Low-temperature-resistant non-foaming polyurethane material and preparation method thereof

Abstract

The invention discloses a low-temperature-resistant non-foaming polyurethane material and a preparation method thereof.The low-temperature-resistant non-foaming polyurethane material is composed of a component A and a component B. The component A comprises, by mass, 100 parts of polyether polyol a, 10-20 parts of polyether polyol b, 8-10 parts of a chain extender, 0.2-0.5 part of a catalyst, 0.2-0.5 part of an anti-yellowing agent a and 0.5-1 part of an antioxidant a; the component B is prepared from 40 to 50 parts of polyether polyol a, 50 to 60 parts of isocyanate, 0.5 to 1 part of antioxidant b and 0.03 to 0.05 part of polymerization inhibitor, and the mass ratio of the component A to the component B is 100 to (40 to 50). The polyurethane material is composed of the component A with a specific formula and the component B with a specific formula, the specific polyether polyol is selected in the component A, and by adding side chain groups, the low-temperature flexibility of molecules is improved, and the low-temperature crystallization hardness of the polyether polyol is reduced, so that the low-temperature performance of the low-temperature-resistant polyurethane material is greatly improved, and the service life of the low-temperature-resistant polyurethane material is prolonged. The product does not shrink under the temperature condition of minus 20 DEG C, and still keeps soft and good elasticity.

Description

Technical Field

[0001] The invention relates to the technical field of polyurethane, and in particular to a low-temperature resistant non-foaming polyurethane material and a preparation method thereof. Background Art

[0002] Polyurethane, the full name of which is polyurethane, is a high molecular polymer with repeating groups of carbamate in the main chain and properties between rubber and plastic. It is made by the reaction of polyols and isocyanates. It is characterized by adjustable density, wide range of hardness changes, and wide application fields. The molecular structure of polyurethane is composed of soft and hard segments, among which the soft segment is composed of long-chain polyester polyols, polyether polyols and other polyols with special structures, and the hard segment is obtained by the reaction of isocyanates with active hydrogen-containing substances such as small molecule polyols or small molecule polyamines.

[0003] Materials made of polyurethane have the characteristic of easy adjustment of performance. By adjusting the formula of polyurethane materials, polyurethane 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 of the soft segment of polyurethane is hindered, the flexibility and elasticity are reduced, and repeated twists and turns during use are prone to breakage.

[0004] At present, polyurethane materials can be divided into two types: foaming type and non-foaming type. Among them, foaming type materials are generally formed by in-mold molding method, with lower performance and high dependence on workers' experience, which greatly limits their application scope; while non-foaming type materials are formed by casting method, with low dependence on workers' experience, stable product quality, high material performance, and can be made into various complex shapes. Summary of the invention

[0005] The present invention aims to solve the problems existing in the prior art and provide a low-temperature resistant non-foaming polyurethane material and a preparation method thereof.

[0006] In order to achieve the above-mentioned purpose, the present invention proposes the following technical scheme: a low-temperature resistant non-foaming polyurethane material, composed of component A and component B, wherein, by weight, the 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; the component B comprises 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 the component A to the component B is 100:40-50.

[0007] Furthermore, the polyether polyol a is a branched polytetrahydrofuran copolymer diol obtained by polymerization of tetrahydrofuran and branched small molecule alcohol, and 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; Furthermore, the branched small molecule alcohol is a combination of one or more of 1,3-butanediol, 1,4-butanediol, 1,2-propylene glycol, neopentyl glycol, and 1,6-hexanediol.

[0008] Furthermore, the functionality of the polyether polyol a is 2-2.1, and the hydroxyl value is 50-60 mgKOH / g, and PTXG produced by Asahi Kasei Corporation is preferred.

[0009] Furthermore, the isocyanate is a composition of 4,4-diphenylmethane diisocyanate and carbodiimide-modified MDI, wherein the weight of carbodiimide-modified MDI accounts for 7-10% of the total weight of the B component.

[0010] Furthermore, the isocyanate is a composition of MDI-100 (Wanhua Chemical Group Co., Ltd.) and Wannate MDI-100L (Wanhua Liquefied MDI).

[0011] Furthermore, the NCO content of the isocyanate is 16-17%. The use of the isocyanate of the B component can well improve its tensile properties and softness while ensuring the mechanical properties.

[0012] Furthermore, the polyether polyol has a functionality b of 3 and a hydroxyl value of 25-30 mgKOH / g, and is preferably the polyether polyol MN-1000 produced by Nanxing Dongda.

[0013] Furthermore, the chain extender is dimethylthiotoluenediamine, preferably DMTDA from Guangzhou Yuanda New Materials Co., Ltd.

[0014] Furthermore, the catalyst is a rare earth metal catalyst, preferably CUCAT-HAA produced by Guangzhou Yourun Synthetic Materials Co., Ltd.

[0015] Furthermore, the anti-yellowing agent a is UV-P, preferably UV-P from Wuxi Xinhenghui Materials Co., Ltd.

[0016] Furthermore, the antioxidant a is preferably ChicSY112 produced by Shanghai Chic Fluorosilicone Materials Co., Ltd.

[0017] Furthermore, the antioxidant b is preferably BASF antioxidant 1010.

[0018] Furthermore, the polymerization inhibitor is phosphoric acid.

[0019] The present invention also discloses a method for preparing a low-temperature resistant non-foaming polyurethane material, the method comprising the following steps: The method for preparing the low-temperature resistant non-foaming polyurethane material comprises the following steps: S1. Preparation of component A: The polyether polyol a and the polyether polyol b are put into a reaction kettle, heated to 120°C, and vacuum is turned on to make the pressure reach -0.01MPa for dehydration for 2 hours, and then cooled to 60-80°C, and the remaining chain extender, antioxidant a, anti-yellowing agent a, anti-yellowing agent b, and catalyst are added, and stirred for 20 minutes under vacuum to obtain component A; S2. Preparation of component B: put the polyether polyol a, antioxidant b and inhibitor into a reaction kettle, heat to 120°C, turn on the vacuum at the same time, make the pressure reach -0.01MPa, dehydrate for 2 hours, then cool to 70°C, add isocyanate, keep vacuum, turn on stirring, react at 70°C for 2 hours, take samples for testing, and measure the mass content of NCO to be 16-17%, terminate the reaction, and obtain component B; S3. The components A and B are added to the casting machine tank and mixed; S4. Then, the mixed component A and component B are poured into a mold, and the two components are reacted and formed in the mold to obtain a low-temperature resistant non-foaming polyurethane material.

[0020] Furthermore, the preparation method of 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 vulcanizer with a vacuum function and an aluminum alloy mold. The preparation method includes adding the component A and the component B into a casting machine material tank, then mixing the component A and the component B and pouring them into the mold, pressing and aging to form, opening the mold for 5-6 minutes, and obtaining the shoe sole.

[0021] Furthermore, the mold temperature is 80-90° C., the material temperature: component A is 40-50° C., component B is 30-40° C., the pressure of the flat vulcanizing machine is 60-80 bar, and the vacuuming time is 20-30 s.

[0022] An application of the low-temperature resistant non-foaming polyurethane material is to prepare shoe soles or shock-absorbing blocks.

[0023] Compared with the prior art, the present invention has the following beneficial effects: 1. The present invention comprises a polyurethane material composed of a specific formula of component A and a specific formula of component B. At the same time, a specific polyether polyol is selected in component A, and a side chain group is added to increase the low-temperature flexibility of the molecular chain and reduce the low-temperature crystallization hardness of the polyether polyol, thereby greatly improving the low-temperature performance of the low-temperature resistant polyurethane material. At minus 20 degrees, the product has no shrinkage, little hardness change, and still maintains softness and good elasticity.

[0024] 2. The low-temperature resistant non-foaming polyurethane material of the present invention has increased rigidity, and its strength and wear resistance are greatly improved due to the use of DMTDA with a benzene ring.

[0025] 3. The low-temperature resistant non-foaming polyurethane material of the present invention has a higher friction coefficient on the surface than rubber materials due to the presence of side methyl groups in the molecular structure of the carbamate itself, and can be used as an anti-slip material.

[0026] 4. The low-temperature resistant polyurethane material of the present invention can meet the mold opening requirement of 5-6 minutes. Compared with the foaming material, the process is simple and the yield rate is high, which can save a lot of labor and reduce costs. Moreover, the product is stable and easy to produce. DETAILED DESCRIPTION

[0027] The present invention is further described below by way of examples, but they are not intended to limit the present invention. Example

[0028] A low-temperature resistant non-foaming polyurethane material is mixed by component A and component B, wherein: 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; 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; The mass ratio of component A to component B is 100:40. Example

[0029] Among them: Component A is composed of the following ingredients (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; 1 part of antioxidant a; Component B includes 50 parts of polyether polyol a, 50 parts of isocyanate, 0.1 parts of antioxidant b, and 0.03 parts of inhibitor; The mass ratio of component A to component B is 100:50. Example

[0030] A low-temperature resistant non-foaming polyurethane material is mixed by component A and component B, wherein: 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; 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; The mass ratio of component A to component B is 100:45.

[0031] According to the dosage in the above-mentioned embodiments 1-3, the low-temperature resistant non-foaming polyurethane material is prepared according to the preparation method of the low-temperature resistant non-foaming polyurethane material, which specifically includes the following steps: S1. Preparation of component A: The polyether polyol a and the polyether polyol b are put into a reaction kettle, heated to 120°C, and vacuum is turned on to make the pressure reach -0.01MPa for dehydration for 2 hours, and then cooled to 60-80°C, and the remaining chain extender, antioxidant a, anti-yellowing agent a, anti-yellowing agent b, and catalyst are added, and stirred for 20 minutes under vacuum to obtain component A; S2. Preparation of component B: put the polyether polyol a, antioxidant b and inhibitor into a reaction kettle, heat to 120°C, turn on the vacuum at the same time, make the pressure reach -0.01MPa, dehydrate for 2 hours, then cool to 70°C, add isocyanate, keep vacuum, turn on stirring, react at 70°C for 2 hours, take samples for testing, and measure the mass content of NCO to be 16-17%, terminate the reaction, and obtain component B; S3. The components A and B are added to the casting machine tank and mixed; S4. Then the mixed component A and component B are poured into the mold, and the two components are pressed and matured in the mold. The mold is opened after 5-6 minutes to obtain the sole. The equipment used for preparing the sole is a flat vulcanizer with a vacuum function and an aluminum alloy mold.

[0032] Among them: the mold temperature is 80-90℃, the material temperature: component A is 40-50℃, component B is 30-40℃, the pressure of the flat vulcanizer is 60-80bar, and the vacuum time is 20-30s.

[0033] The present invention is further described below by comparative examples, but they are not intended to limit the present invention.

[0034] Comparative Example 1 Among them: Component A is composed of (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; 1 part of antioxidant a; Component B includes 50 parts of polyether polyol a, 50 parts of isocyanate, 0.1 parts of antioxidant b, and 0.03 parts of inhibitor; The mass ratio of component A to component B is 100:50.

[0035] Comparative Example 2 A low-temperature resistant non-foaming polyurethane material is mixed by component A and component B, wherein: 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; 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; The mass ratio of component A to component B is 100:45.

[0036] Comparative Example 3 Among them: Component A is composed of ingredients (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; 1 part of antioxidant a; Component B includes 50 parts of polyether polyol a, 50 parts of isocyanate, 0.1 parts of antioxidant b, and 0.03 parts of inhibitor; The mass ratio of component A to component B is 100:50.

[0037] Comparative Example 4 Among them: Component A is composed of (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; 0.5 parts of antioxidant a; Component B includes 40 parts of polyether polyol a, 60 parts of isophorone diisocyanate (IPDI), 0.5 parts of antioxidant b, and 0.05 parts of inhibitor; The mass ratio of component A to component B is 100:40.

[0038] According to the dosage in the above comparative examples 1-4, a low-temperature resistant non-foaming polyurethane material is prepared according to the preparation method of the low-temperature resistant non-foaming polyurethane material, and the specific steps are the same as those in the embodiment: Comparative Example 5: The polyurethane slurry used by a domestic customer in shoe sole products was used.

[0039] The low-temperature resistant non-foaming polyurethane materials prepared in Examples 1-3 and Comparative Examples 1-5 and the polyurethane slurry in the comparative examples were prepared into soles of the same density and size, and their performance was tested. The test standard for hardness ASKER A is ASTM D2240; Density g / cm 3 The testing standard is ASTM D792; The testing standard for tensile MPa and elongation % is ASTM D412; DIE-C tear kgf / cm 2 The testing standard is ASTM D624; The test standard for Din wear resistance mm^3 is ASTM D5963; The testing standard for the number of bends is ASTM D1052; The testing standard for anti-slip (dry) and anti-slip (wet) is ASTM-F1677; Shrinkage was detected by hardness change and visual inspection; The test results are shown in the following table.

[0040]

[0041] It can be seen from the above table that the low-temperature resistant non-foaming polyurethane materials prepared in Examples 1-3 have excellent physical performance indicators at room temperature, but the hardness change of Examples 1-3 in low-temperature environments (0°C, -10°C and -20°C) is smaller than that in normal temperature environments (25°C), while the hardness changes of Comparative Examples 1-3 and Comparative Example 5 in low-temperature environments (0°C, -10°C and -20°C) are greater than that in normal temperature environments (25°C).

[0042] Compared with Comparative Example 4, although the hardness change of Comparative Example 4 in low temperature environment (0°C, -10°C and -20°C) is not much different from that in normal temperature environment (25°C), the tensile strength, elongation, DIE-C tearing, Din wear resistance and bending performance of Comparative Example 4 are much worse than those of the low-temperature resistant non-foamed polyurethane material prepared in Examples 1-3.

[0043] Compared with Comparative Example 3, the low-temperature resistant non-foaming polyurethane materials prepared in Examples 1-3 have good tear resistance.

[0044] Compared with Comparative Examples 1-5, the low-temperature resistant non-foaming polyurethane materials prepared in Examples 1-3 have better anti-slip properties.

[0045] Therefore, the use process of the low-temperature resistant non-foaming polyurethane material of the present invention is less affected by temperature, has excellent comprehensive performance, and can meet the requirements of use in sub-zero environments in the north.

[0046] The above description is only a preferred example of the present invention and is not any formal or substantial limitation to the present invention. All technical solutions under the concept of the present invention belong to the protection scope of the present invention. Any equivalent changes and modifications made to the above examples based on the essential technology of the present invention should also be regarded as the protection scope of the present invention.

Claims

1. A low temperature resistant non-foaming polyurethane material, characterized in that: The invention is composed of component A and component B. Calculated by weight, the 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; the component B comprises 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. The mass ratio of the component A to the component B is 100:40-50.

2. The low-temperature resistant non-foaming polyurethane material according to claim 1, characterized in that: The polyether polyol a is a branched polytetrahydrofuran copolymer diol obtained by polymerization of tetrahydrofuran and branched small molecule alcohol, and the weight of the branched small molecule alcohol accounts for 2-5% of the total weight of the tetrahydrofuran and the branched small molecule alcohol.

3. The low-temperature resistant non-foaming polyurethane material according to claim 2, characterized in that: The branched small molecule alcohol is a combination of one or more of 1,3-butanediol, 1,4-butanediol, 1,2-propylene glycol, neopentyl glycol, and 1,6-hexanediol.

4. The low-temperature resistant non-foaming polyurethane material according to claim 2, characterized in that: The functionality of the polyether polyol a is 2-2.1, and the hydroxyl value is 50-60 mgKOH / g.

5. The low-temperature resistant non-foaming polyurethane material according to claim 1, characterized in that: The isocyanate is a composition of 4,4-diphenylmethane diisocyanate and carbodiimide-modified MDI, wherein the weight of carbodiimide-modified MDI accounts for 7-10% of the total weight of the B component.

6. The low-temperature resistant non-foaming polyurethane material according to claim 1, characterized in that: The functionality of the polyether polyol b is 3, and the hydroxyl value is 25-30 mgKOH / g.

7. The method for preparing the low-temperature resistant non-foaming polyurethane material according to any one of claims 1 to 6, characterized in that: The preparation method comprises the following steps: S1. Preparation of component A: put the polyether polyol a and polyether polyol b into a reaction kettle, heat to 120°C, turn on the vacuum at the same time, make the pressure reach -0.01MPa, dehydrate for 2 hours, then cool to 60-80°C, add the remaining chain extender, antioxidant a, anti-yellowing agent a, anti-yellowing agent b, and catalyst, stir and mix for 20 minutes under vacuum to obtain component A; S2. Preparation of component B: put the polyether polyol a, antioxidant b and inhibitor into a reaction kettle, heat to 120°C, turn on the vacuum at the same time, make the pressure reach -0.01MPa, dehydrate for 2 hours, then cool to 70°C, add isocyanate, keep the vacuum, turn on the stirring, react at 70°C for 2 hours, take samples for testing, and measure the mass content of NCO to be 16-17%, end the reaction, and obtain component B; S3. The components A and B are added to the casting machine material tank and mixed; S4. Then, the mixed component A and component B are poured into a mold, and the two components are reacted and formed in the mold to obtain a low-temperature resistant non-foaming polyurethane material.

8. The method for preparing the low-temperature resistant non-foaming polyurethane material according to claim 7, characterized in that: The preparation method of the low-temperature resistant non-foaming polyurethane material is used to prepare a sole. The equipment used for preparing the sole is a flat vulcanizer with a vacuuming function and an aluminum alloy mold. The preparation method comprises adding the component A and the component B into a casting machine material tank, then mixing the component A and the component B and pouring them into a mold, pressing and aging to form, opening the mold for 5-6 minutes, and obtaining the sole.

9. The method for preparing the low-temperature resistant non-foaming polyurethane material according to claim 8, characterized in that: The mold temperature is 80-90°C, the material temperature: component A is 40-50°C, component B is 30-40°C, the pressure of the flat vulcanizing machine is 60-80bar, and the vacuum time is 20-30s.

10. Use of the low-temperature resistant non-foaming polyurethane material according to claims 1 to 6 in shoe soles or shock-absorbing blocks.

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