the combined polyether is composed of 25 parts of polyether polyol A3 (prepared in Example 3), 36.5 parts of polyether polyol B, 25 parts of polyether polyol C and 6 parts of polyether polyol D. The catalyst is composed of pentamethyldiethylenetriamine, dimethylcyclohexylamine and potassium acetate, wherein pentamethyldiethylenetriamine: dimethylcyclohexylamine: potassium acetate = 1:5:2 (mass ratio).

[0100] The preparation method is as follows: 1) Mix polyether polyol A3, polyether polyol B, polyether polyol C and polyether polyol D to obtain a combined polyether; mix pentamethyldiethylenetriamine, dimethylcyclohexylamine and potassium acetate evenly to obtain a catalyst. Mix the combined polyether, surfactant, catalyst and water evenly to obtain a composition; 2) Mix the composition evenly with the physical foaming agent cyclopentane; 3) Mix the product of step 2) with polyisocyanate through a high-pressure foaming machine to obtain a polyurethane rigid foam. The operating parameters of the high-pressure foaming machine are: material temperature: 18-22°C, pressure 110-130MPa. The overfilling rate of the mixture in the mold is 115%, the curing time is 200s, and then the mold is opened to take out the finished polyurethane rigid foam.

[0101] Comparative Example 1

[0102] This comparative example provides a polyurethane rigid foam using DIT-tmtaa polyether polyol, and its raw material composition is as follows:

[0103] The mass ratio of the composition to cyclopentane (CP) and polyisocyanate (Wanhua PM-200) is 100:16:148.48; wherein, by weight, the composition is composed of 92.1 parts of combined polyether, 85253.0 parts of surfactant B, 2.8 parts of catalyst and 2.1 parts of distilled water. By weight, the combined polyether is composed of 47.1 parts of polyether polyol B, 30 parts of polyether polyol C and 5 parts of polyether polyol D. The catalyst is composed of pentamethyldiethylenetriamine, dimethylcyclohexylamine and potassium acetate, wherein pentamethyldiethylenetriamine: dimethylcyclohexylamine: potassium acetate = 1:6:2 (mass ratio).

[0104] The preparation method is as follows: 1) Mix polyether polyol B, polyether polyol C and polyether polyol D to obtain a combined polyether; mix pentamethyldiethylenetriamine, dimethylcyclohexylamine and potassium acetate evenly to obtain a catalyst. Mix the combined polyether, surfactant, catalyst and water evenly to obtain a composition; 2) Mix the composition evenly with the physical foaming agent cyclopentane; 3) Mix the product of step 2) with polyisocyanate through a high-pressure foaming machine to obtain a polyurethane rigid foam. The operating parameters of the high-pressure foaming machine are: material temperature: 18-22°C, pressure 110-130MPa. The overfilling rate of the mixture in the mold is 115%, the curing time is 200s, and then the mold is opened to take out the finished polyurethane rigid foam.

[0105] Test Case

[0106] The performance test of the polyurethane rigid foam prepared in each embodiment and comparative example is as follows:

[0107] The flow index test is as follows: prepare a mold with a length*width*height of 30mm*50mm*1100mm, and the mold temperature is 45℃. Inject a certain weight of the mixture from the bottom of the mold so that the weight when the mold is just filled is xg, the mold height is 1100mm, and the mold height divided by x is the flow index. The foam core density test is in accordance with the standard: GB / T 6343-2009; the foam thermal conductivity test is in accordance with the standard: GB / T 10295-2008 test; the foam compression strength test is in accordance with the standard: GB / T 8813-2008 test; the foam dimensional stability test is in accordance with the standard: GB / T 8811-2008 test; test conditions: test at 0.1MPa pressure for 30min, and calculate the dimensional stability based on the volume change before and after compression. Observe the number of surface defects and record the number of defects with a diameter ≥3cm.

[0108] The results are shown in Table 1.

[0109] Table 1 Properties of polyurethane rigid foam

[0110]

[0111] Compared with Comparative Example 1, the compression strength of the polyurethane rigid foams prepared in each embodiment of the present invention is significantly improved, the deformation rate is significantly reduced, the number of surface defects is significantly reduced, the flow index is significantly improved, and the thermal conductivity is also reduced, indicating that these polyurethane rigid foams have low thermal conductivity, high foam strength, good fluidity and excellent anti-aging ability, especially Example 8, and the foam core density of the polyurethane rigid foam of the present invention is 32-33 Kg / m 3 This shows that these polyurethane rigid foams also have low density properties.

[0112] Obviously, the above embodiments are merely examples for the purpose of clear explanation, and are not intended to limit the implementation methods. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived therefrom are still within the scope of protection of the invention.

Claims

1. A compound, characterized in that Its structural formula is shown in formula (I):

2. A polyether polyol, characterized in that Its structural formula is shown in formula (II): Wherein, n1, n2, n3 and n4 are each independently any integer from 0 to 4, m1, m2, m3 and m4 are each independently any integer from 0 to 7, and n1, n2, n3, n4, m1, m2, m3 and m4 are not 0 at the same time.

3. The polyether polyol according to claim 2, characterized in that n1, n2, n3 and n4 are each independently any integer from 1 to 3; and / or m1, m2, m3 and m4 are each independently any integer from 1 to 5.

4. The polyether polyol according to claim 2 or 3, characterized in that The polyether polyol has a hydroxyl value of 100 to 260 mg KOH / g, preferably 135 to 145 mg KOH / g, and a functionality of 2.0 to 4.0, preferably 2.5 to 3.

5.

5. A method for preparing the compound according to claim 1, characterized in that: The method comprises reacting a dibenzotetraaza[14]cycloolefin represented by formula (III) with m-toluene dicarbonyl chloride in the presence of an organic solvent to obtain; Optionally, the organic solvent is one or more of acetonitrile, methanol, and acetone; Optionally, the mass ratio of the dibenzotetraaza[14]cycloolefin represented by formula (III) to m-toluene dichloride is 3:1 to 1:

1.

6. A method for preparing a polyether polyol, characterized in that: The method comprises the following steps: subjecting a compound represented by formula (I) to addition polymerization with ethylene oxide and / or propylene oxide in the presence of a solvent to obtain a product; Optionally, the reaction temperature of the addition polymerization is 90 to 140°C; Optionally, the addition polymerization occurs under a protective atmosphere; Optionally, the mass ratio of ethylene oxide to propylene oxide is 1:1.6-2.5; Optionally, the solvent is water; Optionally, the addition polymerization further includes filtering and drying steps.

7. The method for preparing a polyether polyol according to claim 6, characterized in that: The preparation method of the polyether polyol comprises the following steps: dissolving the compound represented by formula (I) in water, replacing the water with nitrogen, adding ethylene oxide, reacting at 90-140° C., stopping the reaction when the pressure remains constant, and obtaining a crude polyether; filtering the crude polyether and drying the product.

8. A polyurethane rigid foam, characterized in that: The raw materials for preparing the polyurethane rigid foam include the polyether polyol described in any one of claims 2 to 4 or the polyether polyol prepared by the preparation method described in claim 6 or 7; preferably, the raw materials for preparing the polyurethane rigid foam include the following components in parts by weight: (1) Composition: 90-100 parts, preferably 95-100 parts; (2) physical foaming agent: 5 to 25 parts, preferably 10 to 18 parts; (3) 130 to 160 parts, preferably 130 to 150 parts, of a polyisocyanate; wherein the composition comprises a combined polyether, a surfactant, a catalyst and water in a mass ratio of 88 to 96.6:1.0 to 4.0:1.0 to 5.0:1.5 to 3, and the combined polyether comprises the polyether polyol described in any one of claims 2 to 4 or the polyether polyol prepared by the preparation method described in claim 6 or 7.

9. The polyurethane rigid foam according to claim 8, characterized in that: The composite polyether comprises the following components in parts by weight: (a) polyether polyol A, 20 to 55 parts, preferably 20 to 30 parts, of the polyether polyol according to any one of claims 2 to 4 or the polyether polyol prepared by the preparation method according to claim 6 or 7; (b) polyether polyol B, 15 to 40 parts, preferably 30 to 35 parts, of polyether polyol B prepared by addition reaction of sucrose as an initiator with propylene oxide; (c) polyether polyol C, prepared by addition reaction of sorbitol as an initiator with propylene oxide to obtain 20 to 30 parts, preferably 25 to 30 parts, of polyether polyol C; (d) polyether polyol D, prepared by addition reaction of diethylene glycol as an initiator with propylene oxide to obtain 5 to 15 parts, preferably 5 to 10 parts, of polyether polyol D; Preferably, the hydroxyl value of the polyether polyol B is 350-430 mgKOH / g, and the functionality is 5.7-6.4; the hydroxyl value of the polyether polyol C is 410-485 mgKOH / g, and the functionality is 5.0-7.0; the hydroxyl value of the polyether polyol D is 180-275 mgKOH / g, and the functionality is 1.8-2.

5.

10. A method for preparing the polyurethane rigid foam according to claim 8 or 9, comprising the following steps: mixing raw materials except polyisocyanate, then mixing with polyisocyanate, and foaming to obtain the polyurethane rigid foam.

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