Rigid polyurethane foam and application thereof

Abstract

The invention belongs to the technical field of polyurethane foam, and particularly relates to rigid polyurethane foam and application thereof. The invention provides rigid polyurethane foam. The rigid polyurethane foam comprises a component A and a component B which are independently subpackaged, the component A comprises the following components in parts by mass: 100 parts of polyol, 1-5 parts of an organosilicon surfactant, 0.5-5.0 parts of a catalyst, 5-15 parts of a foaming agent and 10-20 parts of a flame retardant; the polyol comprises polyether polyol, polyester polyol and castor oil; and the component B comprises isocyanate. The rigid polyurethane foam provided by the invention has good strength, dimensional stability and ultralow heat conductivity coefficient in an ultralow temperature environment.

Description

Technical Field

[0001] The invention belongs to the technical field of polyurethane foam, and in particular relates to a hard polyurethane foam and application thereof. Background Art

[0002] After 30 years of technological innovation in the field of LNG ships, France's GTT has become a leader in the field of LNG maintenance systems. LNG ship manufacturers in South Korea and China all use GTT technology Mark III and No. 96 systems. GTT technology accounts for more than 90% of global LNG ship orders. Rigid polyurethane foam insulation material is a key factor in LNG liquid cargo maintenance systems. Physical foaming agents are important components in the preparation of rigid polyurethane foam. They vaporize and expand during the cross-linking chemical reaction of liquid polyurethane raw materials, thereby forming a lightweight and porous material for polyurethane, improving the thermal insulation performance of polyurethane foam and reducing the density of polyurethane foam. A 174,000m 3 An LNG carrier requires about 1,800 tons of rigid polyurethane foam, of which more than 70 tons are used as blowing agents. At present, the blowing agents of GTT's rigid polyurethane foam are hydrofluorocarbons (such as HFC-245fa); although HFC-245fa is a blowing agent with zero ozone depletion potential (ODP), its greenhouse gas effect value (GWP) reaches 1030. Therefore, starting from July 1, 2024, GTT will only approve polyurethane foam made with blowing agents with low GWP values.

[0003] The prior art discloses a highly flame-retardant glass fiber reinforced rigid polyurethane ultra-low temperature insulation material and its preparation method. The technology uses hydrofluorocarbon pentafluoropropane (HFC-245fa) and pentafluorobutane (HFC-365mfc) for foaming, and the foaming agent is a high GWP value substance. The Chinese patent with publication number CN108264625A discloses an LNG insulation material. The technology also uses pentafluoropropane (HFC-245fa) and pentafluorobutane (HFC-365mfc) for foaming; and it uses high-boiling point chlorofluorocarbon compounds (such as carbon tetrachloride) as auxiliary agents. Chlorofluorocarbon compounds are not only high GWP substances, but also ozone depleting substances.

[0004] Therefore, there is an urgent need to develop a rigid polyurethane foam for LNG cold preservation foamed with a zero ODP value and a low GWP value foaming agent. Summary of the invention

[0005] The purpose of the present invention is to provide a rigid polyurethane foam and its application. The rigid polyurethane foam provided by the present invention has good strength, dimensional stability and ultra-low thermal conductivity in an ultra-low temperature environment, and complies with the requirements of regulations such as the Montreal Protocol on protecting the ozone layer and the Kyoto Protocol on reducing greenhouse gas emissions.

[0006] In order to achieve the above object, the present invention provides the following technical solutions:

[0007] The present invention provides a rigid polyurethane foam, comprising independently packaged component A and component B;

[0008] In parts by mass, the component A comprises 100 parts of polyol, 1 to 5 parts of organosilicon surfactant, 0.5 to 5.0 parts of catalyst, 5 to 15 parts of foaming agent and 10 to 20 parts of flame retardant;

[0009] The polyols include polyether polyols, polyester polyols and castor oil;

[0010] The component B comprises isocyanate.

[0011] Preferably, the polyether polyol has a hydroxyl value of 300 to 600 mgKOH / g and a functionality of 4.0 to 6.0;

[0012] The polyester polyol has a hydroxyl value of 150 to 350 mgKOH / g and a functionality of 2.0;

[0013] The castor oil has a hydroxyl value of 160-165 mgKOH / g and a functionality of 2.7.

[0014] Preferably, the viscosity of the polyether polyol is 3000-10000 mPa·s; the viscosity of the polyester polyol is 1000-10000 mPa·s; and the viscosity of the castor oil is 600-800 mPa·s.

[0015] Preferably, the mass ratio of the polyether polyol, polyester polyol and castor oil is 50-70:10-20:20-30.

[0016] Preferably, the catalyst includes a foaming catalyst, a gel catalyst and a trimerization catalyst;

[0017] The foaming catalyst includes one or more of pentamethyldiethylenetriamine, dimorpholine diethyl ether and bis(dimethylaminoethyl) ether; the gel catalyst includes N,N-dimethylcyclohexylamine and / or triethylenediamine; the trimerization catalyst includes one or more of 1,3,5-tris(dimethylaminopropyl)hexahydrotriazine, 2,4,6-tris(dimethylaminomethyl)phenol, quaternary ammonium salt, soluble potassium salt and soluble sodium salt;

[0018] The mass ratio of the foaming catalyst, the gel catalyst and the trimerization catalyst is 1:3:2.

[0019] Preferably, the foaming agent comprises a hydrofluoroolefin foaming agent; the hydrofluoroolefin foaming agent comprises one or more of chlorotrifluoropropylene, tetrafluoropropylene and hexafluorobutene;

[0020] The flame retardant includes one or more of tris(2-chloropropyl)phosphate, tris(2-chloroethyl)phosphate, triethyl phosphate, dimethyl methylphosphonate and diethyl-N,N-bis(2-hydroxyethyl)aminomethylphosphonate.

[0021] Preferably, the isocyanate comprises polyphenyl polymethylene polyisocyanate.

[0022] Preferably, the polyphenyl polymethylene polyisocyanate has a viscosity of 150 to 700 mPa.s, an NCO content of 30 to 32%, and a functionality of 2.6 to 3.0.

[0023] Preferably, the mass ratio of component A to component B is 100:80-130.

[0024] The present invention also provides application of the rigid polyurethane foam described in the above technical solution in a liquid cargo tank system of an LNG ship.

[0025] The present invention provides a rigid polyurethane foam, comprising independently packaged component A and component B; in terms of mass fractions, the component A comprises 100 parts of polyol, 1 to 5 parts of organosilicon surfactant, 0.5 to 5.0 parts of catalyst, 5 to 15 parts of foaming agent and 10 to 20 parts of flame retardant; the polyol comprises polyether polyol, polyester polyol and castor oil; and the component B comprises isocyanate. The present invention adopts high-functionality, high-hydroxyl polyether polyol in combination with low-functionality, low-hydroxyl castor oil and low-hydroxyl polyester polyol, thereby avoiding the brittle transition of foam caused by ultra-low temperature and ensuring the dimensional stability and strength of polyurethane foam. DETAILED DESCRIPTION

[0026] The present invention provides a rigid polyurethane foam, comprising independently packaged component A and component B;

[0027] In parts by mass, the component A comprises 100 parts of polyol, 1 to 5 parts of organosilicon surfactant, 0.5 to 5.0 parts of catalyst, 5 to 15 parts of foaming agent, and 10 to 20 parts of flame retardant;

[0028] The polyols include polyether polyols, polyester polyols and castor oil;

[0029] The component B comprises isocyanate.

[0030] In parts by mass, component A provided by the present invention includes 100 parts of polyols. In the present invention, the polyols include polyether polyols, polyester polyols and castor oil. In the present invention, the hydroxyl value of the polyether polyol is preferably 300-600 mgKOH / g, more preferably 400-500 mgKOH / g; the functionality is preferably 4.0-6.0, more preferably 5.0. In the present invention, the viscosity of the polyether polyol is preferably 3000-10000 mPa·s, 5000-8000 mPa·s, more preferably 6000-7000 mPa·s. In a specific embodiment of the present invention, the polyether polyol is preferably YD-8345 of Hebei Yadong Chemical Group Co., Ltd.

[0031] In the present invention, the hydroxyl value of the polyester polyol is preferably 150-350 mgKOH / g, more preferably 200-300 mgKOH / g, and more preferably 250-280 mgKOH / g; the functionality is preferably 2.0. In the present invention, the viscosity of the polyester polyol is preferably 1000-10000 mPa·s, more preferably 3000-8000 mPa·s, and more preferably 5000-6000 mPa·s. In a specific embodiment of the present invention, the polyester polyol is preferably AK-POL-1001 of Aekyung (Ningbo) Chemical Co., Ltd.

[0032] In the present invention, the hydroxyl value of the castor oil is preferably 160-165 mgKOH / g, more preferably 162-163 mgKOH / g; the functionality is preferably 2.7. In the present invention, the viscosity of the castor oil is preferably 600-800 mPa·s, more preferably 600-700 mPa·s. In a specific embodiment of the present invention, the castor oil is preferably purchased from Jinan Sanen Chemical Co., Ltd.

[0033] In the present invention, the mass ratio of the polyether polyol, the polyester polyol and the castor oil is preferably 50-70:10-20:20-30, and more preferably 55-60:12-15:25-26.

[0034] In parts by mass, component A provided by the present invention includes 1 to 5 parts of an organosilicon surfactant, more preferably 2 to 4 parts, and more preferably 3 parts. In the present invention, the organosilicon surfactant preferably includes the S series surfactant of Shanghai Maihao Chemical Technology Co., Ltd., the B series surfactant of Evonik Group, the L series surfactant of Maitu High-tech Materials, or the AK series surfactant of Jiangsu Meside Chemical Co., Ltd. In a specific embodiment of the present invention, the organosilicon surfactant is specifically the S-8875 surfactant of Shanghai Maihao Chemical Technology Co., Ltd.

[0035] In parts by mass, component A provided by the present invention includes 0.5 to 5.0 parts of catalyst, more preferably 1.0 to 4.0 parts, and more preferably 2.0 to 3.0 parts. In the present invention, the catalyst preferably includes a foaming catalyst, a gel catalyst and a trimerization catalyst; the foaming catalyst preferably includes one or more of pentamethyldiethylenetriamine, dimorpholine diethyl ether and bis(dimethylaminoethyl) ether; the gel catalyst preferably includes N,N-dimethylcyclohexylamine and / or triethylenediamine; the trimerization catalyst preferably includes one or more of 1,3,5-tris(dimethylaminopropyl)hexahydrotriazine, 2,4,6-tris(dimethylaminomethyl)phenol, quaternary ammonium salt, soluble potassium salt and soluble sodium salt. In a specific embodiment of the present invention, the foaming catalyst is specifically pentamethyldiethylenetriamine (PC5), the gel catalyst is specifically triethylenediamine (A33), and the trimerization catalyst is specifically 1,3,5-tris(dimethylaminopropyl)hexahydrotriazine (PC41). In the present invention, the mass ratio of the foaming catalyst, the gel catalyst and the trimerization catalyst is preferably 1-3:3-9:2-4, and specifically preferably 1:3:2.

[0036] In parts by mass, component A provided by the present invention includes 5 to 15 parts of a blowing agent, more preferably 8 to 12 parts, and more preferably 9 to 10 parts. In the present invention, the blowing agent preferably includes a hydrofluoroolefin blowing agent. In the present invention, the ozone depletion potential of the hydrofluoroolefin blowing agent is preferably 0 and preferably has a low GWP value. In the present invention, the hydrofluoroolefin (HFO) blowing agent preferably includes one or more of monochlorotrifluoropropylene (HFO-1233), tetrafluoropropylene (HFO-1234) and hexafluorobutene (HFO-1336).

[0037] In parts by mass, component A provided by the present invention includes 10 to 20 parts of flame retardant, more preferably 12 to 18 parts, and more preferably 15 to 16 parts. In the present invention, the flame retardant preferably includes one or more of tris(2-chloropropyl) phosphate (TCPP), tris(2-chloroethyl) phosphate (TCEP), triethyl phosphate (TEP), dimethyl methylphosphonate (DMMP) and diethyl-N,N-bis(2-hydroxyethyl)aminomethylphosphonate (WSFR-6). In a specific embodiment of the present invention, the flame retardant is preferably TCPP and WSFR-6, and the mass ratio of TCPP to WSFR-6 is preferably 1:1.

[0038] In the present invention, the preparation method of component A preferably comprises the following steps: stirring and mixing the components included in component A, and then standing and defoaming to obtain component A. In the present invention, the stirring and mixing speed is preferably 500 rpm, and the time is preferably 0.5 to 1 hour; the mixing is preferably carried out in a stainless steel mixing kettle; and the standing and defoaming time is preferably 0.5 to 1 hour.

[0039] In the present invention, the isocyanate preferably includes polyphenyl polymethylene polyisocyanate. In the present invention, the viscosity of the polyphenyl polymethylene polyisocyanate is preferably 150-700mPa.s, more preferably 300-600mPa.s, more preferably 400-500mPa.s; the NCO content is preferably 30-32%, more preferably 30-31%; the functionality is preferably 2.6-3.0. In the present invention, the polyphenyl polymethylene polyisocyanate preferably includes PM200 of Wanhua Group; the NCO content of PM200 is 31.5% and the viscosity is 200-250mPa.s.

[0040] In the present invention, the mass ratio of component A to component B is preferably 100:80-130, more preferably 100:90-120, and even more preferably 100:100-110.

[0041] In the present invention, the method for preparing the rigid polyurethane foam preferably comprises the following steps:

[0042] The independently packaged components A and B are mixed and foamed to obtain the rigid polyurethane foam. In the present invention, the foaming is preferably carried out in a mold in which glass fiber mat is pre-evenly laid, and the amount of the glass fiber mat is preferably 10% of the polyurethane foam; the glass fiber mat is evenly distributed in the polyurethane foam during the foaming process. After the foaming, the present invention also preferably includes room temperature aging of the obtained foam, and the room temperature aging time is preferably 48 hours.

[0043] The present invention also provides the application of the rigid polyurethane foam described in the above technical solution in the liquid cargo tank system of an LNG ship. The present invention has no special limitation on the specific implementation of the application, and any method known to those skilled in the art can be adopted.

[0044] Unless otherwise specified, the materials and equipment used in the present invention are all commercially available products in the art.

[0045] The technical solutions in the present invention will be described clearly and completely below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a 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 ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0046] The raw materials used in the following examples and comparative examples are as follows:

[0047] Polyether polyol: YD-8345, hydroxyl value 455 mgKOH / g, viscosity 7000 mPa.s, purchased from Hebei Yadong Chemical Group Co., Ltd.;

[0048] Polyester polyol: AK-POL-1001, hydroxyl value of 325 mgKOH / g, viscosity of 2100 mPa.s, purchased from Aekyung (Ningbo) Chemical Co., Ltd.;

[0049] Castor oil, hydroxyl value of 163 mgKOH / g, viscosity of 680 mPa.s, purchased from Jinan Sanen Chemical Co., Ltd.;

[0050] Silicone surfactant: S-8875, purchased from Shanghai Maihao Chemical Technology Co., Ltd.;

[0051] Catalysts pentamethyldiethylenetriamine (PC5), triethylenediamine (A33), and 1,3,5-tris(dimethylaminopropyl)hexahydrotriazine (PC41) were purchased from Evonik Specialty Chemicals (Shanghai) Co., Ltd.;

[0052] Flame retardant TCPP, purchased from Zhejiang Wansheng Co., Ltd.;

[0053] Flame retardant WSFR-6, purchased from Zhejiang Wansheng Co., Ltd.;

[0054] Hydrofluoroolefin blowing agent HFO-1234 was purchased from Sinochem Blue Sky Honeywell New Materials Co., Ltd.;

[0055] Polyphenyl polymethylene polyisocyanate: PM200, NCO content of 31.5%, viscosity of 200-250 mPa.s, purchased from Wanhua Chemical.

[0056] Examples 1 to 6

[0057] The formulations of Examples 1 to 6 are shown in Table 1;

[0058] Table 1 Formulations of Examples 1 to 6 (unit / portion)

[0059]

[0060] The components included in component A were stirred and mixed at a speed of 500 rpm for 0.5 h, and allowed to stand for defoaming for 1.0 h to obtain component A. Component A and component B were fully mixed according to the proportion, poured into a mold with glass fiber mat, and after foaming reaction, rigid polyurethane foam was obtained. After the foam was matured at room temperature for 48 hours, various properties were tested.

[0061] Comparative Examples 1 to 3

[0062] The formulations of Comparative Examples 1 to 3 are shown in Table 2.

[0063] Table 2 Formulas of Comparative Examples 1 to 3 (unit / portion)

[0064]

[0065]

[0066] A rigid polyurethane foam was prepared according to the preparation method of Example 1, and various properties were tested.

[0067] Performance Testing

[0068] The rigid polyurethane foam models prepared in Examples 1 to 6 and Comparative Examples 1 to 3 were subjected to performance tests; the test standards adopted in the performance tests were: ASTM D1622 for apparent density, ASTM D6226 for closed cell rate, ASTM D1621 for compression strength, and ASTM D1623 for tensile strength; and DIN 4102 and ISO 9772 for flame retardancy.

[0069] The test results obtained are shown in Table 3;

[0070] Table 3 Performance test results of rigid polyurethane foam obtained in Examples and Comparative Examples

[0071]

[0072] As can be seen from Table 3, the density of the rigid polyurethane foam provided by the present invention ranges from 90 kg / m 3 Up to 160kg / m 3 , has good thermal insulation performance, excellent mechanical properties (especially in ultra-low temperature environment, there is no obvious brittle transition, resulting in reduced tensile properties), and good flame retardant properties. The rigid polyurethane foam provided by the present invention can meet the requirements of MARK III, NO96 and NO96 Super LNG ship membrane enclosure technology; and at the same time meet the requirements of GST LNG land storage tank membrane enclosure technology.

[0073] Although the above embodiment describes the present invention in detail, it is only a part of the embodiments of the present invention, not all of the embodiments. Other embodiments can be obtained based on this embodiment without creativity, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A rigid polyurethane foam, characterized in that: Comprising independently packaged component A and component B; In parts by mass, the component A comprises 100 parts of polyol, 1 to 5 parts of organosilicon surfactant, 0.5 to 5.0 parts of catalyst, 5 to 15 parts of foaming agent and 10 to 20 parts of flame retardant; The polyols include polyether polyols, polyester polyols and castor oil; The component B comprises isocyanate.

2. The rigid polyurethane foam according to claim 1, characterized in that The polyether polyol has a hydroxyl value of 300 to 600 mgKOH / g and a functionality of 4.0 to 6.0; The polyester polyol has a hydroxyl value of 150 to 350 mgKOH / g and a functionality of 2.0; The castor oil has a hydroxyl value of 160-165 mgKOH / g and a functionality of 2.

7.

3. The rigid polyurethane foam according to claim 1 or 2, characterized in that: The viscosity of the polyether polyol is 3000-10000 mPa·s; the viscosity of the polyester polyol is 1000-10000 mPa·s; and the viscosity of the castor oil is 600-800 mPa·s.

4. The rigid polyurethane foam according to claim 1, characterized in that The mass ratio of the polyether polyol, polyester polyol and castor oil is 50-70:10-20:20-30.

5. The rigid polyurethane foam according to claim 1, characterized in that The catalyst includes a foaming catalyst, a gel catalyst and a trimerization catalyst; The foaming catalyst includes one or more of pentamethyldiethylenetriamine, dimorpholine diethyl ether and bis(dimethylaminoethyl) ether; the gel catalyst includes N,N-dimethylcyclohexylamine and / or triethylenediamine; the trimerization catalyst includes one or more of 1,3,5-tris(dimethylaminopropyl)hexahydrotriazine, 2,4,6-tris(dimethylaminomethyl)phenol, quaternary ammonium salt, soluble potassium salt and soluble sodium salt; The mass ratio of the foaming catalyst, the gel catalyst and the trimerization catalyst is 1-3:3-9:2-4.

6. The rigid polyurethane foam according to claim 1, characterized in that The foaming agent includes a hydrofluoroolefin foaming agent; the hydrofluoroolefin foaming agent includes one or more of monochlorotrifluoropropylene, tetrafluoropropylene and hexafluorobutene; The flame retardant includes one or more of tris(2-chloropropyl)phosphate, tris(2-chloroethyl)phosphate, triethyl phosphate, dimethyl methylphosphonate and diethyl-N,N-bis(2-hydroxyethyl)aminomethylphosphonate.

7. The rigid polyurethane foam according to claim 1, characterized in that The isocyanate includes polyphenyl polymethylene polyisocyanate.

8. The rigid polyurethane foam according to claim 7, characterized in that The polyphenyl polymethylene polyisocyanate has a viscosity of 150 to 700 mPa.s, an NCO content of 30 to 32%, and a functionality of 2.6 to 3.

0.

9. The rigid polyurethane foam according to claim 1, characterized in that: The mass ratio of component A to component B is 100:80-130.

10. Use of the rigid polyurethane foam according to any one of claims 1 to 9 in a liquid cargo tank system of an LNG ship.

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