An organosilicon-modified polyurethane composition, its preparation method and applications

Abstract

The present invention provides a silicone-modified polyurethane composition, a preparation method and an application thereof. The silicone-modified polyurethane composition comprises component A and component B. Component A comprises a combination of a polymeric polyol A, a hydroxyl-terminated polysiloxane A, a blowing agent, a chain extender and a catalyst. Component B comprises a polymeric polyol-modified isocyanate prepolymer. By adding the hydroxyl-terminated polysiloxane A to component A and adding the polymeric polyol-modified isocyanate prepolymer to component B simultaneously, the obtained silicone-modified polyurethane composition has excellent low-temperature resistance and aging resistance, and also has excellent mechanical properties, and is suitable for use as a damping material.

Description

Technical Field

[0001] The present invention belongs to the technical field of polyurethanes, and particularly relates to a silicone-modified polyurethane composition, a preparation method thereof, and an application thereof. Background Art

[0002] With the continuous development of domestic high-speed railways, higher requirements are put forward for elastomeric damping materials. Traditional rubber materials can no longer meet the requirements of high-speed railways, and polyurethane microcellular elastomers with performance far superior to rubber materials have been widely used in high-speed railways. Polyurethane microcellular elastomer is a material between elastomer and foam, which combines the properties of elastomer and foam, has excellent impact resistance and energy absorption and buffering performance, and at the same time has a lower density. However, with the increasing speed of high-speed railways and the laying of different environmental sections, higher requirements are put forward for the low-temperature resistance and aging resistance of polyurethane microcellular elastomers.

[0003] The traditional method for improving the low-temperature performance of polyurethane microcellular elastomers is to use polytetrahydrofuran glycol or polycaprolactone as the polyol component and the prepolymer component of isocyanate. At the same time, a relatively large amount of anti-aging additives is also added to the raw materials for preparation to improve the anti-aging performance of polyurethane microcellular elastomers. CN107602817A discloses a highly cold-resistant polyurethane shock pad and its preparation method. The polyurethane shock pad is formed by mixing and crosslinking component A and component B; among them, component A is a polyol composition, including the following raw materials: caprolactone-modified polyether polyol, polyether polyol, hydroxyl-terminated polybutadiene, terminal primary hydroxyl silicone, chain extender, catalyst, foam stabilizer, foaming agent; component B is an NCO-terminated isocyanate prepolymer, including the following raw materials: caprolactone-modified polyether polyol, 4,4-diphenylmethane diisocyanate, side reaction inhibitor; the highly cold-resistant polyurethane shock pad prepared by this invention has good shock absorption performance and excellent dynamic fatigue resistance, and its low-temperature performance has been significantly improved. CN111574685A discloses a cold-resistant polyurethane pad for heavy-haul railways and its preparation method. It is prepared by mixing component A and component B in a mass ratio of 100:(91-107); the component A includes the following raw materials: polyol A, chain extender, additives; the component B includes the following raw materials: polyol B, diisocyanate, inhibitor; the cold-resistant polyurethane pad in this invention has excellent mechanical properties, lower compression set and dynamic-static ratio, and better shock absorption effect; the polyurethane elastic pad of this invention has a lower low-temperature brittleness temperature, meets the use requirements, and has excellent low-temperature resistance, and is suitable for the construction of railways in cold regions such as Xinjiang, Inner Mongolia, and Northeast China in China. However, simply selecting specific polymeric polyols, such as polytetrahydrofuran glycol or polycaprolactone as the polyol, has very limited improvement on the low-temperature performance, and cannot well improve the anti-aging performance of polyurethane microcellular elastomers. And adding a relatively large amount of anti-aging and cold-resistant additives will also increase the odor of polyurethane microcellular elastomers and affect their use.

[0004] Therefore, developing an organosilicon-modified polyurethane composition with excellent low-temperature resistance and anti-aging performance is an urgent technical problem to be solved in the field. Summary of the Invention

[0005] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide an organosilicon-modified polyurethane composition, its preparation method and application. The organosilicon-modified polyurethane composition includes component A and component B. By adding hydroxyl-terminated polysiloxane A to component A and combining with adding polymeric polyol-modified isocyanate prepolymer to component B, the anti-aging performance and low-temperature resistance of the organosilicon-modified polyurethane composition are effectively improved.

[0006] To achieve this purpose, the present invention adopts the following technical solutions:

[0007] In a first aspect, the present invention provides a silicone-modified polyurethane composition, which comprises component A and component B;

[0008] Component A comprises a combination of a polymeric polyol A, a hydroxyl-terminated polysiloxane A, a blowing agent, a chain extender, and a catalyst;

[0009] Component B comprises a polymeric polyol-modified isocyanate prepolymer. The present invention provides a silicone-modified polyurethane composition by adding the hydroxyl-terminated polysiloxane A to be combined with the polymeric polyol A in component A, and adding the polymeric polyol-modified isocyanate prepolymer in component B, and combining component A and component B to obtain the silicone-modified polyurethane composition, effectively improving the low-temperature resistance and aging resistance of the polyurethane foamed elastic material prepared by using the silicone-modified polyurethane composition.

[0010] Specifically, adding silicone in component A can make the silicone chain segment become a part of the main chain of the foamed polyurethane, and then the hydrophilic and lipophilic characteristics of the silicone chain segment itself can be utilized to improve the compatibility with each component, which further helps to improve the comprehensive performance of the silicone-modified polyurethane composition, further enhancing the aging resistance and low-temperature resistance, and can also ensure that the polyurethane foamed material prepared by using the silicone-modified polyurethane composition has finer and more stable foam cells.

[0011] Preferably, component A comprises the following components by weight:

[0012]

[0013] Among them, the polymeric polyol A can be 53 parts by weight, 56 parts by weight, 59 parts by weight, 62 parts by weight, 65 parts by weight, 68 parts by weight, 71 parts by weight, 74 parts by weight, 77 parts by weight, etc.

[0014] The hydroxyl-terminated polysiloxane A can be 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, etc.

[0015] The blowing agent can be 0.05 parts by weight, 0.1 parts by weight, 0.2 parts by weight, 0.5 parts by weight, 1 part by weight, 1.3 parts by weight, 1.6 parts by weight, 1.9 parts by weight, 2.1 parts by weight, 2.4 parts by weight, 2.7 parts by weight, etc.

[0016] The chain extender can be 5 parts by weight, 7 parts by weight, 9 parts by weight, 11 parts by weight, 13 parts by weight, 15 parts by weight, 17 parts by weight, 19 parts by weight, etc.

[0017] The catalyst may be 0.03 parts by weight, 0.05 parts by weight, 0.1 parts by weight, 0.5 parts by weight, 0.7 parts by weight, 0.9 parts by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, etc.

[0018] Preferably, the number average molecular weight of the polyol A is 500 to 4000, such as 1000, 1500, 2000, 2500, 3000, or 3500, etc.

[0019] Preferably, the functionality of the polyol A is 2 to 4, such as 2.2, 2.4, 2.6, 2.8, 3, 3.2, 3.4, 3.6, or 3.8, etc.

[0020] Preferably, the hydroxyl value of the polyol A is 20 to 150 mgKOH / g, such as 30 mgKOH / g, 40 mgKOH / g, 50 mgKOH / g, 60 mgKOH / g, 70 mgKOH / g, 80 mgKOH / g, 90 mgKOH / g, 100 mgKOH / g, 120 mgKOH / g, or 140 mgKOH / g, etc.

[0021] Preferably, the polyol A includes polyether polyol and / or polyester polyol.

[0022] Preferably, the polyether polyol includes any one or a combination of at least two of polypropylene oxide polyol, poly(propylene oxide - ethylene oxide) copolymer polyol, polytetrahydrofuran polyol, or polyolefin polyol.

[0023] Preferably, the polyester polyol includes polycaprolactone polyol.

[0024] Preferably, the chain extender includes any one or a combination of at least two of ethylene glycol, 1,3 - propanediol, diethylene glycol, dipropylene glycol, 1,3 - propanediol, 1,2 - propanediol, 1,3 - butanediol, 1,4 - butanediol, diethanolamine, methyldiethanolamine, 1,4 - cyclohexanediol, tripropylene glycol, diethyltoluenediamine, hydroquinone bis - β - hydroxyethyl ether, or resorcinol hydroxy ether.

[0025] Preferably, the blowing agent includes water.

[0026] Preferably, the catalyst includes any one or a combination of at least two of triethylenediamine, bis(dimethylaminoethyl) ether, pentamethyldipropylenetriamine, pentamethyldiethylenetriamine, N,N - dimethylcyclohexylamine, N - benzyldimethylamine, dibutyltin dilaurate, or stannous octoate.

[0027] Preferably, the component A further comprises any one or a combination of at least two of a silicone surfactant, an antioxidant, a crosslinking agent or an abrasion-resistant agent.

[0028] Preferably, the content of the silicone surfactant in the component A is 0 to 2 parts by weight and not equal to 0, such as 0.2 parts by weight, 0.4 parts by weight, 0.6 parts by weight, 0.8 parts by weight, 1 part by weight, 1.2 parts by weight, 1.4 parts by weight, 1.6 parts by weight or 1.8 parts by weight, etc.

[0029] Preferably, the content of the abrasion-resistant agent in the component A is 0 to 8 parts by weight and not equal to 0, such as 2 parts by weight, 4 parts by weight or 6 parts by weight, etc.

[0030] Preferably, the abrasion-resistant agent comprises polysiloxane and / or polyolefin wax powder.

[0031] Preferably, the content of the antioxidant in the component A is 0.01 to 3 parts by weight, such as 0.05 parts by weight, 0.07 parts by weight, 0.1 parts by weight, 0.3 parts by weight, 0.6 parts by weight, 0.9 parts by weight, 1.2 parts by weight, 1.5 parts by weight, 1.8 parts by weight, 2.1 parts by weight, 2.4 parts by weight or 2.7 parts by weight, etc.

[0032] Preferably, the antioxidant comprises a hindered phenol antioxidant and / or a phosphite antioxidant.

[0033] Preferably, the content of the crosslinking agent in the component A is 0 to 10 parts by weight and not equal to 0, such as 2 parts by weight, 4 parts by weight, 6 parts by weight or 8 parts by weight, etc.

[0034] Preferably, the crosslinking agent comprises any one or a combination of at least two of glycerol, trimethylolpropane, triethanolamine, 1,2,6-hexanetriol, ethoxylated trimethylolpropane or ethoxylated glycerol.

[0035] Preferably, the mass percentage content of the NCO group in the component B is 8 to 15%, such as 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14% or 14.5%, etc.

[0036] Preferably, the polymer polyol modified isocyanate prepolymer is prepared by the following method, which includes: reacting polymer polyol B and diisocyanate A to obtain the polymer polyol modified isocyanate prepolymer.

[0037] Preferably, the temperature of the reaction is 60 to 90 °C, such as 65 °C, 70 °C, 75 °C, 80 °C or 85 °C, etc.

[0038] Preferably, the reaction time is 2 to 5 °C, such as 2.5 °C, 3 °C, 3.5 °C, 4 °C, or 4.5 °C, etc.

[0039] Preferably, the mass percentage content of NCO in the polymerized polyol-modified isocyanate prepolymer is 6 to 20%, such as 8%, 10%, 12%, 14%, 16%, or 18%, etc.

[0040] Preferably, the component B further includes a hydroxyl-terminated polysiloxane-modified isocyanate prepolymer.

[0041] As a preferred technical solution of the present invention, a hydroxyl-terminated polysiloxane-modified isocyanate prepolymer is further added to the component B. By utilizing the characteristic that the hydroxyl-terminated polysiloxane and isocyanate have good reaction activity, the reaction product thereof, the hydroxyl-terminated polysiloxane-modified isocyanate prepolymer, is added to the component B, which helps to increase the surface tension of the silicone compound molecules, and further helps to improve the reaction dispersion of the silicone compound molecules in the polyurethane system, improve the additivity of the hydroxyl-terminated polysiloxane raw material in the polyurethane, and solve the problem of large mutual repulsion of the silicon-containing raw materials in the polyurethane reaction system.

[0042] Preferably, the content of the hydroxyl-terminated polysiloxane-modified isocyanate prepolymer in the component B is 0 to 40 parts by weight and not equal to 0, such as 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, or 40 parts by weight, etc.

[0043] Preferably, the component B comprises the following components by weight:

[0044] Hydroxyl-terminated polysiloxane-modified isocyanate prepolymer 0 to 40 parts by weight and not equal to 0

[0045] Polymerized polyol-modified isocyanate prepolymer 60 to 100 parts by weight.

[0046] Among them, the polymerized polyol-modified isocyanate prepolymer can be 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight, 80 parts by weight, 85 parts by weight, 90 parts by weight, 95 parts by weight, or 100 parts by weight, etc.

[0047] Preferably, the hydroxyl-terminated polysiloxane-modified isocyanate prepolymer is prepared by the following method, which includes: reacting hydroxyl-terminated polysiloxane B and diisocyanate B to obtain the hydroxyl-terminated polysiloxane-modified isocyanate prepolymer.

[0048] Preferably, the reaction temperature is 70 to 95 °C, such as 72 °C, 74 °C, 76 °C, 78 °C, 80 °C, 82 °C, 84 °C, 86 °C, 88 °C, 90 °C, 92 °C, or 94 °C, etc.

[0049] Preferably, the reaction time is 2 to 5 h, such as 2.3 h, 2.6 h, 2.9 h, 3.2 h, 3.5 h, 3.8 h, 4.1 h, 4.4 h or 4.7 h, etc.

[0050] Preferably, the mass percentage content of NCO in the hydroxyl-terminated polysiloxane-modified isocyanate prepolymer is 8 to 15%, such as 9%, 10%, 11%, 12%, 13% or 14%, etc.

[0051] Preferably, the functionality of the hydroxyl-terminated polysiloxane A and the hydroxyl-terminated polysiloxane B is 2 to 5, such as 3 or 4, etc.

[0052] In the present invention, the hydroxyl-terminated polysiloxane A and the hydroxyl-terminated polysiloxane B can each independently be selected from any one or a combination of at least two of the hydroxyl-terminated polysiloxanes having the structures shown in the following formulas I - V:

[0053]

[0054]

[0055] Among them, n1 - n5 are each independently selected from integers between 1 and 30, such as 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26 or 28, etc.; m is selected from integers between 0 and 20, such as 2, 4, 6, 8, 10, 12, 14, 16, 18, etc.; x1 - x5, y1 - y5 are each independently selected from integers between 0 and 30, such as 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26 or 28, etc.

[0056] The present invention does not impose special restrictions on the preparation method of the hydroxyl groups of the hydroxyl-terminated polysiloxanes having the above structures provided above.

[0057] Preferably, the diisocyanate A and the diisocyanate B each independently include any one or a combination of at least two of diphenylmethane diisocyanate, toluene diisocyanate, dicyclohexylmethane diisocyanate, p-phenylene diisocyanate or 1,5-naphthalene diisocyanate.

[0058] Preferably, the polymeric polyol B includes polyether polyol and / or polyester polyol.

[0059] Preferably, the polyether polyol includes any one or a combination of at least two of polypropylene oxide polyol, poly(propylene oxide - ethylene oxide) copolymer polyol, polytetrahydrofuran polyol or polyolefin polyol.

[0060] Preferably, the polyester polyol includes polycaprolactone polyol.

[0061] Preferably, the mass ratio of component A to component B is 1:(0.5 - 1.8), such as 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.4 or 1:1.6, etc.

[0062] In a second aspect, the present invention provides a method for preparing an organosilicon - modified polyurethane composition as described in the first aspect. The preparation method includes: mixing a polymeric polyol A, a hydroxyl - terminated polysiloxane A, a foaming agent, a chain extender, a catalyst, optionally a silicone oil, optionally an antioxidant, optionally a cross - linker, and optionally an abrasion - resistant agent to obtain component A;

[0063] Mixing a polymeric polyol - modified isocyanate prepolymer and optionally a hydroxyl - terminated polysiloxane - modified isocyanate prepolymer to obtain component B.

[0064] In a third aspect, the present invention provides an organosilicon - modified polyurethane foam material, which is obtained by mixing and curing component A in the organosilicon - modified polyurethane composition as described in the second aspect and component B as described in the first aspect.

[0065] In a fourth aspect, the present invention provides an application of the organosilicon - modified polyurethane foam material as described in the third aspect as a shock - absorbing material.

[0066] Compared with the prior art, the present invention has the following beneficial effects:

[0067] (1) In the organosilicon - modified polyurethane composition provided by the present invention, hydroxyl - terminated polysiloxane A is added to be paired with polymeric polyol A in component A, and a polymeric polyol - modified isocyanate prepolymer is added in component B. The combination of the two not only effectively improves the aging resistance and low - temperature resistance of the organosilicon - modified polyurethane composition, but also ensures that the polyurethane foam material prepared using the polyurethane composition provided by the present invention has finer and more stable foam cells, and is suitable for use as a shock - absorbing material.

[0068] (2) By further defining the addition amounts of the polymeric polyol and the hydroxyl-terminated polysiloxane A in Component A of the organosilicon-modified polyurethane composition, and the addition amount of the polymeric polyol-modified isocyanate prepolymer in Component B, the static stiffness of the obtained organosilicon-modified polyurethane composition can reach 21.5 - 23.6 KN / mm, the change rate of the low-temperature static stiffness at -30 °C is 3.2 - 5.7%, the Tg is -37.2 - -35.2 °C, the tensile strength before aging is 2.05 - 3.29 MPa, the elongation at break is 275 - 397%, the tensile strength after aging is 1.85 - 2.92 MPa, the elongation at break is 237 - 326%, the rebound of the falling ball is 57 - 62%, and the 30% permanent deformation is 3.6 - 5.3%. Detailed Embodiments

[0069] The technical solutions of the present invention will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations on the present invention.

[0070] The detailed information of the raw materials involved in the specific embodiments is as follows:

[0071] (1) Hydroxyl-terminated polysiloxane a: having the structure shown in Formula I, where n1 = 8, the functionality is 2, and the hydroxyl value is 160 mg KOH / g;

[0072] (2) Hydroxyl-terminated polysiloxane b: having the structure shown in Formula II, where n2 = 6, x1 = 5, y1 = 3, the functionality is 2, and the hydroxyl value is 112 mg KOH / g;

[0073] (3) Hydroxyl-terminated polysiloxane c: having the structure shown in Formula III, where n3 = 9, x2 = 26, y2 = 15, the functionality is 3, and the hydroxyl value is 56 mg KOH / g;

[0074] (4) Hydroxyl-terminated polysiloxane d: having the structure shown in Formula IV, where n4 = 1, m = 5, x3, x4 = 14, y3, y4 = 8, the functionality is 2, and the hydroxyl value is 56 mg KOH / g;

[0075] (5) Hydroxyl-terminated polysiloxane e: having the structure shown in Formula V, where n5, n6 = 7, x5 = 22, y5 = 11, the functionality is 2, and the hydroxyl value is 56 mg KOH / g; (6) Polytetrahydrofuran ether diol: the functionality is 2, the number-average molecular weight is 2000, the hydroxyl value is 56 mg KOH / g, purchased from BASF;

[0076] (7) Poly(propylene oxide - ethylene oxide) copolymer polyol: the molecular weight is 4800, the content of propylene oxide is 85%, the hydroxyl value is 35 mg KOH / g, purchased from Wanhua Chemical Group Co., Ltd.;

[0077] (8) Silicone surfactant: DABCO DC6070, purchased from Evonik Industries AG;

[0078] (9) Catalyst a: KC152, purchased from Wanhua Chemical (Beijing) Co., Ltd.;

[0079] (10) Catalyst b: KC135, purchased from Wanhua Chemical (Beijing) Co., Ltd.;

[0080] (11) Antioxidant: Irganox 1010, purchased from BASF;

[0081] (12) Wear-resistant agent: PMX-200, purchased from Dow Corning.

[0082] Preparation Example 1

[0083] A hydroxyl-terminated polysiloxane-modified isocyanate prepolymer with an NCO content of 12.2%;

[0084] Its preparation method includes: reacting hydroxyl-terminated polysiloxane a and 4,4-diphenylmethane diisocyanate with a mass ratio of 47:53 at 80 °C for 3 h to obtain the hydroxyl-terminated polysiloxane-modified isocyanate prepolymer.

[0085] Preparation Example 2

[0086] A hydroxyl-terminated polysiloxane-modified isocyanate prepolymer with an NCO content of 12.2%;

[0087] Its preparation method includes: reacting hydroxyl-terminated polysiloxane b and 4,4-diphenylmethane diisocyanate with a mass ratio of 51.2:48.8 at 80 °C for 3 h to obtain the hydroxyl-terminated polysiloxane-modified isocyanate prepolymer.

[0088] Preparation Example 3

[0089] A polyol-modified isocyanate prepolymer with an NCO content of 12.2%;

[0090] Its preparation method includes: reacting polytetrahydrofuran ether glycol and 4,4-diphenylmethane diisocyanate with a mass ratio of 56.5:43.5 at 80 °C for 3 h to obtain the polyol-modified isocyanate prepolymer.

[0091] Example 1

[0092] An organosilicon-modified polyurethane composition, the organosilicon-modified polyurethane composition comprising component A and component B with a mass ratio of 48:52:

[0093] The A component comprises the following components by weight parts:

[0094]

[0095] The B component comprises the following components by weight parts:

[0096] Hydroxyl-terminated polysiloxane-modified isocyanate prepolymer 25 parts by weight

[0097] Polymeric polyol-modified isocyanate prepolymer 75 parts by weight;

[0098] The preparation method of the silicone-modified polyurethane composition provided in this example includes:

[0099] (1) Mix polytetrahydrofuran ether glycol, hydroxyl-terminated polysiloxane c, water, 1,4-butanediol, catalyst a, catalyst b, trimethylolpropane, silicone surfactant, antioxidant and wear-resistant agent to obtain the A component;

[0100] (2) Mix hydroxyl-terminated polysiloxane-modified isocyanate prepolymer (Preparation Example 1) and polymeric polyol-modified isocyanate prepolymer (Preparation Example 3) to obtain the B component.

[0101] Example 2

[0102] A silicone-modified polyurethane composition, which is different from Example 1 in that hydroxyl-terminated polysiloxane d is used to replace hydroxyl-terminated polysiloxane c in the A component, and other components, dosages and preparation methods are the same as those in Example 1.

[0103] Example 3

[0104] A silicone-modified polyurethane composition, which is different from Example 1 in that hydroxyl-terminated polysiloxane e is used to replace hydroxyl-terminated polysiloxane c in the A component, and other components, dosages and preparation methods are the same as those in Example 1.

[0105] Example 4

[0106] A silicone-modified polyurethane composition, which is different from Example 1 only in that the addition amount of polytetrahydrofuran ether glycol in the A component is 80 parts by weight, and the addition amount of hydroxyl-terminated polysiloxane c is 10 parts by weight, and other components, dosages and preparation methods are the same as those in Example 1.

[0107] Example 5

[0108] A silicone-modified polyurethane composition, which is different from Example 1 only in that the addition amount of polytetrahydrofuran ether glycol in the A component is 85 parts by weight, and the addition amount of hydroxyl-terminated polysiloxane c is 5 parts by weight, and other components, dosages and preparation methods are the same as those in Example 1.

[0109] Example 6

[0110] An organosilicon-modified polyurethane composition, which is different from Example 1 in that the addition amount of polytetrahydrofuran ether diol in Component A is 45 parts by weight, and the addition amount of terminal hydroxyl polydimethylsiloxane c is 45 parts by weight, and the other components, amounts used and preparation methods are the same as those in Example 1.

[0111] Example 7

[0112] An organosilicon-modified polyurethane composition, which is different from Example 1 in that the terminal hydroxyl polydimethylsiloxane-modified isocyanate prepolymer obtained in Preparation Example 2 is used to replace the terminal hydroxyl polydimethylsiloxane-modified isocyanate prepolymer obtained in Preparation Example 1 in Component B, and the other components, amounts used and preparation methods are the same as those in Example 1.

[0113] Example 8

[0114] An organosilicon-modified polyurethane composition, which is different from Example 7 in that Component A uses terminal hydroxyl polydimethylsiloxane d to replace terminal hydroxyl polydimethylsiloxane c, and the other components, amounts used and preparation methods are the same as those in Example 7.

[0115] Example 9

[0116] An organosilicon-modified polyurethane composition, which is different from Example 7 in that Component A uses terminal hydroxyl polydimethylsiloxane e to replace terminal hydroxyl polydimethylsiloxane c, and the other components, amounts used and preparation methods are the same as those in Example 7.

[0117] Example 10

[0118] An organosilicon-modified polyurethane composition, which is different from Example 7 in that the addition amount of polytetrahydrofuran ether diol in Component A is 50 parts by weight, and 20 parts by weight of poly(propylene oxide-ethylene oxide) copolymerized polyol is also added, and the other components, amounts used and preparation methods are the same as those in Example 7.

[0119] Example 11

[0120] An organosilicon-modified polyurethane composition, which is different from Example 1 only in that the addition amount of the terminal hydroxyl polydimethylsiloxane-modified isocyanate prepolymer in Component B is 45 parts by weight, and the addition amount of the polymerized polyol-modified isocyanate prepolymer is 55 parts by weight, and the other components, amounts used and preparation methods are the same as those in Example 1.

[0121] Example 12

[0122] An organosilicon-modified polyurethane composition, which is only different from Example 1 in that the addition amount of the hydroxyl-terminated polysiloxane-modified isocyanate prepolymer in Component B is 15 parts by weight, and the addition amount of the polyether polyol-modified isocyanate prepolymer is 85 parts by weight, and the other components, dosages and preparation methods are the same as those in Example 1.

[0123] Example 13

[0124] An organosilicon-modified polyurethane composition, which is only different from Example 1 in that the addition amount of the hydroxyl-terminated polysiloxane-modified isocyanate prepolymer in Component B is 5 parts by weight, and the addition amount of the polyether polyol-modified isocyanate prepolymer is 95 parts by weight, and the other components, dosages and preparation methods are the same as those in Example 1.

[0125] Example 14

[0126] An organosilicon-modified polyurethane composition, which is only different from Example 1 in that the hydroxyl-terminated polysiloxane-modified isocyanate prepolymer is not added in Component B, and the addition amount of the polyether polyol-modified isocyanate prepolymer is 100 parts by weight, and the other components, dosages and preparation methods are the same as those in Example 1.

[0127] Comparative Example 1

[0128] An organosilicon-modified polyurethane composition, which is only different from Example 1 in that hydroxyl-terminated polysiloxane c is not added in Component A, and the addition amount of polytetrahydrofuran glycol is 90 parts by weight, and the other components, dosages and preparation methods are the same as those in Example 1.

[0129] Comparative Example 2

[0130] An organosilicon-modified polyurethane composition, which is only different from Example 1 in that the polyether polyol-modified isocyanate prepolymer is not added in Component B, and the addition amount of the hydroxyl-terminated polysiloxane-modified isocyanate prepolymer is 100 parts by weight, and the other components, dosages and preparation methods are the same as those in Example 1.

[0131] Comparative Example 3

[0132] An organosilicon-modified polyurethane composition, which is only different from Example 1 in that hydroxyl-terminated polysiloxane c is not added in Component A, and the addition amount of polytetrahydrofuran glycol is 90 parts by weight, and the hydroxyl-terminated polysiloxane-modified isocyanate prepolymer polyether polyol is not added in Component B, and the addition amount of the polyether polyol-modified isocyanate prepolymer is 100 parts by weight, and the other components, dosages and preparation methods are the same as those in Example 1.

[0133] Performance test:

[0134] The A and B components in the silicone-modified polyurethane compositions obtained in the examples and comparative examples were mixed at a mass ratio of 48:52 at 35 °C for 7 s, and then quickly poured into an aluminum mold of 20×15×1 cm at 80 °C. The mold was kept open, and the sample was taken out for testing after 8 min;

[0135] (1) Static stiffness, low-temperature performance and aging performance: Tested according to the method provided in 《GB / T 21527-2008》;

[0136] (2) Ball-drop rebound: Tested according to the test method provided in 《GB / T 6670》;

[0137] (5) 30% permanent deformation: Tested according to the test standard provided in 《GB / T 7759.2-2014》.

[0138] The silicone-modified polyurethane compositions provided in Examples 1 to 14 and Comparative Examples 1 to 3 were tested according to the above test methods, and the test results are shown in Table 1:

[0139] Table 1

[0140]

[0141] It can be seen from the data in Table 1 that the silicone-modified polyurethane composition provided by the present invention has excellent low-temperature resistance and aging resistance, and also has excellent mechanical properties; at the same time, by further limiting the ratio of the polymeric polyol and the terminal hydroxyl polyorganosiloxane A in the A component, and the addition amount of the polymeric polyol-modified isocyanate prepolymer in the B component, the static stiffness of the obtained silicone-modified polyurethane composition can reach 21.5-23.6 KN / mm, the low-temperature static stiffness change rate at -30 °C is 3.2-5.7%, the Tg is -37.2--35.2 °C, the tensile strength before aging is 2.05-3.29 MPa, the elongation at break is 275-397%, the tensile strength after aging is 1.85-2.92 MPa, the elongation at break is 237-326%, the ball-drop rebound is 57-62%, and the 30% permanent deformation is 3.6-5.3%.

[0142] According to the data comparison of Example 1 and Comparative Examples 1 and 3, it can be found that without adding the terminal hydroxyl polyorganosiloxane c in the A component, the low-temperature static stiffness change rate of the obtained polyurethane composition at -30 °C is relatively high, indicating that the low-temperature resistance becomes worse, and the 30% permanent deformation is relatively high.

[0143] By comparing the data of Example 1 and Comparative Example 2, it can also be found that without adding the polymeric polyol-modified isocyanate prepolymer in the B component, the comprehensive performance of the obtained polyurethane composition will decrease.

[0144] Comparing the data of Example 1 with those of Examples 5-6, Example 11, and Example 14, it can also be found that when the addition amounts of the polymeric polyol and the hydroxy-terminated polysiloxane in Component A are not within the scope defined in the present invention, and when the polymeric polyol-modified isocyanate prepolymer in Component B is not within the scope defined in the present invention, the low-temperature performance and aging performance of the finally obtained polyurethane composition will also be affected.

[0145] The applicant declares that the present invention uses the above-mentioned examples to illustrate a silicone-modified polyurethane composition, its preparation method, and its application. However, the present invention is not limited to the above-mentioned examples, that is, it does not mean that the present invention must rely on the above-mentioned examples to be implemented. Those skilled in the art should understand that any improvement to the present invention, the equivalent substitution of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc. all fall within the protection scope and the disclosure scope of the present invention.

Claims

1. A silicone-modified polyurethane composition, characterized in that, The silicone-modified polyurethane composition comprises Component A and Component B; Component A comprises the following components by weight parts: The polymeric polyol A comprises a polyether polyol and / or a polyester polyol; When the polymeric polyol A is selected from polyether polyols, the polyether polyol is any one or a combination of at least two of polypropylene oxide polyol, poly(propylene oxide-ethylene oxide) copolymer polyol, polytetrahydrofuran polyol or polyolefin polyol; Component B comprises a polymeric polyol-modified isocyanate prepolymer and a hydroxyl-terminated polysiloxane-modified isocyanate prepolymer; Component B comprises the following components by weight parts: Hydroxyl-terminated polysiloxane-modified isocyanate prepolymer 0 to 40 parts by weight and not equal to 0; Polymeric polyol-modified isocyanate prepolymer 60 to 100 parts by weight; The polymeric polyol-modified isocyanate prepolymer is prepared by the following method, which includes: reacting a polymeric polyol B and a diisocyanate A to obtain the polymeric polyol-modified isocyanate prepolymer; The polymeric polyol B comprises a polyether polyol and / or a polyester polyol; When the polymeric polyol B is selected from polyether polyols, the polyether polyol is any one or a combination of at least two of polypropylene oxide polyol, poly(propylene oxide-ethylene oxide) copolymer polyol, polytetrahydrofuran polyol or polyolefin polyol.

2. The silicone-modified polyurethane composition according to claim 1, characterized in that, The number-average molecular weight of the polymeric polyol A is 500 to 4000.

3. The silicone-modified polyurethane composition according to claim 1, characterized in that, The functionality of the polymeric polyol A is 2 to 4.

4. The silicone-modified polyurethane composition according to claim 1, characterized in that, The hydroxyl value of the polymeric polyol A is 20 to 150 mgKOH / g.

5. The organosilicon-modified polyurethane composition according to claim 1, characterized in that, The polyester polyol comprises polycaprolactone polyol.

6. The organosilicon-modified polyurethane composition according to claim 1, characterized in that, The chain extender comprises any one or a combination of at least two of ethylene glycol, 1,3-propanediol, diethylene glycol, dipropylene glycol, 1,3-propanediol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, diethanolamine, methyldiethanolamine, 1,4-cyclohexanediol, tripropylene glycol, diethyltoluenediamine, hydroquinone bis-β-hydroxyethyl ether or resorcinol hydroxy ether.

7. The organosilicon-modified polyurethane composition according to claim 1, characterized in that, The foaming agent comprises water.

8. The silicone-modified polyurethane composition according to claim 1, wherein The catalyst comprises any one or a combination of at least two of triethylenediamine, bis(dimethylaminoethyl) ether, pentamethyldipropyltriamine, pentamethyldiethyltriamine, N,N-dimethylcyclohexylamine, N-benzyl dimethylamine, dibutyltin dilaurate or stannous octoate.

9. The silicone-modified polyurethane composition according to claim 1, wherein Component A further comprises any one or a combination of at least two of a silicone surfactant, an antioxidant, a crosslinking agent or an abrasion-resistant agent.

10. The silicone-modified polyurethane composition according to claim 9, wherein The content of the silicone surfactant in Component A is 0 to 2 parts by weight and not equal to 0.

11. The silicone-modified polyurethane composition according to claim 9, wherein The content of the abrasion-resistant agent in Component A is 0 to 8 parts by weight and not equal to 0.

12. The organosilicon-modified polyurethane composition according to claim 9, characterized in that, The abrasion-resistant agent comprises polysiloxane and / or polyolefin wax powder.

13. The silicone-modified polyurethane composition according to claim 9, characterized in that, The content of the antioxidant in Component A is 0.01 to 3 parts by weight.

14. The organosilicon-modified polyurethane composition according to claim 9, characterized in that, The antioxidant comprises a hindered phenol antioxidant and / or a phosphite antioxidant.

15. The silicone-modified polyurethane composition according to claim 9, characterized in that, The content of the crosslinking agent in Component A is 0 to 10 parts by weight and not equal to 0.

16. The silicone-modified polyurethane composition according to claim 9, wherein The crosslinking agent comprises any one or a combination of at least two of glycerol, trimethylolpropane, triethanolamine, 1,2,6-hexanetriol, ethoxylated trimethylolpropane or ethoxylated glycerol.

17. The silicone-modified polyurethane composition according to claim 1, characterized in that, The mass percentage content of NCO groups in the component B is 8-15%.

18. The silicone-modified polyurethane composition according to claim 1, wherein In the preparation method of the polymer polyol-modified isocyanate prepolymer, the reaction temperature is 60-90 °C.

19. The organosilicon-modified polyurethane composition according to claim 1, wherein In the preparation method of the polymer polyol-modified isocyanate prepolymer, the reaction time is 2-5 h.

20. The organosilicon-modified polyurethane composition according to claim 1, wherein The mass percentage content of NCO in the polymer polyol-modified isocyanate prepolymer is 6-20%.

21. The organosilicon-modified polyurethane composition according to claim 1, characterized in that, The hydroxyl-terminated polydimethylsiloxane-modified isocyanate prepolymer is prepared by the following method, which includes: reacting hydroxyl-terminated polydimethylsiloxane B with diisocyanate B to obtain the hydroxyl-terminated polydimethylsiloxane-modified isocyanate prepolymer.

22. The silicone-modified polyurethane composition according to claim 21, characterized in that, The temperature of the reaction is 70-95 °C.

23. The silicone-modified polyurethane composition according to claim 21, wherein, The time of the reaction is 2-5 h.

24. The organosilicon-modified polyurethane composition according to claim 1, wherein The mass percentage content of NCO in the hydroxyl-terminated polydimethylsiloxane-modified isocyanate prepolymer is 8-15%.

25. The silicone-modified polyurethane composition according to claim 1, characterized in that, The diisocyanate A includes any one or a combination of at least two of diphenylmethane diisocyanate, toluene diisocyanate, dicyclohexylmethane diisocyanate, p-phenylene diisocyanate or 1,5-naphthalene diisocyanate.

26. The organosilicon-modified polyurethane composition according to claim 21, wherein The diisocyanate B includes any one or a combination of at least two of diphenylmethane diisocyanate, toluene diisocyanate, dicyclohexylmethane diisocyanate, p-phenylene diisocyanate or 1,5-naphthalene diisocyanate.

27. According to the organosilicon-modified polyurethane composition of claim 1, the polyester polyol includes polycaprolactone polyol.

28. The silicone-modified polyurethane composition according to claim 1, characterized in that, The mass ratio of the component A to the component B is 1:(0.5-1.8).

29. A method for preparing the organosilicon-modified polyurethane composition according to claim 1, characterized in that, The preparation method includes: mixing polymer polyol A, hydroxyl-terminated polydimethylsiloxane A, foaming agent, chain extender, catalyst, optionally silicone surfactant, optionally antioxidant, optionally crosslinking agent and optionally wear-resistant agent to obtain component A; Mixing the polymer polyol-modified isocyanate prepolymer and the hydroxyl-terminated polydimethylsiloxane-modified isocyanate prepolymer to obtain component B.

30. A silicone-modified polyurethane foaming material, characterized in that, The organosilicon-modified polyurethane foam material is obtained by mixing and curing the component A and the component B in the organosilicon-modified polyurethane composition according to any one of claims 1-29.

31. Use of an organosilicon-modified polyurethane foam material according to claim 30 as a shock-absorbing material.

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