Polyurethane resin a and use thereof

Abstract

The application provides a polyurethane resin A material and application thereof, the polyurethane resin A material comprises a polyester polyol, an amine chain extender and a tertiary amine catalyst; the polyurethane resin A material comprises 2-8% of the amine chain extender and 0.5-1.5% of the tertiary amine catalyst in terms of mass percentage.The polyurethane resin A material provided by the application is compounded by a specific type of amine chain extender and a tertiary amine catalyst, so that the polyurethane resin A material has high reactivity in the presence of the catalyst for a long time, the polyurethane resin product has excellent performance, the production efficiency is improved, and the polyurethane resin A material is especially suitable for the production of transparent materials.

Description

Technical Field

[0001] This invention belongs to the field of polyurethane materials technology, specifically relating to a polyurethane resin A and its application. Background Technology

[0002] Traditional footwear polyurethane resin A mainly consists of polyester polyol components, small molecule alcohol chain extenders, catalysts, etc. To avoid catalyst deactivation, the polyester polyol components and small molecule alcohol chain extenders are premixed before production, and the catalyst is added when used, especially for tertiary amine catalysts.

[0003] For example, CN110885547A discloses a lightweight injection-molded shoe sole material and its processing technology. The shoe sole material formulation includes polyurethane, chain extender, foam stabilizer, foaming agent, lubricant, activated carbon powder, polyester polyol, isocyanate, and catalyst. The processing technology includes first preparing component A from polyurethane, chain extender, foam stabilizer, foaming agent, lubricant, and activated carbon powder; then reacting a portion of the polyester polyol with isocyanate to obtain component B; finally, mixing component A with the catalyst for a certain period of time, then adding component B and mixing evenly, followed by injection molding to obtain the shoe sole material. However, adding a catalyst externally not only affects the use but also the material properties.

[0004] CN109957092A discloses a solvent-free polyurethane interlayer resin, its preparation method, and its application in sports and leisure footwear. The polyurethane interlayer resin consists of component A and component B. Component A includes furan-modified polyether diol, polyether triol, chain extender, foaming agent, foam stabilizer, foaming catalyst, and gel catalyst. Component B consists of aliphatic triisocyanate, aromatic polyisocyanate, polyether diol, and N-(2-hydroxyethyl)maleimide. The preparation method of the resin includes: first reacting furan-modified polyether diol, polyether triol, chain extender, and foaming agent; then adding the catalyst; and finally mixing with component B to obtain the polyurethane resin. However, this method also requires adding a catalyst during use, which is inconvenient.

[0005] A common drawback of existing technologies is that polyurethane resins are produced by adding external catalysts, which greatly affects the ease of use, especially for the production of transparent materials. External addition also causes bubbles generated during stirring and moisture absorbed from the air to directly affect production efficiency and quality. On the other hand, polyurethane A material obtained by using internal catalysts cannot be stored for a long time.

[0006] Therefore, developing a polyurethane resin that can be internally added to a catalyst and retains high reactivity over a long period of time is an urgent problem to be solved in this field. Summary of the Invention

[0007] To address the shortcomings of existing technologies, the present invention aims to provide a polyurethane resin A material and its application. The polyurethane resin A material is compounded with an amine chain extender and a tertiary amine catalyst, which enables the polyurethane resin A material to maintain high reactivity even after long-term storage. Moreover, the catalyst is added only when not in use, making it convenient to use. The properties of the polyurethane resin including the polyurethane resin A material are also improved.

[0008] To achieve this objective, the present invention adopts the following technical solution:

[0009] In a first aspect, the present invention provides a polyurethane resin A material, wherein the polyurethane resin A material comprises a polymeric polyol, an amine chain extender and a tertiary amine catalyst; the polyurethane resin A material comprises 2-8% amine chain extender and 0.5-1.5% tertiary amine catalyst by mass percentage.

[0010] In this invention, by combining specific types and amounts of amine chain extenders and tertiary amine catalysts, the catalyst retains high catalytic activity even after long-term storage of the polyurethane resin A material, thereby improving product performance and making it convenient to use and highly efficient in production.

[0011] Preferably, the polyurethane resin A material comprises 2-8% amine chain extender by weight percentage, for example, 2.2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 5.8%, 6%, 6.4%, 6.8%, 7%, 7.2%, 7.4%, 7.8%, etc.

[0012] Preferably, the mass percentage of the tertiary amine catalyst is 0.5% to 1.5%, for example, it can be 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.45%, etc.

[0013] Preferably, the polymeric polyol comprises polyester polyol and / or polyether polyol.

[0014] Preferably, the polymer polyol content in the polyurethane resin A is 90-95% by mass, for example, it can be 91%, 92%, 93%, 94%, 95%, etc.

[0015] Preferably, the mass ratio of polymer polyol, amine chain extender and tertiary amine catalyst in the polyurethane resin A is (90-95):(2-8):(0.5-1.5), for example, it can be 90:8:0.5, 92:6:0.5, 94:4:0.5, 95:3:0.5, 94.5:3:1, 95:2:1.5, etc.

[0016] In this invention, when the mass ratio of polymer polyol, amine chain extender and tertiary amine catalyst in polyurethane resin A is less than 90:8:1.5, the early gelation is too fast and the hardness is too high; when it is greater than 95:2:0.5, the hardness is too low and the molding is too slow.

[0017] Preferably, the amine chain extender includes aromatic amine chain extenders.

[0018] Preferably, the aromatic amine chain extender includes any one or a combination of at least two of diethyltoluenediamine, 3,5-dimethylthiotoluenediamine, or 3,3′-dichloro-4,4′-diphenylmethanediamine.

[0019] In this invention, the amine chain extender selected is an aromatic amine chain extender, which can improve the shelf life of polyurethane resin A and has high catalytic activity. When an aliphatic amine chain extender is selected, the reaction activity is too fast and the reaction efficiency is difficult to control.

[0020] Preferably, the tertiary amine catalyst comprises any one or a combination of at least two of triethylenediamine, bis(dimethylaminoethyl) ether, or N,N-dimethylcyclohexylamine.

[0021] In this invention, the polyurethane resin A is prepared by the following method, which includes: mixing polyester polyol, amine chain extender and tertiary amine catalyst to obtain the polyurethane resin A.

[0022] In this invention, the polyurethane resin A containing the catalyst can be stored for a long time, and the catalyst does not become deactivated, so there is no need to add the catalyst when using it.

[0023] The polyurethane resin A material provided by this invention is compounded with polymer polyol, amine chain extender and tertiary amine catalyst, which enables the polyurethane A material to be stored for a long time without deactivation, and the resulting polyurethane finished product has moderate hardness, good processability, good tensile strength and hydrolysis resistance.

[0024] In this invention, when the polyurethane hardness is ≥70 Shore A, it is not conducive to processing.

[0025] In a second aspect, the present invention provides a polyurethane resin, the polyurethane resin comprising polyurethane resin component A and component B as described in the first aspect; the component B comprising a polyurethane prepolymer.

[0026] Preferably, the polyurethane resin comprises 50-70 parts of polyurethane resin A and 95-105 parts of polyurethane resin B by weight.

[0027] Preferably, the polyurethane resin comprises 50 to 70 parts by weight of polyurethane resin A, for example, 52 parts, 54 parts, 56 parts, 58 parts, 60 parts, 62 parts, 64 parts, 66 parts, 68 parts, etc.

[0028] Preferably, the polyurethane resin comprises 95 to 105 parts by weight of component B, for example, 96 parts, 97 parts, 98 parts, 99 parts, 100 parts, 101 parts, 102 parts, 103 parts, 104 parts, etc.

[0029] Preferably, the raw materials for the polyurethane prepolymer include polymeric polyols and polyisocyanates.

[0030] In this invention, the polyisocyanate refers to the polyisocyanate group having a number of ≥2.

[0031] In this invention, the polymer polyol refers to a polyol with ≥2 hydroxyl groups.

[0032] Preferably, the mass percentage of isocyanate groups (NCO) in the polyurethane prepolymer is 3-15%, for example, it can be 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, etc.

[0033] Preferably, the polymeric polyol comprises polyester polyol and / or polyether polyol.

[0034] Preferably, the polyurethane prepolymer is prepared by the following method, which includes reacting a polymeric polyol with a polyisocyanate to obtain the polyurethane prepolymer.

[0035] Preferably, the reaction temperature is 70-80°C, for example, 72°C, 74°C, 75°C, 76°C, 78°C, 80°C, etc.

[0036] Preferably, the reaction time is 2 to 5 hours, for example, 2 hours, 3 hours, 4 hours, 5 hours, etc.

[0037] Thirdly, the present invention provides a method for preparing the polyurethane resin according to the second aspect, the method comprising:

[0038] The polyurethane resin A and B are mixed and molded to obtain the polyurethane resin.

[0039] Preferably, the mixing temperature is 50-60°C, for example, 52°C, 54°C, 56°C, 58°C, etc.

[0040] Preferably, the mixing time is 1 to 2 seconds, for example, 1 second, 1.5 seconds, 2 seconds, etc.

[0041] Preferably, the molding method includes injection molding.

[0042] As a preferred technical solution of the present invention, the preparation method includes:

[0043] The polyurethane resin A and B are mixed at a temperature of 50-60°C for 1-2 seconds and then injection molded to obtain the polyurethane resin.

[0044] In this invention, the catalyst is added internally, so the polyurethane A material does not need to be degassed before mixing with the B material. However, when the catalyst is added externally, bubbles are easily generated and moisture from the air is absorbed during the mixing of polyurethane A material and the catalyst during the preparation of polyurethane. Therefore, vacuum degassed is required before mixing with the B material, which increases the cost and makes the process more complicated.

[0045] Fourthly, the present invention provides a sole material comprising polyurethane resin A as described in the first aspect and / or polyurethane resin as described in the second aspect.

[0046] The numerical range described in this invention includes not only the point values ​​listed above, but also any point values ​​within the numerical ranges not listed above. Due to space limitations and for the sake of brevity, this invention will not exhaustively list all the specific point values ​​included in the range.

[0047] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0048] The polyurethane resin A material provided by this invention, by selecting specific types and amounts of amine chain extenders and tertiary amine catalysts, ensures that the polyurethane A material still has high reactivity after being stored for 6 months, and the catalyst does not become deactivated, avoiding the need to add catalyst during use, making it convenient to use, with high production efficiency, and also improving the performance of the product. Detailed Implementation

[0049] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0050] The polyurethane prepolymers in the embodiments and comparative examples of this invention are prepared by the following method, which includes:

[0051] The polyurethane prepolymer was obtained by reacting the polymeric polyol with the polyisocyanate at 75°C for 2.5 h.

[0052] Example 1

[0053] This embodiment provides a polyurethane resin A, which, by weight, comprises 95 parts polyester polyol (Huafeng, 244 / 2000), 3 parts aromatic amine chain extender, and 0.5 parts triethylenediamine; the aromatic amine chain extender comprises diethyltoluenediamine and 3,3′-dichloro-4,4′-diphenylmethanediamine in a mass ratio of 1:1; the preparation method of the polyurethane resin A includes: mixing the polyester polyol, the aromatic amine chain extender, and the triethylenediamine to obtain the polyurethane resin A.

[0054] This embodiment provides a polyurethane resin, which includes 60 parts of polyurethane A material and 100 parts of polyurethane prepolymer. The raw materials of the polyurethane prepolymer include polyester polyol (Huafeng, 244 / 1000) and polyisocyanate (Wanhua, MDI).

[0055] This embodiment provides a method for preparing polyurethane resin, the specific steps of which include:

[0056] The polyurethane resin A and the polyurethane prepolymer are mixed evenly at 55°C and then injection molded to obtain the polyurethane resin.

[0057] Example 2

[0058] This embodiment provides a polyurethane resin A, which, by weight, comprises 94 parts polyester polyol (Huafeng, MX-706), 4 parts aromatic amine chain extender, and 0.5 parts triethylenediamine; the aromatic amine chain extender comprises diethyltoluenediamine and 3,3′-dichloro-4,4′-diphenylmethanediamine in a mass ratio of 1:1.5; the preparation method of the polyurethane resin A includes: mixing the polyester polyol, the aromatic amine chain extender, and the triethylenediamine to obtain the polyurethane resin A.

[0059] This embodiment provides a polyurethane resin comprising 55 parts of polyurethane A material and 100 parts of polyurethane prepolymer. The raw materials of the polyurethane prepolymer include polyether polyol (Dow 2000LM) and polyisocyanate (Wanhua, L-MDI).

[0060] This embodiment provides a method for preparing polyurethane resin, the specific steps of which include:

[0061] The polyurethane resin A and the polyurethane prepolymer are mixed evenly at 55°C and then injection molded to obtain the polyurethane resin.

[0062] Example 3

[0063] This embodiment provides a polyurethane resin A material, which comprises 95 parts of polyester polyol (Huafeng, MX-706), 3 parts of diethyltoluene diamine and 0.5 parts of bis(dimethylaminoethyl) ether; the preparation method of the polyurethane resin A material includes: mixing polyester polyol, diethyltoluene diamine and bis(dimethylaminoethyl) ether to obtain the polyurethane resin A material.

[0064] This embodiment provides a polyurethane resin, which includes 55 parts of polyurethane A material and 100 parts of polyurethane prepolymer. The raw materials of the polyurethane prepolymer include polyester polyol (Huafeng, MX-706) and polyisocyanate (Wanhua, MDI).

[0065] This embodiment provides a method for preparing polyurethane resin, the specific steps of which include:

[0066] The polyurethane resin A and the polyurethane prepolymer are mixed evenly at 55°C to obtain the polyurethane resin.

[0067] Example 4

[0068] This embodiment provides a polyurethane resin A material, which comprises 93 parts of polyester polyol (Huafeng, MX-2325), 4.5 parts of 3,3′-dichloro-4,4′-diphenylmethanediamine and 1 part of N,N-dimethylcyclohexylamine; the preparation method of the polyurethane resin A material is the same as that in Example 1.

[0069] This embodiment provides a polyurethane resin comprising 70 parts of polyurethane A material and 100 parts of polyurethane prepolymer. The raw materials of the polyurethane prepolymer include polyether polyol (Jiahua D220) and polyisocyanate (Wanhua, L-MDI).

[0070] This embodiment provides a method for preparing polyurethane resin, and the specific steps are the same as in Embodiment 1.

[0071] Example 5

[0072] This embodiment provides a polyurethane resin A material, which differs from Example 3 only in that diethyltoluene diamine is replaced with an equal amount of dimethyldiaminodicyclohexylmethane. The other raw materials, dosages, and preparation methods are the same as in Example 3.

[0073] This embodiment provides a polyurethane resin, which differs from Embodiment 3 only in that it uses polyurethane resin A provided in Embodiment 5, while the other raw materials, dosages and preparation methods are the same as in Embodiment 3.

[0074] Comparative Example 1

[0075] This comparative example provides a polyurethane resin A material, which differs from Example 3 only in that diethyltoluene diamine is replaced with the amount of ethylene glycol required to obtain the same product hardness. All other raw materials, amounts, and preparation methods are the same as in Example 3.

[0076] This comparative example provides a polyurethane resin, which differs from Example 3 only in that it uses polyurethane resin A provided in Comparative Example 1, while the other raw materials, amounts, and preparation methods are the same as in Example 3.

[0077] Comparative Example 2

[0078] This comparative example provides a polyurethane resin A, which differs from Example 3 only in that bis(dimethylaminoethyl) ether is replaced with an equal mass of stannous octoate. All other raw materials, amounts, and preparation methods are the same as in Example 3.

[0079] This comparative example provides a polyurethane resin, which differs from Example 3 only in that it uses polyurethane resin A provided in Comparative Example 2, while the other raw materials, amounts, and preparation methods are the same as in Example 3.

[0080] Comparative Example 3

[0081] This comparative example provides a polyurethane resin A material, which differs from Example 3 only in that the mass ratio of the polyester polyol, amine chain extender and tertiary amine catalyst is 88:10:0.5. The other raw materials, dosages and preparation methods are the same as in Example 3.

[0082] This comparative example provides a polyurethane resin, which differs from Example 3 only in that the polyurethane resin A provided in Comparative Example 3 is used, while the other raw materials, amounts and preparation methods are the same as in Example 3.

[0083] Comparative Example 4

[0084] This comparative example provides a polyurethane resin A material, which differs from Example 3 only in that the mass ratio of the polyester polyol, amine chain extender and tertiary amine catalyst is 95.5:1:2. The other raw materials, dosages and preparation methods are the same as in Example 3.

[0085] This comparative example provides a polyurethane resin, which differs from Example 3 only in that it uses polyurethane resin A provided in Comparative Example 4. The other raw materials, amounts, and preparation methods are the same as in Example 3.

[0086] Comparative Example 5

[0087] This comparative example provides a polyurethane A material, which differs from Example 3 only in that the polyurethane A material does not contain a catalyst, while the other raw materials, dosages, and preparation methods are the same as in Example 3.

[0088] This comparative example provides a polyurethane resin and its preparation method. The only difference between this example and Example 3 is that the preparation method includes: mixing the polyurethane A material with an equal amount of bis(dimethylaminoethyl) ether of the polyurethane resin provided in Example 3, degassing under vacuum, and then mixing it uniformly with the polyurethane prepolymer at 55°C to obtain the polyurethane resin.

[0089] Performance testing

[0090] (1) Reactivity: Polyurethane resin A and B provided in Examples 1-5 and Comparative Examples 1-4 were directly mixed. In Comparative Example 5, the catalyst was added to polyurethane resin A and then mixed with B. The curing time required to obtain the polyurethane finished product by injection molding was recorded as t1. After polyurethane resin A was stored for 6 months, polyurethane resin A and B provided in Examples 1-5 and Comparative Examples 1-4 were directly mixed. In Comparative Example 5, the catalyst was added to polyurethane resin A and then mixed with B. The curing time required to obtain the polyurethane finished product by injection molding was recorded as t2. If t2 does not exceed 20% of t1, it is marked as "qualified"; otherwise, it is "unqualified". "Qualified" is divided into "excellent", "good" and "average" according to the reactivity effect.

[0091] (2) Hardness: The JIS K6301 method was used for testing.

[0092] (3) Tensile strength: Tested according to GB / T 528 method.

[0093] (4) Hydrolysis resistance retention rate: After being placed at 70℃ and 95% humidity for 7 days, the ratio of the hydrolysis strength to the initial tensile strength is calculated.

[0094] The specific test results are shown in Table 1:

[0095] Table 1

[0096]

[0097] As shown in the table above, the polyurethane resin A material provided by the present invention, by selecting specific types and amounts of amine chain extenders and tertiary amine catalysts, ensures that the polyurethane A material still has high reactivity after being stored for 6 months, and the catalyst does not deactivate, avoiding the need to add catalyst during use, making it convenient to use, with high production efficiency, and also improving the performance of the product. As shown in Examples 1 to 4, the hardness of the polyurethane is 62 to 66A, the tensile strength is 19.6 to 25.2 MPa, and the hydrolysis resistance retention rate is 49.5 to 54.2%.

[0098] A comparison of Examples 1-4 with Example 5 and Comparative Examples 1-4 shows that, without the specific composition and proportions of this invention, the reactivity of polyurethane A material decreases, and the overall performance of the polyurethane is reduced. Furthermore, a comparison of Example 3 with Comparative Example 5 shows that even with the addition of an external catalyst, the polyurethane prepared in Comparative Example 5 exhibits only average overall performance.

[0099] In summary, the polyurethane resin A material provided by this invention, through the combination of amine chain extenders and tertiary amine catalysts, enables the catalyst to be internally added, meaning it does not need to be added during use, and it can be stored for a long time without deactivation, maintaining its reactivity, thus improving production efficiency and product performance.

[0100] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above descriptions are merely specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method of using polyurethane resin A, characterized in that, No catalyst is added when the polyurethane resin A is used. The polyurethane resin A is composed of polymeric polyol, amine chain extender and tertiary amine catalyst. The polyurethane resin A material does not lose its activity after being stored for 6 months. The mass ratio of polymer polyol, amine chain extender and tertiary amine catalyst in the polyurethane resin A is (90~95):(2~6):(0.5~1.5); The amine chain extender is an aromatic amine chain extender, and the aromatic amine chain extender is diethyltoluenediamine; The polymeric polyols include polyester polyols and / or polyether polyols.

2. The method of use according to claim 1, characterized in that, The tertiary amine catalyst includes triethylenediamine, bis(dimethylaminoethyl) ether, or... N,N - Any one or a combination of at least two of dimethylcyclohexylamine.

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