In-situ inorganic hybridization reinforced polyurethane resin and preparation method thereof

Abstract

The invention discloses an in-situ inorganic hybridization reinforced polyurethane resin and a preparation method thereof. An inorganic in-situ bonding structure of the in-situ inorganic hybridization reinforced polyurethane resin can effectively control the strength and hardness of the polyurethane resin; and the organic auxiliary agent can effectively reduce the curing speed of the high-activity component, so that the system resin can be simultaneously applied to use scenes with different curing speeds and different hardness requirements. The in-situ inorganic hybridization reinforced polyurethane resin comprises a component A and a component B. The component A is prepared from the following components in parts by mass: 100 parts of isocyanate-terminated polyurethane oligomer, 4.5 to 102 parts of monomer polyisocyanate b, 2.9 to 4.4 parts of reaction speed regulator and 0 to 1.2 parts of catalyst a; the component B is prepared from the following components in parts by mass: 14.5 to 89.6 parts of silanol, 0 to 2 parts of glycerol and 0 to 1.2 parts of catalyst b; wherein in use, the component A and the component B are mixed according to the mass ratio of (1.66-7.1): 1 to obtain the in-situ inorganic hybridization reinforced polyurethane resin.

Description

Technical Field

[0001] The invention relates to a polyurethane resin and a preparation method thereof, and more specifically to an in-situ inorganic hybrid enhanced polyurethane resin and a preparation method thereof, belonging to the field of polymer materials. Background Art

[0002] With the vigorous development of polyurethane materials, it can be applied to more and more industries, such as synthetic leather slurry, soft foam, hard foam, coating, elastomer, adhesive, spandex, sole stock solution, etc. In the current polyurethane system, inorganic materials are often used for reinforcement to achieve good mechanical strength. In addition, the general inorganic filler is relatively low in price, which can greatly reduce the cost. However, the addition of fillers will increase the viscosity of the resin accordingly, limiting its application in some fields with high fluidity requirements. More importantly, some fillers have poor compatibility with the resin and poor dispersibility, resulting in uneven resin hardness and varying degrees of decrease in tensile strength and elongation at break. The in-situ hybridization method can avoid some problems caused by physical blending. For example, the Chinese patent with publication number CN 116606596 A discloses a preparation process of a modified waterborne polyurethane OCA glue, in which the unique hydrophilicity of nano-silica makes the performance of waterborne polyurethane more stable and the mechanical properties are significantly improved. The Chinese patent with publication number CN 115490898 A discloses a method for preparing a high-strength transparent conductive silver nanowire-polyurethane composite film, wherein the silica sol forms silanol and polycondenses during the hydrolysis process, and further polycondenses during the drying and curing process of the composite film to form an inorganic polymer network, which forms a hybrid cross-linked network structure with the polyurethane molecules, and enhances the cohesion of the composite film and increases the mechanical strength of the composite film without changing the transparency of the polyurethane film in the visible light region. The Chinese patent with publication number CN 104804699 A discloses a hot melt adhesive, wherein the silanol generates a stable polyurethane silicon-oxygen-silicon cross-linked network structure through intermolecular dehydration condensation or dehydration condensation with the hydroxyl group on the surface of the bonding substrate, thereby greatly improving the bonding strength of the hot melt adhesive to substrates such as glass, metal and plastic.

[0003] Traditional polyurethane chain extenders are generally organic curing agents such as polyether polyols, small molecule alcohols or amines; most of them cost more than inorganic materials, and face problems such as moisture sensitivity, long production cycle, and being greatly affected by upstream raw material prices. Therefore, the development and application of inorganic chain extenders have become a better solution. The Chinese patent with publication number CN 118325020 A provides a mine water plugging fly ash / polyurethane / water glass grouting composite material and its preparation method, wherein water glass, glycerin, and catalyst are mixed evenly, recorded as component A; isocyanate and fly ash are mixed evenly, recorded as component B; after the A component and the B component are mixed evenly, the composite grouting material is obtained by standing and curing; the composite grouting material has excellent mechanical properties, short curing time, high compressive and shear strength, and no heavy metals in fly ash will seep out, avoiding groundwater pollution, safe and environmentally friendly, and meets the safety use standards of the mine water plugging polymer material industry. The Chinese patent with publication number CN 113105600 A discloses a silicate / isocyanate composite elastomer and a preparation method thereof. The method uses water glass silicate as a main raw material for preparing the elastomer, replacing polyether polyol or polyester polyol, and the cost of the prepared composite elastomer is significantly reduced; and the process method of preparing the silicate / isocyanate composite elastomer of the invention is simple, and the A and B components can be mixed and reacted at room temperature, without heating high temperature reaction, which is environmentally friendly and energy-saving. The Chinese patent with publication number CN 115651150 A discloses a water glass filled modified flame retardant polyurethane foam and a preparation method thereof, wherein the addition of water glass can reduce the amount of raw materials used and thus save raw materials. Compared with traditional halogen-containing and phosphorus-containing flame retardants, it can significantly reduce the production cost of flame retardant polyurethane and has broad application value.

[0004] However, the in-situ inorganic hybridized polyurethane resin prepared in the prior art, including the above-mentioned prior art, is difficult to have a wide range of hardness, a long curing time, and good adhesion to metals, various plastic substrates, and composite panels. Therefore, it is necessary to develop a new in-situ inorganic hybrid enhanced polyurethane resin and a preparation method thereof to solve the problems existing in the prior art and meet the requirements that the polyurethane resin can be simultaneously applied to use scenarios with different curing speeds and different hardness requirements. Summary of the invention

[0005] The present invention solves the deficiencies and problems existing in the above-mentioned prior art and provides an in-situ inorganic hybridized polyurethane resin, the inorganic in-situ bonding structure of the in-situ inorganic hybridized polyurethane resin can effectively control the strength and hardness of the polyurethane resin; the organic additive can effectively reduce the curing speed of the highly active components, so that the system resin can be simultaneously applied to usage scenarios with different curing speeds and different hardness requirements.

[0006] The invention also provides a method for preparing the in-situ inorganic hybridized polyurethane resin. The preparation method is simple and easy to implement, has mild conditions and is low in cost.

[0007] The present invention is achieved through the following technical solutions:

[0008] The in-situ inorganic hybrid reinforced polyurethane resin of the present invention comprises component A and component B, wherein the mass ratio of each component of component A is:

[0009]

[0010] The mass ratio of each component of the B component is:

[0011] 14.5-89.6 parts of silanol

[0012] Glycerin 0-2 parts

[0013] Catalyst b 0-1.2 parts;

[0014] When used, the mass ratio of components A and B is component A: component B = 1.66-7.1:1, and the in-situ inorganic hybrid reinforced polyurethane resin is obtained by mixing.

[0015] The above-mentioned in-situ inorganic hybrid enhanced polyurethane resin of the present invention has a further technical solution having the following structure as shown in Formula I:

[0016]

[0017] Wherein, R1 is methylenediphenylene or tolyl or hexylene or polymethylenepolyphenylene; R2 is (C3H6O) m -(C2H4O) n -C2H4 or (C3H6O) m -C3H6, wherein m is a positive integer within the range of 7 to 140, and n is a positive integer within the range of 0 to 28; wherein, after the silanol reacts with the isocyanate, a symbiotic structure containing inorganic nano-scale sodium silicate-organic carbamate-organic polyurea is generated to form an in-situ inorganic hybrid reinforced polyurethane resin.

[0018] The above-mentioned in-situ inorganic hybrid reinforced polyurethane resin of the present invention can also be further technically solved in that the terminal isocyanate polyurethane oligomer is prepolymerized from monomer polyisocyanate a and polyether polyol; the monomer polyisocyanate a or monomer polyisocyanate b is one or a combination of p-phenylene diisocyanate, diphenylmethane diisocyanate, polyphenyl polymethylene polyisocyanate, hexamethylene diisocyanate, isophordine diisocyanate, dimethyl biphenyl diisocyanate; the reaction rate regulator is one or more of 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, triethyl phosphate, polydecene, and polydodecene; the catalyst a is an organic bismuth catalyst; the catalyst b is a hydroxy tertiary amine catalyst; the glycerol; the silanol is one or a combination of dimethylphenyl silanol, vinyl silanol, trimethyl silanol, triethyl silanol, and water glass with a molar number of 2.0 to 3.3. A further technical solution is that the molecular weight of the polyether polyol is 2000-3000, the functionality is 2-3, and it is 100% propoxy polyether polyol; the monomer polyisocyanate a or the monomer polyisocyanate b is one or a combination of polyphenyl polymethylene polyisocyanate, diphenylmethane diisocyanate or hexamethylene diisocyanate; the reaction rate regulator is polyquine or 2,2,4-trimethyl-1,3-pentanediol diisobutyrate; the silanol is water glass with a molar number of 2.0-2.5. A further technical solution can also be that in the mixture of the terminal isocyanate polyurethane oligomer and the monomer polyisocyanate b, the mass ratio of isocyanate is preferably 3-25%.

[0019] A further technical solution of the in-situ inorganic hybrid reinforced polyurethane resin of the present invention is that the mass ratio of the isocyanate group is preferably 5 to 20%.

[0020] The method for preparing the above-mentioned in-situ inorganic hybrid enhanced polyurethane resin of the present invention comprises the following steps:

[0021] Preparation of component A:

[0022] The polyether polyol of the required mass for preparing the polyurethane oligomer with terminal isocyanate group is added into the reaction kettle, and the mixture is stirred and heated to 40-50° C.; the stirring is maintained, and the monomer polyisocyanate a of the required mass for preparing the polyurethane oligomer with terminal isocyanate group is added into the reaction kettle, and the temperature of the reaction kettle is controlled to 75-95° C. The reaction is carried out under stable stirring for 4-6 hours at this temperature to obtain the polyurethane oligomer with terminal isocyanate group; the corresponding mass of the monomer polyisocyanate b is then added into the reaction kettle; in addition, according to the required curing time of the resin, the corresponding mass of the catalyst a or the reaction rate regulator or the catalyst a and the reaction rate regulator is added, and the mixture is stirred for more than 30 minutes to obtain the A component;

[0023] Preparation of component B:

[0024] Take the corresponding mass of silanol or silanol and glycerol and add them into the reaction kettle; in addition, according to the required curing time of the resin, add the corresponding mass of catalyst b, start stirring and heat to 40-50°C, stir for more than 30 minutes, and obtain component B;

[0025] Preparation of polyurethane resin enhanced by in-situ inorganic hybridization:

[0026] The component A and the component B are uniformly mixed at a mass ratio of 1.66 to 7.11:1 at room temperature and pressure to obtain an in-situ inorganic hybrid reinforced polyurethane resin.

[0027] Compared with the prior art, the present invention has the following beneficial effects:

[0028] The present invention adopts a dual control path of inorganic in-situ bonding and organic auxiliary agent regulating reaction speed, so that the in-situ inorganic hybridized polyurethane resin has an ultra-wide hardness of Shore A40 to Shore D85 and an operation time of up to 60 minutes; at the same time, the prepared in-situ inorganic hybridized polyurethane resin has no foaming phenomenon, and the in-situ generated nano-level material can provide good flame retardancy; the in-situ inorganic hybridized polyurethane resin of the present invention has high ductility under medium and high hardness and good adhesion to various metals, polar plastics and other composite plates, and can also be used for casting resin sheets.

[0029] The part of active hydroxyl groups provided by silanol has a silicon-oxygen bond energy greater than that of carbon-oxygen bonds. Compared with urethane bonds and polyurea bonds, the polyurethane-oxygen-silicon network structure generated by the reaction of silicon hydroxyl groups with isocyanate has stronger tensile strength, tear strength, elongation at break, and better flame retardancy, water resistance, weather resistance, and aging resistance. The free silicon hydroxyl groups can generate covalent bonds or chemical reactions with polar groups and metal ions on the surfaces of different substrates to achieve a synergistic bonding effect. Therefore, the polyurethane system of the present invention exhibits higher bonding strength to different substrates.

[0030] Nanomaterials are generated in situ during the chemical reaction of the matrix, so they are more evenly dispersed and have a more concentrated particle size distribution, and have a homogeneous self-reinforcement effect. This form is superior to traditional filler reinforcement and avoids problems such as complex powder pre-treatment processes, uneven dispersion, and poor anti-sedimentation effects.

[0031] The introduction of organic additives as reaction rate regulators not only does not affect the intrinsic properties of the resin within a certain range, but can also effectively inhibit the reactivity of highly active components, extend the operability time of the resin, and broaden the application field of the polyurethane resin of this system. DETAILED DESCRIPTION

[0032] The present invention is described below by means of specific examples, but the present invention is not limited to these examples.

[0033] The sources of raw materials in the embodiment are as follows:

[0034] Polyether polyol BDa-bcdeA series (a, b, c, d, e represent integers of 0 to 9, for example, BD2-4000A polyether polyol) is a product of Jiangsu Bader Polyurethane Co., Ltd. DESMODOR-0129 monomer polyisocyanate is a product of Covestro Polymer (China) Co., Ltd. HT-100 monomer polyisocyanate is a product of Jinan Linyan Mandy New Materials Co., Ltd. PMDI monomer polyisocyanate is a product of Wanhua Chemical Group Co., Ltd. Water glass with molar numbers of 2.0 and 2.5 is a product of Jiangsu Jufeng Chemical Technology Co., Ltd., glycerol is a product of Jinan Mingxin Chemical Co., Ltd., TXIB (2,2,4-trimethyl-1,3-pentanediol diisobutyrate) is a product of Shenzhen Xiangrun New Materials Co., Ltd., and PAO6 (polyisocyanate) is a product of Chevron Corporation.

[0035] Example 1

[0036] Preparation of component A:

[0037] Take 79.05 parts of BD2-2000A polyether polyol and add them to the reactor, start stirring and heat to 40°C; maintain stirring, take 20.95 parts of DESMODUR-0129 monomer polyisocyanate and add them to the reactor, control the temperature of the reactor to 75°C, and react at this temperature with stable stirring for 4 hours to obtain a terminal isocyanate polyurethane oligomer; then take 4.5 parts of DESMODOR-0129 monomer polyisocyanate and add them to the reactor, stir for 30 minutes, and obtain component A.

[0038] Preparation of component B:

[0039] 14.7 parts of 2.0 mole of water glass and 0.01 parts of hydroxyalkyl tertiary amine were added to a reaction kettle, heated to 40° C. with stirring, and stirred for 30 minutes to obtain component B.

[0040] Preparation of polyurethane resin enhanced by in-situ inorganic hybridization:

[0041] Component A and component B are mixed uniformly at a mass ratio of 7.09:1 at room temperature and pressure to obtain an in-situ inorganic hybrid reinforced polyurethane resin. The tested properties are shown in Table 1. The structural formula is as follows:

[0042]

[0043] Wherein, R1 is methylene diphenylene; R2 is (C3H6O) 34 —C3H6

[0044] Example 2

[0045] Preparation of component A:

[0046] Take 79.05 parts of BD2-2000A polyether polyol and add them to the reactor, start stirring and heat to 50°C; maintain stirring, take 20.95 parts of DESMODUR-0129 monomer polyisocyanate and add them to the reactor, control the temperature of the reactor to 80°C, and react at this temperature with stable stirring for 5 hours to obtain a terminal isocyanate polyurethane oligomer; then take 3 parts of HT-100 monomer polyisocyanate and add them to the reactor, stir for 30 minutes to obtain component A.

[0047] Preparation of component B:

[0048] 18.2 parts of 2.0 mole water glass and 0.015 parts of dimethylhydroxyethylamine were added to a reaction kettle, heated to 50° C. with stirring, and stirred for 30 minutes to obtain component B.

[0049] Preparation of polyurethane resin enhanced by in-situ inorganic hybridization:

[0050] Component A and component B are mixed uniformly at a mass ratio of 7.1:1 at room temperature and pressure to obtain an in-situ inorganic hybrid reinforced polyurethane resin. The tested properties are shown in Table 1. The structural formula is as follows:

[0051]

[0052] Wherein, R1 is methylene diphenylene; R2 is (C3H6O) 34 —C3H6.

[0053] Example 3

[0054] Preparation of component A:

[0055] Take 79.05 parts of BD3-3000A polyether polyol and add them to the reactor, start stirring and heat to 55°C; maintain stirring, take 20.95 parts of DESMODUR-0129 monomer polyisocyanate and add them to the reactor, control the temperature of the reactor to 80°C, and react at this temperature with stable stirring for 4 hours to obtain a terminal isocyanate polyurethane oligomer; then take 5.5 parts of HT-100 monomer polyisocyanate and add them to the reactor, stir for 30 minutes to obtain component A.

[0056] Preparation of component B:

[0057] 17.9 parts of 2.0 mole water glass and 0.18 parts of glycerol were added to a reaction kettle, heated to 40°C with stirring, and stirred for 30 minutes to obtain component B.

[0058] Preparation of polyurethane resin enhanced by in-situ inorganic hybridization:

[0059] Component A and component B are mixed uniformly at a mass ratio of 5.89:1 at room temperature and pressure to obtain an in-situ inorganic hybrid reinforced polyurethane resin. The tested properties are shown in Table 1. The structural formula is as follows:

[0060]

[0061] Wherein, R1 is methylene diphenylene; R2 is (C3H6O) 51 —C3H6.

[0062] Example 4

[0063] Preparation of component A:

[0064] Take 79.81 parts of BD2-0400A polyether polyol and add them to the reactor, start stirring and heat to 50°C; maintain stirring, take 20.19 parts of DESMODUR-T80 monomer polyisocyanate and add them to the reactor, control the temperature of the reactor to 95°C, and react at this temperature with stable stirring for 4 hours to obtain a terminal isocyanate polyurethane oligomer; then add 14.7 parts of HT-100 monomer polyisocyanate to the reactor; according to the required curing time of the resin, add 2.9 parts of reaction rate regulator PAO6, stir for 30 minutes, and obtain component A.

[0065] Preparation of component B:

[0066] 29.4 parts of 2.0 mole water glass and 0.44 parts of glycerol were added to a reaction kettle, heated to 50°C with stirring, and stirred for 30 minutes to obtain component B.

[0067] Preparation of polyurethane resin enhanced by in-situ inorganic hybridization:

[0068] Component A and component B are mixed uniformly at a mass ratio of 4:1 at room temperature and pressure to obtain an in-situ inorganic hybrid reinforced polyurethane resin. The tested properties are shown in Table 1. The structural formula is as follows:

[0069]

[0070] Among them, R1 is tolyl; R2 is (C3H6O)7-C3H6.

[0071] Example 5

[0072] Preparation of component A:

[0073] Take 79.81 parts of BD2-2000A polyether polyol and add them to the reactor, start stirring and heat to 40°C; maintain stirring, take 20.19 parts of DESMODUR-T80 monomer polyisocyanate and add them to the reactor, control the temperature of the reactor to 75°C, and react stably with stirring at this temperature for 6 hours to obtain a terminal isocyanate polyurethane oligomer; then add 14.7 parts of HT-100 monomer polyisocyanate to the reactor; according to the required curing time of the resin, add 4.4 parts of reaction rate regulator PAO6, stir for 30 minutes, and obtain component A.

[0074] Preparation of component B:

[0075] 29.4 parts of 2.0 mole of water glass, 0.22 parts of glycerol and 0.002 parts of dimethylhydroxyethylamine were added to a reaction kettle, heated to 50° C. with stirring, and stirred for 30 minutes to obtain component B.

[0076] Preparation of polyurethane resin enhanced by in-situ inorganic hybridization:

[0077] Component A and component B are mixed uniformly at a mass ratio of 4.05:1 at room temperature and pressure to obtain an in-situ inorganic hybrid reinforced polyurethane resin. The tested properties are shown in Table 1. The structural formula is as follows:

[0078]

[0079] Wherein, R1 is tolyl; R2 is (C3H6O) 34 —C3H6.

[0080] Example 6

[0081] Preparation of component A:

[0082] Take 143.66 parts of BD2-2000A polyether polyol and add them to the reactor, start stirring and heat to 40°C; maintain stirring, take 36.34 parts of DESMODOR-0129 monomer polyisocyanate and add them to the reactor, control the temperature of the reactor to 95°C, and react at this temperature with stable stirring for 5 hours to obtain a terminal isocyanate polyurethane oligomer; then add 14.7 parts of HT-100 monomer polyisocyanate to the reactor, stir for 30 minutes, and obtain component A.

[0083] Preparation of component B:

[0084] 29.4 parts of 2.0 mole water glass and 0.2 parts of glycerol were added into a reaction kettle, heated to 50° C. with stirring, and stirred for 30 minutes to obtain component B.

[0085] Preparation of polyurethane resin enhanced by in-situ inorganic hybridization:

[0086] Component A and component B are mixed uniformly at a mass ratio of 6.2:1 at room temperature and pressure to obtain an in-situ inorganic hybrid reinforced polyurethane resin. The tested properties are shown in Table 1. The structural formula is as follows:

[0087]

[0088] Wherein, R1 is methylene diphenylene; R2 is (C3H6O) 34 —C2H4.

[0089] Example 7

[0090] Preparation of component A:

[0091] Take 79.81 parts of BD2-4000A polyether polyol and add them to the reactor, start stirring and heat to 40°C; maintain stirring, take 20.19 parts of DESMODOR-0129 monomer polyisocyanate and add them to the reactor, control the temperature of the reactor to 80°C, and react stably with stirring at this temperature for 5 hours to obtain a terminal isocyanate polyurethane oligomer; then add 14.7 parts of HT-100 monomer polyisocyanate to the reactor; according to the required curing time of the resin, add 2.9 parts of reaction rate regulator TXIB, stir for 30 minutes, and obtain component A.

[0092] Preparation of component B:

[0093] 29.4 parts of 2.0 mole water glass and 0.36 parts of glycerol were added to a reaction kettle, heated to 50°C with stirring, and stirred for 30 minutes to obtain component B.

[0094] Preparation of polyurethane resin enhanced by in-situ inorganic hybridization:

[0095] Component A and component B are mixed uniformly at a mass ratio of 4:1 at room temperature and pressure to obtain an in-situ inorganic hybrid reinforced polyurethane resin. The tested properties are shown in Table 1. The structural formula is as follows:

[0096]

[0097] Wherein, R1 is methylenediphenylene or tolyl or hexylene or polymethylenepolyphenylene; R2 is (C3H6O) 68 —C3H6.

[0098] Example 8

[0099] Preparation of component A:

[0100] Take 79.81 parts of BD2-4000A polyether polyol and add them to the reactor, start stirring and heat to 50°C; maintain stirring, take 20.19 parts of WANNATE-H100 monomer polyisocyanate and add them to the reactor, control the temperature of the reactor to 95°C, and react stably with stirring at this temperature for 6 hours to obtain a polyurethane oligomer with terminal isocyanate groups; then add 14.7 parts of HT-100 monomer polyisocyanate to the reactor; according to the required curing time of the resin, add 4.4 parts of reaction rate regulator TXIB, stir for 30 minutes, and obtain component A.

[0101] Preparation of component B:

[0102] 29.4 parts of 2.0 mole of water glass and 0.0002 g of bismorpholine diethyl ether were added to a reaction kettle, heated to 50° C. with stirring, and stirred for 30 minutes to obtain component B.

[0103] Preparation of polyurethane resin enhanced by in-situ inorganic hybridization:

[0104] Component A and component B are mixed uniformly at a mass ratio of 4.05:1 at room temperature and pressure to obtain an in-situ inorganic hybrid reinforced polyurethane resin. The tested properties are shown in Table 1. The structural formula is as follows:

[0105]

[0106] Wherein, R1 is hexanediol; R2 is (C3H6O) 68 —C3H6.

[0107] Example 9

[0108] Preparation of component A:

[0109] Take 79.81 parts of BD3-3000A polyether polyol and add them to the reactor, start stirring and heat to 40°C; maintain stirring, take 20.19 parts of DESMODOR-0129 monomer polyisocyanate and add them to the reactor, control the temperature of the reactor to 80°C, and react stably with stirring at this temperature for 5 hours to obtain a terminal isocyanate polyurethane oligomer; then add 14.7 parts of HT-100 monomer polyisocyanate to the reactor; according to the required curing time of the resin, add 0.012 parts of an organic bismuth catalyst, stir for 30 minutes, and obtain component A.

[0110] Preparation of component B:

[0111] Take 29.4 parts of 2.0 mole of water glass and add it into the reaction kettle. Heat it to 50°C with stirring and stir for 30 minutes to obtain component B.

[0112] Preparation of polyurethane resin enhanced by in-situ inorganic hybridization:

[0113] Component A and component B are mixed uniformly at a mass ratio of 3.94:1 at room temperature and pressure to obtain an in-situ inorganic hybrid reinforced polyurethane resin. The tested properties are shown in Table 1. The structural formula is as follows:

[0114]

[0115] Wherein, R1 is methylene diphenylene; R2 is (C3H6O) 22 —(C2H4O) 11 -C2H4.

[0116] Example 10

[0117] Preparation of component A:

[0118] Take 79.81 parts of BD3-3000A polyether polyol and add them to the reactor, start stirring and heat to 40°C; maintain stirring, take 20.19 parts of DESMODOR-0129 monomer polyisocyanate and add them to the reactor, control the temperature of the reactor to 78°C, and react at this temperature with stable stirring for 4 hours to obtain a terminal isocyanate polyurethane oligomer; then add 14.7 parts of HT-100 monomer polyisocyanate to the reactor, stir for 30 minutes, and obtain component A.

[0119] Preparation of component B:

[0120] 29.4 parts of 2.0 mole water glass were added into the reaction kettle, and the mixture was heated to 40° C. with stirring. According to the required curing time of the resin, 0.002 parts of tertiary hydroxylamine catalyst were added, and the mixture was stirred for 30 minutes to obtain component B.

[0121] Preparation of polyurethane resin enhanced by in-situ inorganic hybridization:

[0122] Component A and component B are mixed uniformly at a mass ratio of 3.94:1 at room temperature and pressure to obtain an in-situ inorganic hybrid reinforced polyurethane resin. The tested properties are shown in Table 1. The structural formula is as follows:

[0123]

[0124] Wherein, R1 is methylene diphenylene; R2 is C3H6O) 22 —(C2H4O) 11 -C2H4

[0125] Embodiment 11

[0126] Preparation of component A:

[0127] Take 79.37 parts of BD3-6000A polyether polyol and add them to the reactor, start stirring and heat to 50°C; maintain stirring, take 21.63 parts of DESMODOR-44C monomer polyisocyanate and add them to the reactor, control the temperature of the reactor to 75°C, and react at this temperature with stable stirring for 6 hours to obtain a terminal isocyanate polyurethane oligomer; then add 30 parts of DESMODOR-0129 monomer polyisocyanate to the reactor, stir for 30 minutes, and obtain component A.

[0128] Preparation of component B:

[0129] Take 42 parts of water glass with a mole number of 2.0 and add it into the reaction kettle. Heat it to 50°C with stirring and stir for 30 minutes to obtain component B.

[0130] Preparation of polyurethane resin enhanced by in-situ inorganic hybridization:

[0131] Component A and component B are mixed uniformly at a mass ratio of 3.1:1 at room temperature and pressure to obtain an in-situ inorganic hybrid reinforced polyurethane resin. The tested properties are shown in Table 1. The structural formula is as follows:

[0132]

[0133] Wherein, R1 is methylene diphenylene; R2 is C3H6O) 83 —(C2H4O) 22 -C2H4

[0134] Example 12

[0135] Preparation of component A:

[0136] Take 59.7 parts of BD3-6000A polyether polyol and add them to the reactor, start stirring and heat to 50°C; maintain stirring, take 40.3 parts of DESMODOR-0129 monomer polyisocyanate and add them to the reactor, control the temperature of the reactor to 95°C, and react at this temperature with stable stirring for 4 hours to obtain a terminal isocyanate polyurethane oligomer; then add 16.8 parts of HT-100 monomer polyisocyanate to the reactor, stir for 30 minutes, and obtain component A.

[0137] Preparation of component B:

[0138] Take 48 parts of water glass with a molar number of 2.5 and add it into a reaction kettle, start stirring and heat to 40°C, stir for 30 minutes, and obtain component B.

[0139] Preparation of polyurethane resin enhanced by in-situ inorganic hybridization:

[0140] Component A and component B are mixed uniformly at a mass ratio of 2.43:1 at room temperature and pressure to obtain an in-situ inorganic hybrid reinforced polyurethane resin. The tested properties are shown in Table 1. The structural formula is as follows:

[0141]

[0142] Wherein, R1 is methylenediphenylene or tolyl or hexylene or polymethylenepolyphenylene; R2 is C3H6O) 85 —(C2H4O) 28 -C2H4.

[0143] Example 13

[0144] Preparation of component A:

[0145] Take 51.73 parts of BD2-4000A polyether polyol and add them to the reactor, start stirring and heat to 50°C; maintain stirring, take 48.27 parts of DESMODOR-44C monomer polyisocyanate and add them to the reactor, control the temperature of the reactor to 95°C, and react at this temperature with stable stirring for 4 hours to obtain a terminal isocyanate polyurethane oligomer; then add 18.5 parts of HT-100 monomer polyisocyanate to the reactor, stir for 30 minutes, and obtain component A.

[0146] Preparation of component B:

[0147] 89.6 parts of 2.5 mole water glass and 2 parts of glycerol were added to a reaction kettle, heated to 50°C with stirring, and stirred for 30 minutes to obtain component B.

[0148] Preparation of polyurethane resin enhanced by in-situ inorganic hybridization:

[0149] Component A and component B are mixed uniformly at a mass ratio of 2.13:1 at room temperature and pressure to obtain an in-situ inorganic hybrid reinforced polyurethane resin. The tested properties are shown in Table 1. The structural formula is as follows:

[0150]

[0151] Wherein, R1 is methylene diphenylene; R2 is C3H6O) 57 —(C2H4O) 15 -C2H4.

[0152] Embodiment 14

[0153] Preparation of component A:

[0154] Take 57.05 parts of BD3-8000A polyether polyol and add them to the reactor, start stirring and heat to 40°C; maintain stirring, take 42.95 parts of DESMODOR-44C monomer polyisocyanate and add them to the reactor, control the temperature of the reactor to 75°C, and react at this temperature with stable stirring for 4 hours to obtain a terminal isocyanate polyurethane oligomer; then add 27.2 parts of HT-100 monomer polyisocyanate to the reactor, stir for 30 minutes, and obtain component A.

[0155] Preparation of component B:

[0156] 76.6 parts of 2.5 mole water glass and 0.8 parts of glycerol were added to a reaction kettle, heated to 50° C. with stirring, and stirred for 30 minutes to obtain component B.

[0157] Preparation of polyurethane resin enhanced by in-situ inorganic hybridization:

[0158] Component A and component B are mixed uniformly at a mass ratio of 1.66:1 at room temperature and pressure to obtain an in-situ inorganic hybrid reinforced polyurethane resin. The tested properties are shown in Table 1. The structural formula is as follows:

[0159]

[0160] Wherein, R1 is methylene diphenylene; R2 is (C3H6O) 140 —C3H6.

[0161] Embodiment 15

[0162] Preparation of component A:

[0163] Take 79.05 parts of BD3-6000A polyether polyol and add them to the reactor, start stirring and heat to 50°C; maintain stirring, take 20.95 parts of DESMODOR-44C monomer polyisocyanate and add them to the reactor, control the temperature of the reactor to 75°C, and react at this temperature with stable stirring for 5 hours to obtain a terminal isocyanate polyurethane oligomer; then add 102 parts of PMDI monomer polyisocyanate to the reactor, stir for 30 minutes, and obtain component A.

[0164] Preparation of component B:

[0165] 89.6 parts of 2.5 mole water glass and 1.25 parts of glycerol were added to a reaction kettle, heated to 50°C with stirring, and stirred for 30 minutes to obtain component B.

[0166] Preparation of polyurethane resin enhanced by in-situ inorganic hybridization:

[0167] Component A and component B are mixed uniformly at a mass ratio of 2.25:1 at room temperature and pressure to obtain an in-situ inorganic hybrid reinforced polyurethane resin. The tested properties are shown in Table 1. The structural formula is as follows:

[0168]

[0169] Among them, R1 is methylenediphenylene; R2 is (C3H6O)-C2H4.

[0170] Comparative Example 1

[0171] Preparation of component A:

[0172] Take 84.1 parts of BD2-2000A polyether polyol and add them to the reactor, start stirring and heat to 40°C; maintain stirring, take 15.9 parts of DESMODOR-0129 monomer polyisocyanate and add them to the reactor, control the temperature of the reactor to 95°C, and react at this temperature with stable stirring for 5 hours to obtain component A.

[0173] Preparation of component B:

[0174] Take 9 parts of water glass with a molar number of 2.0 and add it into the reaction kettle. Heat it to 40°C with stirring and stir for 30 minutes to obtain component B.

[0175] Preparation of polyurethane resin enhanced by in-situ inorganic hybridization:

[0176] Component A and component B were uniformly mixed at a mass ratio of 11.5:1 at room temperature and pressure to obtain an in-situ inorganic hybrid reinforced polyurethane resin. The tested properties are shown in Table 2.

[0177] Comparative Example 2

[0178] Preparation of component A:

[0179] Take 57.05 parts of DL-2200 polyether polyol and add them to the reactor, start stirring and heat to 50°C; maintain stirring, take 42.95 parts of DESMODOR-0129 monomer polyisocyanate and add them to the reactor, control the temperature of the reactor to 75-95°C, and react at this temperature with stable stirring for 6 hours to obtain a polyurethane oligomer with terminal isocyanate groups; then add 27.2 parts of HT-100 monomer polyisocyanate and 812 parts of DESMODOR-0129 monomer polyisocyanate to the reactor, stir for 30 minutes, and obtain component A.

[0180] Preparation of component B:

[0181] 298 parts of water glass with a molar number of 2.5 and 15 parts of polyether DL-2200 were added to a reaction kettle, heated to 50° C. with stirring, and stirred for 30 minutes to obtain component B.

[0182] Preparation of polyurethane resin enhanced by in-situ inorganic hybridization:

[0183] Component A and component B were uniformly mixed at a mass ratio of 3.15:1 at room temperature and pressure to obtain an in-situ inorganic hybrid reinforced polyurethane resin. The tested properties are shown in Table 2.

[0184] Comparative Example 3

[0185] Preparation of component A:

[0186] Take 80.13 parts of BD3-6000A polyether polyol and add them to the reactor, start stirring and heat to 40°C; maintain stirring, take 19.87 parts of DESMODOR-0129 monomer polyisocyanate and add them to the reactor, control the temperature of the reactor to 75-95°C, and react at this temperature with stable stirring for 4 hours to obtain a terminal isocyanate polyurethane oligomer; then add 14.1 parts of HT-100 monomer polyisocyanate to the reactor, stir for 30 minutes, and obtain component A.

[0187] Preparation of component B:

[0188] 15.4 parts of 2.0 mole water glass and 0.02 g of bismuth isooctanoate catalyst were added to a reaction kettle, heated to 40° C. with stirring, and stirred for 30 minutes to obtain component B.

[0189] Preparation of polyurethane resin enhanced by in-situ inorganic hybridization:

[0190] Component A and component B were uniformly mixed at a mass ratio of 7.41:1 at room temperature and pressure to obtain an in-situ inorganic hybrid reinforced polyurethane resin. The tested properties are shown in Table 2.

[0191] The prepared resin was cast into a circular test piece with a diameter of 7 cm, and after aging at 50°C for 72 hours, it was measured with a Shore hardness tester; the prepared resin was cast into a square test piece of 13*13 cm, and after aging at 50°C for 72 hours, it was cut according to the mechanical property test according to GB / T2567-2008, and the mechanical properties of the material were measured; the measurement results are shown in Tables 1 and 2.

[0192] Table 1:

[0193]

[0194] Table 2:

[0195] Comparative Example 1 2 3 Hardness / Shore A 28 — Foaming Hardness / Shore D — 75 No flow time / min 26 ＜1 ＜1 Tensile strength(MPa) 1 20 — Tear strength (KN / m) 8 121 —

[0196] As shown in Table 1 and Table 2, the present invention achieves a wide range of hardness and curing time by adjusting the ratio and type of active components and effectively utilizing different additives. The benzene ring contained in the monomer polyisocyanate, the short carbon chain glycerol, the water glass containing the silicon component, and the structures such as the carbamate and polyurea formed during the reaction can all provide effective hard segments; the isocyanate oligomer modified by the high molecular weight polyether polyol can reduce the hardness of the resin and impart elastic deformation performance; the tertiary amine catalyst added to the cyanate reaction component, or the rare metal salt catalyst added to the isocyanate component can effectively adjust the reaction curing speed and stably preserve it; in the isocyanate reaction component, the highly hydrophilic small molecule alcohol chain extender has better compatibility than the high molecular weight polyether polyol.

[0197] Obviously, many modifications and changes can be made according to the content of this specification. The embodiments are only partial implementation methods of the technical solution of the present invention and are not comprehensive. Based on the general concept of the present invention, all other embodiments obtained by those skilled in the art fall within the scope of protection of the present invention.

Claims

1. An in-situ inorganic hybrid reinforced polyurethane resin, comprising component A and component B, characterized in that: The mass ratio of each component of the A component is: The mass ratio of each component of the B component is: 14.5-89.6 parts of silanol Glycerin 0-2 parts Catalyst b 0-1.2 parts; When used, the mass ratio of components A and B is component A: component B = 1.66-7.1:1, and the in-situ inorganic hybrid reinforced polyurethane resin is obtained by mixing.

2. The in-situ inorganic hybrid reinforced polyurethane resin according to claim 1, characterized in that: It has the following structure as shown in Formula I: Wherein, R1 is methylenediphenylene or tolyl or hexylene or polymethylenepolyphenylene; R2 is (C3H6O) m -(C2H4O) n -C2H4 or (C3H6O) m -C3H6, wherein m is a positive integer within the range of 7 to 140, and n is a positive integer within the range of 0 to 28; wherein, after the silanol reacts with the isocyanate, a symbiotic structure containing inorganic nano-scale sodium silicate-organic carbamate-organic polyurea is generated to form an in-situ inorganic hybrid reinforced polyurethane resin.

3. The in-situ inorganic hybrid reinforced polyurethane resin according to claim 1, characterized in that: The isocyanate-terminated polyurethane oligomer is prepared by prepolymerization of a monomer polyisocyanate a and a polyether polyol; the monomer polyisocyanate a or the monomer polyisocyanate b is one or a combination of p-phenylene diisocyanate, diphenylmethane diisocyanate, polyphenyl polymethylene polyisocyanate, hexamethylene diisocyanate, isophordione diisocyanate, and dimethylbiphenyl diisocyanate; the reaction rate regulator is one or more of 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, triethyl phosphate, polydecene, and polydodecene; the catalyst a is an organic bismuth catalyst; the catalyst b is a hydroxyl tertiary amine catalyst; the glycerol; the silanol is one or a combination of dimethylphenyl silanol, vinyl silanol, trimethyl silanol, triethyl silanol, and water glass with a molar number of 2.0 to 3.

3.

4. The in-situ inorganic hybrid reinforced polyurethane resin according to claim 3, characterized in that: The polyether polyol has a molecular weight of 400 to 8000, a functionality of 2 to 3, and is a 100% alkoxy polyether polyol; the monomer polyisocyanate a or the monomer polyisocyanate b is one or a combination of polyphenyl polymethylene polyisocyanate, diphenylmethane diisocyanate or hexamethylene diisocyanate; the reaction rate regulator is polyocene or 2,2,4-trimethyl-1,3-pentanediol diisobutyrate; and the silanol is water glass with a molar number of 2.0 to 2.

5.

5. The in-situ inorganic hybrid reinforced polyurethane resin according to claim 3, characterized in that: In the mixture of the isocyanate-terminated polyurethane oligomer and the monomeric polyisocyanate B, the mass ratio of isocyanate is 3-25%.

6. The in-situ inorganic hybrid reinforced polyurethane resin according to claim 5, characterized in that: The mass ratio of the isocyanate is 5-20%.

7. A method for preparing an in-situ inorganic hybrid reinforced polyurethane resin as claimed in any one of claims 1 to 6, characterized in that: The following steps are involved: Preparation of component A: The polyether polyol of the required mass for preparing the polyurethane oligomer with terminal isocyanate group is added into the reaction kettle, and the mixture is stirred and heated to 40-50° C.; the stirring is maintained, and the monomer polyisocyanate a of the required mass for preparing the polyurethane oligomer with terminal isocyanate group is added into the reaction kettle, and the temperature of the reaction kettle is controlled to 75-95° C. The reaction is carried out under stable stirring for 4-6 hours at this temperature to obtain the polyurethane oligomer with terminal isocyanate group; the corresponding mass of the monomer polyisocyanate b is then added into the reaction kettle; in addition, according to the required curing time of the resin, the corresponding mass of the catalyst a or the reaction rate regulator or the catalyst a and the reaction rate regulator is added, and the mixture is stirred for more than 30 minutes to obtain the A component; Preparation of component B: Take the corresponding mass of silanol or silanol and glycerol and add them into the reaction kettle; in addition, according to the required curing time of the resin, add the corresponding mass of catalyst b, start stirring and heat to 40-50°C, stir for more than 30 minutes, and obtain component B; Preparation of polyurethane resin enhanced by in-situ inorganic hybridization: The component A and the component B are uniformly mixed at a mass ratio of 1.66 to 7.11:1 at room temperature and pressure to obtain an in-situ inorganic hybrid reinforced polyurethane resin.

Images