A polyurethane thermal insulation material and its application

Abstract

The present invention discloses a polyurethane thermal insulation material and applications thereof. The polyurethane thermal insulation material adopts boron-aluminum hybrid polysiloxane-modified polyol and fluorine-modified polyisocyanate n-polymer as corresponding components in component A and component B, respectively. Practice has shown that the polyurethane thermal insulation material not only greatly improves the temperature resistance of the polyurethane thermal insulation material (can be used for a long time at 160°C), but also has a high flame retardancy (limiting oxygen index can reach 30%), and also has both hydrophobic and oleophobic properties, so-called ambiphobic function, with dual effects of water resistance and oil resistance. The polyurethane thermal insulation material has a contact angle with water greater than 140° and a contact angle with linseed oil greater than 125°, and can be preferably used in building thermal insulation and thermal pipeline equipment.

Description

Technical Field

[0001] The present invention relates to the technical field of thermal insulation materials, and in particular to a polyurethane thermal insulation material and application thereof. Background Art

[0002] Thermal insulation materials are designed to reduce thermal conductivity and conduction coefficient by increasing the gas phase void ratio or forming closed-cell bubbles, thereby achieving the effect of thermal insulation. Commonly used inorganic insulation materials, such as aluminum silicate, calcium silicate, glass wool, rock wool, etc., form gas phase voids of open-pore structure. Although these inorganic materials are difficult to burn or non-flammable, they easily absorb moisture during use, which can cause the material to harden or powder and fall off over time, resulting in insulation failure. It can also cause severe corrosion under the insulation layer, leading to perforation and leakage of pipes or equipment, and safety accidents. The bubbles formed by rigid polyurethane insulation materials are closed-pore structures and do not absorb moisture. Due to their low density, light weight, good thermal insulation performance, and low thermal conductivity, they are widely used in engineering projects such as building insulation and thermal pipeline equipment.

[0003] However, while existing rigid polyurethane foam insulation materials have better insulation efficiency than the aforementioned inorganic insulation materials, they are easily flammable, have low safety performance, low mechanical strength, low heat resistance, and poor corrosion resistance, which greatly limits the application scope of rigid polyurethane foam insulation materials. Currently, in order to overcome the flammability of polyurethane foam insulation materials, flame retardants or fillers are often added to polyurethane foam insulation materials, which improves their flame retardancy and heat resistance to a certain extent. However, the flame retardant layer of the additional flame retardants or fillers is prone to falling off after long-term operation. The addition of fillers also destroys the closed-cell structure, thereby reducing the thermal insulation performance and corrosion resistance. In particular, it can only be used in working conditions below 100°C and without oil pollution. Summary of the Invention

[0004] The purpose of the present invention is to overcome one or more deficiencies in the prior art and to provide an improved polyurethane thermal insulation material which not only has excellent water and oil resistance but also has greatly improved flame retardancy and temperature resistance.

[0005] The present invention also provides an application of the polyurethane thermal insulation material in building thermal insulation and thermal pipeline equipment.

[0006] In order to achieve the above object, a technical solution adopted by the present invention is:

[0007] A polyurethane thermal insulation material comprises component A and component B, wherein component A comprises a foaming agent and component B comprises a polyisocyanate, wherein:

[0008] The component A further comprises a boron-aluminum hybrid polysiloxane modified polyol, and the preparation method of the boron-aluminum hybrid polysiloxane modified polyol comprises:

[0009] (i) subjecting the compound represented by formula (I) and the compound represented by formula (II) to hydrolysis and condensation in water to produce intermediate 1;

[0010] Among them, R a Selected from C 1-6 Alkyl, R b 、R c Selected from C 1-6 Alkoxy, C 1-6 Alkyl, halogenated C 1-6 Alkyl, phenyl, halogenated phenyl, C 1-6 Alkyl-substituted phenyl, C 2-6 alkenyl;

[0011] wherein R1, R2, R3, R4, R5, and R6 are independently selected from unsubstituted or substituted fluorine, chlorine, bromine, C 1-6 The following groups substituted by one, two, three or more substituents in the alkyl group: C 1-6 Alkyl, phenyl, C 2-6 Alkenyl, C 2-6 Alkynyl;

[0012] (ii) reacting intermediate 1 with a product containing an aluminum hydroxyl group obtained by hydrolyzing an aluminum alkylate to produce intermediate 2;

[0013] (iii) reacting the intermediate 2 with a boron hydroxyl-containing product obtained by hydrolysis of an alkyl borate to produce a boron-aluminum hybrid polysiloxane containing a hydroxyl group;

[0014] (iv) reacting the boron-aluminum hybrid polysiloxane containing hydroxyl groups with a polyol to generate a boron-aluminum hybrid polysiloxane-modified polyol;

[0015] The polyisocyanate comprises a fluorine-modified polyisocyanate n-mer, and the n-mer is a trimer, a tetramer or more.

[0016] In the present invention, without limitation, C 1-6 Alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, neopentyl, isopentyl, n-hexyl, isohexyl, and the like.

[0017] In the present invention, without limitation, C 2-6 Alkenyl groups include, but are not limited to, vinyl, methylvinyl, ethylvinyl, propylvinyl, isopropylvinyl, and the like.

[0018] In the present invention, without limitation, C2-6 Alkynyl groups include, but are not limited to, ethynyl, methylethynyl, and the like.

[0019] In the present invention, "halogenated" refers to being substituted by one, two, three or more groups selected from fluorine, chlorine, bromine and iodine, preferably, being substituted by fluorine, chlorine or bromine.

[0020] In the present invention, trimer is a basic concept in polymer synthesis and is the product of a trimerization reaction, that is, three identical molecules A are polymerized into one molecule A3, which is called a trimer and is a low molecular weight polymer. Other low molecular weight polymers of the same concept include dimers, tetramers, pentamers, etc.; that is, a polyisocyanate n-polymer is a polymer formed by the polymerization of n polyisocyanates, where n is greater than or equal to 3.

[0021] In some embodiments of the present invention, in step (i), step (ii), and step (iii), each reaction is carried out at 75-90°C, for example, at 80-90°C.

[0022] In some embodiments of the present invention, in step (i), step (ii), and step (iii), each reaction is carried out in the presence of a hydrolysis catalyst, and the hydrolysis catalyst comprises glacial acetic acid and / or trifluoroacetic acid.

[0023] In some embodiments of the present invention, in step (iv), the reaction is carried out at 130-165°C, for example, at 140-160°C.

[0024] In some embodiments of the present invention, in step (iv), the reaction is carried out in the presence of zinc acetate.

[0025] According to some preferred and specific aspects of the present invention, in step (i), the compound represented by formula (I) participating in the reaction is selected from the following combination: dialkyldihydrocarbyloxysilane, diaryldihydrocarbyloxysilane, and selective alkenyltrihydrocarbyloxysilane and / or aromatic trihydrocarbyloxysilane. In some embodiments of the present invention, the dialkyldihydrocarbyloxysilane can be dimethyldimethoxysilane, diethyldimethoxysilane, dimethyldiethoxysilane, etc., the diaryldihydrocarbyloxysilane can be diphenyldimethoxysilane, diphenyldiethoxysilane, etc., the alkenyltrihydrocarbyloxysilane can be vinyltrimethoxysilane, vinyltriethoxysilane, and the aromatic trihydrocarbyloxysilane can be phenyltrimethoxysilane, phenyltriethoxysilane.

[0026] Furthermore, the compound represented by formula (I) participating in the reaction is selected from the following combination: diphenyldimethoxysilane, dimethyldimethoxysilane; and selectively vinyltrimethoxysilane and / or phenyltrimethoxysilane.

[0027] In some embodiments of the present invention, the compound represented by formula (II) is at least one selected from divinyltetramethyldisiloxane, hexaphenyldisiloxane and hexamethyldisiloxane.

[0028] In some embodiments of the present invention, the molar ratio of the compound represented by formula (I), aluminum alkyl alcohol, and alkyl borate is 1.5-10:0.8-1.2:1. Furthermore, the molar ratio of the compound represented by formula (I), aluminum alkyl alcohol, and alkyl borate is 1.6-8:0.8-1.2:1, or 1.6-6:0.8-1.2:1.

[0029] In some embodiments of the present invention, the aluminum alkylate is selected from at least one compound represented by formula (III): (R d O)3Al(Ⅲ), R d Selected from C 1-6 In some embodiments of the present invention, the aluminum alkyl alkoxide is selected from aluminum isopropoxide, aluminum triethoxide, aluminum isobutoxide, and the like.

[0030] In some embodiments of the present invention, the alkyl borate is selected from at least one compound represented by formula (IV): (R e O)3B(Ⅳ), R e Selected from C 1-6 In some embodiments of the present invention, the alkyl borate is selected from trimethyl borate, triethyl borate, tributyl borate, trioctyl borate, and the like.

[0031] According to some preferred and specific aspects of the present invention, in step (iv), the mass ratio of the boroaluminum hybrid polysiloxane containing hydroxyl groups to the polyol is 1:2-8, for example, 1:2.5-6.

[0032] In some embodiments of the present invention, the boroaluminum hybrid polysiloxane containing hydroxyl groups has a hydroxyl value of 200-600 mgKOH / g.

[0033] In some embodiments of the present invention, the molecular weight of the boroaluminum hybrid polysiloxane containing a hydroxyl group is 500 to 6000. In some embodiments, the molecular weight of the boroaluminum hybrid polysiloxane containing a hydroxyl group is 550 to 4500.

[0034] In some embodiments of the present invention, in the boron-aluminum hybrid polysiloxane containing hydroxyl groups, the molar ratio of aluminum to boron is 1:0.8-1.2, and the molar ratio of silicon to aluminum is 1.5-8:1.

[0035] In some preferred embodiments of the present invention, the preparation of the boron-aluminum hybrid polysiloxane containing hydroxyl groups includes: adding water and a hydrolysis catalyst to a reactor, heating to a preset reaction temperature (80-90°C), dropwise adding a mixture of the compound represented by formula (I) and the compound represented by formula (II), reflux reaction and removing the generated alcohol substances, then adding alkyl alcohol aluminum, continuing the reflux reaction and removing the generated alcohol substances, then adding alkyl borate, continuing the reflux reaction and removing the generated alcohol substances, cooling to room temperature after the reaction is completed, extracting with an organic solvent, removing the water layer, and separating the boron-aluminum hybrid polysiloxane containing hydroxyl groups from the organic layer.

[0036] In some embodiments of the present invention, the hydrolysis catalyst may be glacial acetic acid or trifluoroacetic acid.

[0037] In some embodiments of the present invention, in the preparation of the boron-aluminum hybrid polysiloxane containing hydroxyl groups, the water may be distilled water.

[0038] In some embodiments of the present invention, in the preparation of the boron-aluminum hybrid polysiloxane containing hydroxyl groups, the mixture of the compound represented by formula (I) and the compound represented by formula (II) is controlled to be added dropwise within 15-35 minutes.

[0039] In some embodiments of the present invention, in the preparation of the boroaluminum hybrid polysiloxane containing hydroxyl groups, the organic solvent is diethylene glycol ethyl ether acetate and / or propylene glycol methyl ether acetate.

[0040] In some embodiments of the present invention, in the embodiment of preparing the boron-aluminum hybrid polysiloxane containing hydroxyl groups, the method for separating the boron-aluminum hybrid polysiloxane containing hydroxyl groups from the organic layer can be vacuum distillation to remove diethylene glycol ethyl ether acetate and / or propylene glycol methyl ether acetate and low molecular weight substances.

[0041] In some embodiments of the present invention, the boron-aluminum hybrid polysiloxane containing hydroxyl groups is in a viscous liquid, solid, paste, or other form at 25°C.

[0042] In the present invention, the structure of the boron-aluminum hybrid polysiloxane containing hydroxyl groups is roughly as follows:

[0043] Wherein: R1, R2, R3, R4, R5, R6 are independently selected from unsubstituted or selected from fluorine, chlorine, bromine, C 1-6 The following groups substituted by one, two, three or more substituents in the alkyl group: C 1-6 Alkyl, phenyl, C 2-6 Alkenyl, C 2-6 Alkynyl;

[0044] Q contains at least repeating unit Q1, repeating unit Q2, and repeating unit Q3;

[0045] Q1 is selected from Q2 is selected from

[0046] Q3 is selected from at least one of the following structures: R7, R8 are independently selected from hydroxyl, C 1-6 Alkyl, halogenated C 1-6 Alkyl, phenyl, halogenated phenyl, C 1-6 Alkyl-substituted phenyl, C 2-6 Alkenyl.

[0047] In some embodiments, R7 and R8 are independently selected from hydroxy, methyl, ethyl, propyl, isopropyl, phenyl, methylphenyl, fluorophenyl, fluoromethyl, fluoroethyl, vinyl, and methylvinyl.

[0048] In some embodiments, Q3 is selected from at least one of the following structures:

[0049] wherein t1, t2, t5, t7 are independently selected from 0, 1, 2, t3, t4, t6 are independently selected from 1, 2, 3, 4, R9 is selected from hydrogen, fluorine, chlorine, bromine, methyl, ethyl, R 10 、R 11 Independently selected from hydrogen, methyl, ethyl, propyl, isopropyl.

[0050] In some embodiments, Q is selected from the following structures:

[0051]

[0052] Wherein, p1, p2, p3, p4, p5, p6, p7, p8, p9, p10, and p11 are independently selected from integers ranging from 1 to 100, and the repeating units corresponding to each of p1, p2, p3, p4, p5, p6, p7, p8, p9, p10, and p11 can be combined in any order in their respective structures.

[0053] Furthermore, p1, p2, p3, p4, p5, p6, p7, p8, p9, p10, and p11 are independently selected from integers of 1-50, and specific examples include 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 35, 40, 50, etc.

[0054] In some embodiments, R1, R2, and R3 have at least one selected from C 2-6 Alkenyl, C 2-6 Alkynyl, R4, R5, R6 have at least one selected from C 2-6 Alkenyl, C 2-6 Alkynyl.

[0055] In some embodiments, Q comprises an alkenyl or alkynyl group.

[0056] In some embodiments, the boron-aluminum hybrid polysiloxane containing hydroxyl groups is selected from the compounds represented by formula (I-1) to formula (I-4):

[0057] In the formula, a1, b1, c1, and d1 are independently selected from integers between 1 and 100; the repeating units corresponding to a1, b1, c1, and d1 can be combined in any order in the structure;

[0058] In the formula, a2, b2, c2, d2, and e2 are independently selected from integers between 1 and 100; the repeating units corresponding to a2, b2, c2, d2, and e2 can be combined in any order in the structure;

[0059] In the formula, a3, b3, c3, d3, and e3 are independently selected from integers between 1 and 100; the repeating units corresponding to a3, b3, c3, d3, and e3 can be combined in any order in the structure;

[0060] In the formula, a4, b4, c4, d4, and e4 are independently selected from integers ranging from 1 to 100; the repeating units corresponding to a4, b4, c4, d4, and e4 can be combined in any order in the structure.

[0061] The hydroxyl-containing boron-aluminum hybrid polysiloxane of the present invention innovatively introduces an aluminum-oxygen bond into the main chain, so that the siloxane polymer is hybridized and modified by boron and aluminum. This not only solves the problem of easy hydrolysis of polyborosiloxane existing alone, but also unexpectedly finds that the hydroxyl-containing boron-aluminum hybrid polysiloxane has the ability to withstand high temperatures of up to 500°C or above due to the synergistic hybridization of boron and aluminum, and can be used in relatively harsh environments. At the same time, the hydroxyl-containing boron-aluminum hybrid polysiloxane has excellent adhesion to substrates such as metal substrate surfaces and significantly improves flame retardancy.

[0062] In some embodiments of the present invention, the polyol is selected from polyether polyol and / or polyester polyol. Further, in some embodiments, the polyol is selected from polypropylene oxide ether triol and / or polypropylene oxide ether tetraol.

[0063] According to a specific aspect of the present invention, the polyol is composed of polypropylene oxide ether triol and polypropylene oxide ether tetraol, and the mass ratio of polypropylene oxide ether triol to polypropylene oxide ether tetraol is 1:1.5-4.

[0064] In some embodiments of the present invention, the method for preparing the fluorine-modified polyisocyanate n-mer comprises: reacting the polyisocyanate n-mer with a fluoroalcohol in a protective atmosphere (eg, a nitrogen atmosphere) to react until the desired NCO content is reached.

[0065] In some embodiments of the present invention, the fluorination reaction is performed in the presence of dibutyltin dilaurate.

[0066] In some embodiments of the present invention, the fluorination reaction is carried out at 80-100°C, or 85-100°C, or 90-100°C.

[0067] In some embodiments of the present invention, the fluoroalcohol comprises perfluoro-1-octanol, the polyisocyanate n-mer is a trimer of diisocyanate, and the feed mass ratio of the fluoroalcohol to the polyisocyanate n-mer is 0.5-0.85:1.

[0068] In some embodiments, the trimer of diisocyanate may be hexamethylene diisocyanate trimer (hereinafter referred to as trimer HDI).

[0069] In some embodiments of the present invention, the expected NCO content is 20%-30%, preferably 23%-27%.

[0070] In some embodiments of the present invention, the polyisocyanate further comprises polyphenylpolymethylene polyisocyanate (abbreviated as crude MDI or PAPI, for example, PM-200 isocyanate), and the feed mass ratio of the fluorine-modified polyisocyanate n-polymer to the polyphenylpolymethylene polyisocyanate is 0.2-0.5:1.

[0071] In some embodiments of the present invention, the raw materials of component A include, by weight: 250-600 parts of polyol, 40-150 parts of boron-aluminum hybrid polysiloxane containing hydroxyl groups, 5-20 parts of foaming agent, 5-20 parts of catalyst, 0.01-2 parts of accelerator, and 10-40 parts of foaming agent.

[0072] Furthermore, the raw materials of component A include, by weight, 300-550 parts of polyol, 70-150 parts of boron-aluminum hybrid polysiloxane containing hydroxyl groups, 8-18 parts of foaming agent, 5-15 parts of catalyst, 0.1-1 part of accelerator, and 15-40 parts of foaming agent.

[0073] In some embodiments of the present invention, among the raw materials of component A, the catalyst is Niax-A33, also known as polyurethane catalyst A33.

[0074] In some embodiments of the present invention, in the raw materials of component A, the foam leveling agent is foam leveling agent SH493, named: polyether siloxane copolymer.

[0075] In some embodiments of the present invention, the method for preparing component A includes: heating the boron-aluminum hybrid polysiloxane containing hydroxyl groups and the polyol to 100-120°C and adding zinc acetate, stirring, heating to 140-160°C, carrying out a grafting reaction, distilling off the low molecular weight products generated by the reaction under reduced pressure, cooling, and sequentially adding the remaining components such as the foaming agent, mixing and setting aside.

[0076] In some embodiments of the present invention, the mass ratio of component A to component B is 1:1.0-1.05.

[0077] Another technical solution provided by the present invention is an application of the above-mentioned polyurethane thermal insulation material in building thermal insulation and thermal pipeline equipment.

[0078] In some embodiments of the present invention, component A and component B are mixed, sprayed or injected onto a workpiece requiring insulation, and foamed at 10-40° C. (or 15-35° C. or room temperature) to generate a polyurethane insulation material.

[0079] Due to the application of the above technical solution, the present invention has the following advantages compared with the prior art:

[0080] The polyurethane thermal insulation material of the present invention adopts boron-aluminum hybrid polysiloxane-modified polyol and fluorine-modified polyisocyanate n-polymer as corresponding components in component A and component B, respectively. Practice has shown that not only the temperature resistance of the polyurethane thermal insulation material is greatly improved (it can be used for a long time at 160°C), but also the flame retardancy is high (the limiting oxygen index can reach 30%), and it also has both hydrophobic and oleophobic properties, so-called ambiphobic function, with dual effects of water resistance and oil resistance. The contact angle with water is greater than 140°, and the contact angle with linseed oil is greater than 125°, thus solving the problems of polyurethane foam thermal insulation materials or flame-retardant polyurethane foam thermal insulation materials in the prior art in terms of temperature resistance, flame retardancy, and corrosion resistance. DETAILED DESCRIPTION

[0081] The above scheme is further described below in conjunction with specific examples; it should be understood that these examples are used to illustrate the basic principles, main features and advantages of the present invention, and the present invention is not limited to the scope of the following examples; the implementation conditions adopted in the examples can be further adjusted according to specific requirements, and the implementation conditions not specified are generally the conditions in routine experiments.

[0082] Unless otherwise specified in the following examples, all raw materials were purchased from commercial sources or prepared by conventional methods in the art.

[0083] Among the following, diphenyldimethoxysilane was purchased from Aite (Shandong) New Materials Co., Ltd.; dimethyldimethoxysilane was purchased from Hangzhou Guibao Chemical Co., Ltd.; vinyltrimethoxysilane was purchased from Nanjing Luoen Silicon Materials Co., Ltd.; phenyltrimethoxysilane was purchased from Zhejiang Woxingman New Materials Technology Co., Ltd.; divinyltetramethyldisiloxane was purchased from Hangzhou Guibao New Materials Co., Ltd.; hexaphenyldisiloxane was purchased from Hangzhou Guibao New Materials Co., Ltd.; hexamethyldisiloxane was purchased from Hangzhou Guibao New Materials Co., Ltd.; aluminum isopropoxide was purchased from Yangzhou Zhongtianli New Materials Co., Ltd.; trimethyl borate was purchased from Shandong Guohua Co., Ltd.; hexamethylene diisocyanate trimer (trimer HDI, HT-100) was purchased from Wanhua Chemical Group Co., Ltd.; PM-200 isocyanate was purchased from Wanhua Chemical Group Co., Ltd.; polypropylene oxide ether triol (H305) was purchased from Nanjing Hongbaoli Group Co., Ltd.; polypropylene oxide ether tetraol (H8404) was purchased from Nanjing Hongbaoli Group Co., Ltd.; foaming agent SH493 was purchased from Hubei Longsheng Sihai New Materials Co., Ltd.; catalyst Niax-A33 was purchased from Henry Polymer Materials (Shenzhen) Co., Ltd.; dibutyltin dilaurate was purchased from Henry Polymer Materials (Shenzhen) Co., Ltd.; blowing agent HCFC-141b was purchased from Changzhou Hongjia Fluorine Technology Co., Ltd.; perfluoro-1-octanol was purchased from Hubei Yamade Biopharmaceutical Co., Ltd.

[0084] Example 1

[0085] This embodiment provides a boron-aluminum hybrid polysiloxane containing hydroxyl groups and a preparation method thereof. The raw material formula of the boron-aluminum hybrid polysiloxane containing hydroxyl groups is shown in Table 1.

[0086] Table 1

[0087]

[0088] During the preparation of the boron-aluminum hybrid polysiloxane containing hydroxyl groups, the reaction schematic process is as follows:

[0089]

[0090] In the above-illustrated reaction process, the repeating units corresponding to a1, b1, c1, and d1 can be combined in any order in their respective structures. The above only exemplifies one arrangement. In the actual preparation process, there may be only one arrangement, or there may be several arrangements forming a mixture.

[0091] The preparation method specifically comprises:

[0092] Add the formulated amount of distilled water and hydrolysis catalyst (trifluoroacetic acid) to a 1000 mL three-necked flask, heat to 80°C, and add the mixture of all silanes and siloxanes in Table 1 dropwise using a dropping funnel. The mixture is added dropwise in about 25 minutes. Stir and reflux the reaction at 85°C to remove the alcohol generated by the reaction. The reaction is continued for 2 hours. Subsequently, the formulated amount of aluminum isopropoxide is added to the flask, and the reaction is continued to reflux and produce alcohol for 2 hours. Then, the formulated amount of trimethyl borate is added, and the reaction is continued to reflux and produce alcohol for 2 hours. The reaction is completed. After the product was cooled to room temperature, it was extracted with an excess of diethylene glycol ethyl ether acetate, the aqueous layer was removed, and finally the organic layer was distilled under reduced pressure in a rotary evaporator to remove diethylene glycol ethyl ether acetate and low molecular weight substances to obtain 174.2 g of boroaluminum hybrid polysiloxane containing hydroxyl groups with a yield of 90.8% (theoretical yield is 191.85 g). GPC (gel permeation chromatography) measured an average molecular weight of 892 and a hydroxyl value of 270.52 mgKOH / g. It was a viscous liquid at 25°C.

[0093] Example 2

[0094] This embodiment provides a boron-aluminum hybrid polysiloxane containing hydroxyl groups and a preparation method thereof. The raw material formula of the boron-aluminum hybrid polysiloxane containing hydroxyl groups is shown in Table 2.

[0095] Table 2

[0096]

[0097]

[0098] During the preparation of the boron-aluminum hybrid polysiloxane containing hydroxyl groups, the reaction schematic process is as follows:

[0099]

[0100] In the above-illustrated reaction process, the repeating units corresponding to a2, b2, c2, d2, and e2 can be combined in any order in their respective structures. The above only gives an exemplary arrangement. In the actual preparation process, there may be only one arrangement, or there may be several arrangements forming a mixture.

[0101] The preparation method specifically comprises:

[0102] The formulated amount of distilled water and hydrolysis catalyst (trifluoroacetic acid) were added to a 1000 mL three-necked flask and heated to 80° C. A dropping funnel was used to dropwise add the mixture of all silanes and siloxanes in Table 2. The mixture was controlled to be dripped in about 25 minutes. The mixture was stirred and refluxed at 85° C. to remove the alcohol generated by the reaction. The reaction was continued for 2 hours. Subsequently, the formulated amount of aluminum isopropoxide was added to the flask, and the reaction was continued to reflux and produce alcohol for 2 hours. The formulated amount of trimethyl borate was then added, and the reaction was continued to reflux and produce alcohol for 2 hours. The reaction was completed and the product was obtained. After cooling to room temperature, extraction was performed with an excess of diethylene glycol ethyl ether acetate, an organic solvent, and the aqueous layer was removed. Finally, the organic layer was distilled under reduced pressure on a rotary evaporator to remove the organic solvent diethylene glycol ethyl ether acetate and low-molecular-weight substances. 133.85 g of boroaluminum hybrid polysiloxane containing hydroxyl groups was obtained with a yield of 91.1% (theoretical yield: 146.93 g). GPC (gel permeation chromatography) measured an average molecular weight of 2187 and a hydroxyl value of 451.85 mgKOH / g. The product was solid at 25°C.

[0103] Example 3

[0104] This embodiment provides a boron-aluminum hybrid polysiloxane containing hydroxyl groups and a preparation method thereof. The raw material formula of the boron-aluminum hybrid polysiloxane containing hydroxyl groups is shown in Table 3.

[0105] Table 3

[0106]

[0107] During the preparation of the boron-aluminum hybrid polysiloxane containing hydroxyl groups, the reaction schematic process is as follows:

[0108]

[0109] In the above-illustrated reaction process, the repeating units corresponding to a3, b3, c3, d3, and e3 can be combined in any order in their respective structures. The above only illustrates one arrangement. In the actual preparation process, there may be only one arrangement, or there may be several arrangements forming a mixture.

[0110] The preparation method specifically comprises:

[0111] Add the formulated amount of distilled water and hydrolysis catalyst (trifluoroacetic acid) to a 1000 mL three-necked flask and heat to 80°C. Use a dropping funnel to add the mixture of all silanes and siloxanes in Table 3 dropwise, and control the dripping to be completed in about 25 minutes. Stir and reflux the reaction at 85°C and remove the alcohol generated by the reaction. React for 2 hours. Then add the formulated amount of aluminum isopropoxide to the flask, continue to reflux and produce alcohol for 2 hours, then add the formulated amount of trimethyl borate, continue to reflux and produce alcohol for 2 hours, and the reaction is completed. After the product was cooled to room temperature, it was extracted with an excess of diethylene glycol ethyl ether acetate, the aqueous layer was removed, and the organic layer was finally distilled under reduced pressure in a rotary evaporator to remove diethylene glycol ethyl ether acetate and low molecular weight substances to obtain 160.03 g of boroaluminum hybrid polysiloxane containing hydroxyl groups with a yield of 91.3% (theoretical yield is 175.28 g). GPC (gel permeation chromatography) measured an average molecular weight of 1309 and a hydroxyl value of 344.22 mgKOH / g. It was in a paste state at 25°C.

[0112] Example 4

[0113] This embodiment provides a boron-aluminum hybrid polysiloxane containing hydroxyl groups and a preparation method thereof. The raw material formula of the boron-aluminum hybrid polysiloxane containing hydroxyl groups is shown in Table 4.

[0114] Table 4

[0115]

[0116] During the preparation of the boron-aluminum hybrid polysiloxane containing hydroxyl groups, the reaction schematic process is as follows:

[0117]

[0118] In the above-illustrated reaction process, the repeating units corresponding to a4, b4, c4, d4, and e4 can be combined in any order in their respective structures. The above only illustrates one arrangement. In the actual preparation process, there may be only one arrangement, or there may be several arrangements forming a mixture.

[0119] The preparation method specifically comprises:

[0120] The formulated amount of distilled water and hydrolysis catalyst (acetic acid) were added to a 1000 mL three-necked flask and heated to 80° C. A dropping funnel was used to dropwise add the mixture of all silanes and siloxanes in Table 4, and the dripping was controlled to be completed in about 25 minutes. Stir and reflux the reaction at 85° C. and remove the alcohol generated by the reaction. The reaction was continued for 2 hours. Subsequently, the formulated amount of aluminum isopropoxide was added to the flask, and the reaction was continued to reflux and produce alcohol for 2 hours. Then, the formulated amount of trimethyl borate was added, and the reaction was continued to reflux and produce alcohol for 2 hours. The reaction was completed and the product was obtained. After cooling to room temperature, extraction was performed with an excess of propylene glycol methyl ether acetate, an organic solvent, and the aqueous layer was removed. Finally, the organic layer was distilled under reduced pressure on a rotary evaporator to remove the organic solvent propylene glycol methyl ether acetate and low molecular weight substances. 129.89 g of boroaluminum hybrid polysiloxane containing hydroxyl groups was obtained with a yield of 90.8% (theoretical yield: 143.05 g). GPC (gel permeation chromatography) measured an average molecular weight of 968 and a hydroxyl value of 268.61 mgKOH / g. The product was a viscous liquid at 25°C.

[0121] Comparative Example 1

[0122] The reaction was essentially the same as Example 2, except that aluminum isopropoxide and trimethyl borate were not added during the reaction. The yield was 103.7 g, a yield of 91.5% (theoretical yield: 113.33 g). The GPC molecular weight was 1397, the hydroxyl number was 280.26 mgKOH / g, and the product was solid at 25°C.

[0123] Comparative Example 2

[0124] The reaction was essentially the same as Example 2, except that trimethyl borate was omitted and replaced with an equimolar amount of aluminum isopropoxide. The total amount of aluminum isopropoxide added was 114.35 parts. The yield was 137.63 g, a yield of 90.9% (theoretical yield: 151.41 g). The GPC molecular weight was 1928, the hydroxyl number was 502.67 mgKOH / g, and the product was solid at 25°C.

[0125] Comparative Example 3

[0126] The reaction was essentially the same as Example 2, except that aluminum isopropoxide was omitted and replaced with an equimolar amount of trimethyl borate. The total amount of trimethyl borate added was 58.18 parts. The yield was 129.91 g, a 91.2% yield (theoretical yield: 142.45 g). The GPC molecular weight was 2132, the hydroxyl number was 518.46 mgKOH / g, and the product was solid at 25°C.

[0127] Examples 5-12 and Comparative Application Examples 1-3

[0128] These embodiments provide a polyurethane thermal insulation material and a preparation method thereof, wherein the polyurethane thermal insulation material comprises component A and component B, wherein the mass ratio of component A to component B is 1:1.03;

[0129] The raw material formula of component A is shown in Table 5;

[0130] Table 5

[0131]

[0132]

[0133] The preparation method of component A comprises:

[0134] In a 1000mL four-necked flask equipped with a stirring paddle and a reflux condenser, polysiloxane, polypropylene oxide triol (H305), and polypropylene oxide tetraol (H8404) in the amounts specified in Table 5 were added, the temperature was raised to 110±5°C, zinc acetate was added, and the mixture was stirred for 30 minutes. The temperature was raised to 150±5°C and the grafting reaction was carried out for 2.5 hours to generate a boron-aluminum hybrid polysiloxane-modified polyol. The low molecular weight products generated by the reaction were then removed by vacuum distillation (pressure of -0.095MPa, time 45min), the temperature was lowered to 35°C, and the amount of foam leveling agent SH493, Niax-A33 catalyst, dibutyltin dilaurate, and blowing agent HCFC-141b were added in sequence. The mixture was stirred and mixed for 30 minutes to obtain component A. The measured hydroxyl value is shown in Table 5. The mixture was sealed and stored for use.

[0135] The following uses the boron-aluminum hybrid polysiloxane containing hydroxyl groups prepared in Example 3 as an example to schematically illustrate the modification process of polyols using the boron-aluminum hybrid polysiloxane containing hydroxyl groups:

[0136]

[0137] In this exemplary process, any hydroxyl group in the structure of the boron-aluminum hybrid polysiloxane containing hydroxyl groups may condense with the polyol, and it may be any one, two, or all of the silanol, aluminum hydroxyl, and boron hydroxyl groups. In the above reaction process, only the modification states of the aluminum hydroxyl group and the boron hydroxyl group are schematically given, that is, it may be connected to the molecular chain of the polyol through the aluminum hydroxyl group, it may be connected to the molecular chain of the polyol through the boron hydroxyl group, or it may be that all of them are condensed to form a variety of connection states.

[0138] The raw materials of component B include: perfluoro-1-octanol, hexamethylene diisocyanate trimer (trimer HDI, HT-100), and PM-200 isocyanate;

[0139] The preparation method of component B comprises:

[0140] ① Preparation of fluorinated HDI trimer:

[0141] Add 56.5 g of perfluoro-1-octanol and 81 g of hexamethylene diisocyanate trimer (trimer HDI, HT-100) to a 1000 mL three-necked flask, heat to 70-75° C., and after all are melted and become transparent, stir for 30 min, add 0.69 g of dibutyltin dilaurate, gradually increase the temperature at a heating rate of about 2° C. / min, and control the temperature at 95±2° C. while stirring to carry out the fluorination reaction. During this period, nitrogen should be passed for reaction protection until the NCO content (25±0.5%) does not change within 30 min;

[0142] The reaction process of perfluoro-1-octanol and hexamethylene diisocyanate trimer is as follows:

[0143]

[0144] ② Preparation of component B:

[0145] After the reaction in step ① is completed, the temperature is lowered to 45° C., 412.6 g of PM-200 isocyanate is added thereto, and the mixture is stirred and mixed for 30 min to obtain component B, about 550 g, with an NCO content of about 25.4%. The mixture is sealed and stored for later use.

[0146] When used, component A and component B are mixed according to the formula, sprayed or injected onto the workpiece that needs insulation, and foamed at room temperature to form polyurethane insulation material.

[0147] Performance Testing

[0148] The following performance tests were performed on the polyurethane thermal insulation materials obtained in Examples 5-12 and Comparative Examples 1-3. The specific results are shown in Table 6.

[0149] Table 6

[0150]

[0151] As shown in Table 6, the comparative example 1 uses pure polysiloxane (not hybrid modified). Even though the polyurethane system contains both fluorine and silicon elements, it still has deficiencies in terms of hydrophobicity and oleophobicity. In particular, the compressive strength, temperature resistance, and flame retardancy are difficult to meet high standards.

[0152] Comparative Example 2 uses aluminum-modified polysiloxane. Although the compressive strength and flame retardancy are improved to a certain extent compared with Comparative Example 1, there are still some deficiencies. In addition, although the hydrophobicity and oleophobicity are slightly improved, the difference is not much compared with Comparative Example 1. It can be seen that simple aluminum modification cannot significantly improve the hydrophobicity and oleophobicity.

[0153] Comparative Example 3 uses boron-modified polysiloxane, which has similar effects to those of aluminum-modified polysiloxane, but also has deficiencies in compressive strength, flame retardancy, hydrophobicity, and oleophobicity.

[0154] In Examples 5-12 of the present invention, boron-aluminum synergistically hybridized polysiloxanes were used. After being applied to the fluorosilicone system, unexpectedly, significant improvements were made in hydrophobicity and oleophobicity, and the compressive strength, flame retardancy, and temperature resistance were greatly improved, achieving surprisingly excellent results.

[0155] The above embodiments are intended only to illustrate the technical concepts and features of the present invention. Their purpose is to enable those skilled in the art to understand the contents of the present invention and implement them accordingly. They are not intended to limit the scope of protection of the present invention. Any equivalent changes or modifications made in accordance with the spirit of the present invention are intended to be covered by the scope of protection of the present invention.

[0156] The endpoints of the ranges and any values ​​disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

Claims

1. A polyurethane thermal insulation material comprising component A and component B, wherein component A comprises a foaming agent and component B comprises a polyisocyanate, characterized in that: The component A further comprises a boron-aluminum hybrid polysiloxane modified polyol, and the preparation method of the boron-aluminum hybrid polysiloxane modified polyol comprises: (i) subjecting the compound represented by formula (I) and the compound represented by formula (II) to hydrolysis and condensation in water to produce intermediate 1; Among them, R a Selected from C 1-6 Alkyl, R b 、R c Selected from C 1-6 Alkoxy, C 1-6 Alkyl, halogenated C 1-6 Alkyl, phenyl, halogenated phenyl, C 1-6 Alkyl-substituted phenyl, C 2-6 alkenyl; wherein R1, R2, R3, R4, R5, and R6 are independently selected from unsubstituted or substituted fluorine, chlorine, bromine, C 1-6 The following groups substituted by one, two, three or more substituents in the alkyl group: C 1-6 Alkyl, phenyl, C 2-6 Alkenyl, C 2-6 Alkynyl; (ii) reacting intermediate 1 with a product containing an aluminum hydroxyl group obtained by hydrolyzing an aluminum alkylate to produce intermediate 2; (iii) reacting the intermediate 2 with a boron hydroxyl-containing product obtained by hydrolysis of an alkyl borate to produce a boron-aluminum hybrid polysiloxane containing a hydroxyl group; (iv) reacting the boron-aluminum hybrid polysiloxane containing hydroxyl groups with a polyol to generate a boron-aluminum hybrid polysiloxane-modified polyol; The polyisocyanate comprises a fluorine-modified polyisocyanate n-mer, and the n-mer is a trimer, a tetramer or more.

2. The polyurethane thermal insulation material according to claim 1, characterized in that: In step (i), step (ii), and step (iii), each reaction is carried out at 75-90° C.; and / or, in step (i), step (ii), and step (iii), each reaction is carried out in the presence of a hydrolysis catalyst, wherein the hydrolysis catalyst comprises glacial acetic acid and / or trifluoroacetic acid; and / or, in step (iv), the reaction is carried out at 130-165° C.; and / or, in step (iv), the reaction is carried out in the presence of zinc acetate.

3. The polyurethane thermal insulation material according to claim 1, characterized in that: In step (i), the compound represented by formula (I) participating in the reaction is selected from the following combination: dialkyldihydrocarbyloxysilane, diaryldihydrocarbyloxysilane, and selectively alkenyltrihydrocarbyloxysilane and / or aromatictrihydrocarbyloxysilane; and / or, the molar ratio of the compound represented by formula (I), alkyl aluminum alkoxide and alkyl borate is 1.5-10:0.8-1.2:1; and / or, the alkyl aluminum alkoxide is selected from at least one of the compounds represented by formula (III): (R d O)3Al(Ⅲ), R d Selected from C 1-6 Alkyl; and / or, the alkyl borate is selected from at least one compound represented by formula (IV): (R e O)3B(Ⅳ), R e Selected from C 1-6 alkyl.

4. The polyurethane thermal insulation material according to claim 1, characterized in that: In step (iv), the mass ratio of the boroaluminum hybrid polysiloxane containing hydroxyl groups to the polyol is 1:2-8; and / or the hydroxyl value of the boroaluminum hybrid polysiloxane containing hydroxyl groups is 200-600 mgKOH / g; and / or the molecular weight of the boroaluminum hybrid polysiloxane containing hydroxyl groups is 500-6000; and / or the polyol is selected from polyether polyol and / or polyester polyol.

5. The polyurethane thermal insulation material according to claim 1, characterized in that: The preparation method of the fluorine-modified polyisocyanate N-polymer comprises: in a protective atmosphere, carrying out a fluorination reaction between the polyisocyanate N-polymer and a fluoroalcohol until the reaction reaches a desired NCO content.

6. The polyurethane thermal insulation material according to claim 5, characterized in that: The fluorination reaction is carried out in the presence of dibutyltin dilaurate; and / or, the fluorination reaction is carried out at 80-100° C.; and / or, the fluoroalcohol contains perfluoro-1-octanol, the polyisocyanate n-mer is a trimer of diisocyanate, and the feed mass ratio of the fluoroalcohol to the polyisocyanate n-mer is 0.5-0.85:1; and / or, the expected NCO content is 20%-30%.

7. The polyurethane thermal insulation material according to claim 5, characterized in that: The expected NCO content is 23%-27%.

8. The polyurethane thermal insulation material according to claim 1, characterized in that: The polyisocyanate further comprises polyphenyl polymethylene polyisocyanate, and the mass ratio of the fluorine-modified polyisocyanate n-polymer to the polyphenyl polymethylene polyisocyanate is 0.2-0.5:

1.

9. The polyurethane thermal insulation material according to claim 1, characterized in that: Calculated by mass, the raw materials of component A include: 250-600 parts of polyol, 40-150 parts of boron-aluminum hybrid polysiloxane containing hydroxyl groups, 5-20 parts of foaming agent, 5-20 parts of catalyst, 0.01-2 parts of accelerator, and 10-40 parts of foaming agent; And / or, the mass ratio of component A to component B is 1:1.0-1.

05.

10. Use of the polyurethane thermal insulation material according to any one of claims 1 to 9 in building thermal insulation and thermal pipeline equipment.

11. The use according to claim 10, characterized in that: After mixing component A and component B, spray or inject them onto the workpiece that needs insulation, and foam them at 10-40℃ to produce polyurethane insulation material.

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