Low temperature resistant non-foamed polyurethane material and method for producing the same

Abstract

The application discloses a kind of low-temperature-resistant non-foaming polyurethane material and preparation method thereof, by component A and component B are formed, by mass fraction, the component A includes polyether polyol a 100 parts, polyether polyol b 10-20 parts, chain extender 8-10 parts, catalyst 0.2-0.5 parts, anti-yellowing agent a 0.2-0.5 parts, antioxidant a 0.5-1 part;The component B includes polyether polyol a 40-50 parts, isocyanate 50-60 parts, antioxidant b 0.5-1 part, polymerization inhibitor 0.03-0.05 parts, and the mass ratio of the component A and component B is 100:40-50.The polyurethane material of the application is formed by the component A of specific formula and the component B of specific formula, and the specific polyether polyol is selected in the component A, the low-temperature flexibility of molecule is increased by adding side chain group, the low-temperature crystalline hardness of the polyether polyol is reduced, so that the low-temperature performance of low-temperature-resistant polyurethane material is greatly improved, the product is not shrinked under the condition of minus 20 degrees temperature, and still maintains soft and good elasticity.

Description

Technical Field

[0001] This invention relates to the field of polyurethane technology, specifically to a low-temperature resistant non-foaming polyurethane material and its preparation method. Background Technology

[0002] Polyurethane, or polyurethane, is a high-molecular-weight polymer containing repeating groups of urethane esters in its main chain. Its properties fall between those of rubber and plastics, and it is produced by the reaction of polyols and isocyanates. Its characteristics include adjustable density, a wide range of hardness variations, and broad applications. The polyurethane molecular structure consists of soft and hard segments. The soft segments are composed of long-chain polyester polyols, polyether polyols, and other polyols with special structures, while the hard segments are obtained by reacting isocyanates with small-molecule polyols or small-molecule polyamines containing active hydrogen.

[0003] Materials made of polyurethane have the advantage of easily adjustable properties; by adjusting the polyurethane formulation, materials with different hardness and density can be prepared. However, when used in low-temperature environments such as winter, the movement of the molecular chain structure in the soft segments of polyurethane is hindered, resulting in decreased flexibility and elasticity, making it prone to breakage during repeated bending.

[0004] Currently, polyurethane materials can be divided into two types: foamed and non-foamed. Foamed materials are generally molded in molds, have lower performance, and are highly dependent on worker experience, which greatly limits their application range. Non-foamed materials, on the other hand, are cast in place, have lower dependence on worker experience, more stable product quality, and higher material performance, allowing them to be made into various complex shapes. Summary of the Invention

[0005] The purpose of this invention is to solve the problems existing in the prior art and to provide a low-temperature resistant non-foaming polyurethane material and its preparation method.

[0006] To achieve the above objectives, the present invention proposes the following technical solution: a low-temperature resistant non-foaming polyurethane material, composed of component A and component B, wherein, by mass parts, component A comprises 100 parts of polyether polyol a, 10-20 parts of polyether polyol b, 8-10 parts of chain extender, 0.2-0.5 parts of catalyst, 0.2-0.5 parts of anti-yellowing agent a, and 0.5-1 parts of antioxidant a; and component B comprises 40-50 parts of polyether polyol a, 50-60 parts of isocyanate, 0.5-1 part of antioxidant b, and 0.03-0.05 parts of polymerization inhibitor, wherein the mass ratio of component A to component B is 100:40-50.

[0007] Furthermore, the polyether polyol a is a branched polytetrahydrofuran copolymer diol obtained by polymerizing tetrahydrofuran with branched small molecule alcohols, wherein the mass of the branched small molecule alcohol accounts for 2-5% of the total weight of the tetrahydrofuran and the branched small molecule alcohol;

[0008] Furthermore, the branched small molecule alcohol is one or a combination of 1,3-butanediol, 1,4-butanediol, 1,2-propanediol, neopentyl glycol, and 1,6-hexanediol.

[0009] Furthermore, the polyether polyol a has a functionality of 2-2.1 and a hydroxyl value of 50-60 mgKOH / g, preferably Asahi Kasei Corporation PTXG.

[0010] Further, the isocyanate is a composition of 4,4-diphenylmethane diisocyanate and carbodiimide-modified MDI, wherein the carbodiimide-modified MDI accounts for 7-10% of the total weight of component B.

[0011] Furthermore, the isocyanate is a composition using MDI-100 (Wanhua Chemical Group Co., Ltd.) and Wannate MDI-100L (Wanhua Liquefied MDI).

[0012] Furthermore, the NCO content of the isocyanate is 16-17%, and the isocyanate using the above-mentioned component B can effectively improve its tensile properties and softness while ensuring mechanical properties.

[0013] Furthermore, the polyether polyol b has a functionality of 3 and a hydroxyl value of 25-30 mgKOH / g, preferably the polyether polyol MN-1000 from Nanxing Dongda.

[0014] Furthermore, the chain extender is dimethylthiotoluene diamine, preferably DMTDA from Guangzhou Yuanda New Materials Co., Ltd.

[0015] Furthermore, the catalyst is a rare earth metal catalyst, preferably CUCAT-HAA from Guangzhou Yourun Synthetic Materials Co., Ltd.

[0016] Furthermore, the anti-yellowing agent a is UV-P, preferably UV-P from Wuxi Xinhenghui Materials Co., Ltd.

[0017] Furthermore, the antioxidant a is preferably ChicSY112 from Shanghai Chic Fluorosilicon Materials Co., Ltd.

[0018] Furthermore, the antioxidant b is preferably BASF antioxidant 1010.

[0019] Furthermore, the polymerization inhibitor is phosphoric acid.

[0020] This invention also discloses a method for preparing a low-temperature resistant, non-foaming polyurethane material, the method comprising the following steps:

[0021] The preparation method of the low-temperature resistant non-foaming polyurethane material includes the following steps:

[0022] S1. Preparation of component A: The polyether polyol a and polyether polyol b are put into a reaction vessel, heated to 120°C, and vacuum is turned on to dehydrate to -0.01MPa for 2 hours. Then the temperature is lowered to 60-80°C, and the remaining chain extender, antioxidant a, anti-yellowing agent a, anti-yellowing agent b, and catalyst are added. The mixture is stirred under vacuum for 20 minutes to obtain component A.

[0023] S2. Preparation of component B: The polyether polyol a, antioxidant b and polymerization inhibitor were added to a reaction vessel, heated to 120°C, and vacuum was turned on to dehydrate to -0.01MPa for 2 hours. Then the temperature was lowered to 70°C, isocyanate was added, vacuum was maintained, and stirring was turned on to react at 70°C for 2 hours. After that, a sample was taken for testing, and the mass content of NCO was found to be 16-17%. The reaction was then terminated to obtain component B.

[0024] S3. Add the components A and B to the material tank of the casting machine and mix them;

[0025] S4. Then, the mixed components A and B are poured into a mold, where they react and solidify to produce a low-temperature resistant, non-foaming polyurethane material.

[0026] Furthermore, the method for preparing the low-temperature resistant non-foaming polyurethane material is used to prepare shoe soles. The equipment used for preparing the shoe soles is a flat vulcanizing machine with vacuum function and an aluminum alloy mold. The preparation method includes adding the A component and the B component to the material tank of the casting machine, then mixing the A component and the B component and pouring it into the mold, pressing and curing it, and opening the mold after 5-6 minutes to obtain the shoe sole.

[0027] Furthermore, the mold temperature is 80-90℃, the material temperature is 40-50℃ for component A and 30-40℃ for component B, the pressure of the flat vulcanizing machine is 60-80 bar, and the vacuuming time is 20-30 seconds.

[0028] An application of the aforementioned low-temperature resistant, non-foaming polyurethane material is used in the manufacture of shoe soles or shock-absorbing blocks.

[0029] Compared with the prior art, the beneficial effects of the present invention are:

[0030] 1. This invention provides a polyurethane material composed of a specific formulation of component A and a specific formulation of component B. Component A uses a specific polyether polyol, and by adding side chain groups, the low-temperature flexibility of the molecular chain is increased, and the low-temperature crystallization hardness of the polyether polyol is reduced. This greatly improves the low-temperature performance of the low-temperature resistant polyurethane material. At -20 degrees Celsius, the product does not shrink, the hardness changes little, and it still maintains softness and good elasticity.

[0031] 2. The low-temperature resistant non-foaming polyurethane material of the present invention, due to the use of DMTDA with benzene rings, has increased rigidity and significantly improved strength and wear resistance.

[0032] 3. The low-temperature resistant non-foaming polyurethane material of the present invention has an increased coefficient of friction on its surface compared to rubber materials due to the presence of side methyl groups in the molecular structure of urethane itself, and can be used as an anti-slip material.

[0033] 4. The low-temperature resistant polyurethane material of the present invention can meet the mold opening requirement of 5-6 minutes. Compared with foamed materials, the process is simple, the yield is high, a lot of labor can be saved, costs can be reduced, and the product is stable and easy to produce. Detailed Implementation

[0034] The present invention will be further illustrated by the following embodiments, but these embodiments are not intended to limit the scope of the invention. Example

[0035] A low-temperature resistant, non-foaming polyurethane material is composed of component A and component B. Component A comprises (by weight): 100 parts of polyether polyol a (functionality 2, hydroxyl value 50); 20 parts of polyether polyol b (functionality 3, hydroxyl value 25); 8 parts of chain extender; 0.2 parts of catalyst; 0.5 parts of anti-yellowing agent a; and 0.5 parts of antioxidant a. Component B comprises 40 parts of polyether polyol a, 60 parts of isocyanate, 0.5 parts of antioxidant b, and 0.05 parts of polymerization inhibitor.

[0036] The mass ratio of component A to component B is 100:40. Example

[0037] Component A consists of the following components (by weight): 100 parts of polyether polyol a (functionality 2.1, hydroxyl value 60); 10 parts of polyether polyol b (functionality 3, hydroxyl value 30); 10 parts of chain extender; 0.5 parts of catalyst; 0.2 parts of anti-yellowing agent a; and 1 part of antioxidant a. Component B consists of 50 parts of polyether polyol a, 50 parts of isocyanate, 0.1 parts of antioxidant b, and 0.03 parts of polymerization inhibitor.

[0038] The mass ratio of component A to component B is 100:50. Example

[0039] A low-temperature resistant, non-foaming polyurethane material is composed of component A and component B. Component A comprises (by weight): 100 parts of polyether polyol a (functionality 2, hydroxyl value 50); 15 parts of polyether polyol b (functionality 3, hydroxyl value 28); 9 parts of chain extender; 0.3 parts of catalyst; 0.3 parts of anti-yellowing agent a; and 0.6 parts of antioxidant a. Component B comprises 45 parts of polyether polyol a, 55 parts of isocyanate, 0.8 parts of antioxidant b, and 0.05 parts of polymerization inhibitor.

[0040] The mass ratio of component A to component B is 100:45.

[0041] The low-temperature resistant non-foaming polyurethane material is prepared according to the dosages in the formulations of Examples 1-3 above, following the specific steps:

[0042] S1. Preparation of component A: The polyether polyol a and polyether polyol b are put into a reaction vessel, heated to 120°C, and vacuum is turned on to dehydrate to -0.01MPa for 2 hours. Then the temperature is lowered to 60-80°C, and the remaining chain extender, antioxidant a, anti-yellowing agent a, anti-yellowing agent b, and catalyst are added. The mixture is stirred under vacuum for 20 minutes to obtain component A.

[0043] S2. Preparation of component B: The polyether polyol a, antioxidant b and polymerization inhibitor were added to a reaction vessel, heated to 120°C, and vacuum was turned on to dehydrate to -0.01MPa for 2 hours. Then the temperature was lowered to 70°C, isocyanate was added, vacuum was maintained, and stirring was turned on to react at 70°C for 2 hours. After that, a sample was taken for testing, and the mass content of NCO was found to be 16-17%. The reaction was then terminated to obtain component B.

[0044] S3. Add the components A and B to the material tank of the casting machine and mix them;

[0045] S4. Then, the mixed components A and B are poured into a mold. The two components are pressed and cured in the mold. The mold is opened after 5-6 minutes to obtain the sole. The equipment used for the preparation of the sole is a flat vulcanizing machine with vacuum function and an aluminum alloy mold.

[0046] The mold temperature is 80-90℃, the material temperature is 40-50℃ for component A and 30-40℃ for component B, the pressure of the flat vulcanizing machine is 60-80 bar, and the vacuuming time is 20-30 seconds.

[0047] The present invention will be further illustrated below with comparative examples, but this should not be construed as limiting the present invention.

[0048] Comparative Example 1

[0049] Component A consists of the following components (by weight): 100 parts of polyether polyol PTMG-2000 (functionality 2.1, hydroxyl value 60); 10 parts of polyether polyol b (functionality 3, hydroxyl value 30); 10 parts of chain extender; 0.5 parts of catalyst; 0.2 parts of anti-yellowing agent a; and 1 part of antioxidant a. Component B consists of 50 parts of polyether polyol a, 50 parts of isocyanate, 0.1 parts of antioxidant b, and 0.03 parts of polymerization inhibitor.

[0050] The mass ratio of component A to component B is 100:50.

[0051] Comparative Example 2

[0052] A low-temperature resistant, non-foaming polyurethane material is composed of component A and component B. Component A comprises (by weight): 100 parts of polyether polyol PTMG-1000 (functionality 2, hydroxyl value 50); 15 parts of polyether polyol b (functionality 3, hydroxyl value 28); 9 parts of chain extender; 0.3 parts of catalyst; 0.3 parts of anti-yellowing agent a; and 0.6 parts of antioxidant a. Component B comprises 45 parts of polyether polyol a, 55 parts of isocyanate, 0.8 parts of antioxidant b, and 0.05 parts of polymerization inhibitor.

[0053] The mass ratio of component A to component B is 100:45.

[0054] Comparative Example 3

[0055] Component A consists of the following components (by weight): 100 parts of polyester polyol PCDL-2000 (functionality 2, hydroxyl value 56); 10 parts of polyether polyol b (functionality 3, hydroxyl value 30); 10 parts of chain extender; 0.5 parts of catalyst; 0.2 parts of anti-yellowing agent a; and 1 part of antioxidant a. Component B consists of 50 parts of polyether polyol a, 50 parts of isocyanate, 0.1 parts of antioxidant b, and 0.03 parts of polymerization inhibitor.

[0056] The mass ratio of component A to component B is 100:50.

[0057] Comparative Example 4

[0058] Component A consists of the following components (by weight): 100 parts of polyether polyol a (functionality 2, hydroxyl value 50); 20 parts of polyether polyol b (functionality 3, hydroxyl value 25); 8 parts of chain extender; 0.2 parts of catalyst; 0.5 parts of anti-yellowing agent a; and 0.5 parts of antioxidant a. Component B consists of 40 parts of polyether polyol a, 60 parts of isophorone diisocyanate (IPDI), 0.5 parts of antioxidant b, and 0.05 parts of polymerization inhibitor.

[0059] The mass ratio of component A to component B is 100:40.

[0060] The low-temperature resistant non-foaming polyurethane material was prepared according to the dosages in the formulations of Comparative Examples 1-4 above, following the same preparation method as in the examples:

[0061] Comparative Example 5: A polyurethane slurry used by a domestic customer for shoe sole products was adopted.

[0062] The low-temperature resistant non-foaming polyurethane materials prepared in Examples 1-3 and Comparative Examples 1-5, as well as the polyurethane slurry in the comparative examples, were used to prepare shoe soles of the same density and size, and their performance was then tested.

[0063] The testing standard for ASKER A hardness is ASTM D2240;

[0064] Density g / cm³ 3 The testing standard is ASTM D792;

[0065] The testing standards for tensile strength (MPa) and elongation (%) are ASTM D412.

[0066] DIE-C tearing capacity (kgf / cm) 2 The testing standard is ASTM D624;

[0067] The testing standard for Din abrasion resistance (mm^3) is ASTM D5963.

[0068] The standard for testing the number of bends is ASTM D1052;

[0069] The testing standard for anti-slip (dry) and anti-slip (wet) properties is ASTM-F1677;

[0070] Shrinkage is detected through changes in hardness and visual inspection.

[0071] The test results are shown in the table below.

[0072]

[0073] As can be seen from the table above, the low-temperature resistant non-foaming polyurethane materials prepared in Examples 1-3 have excellent physical properties at room temperature. However, the hardness changes of Examples 1-3 in low-temperature environments (0℃, -10℃ and -20℃) are smaller than those in the room temperature environment (25℃), while the hardness changes of Comparative Examples 1-3 and Comparative Example 5 in low-temperature environments (0℃, -10℃ and -20℃) are larger than those in the room temperature environment (25℃).

[0074] Compared with Comparative Example 4, although the hardness changes of Comparative Example 4 in low-temperature environments (0℃, -10℃ and -20℃) and in normal temperature environments (25℃) are not much different, the tensile, elongation, DIE-C tear, Din abrasion resistance and bending performance are much worse than those of the low-temperature resistant non-foamed polyurethane materials prepared in Examples 1-3.

[0075] Compared with Comparative Example 3, the low-temperature resistant non-foaming polyurethane materials prepared in Examples 1-3 have good tear resistance.

[0076] Compared with Comparative Examples 1-5, the low-temperature resistant non-foaming polyurethane materials prepared in Examples 1-3 have better anti-slip properties.

[0077] Therefore, the low-temperature resistant non-foaming polyurethane material of the present invention is less affected by temperature during use, has excellent overall performance, and can meet the requirements for use in environments below zero degrees Celsius in northern regions.

[0078] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any form or substance. All technical solutions within the scope of the present invention's concept are within the protection scope of the present invention. Any equivalent changes and modifications made to the above embodiments based on the essential technology of the present invention should also be considered within the protection scope of the present invention.

Claims

1. A low-temperature resistant, non-foaming polyurethane material, characterized in that, Composed of component A and component B, by mass parts, component A includes 100 parts of polyether polyol a, 10-20 parts of polyether polyol b, 8-10 parts of chain extender, 0.2-0.5 parts of catalyst, 0.2-0.5 parts of anti-yellowing agent a, and 0.5-1 parts of antioxidant a; component B includes 40-50 parts of polyether polyol a, 50-60 parts of isocyanate, 0.5-1 parts of antioxidant b, and 0.03-0.05 parts of polymerization inhibitor, and the mass ratio of component A to component B is 100:40-50; The polyether polyol a is a branched polytetrahydrofuran copolymer diol obtained by polymerizing tetrahydrofuran with branched small molecule alcohols, wherein the mass of the branched small molecule alcohol accounts for 2-5% of the total weight of the tetrahydrofuran and the branched small molecule alcohol; The branched small molecule alcohol is one or a combination of 1,3-butanediol, 1,2-propanediol, and neopentyl glycol; The polyether polyol a has a functionality of 2-2.1 and a hydroxyl value of 50-60 mgKOH / g; The isocyanate is a composition of 4,4-diphenylmethane diisocyanate and carbodiimide-modified MDI, wherein the carbodiimide-modified MDI accounts for 7-10% of the total weight of component B. The polyether polyol b has a functionality of 3 and a hydroxyl value of 25-30 mgKOH / g.

2. The method for preparing the low-temperature resistant non-foaming polyurethane material according to claim 1, characterized in that, The preparation method includes the following steps: Preparation of component S1.A: The polyether polyols a and b are added to a reaction vessel, heated to 120°C, and vacuum is turned on to dehydrate to -0.01 MPa for 2 hours. Then the temperature is lowered to 60-80°C, and the remaining chain extender, antioxidant a, anti-yellowing agent a, anti-yellowing agent b, and catalyst are added. The mixture is stirred under vacuum for 20 minutes to obtain component A. Preparation of component S2.B: The polyether polyol a, antioxidant b, and polymerization inhibitor were added to a reaction vessel, heated to 120°C, and vacuum was turned on to dehydrate to -0.01 MPa for 2 hours. Then the temperature was lowered to 70°C, isocyanate was added, vacuum was maintained, and stirring was turned on. The reaction was carried out at 70°C for 2 hours. After that, a sample was taken for testing. The mass content of NCO was found to be 16-17%. The reaction was then terminated to obtain component B. S3. Add the components A and B to the material tank of the casting machine and mix them; S4. Then, the mixed components A and B are poured into a mold, where they react and solidify to produce a low-temperature resistant, non-foaming polyurethane material.

3. The method for preparing the low-temperature resistant non-foaming polyurethane material according to claim 2, characterized in that, The method for preparing the low-temperature resistant non-foaming polyurethane material is used to prepare shoe soles. The equipment used for preparing the shoe soles is a flat vulcanizing machine with vacuum function and an aluminum alloy mold. The preparation method includes adding the A component and the B component into the material tank of the casting machine, then mixing the A component and the B component and pouring it into the mold, pressing and curing it, and opening the mold after 5-6 minutes to obtain the shoe sole.

4. The method for preparing the low-temperature resistant non-foaming polyurethane material according to claim 3, characterized in that, The mold temperature is 80-90℃, the material temperature is 40-50℃ for component A and 30-40℃ for component B, the pressure of the flat vulcanizing machine is 60-80 bar, and the vacuuming time is 20-30 seconds.

5. The application of the low-temperature resistant non-foaming polyurethane material according to claim 1 in shoe soles or shock-absorbing blocks.

Images