Acid value regulator composition for waterborne polyurethane as well as preparation method and application of acid value regulator composition

Abstract

The invention discloses an acid value regulator composition for waterborne polyurethane, a preparation method and application, and belongs to the technical field of waterborne polyurethane preparation.According to the acid value regulator composition for the waterborne polyurethane, protons in organic alcohol are removed through environment-friendly high-valence metal ions; according to the preparation method, a reaction system is extremely strong in acidity, the obtained alkoxy metal salt is extremely easy to dissolve in water, alkoxy of the alkoxy metal salt has good compatibility with imino groups and carbon chains in polyurethane molecules, high-valence metal ions and a prepared-NCO-terminated polyurethane prepolymer can interact to form a coordination bond to a certain degree, and the reaction system is extremely strong in acidity; a special buffer system constructed by the alkoxy metal salt and hydrogen ions removed from alcohol has a good effect of adjusting the pH value of polyurethane, and the mechanical property of the polyurethane synthetic leather is improved.

Description

Technical Field

[0001] The invention relates to the technical field of waterborne polyurethane preparation, and in particular to an acid value regulator composition for waterborne polyurethane, a preparation method and application thereof. Background Art

[0002] During the preparation process, polymer materials have different pH values ​​due to different preparation methods. This has a certain impact on the performance and environmental requirements of the product. At present, although inorganic acids (sulfuric acid, hydrochloric acid, phosphoric acid, etc.) and organic acids (such as acetic acid, glutaric acid, adipic acid, etc.) are used to adjust the acid value of the polymer system, the effects of both are not ideal, and the dosage is large, the cost is high, it is highly corrosive to metal equipment, and it also has a certain impact on the performance of the finished product. The existing preparation methods of water-based polyurethane all adopt the alkaline production method, and some of the thickeners added are also alkaline, which makes the products obtained during the processing of polyurethane alkaline. Summary of the invention

[0003] In order to solve the above technical problems, the present invention provides an acid value regulator composition for waterborne polyurethane, a preparation method and application thereof. The acid value regulator for waterborne polyurethane of the present invention has a good effect in regulating the acid value of polymer polyurethane, and has a small amount of use, is environmentally friendly, non-corrosive and helps to improve the mechanical properties of polyurethane. The contents of the present invention are as follows: The first object of the present invention is to provide an acid value regulator composition for waterborne polyurethane, the technical point of which is that it includes alcohol substances, M2 (SO4) n ·XH2O and catalyst, the alcohol and M2(SO4) n The molar mass ratio of XH2O is (2-3): (1-2), and the mass of the catalyst is alcohol and M2 (SO4) n 0.1-5% of the total mass of XH2O, wherein M is a high-valent metal element, 2≤n≤7, n is a natural number, and X is a natural number.

[0004] In order to better realize the above technical scheme, the alcohol substance in the acid value regulator composition for water-based polyurethane of the present invention is any one of C2~C16 diols and their isomers, triols (such as glycerol), tetraols (such as pentaerythritol) and pentaols (such as xylitol).

[0005] In order to better realize the above technical scheme, the C2-C16 diol in the acid value regulator composition for waterborne polyurethane of the present invention is any one of 1,3-propylene glycol and 1,4-butylene glycol.

[0006] In order to better realize the above technical solution, the M2 (SO4) in the acid value regulator composition for waterborne polyurethane of the present invention is nIn XH2O, M is any one of Al, Zr, Fe, Ti, Sn, Ce, Sb, Bi, La and Mn.

[0007] In order to better realize the above technical solution, the M2 (SO4) in the acid value regulator composition for waterborne polyurethane of the present invention is n In XH2O, M is any one of Al, Zr and Fe.

[0008] In order to better realize the above technical scheme, the catalyst in the acid value regulator composition for waterborne polyurethane of the present invention is sodium benzenesulfonate and isomers of its homologues.

[0009] The second object of the present invention is to provide a method for preparing an acid value regulator for waterborne polyurethane, the technical point of which is that it comprises the following steps: Step 1, accurately weighing an alcohol substance, M2(SO4)n·XH2O and a catalyst and placing them in a reactor to obtain a mixture; Step 2: Grind the mixture in step 1 for 8-12 minutes and then dissolve it with DMF and a small amount of water to obtain the acid value regulator for waterborne polyurethane.

[0010] The third object of the present invention is to provide an application of an acid value regulator for waterborne polyurethane, the technical point of which is that it is used for regulating the pH in waterborne polyurethane.

[0011] To better implement the above technical solution, the application of the acid value regulator for waterborne polyurethane of the present invention includes the following steps: adding 0.5-4wt% of the acid value regulator for waterborne polyurethane to the waterborne polyurethane and stirring at 2000rmp for 5-10min to obtain a waterborne polyurethane slurry.

[0012] Compared with the prior art, the acid value regulator composition for waterborne polyurethane, the preparation method and the application of the present invention can achieve the following beneficial effects: The acid value regulator for waterborne polyurethane of the present invention uses high-valent metal ions required for environmental protection to remove protons in organic alcohol, so that the reaction system is extremely acidic, and the obtained alkoxy metal salt is extremely soluble in water, and the alkoxy group thereof has good compatibility with the imino group and the carbon chain in the polyurethane molecule. The high-valent metal ions interact with the prepared terminal-NCO polyurethane prepolymer to form a certain degree of coordination bond, so that the special buffer system constructed by the alkoxy metal salt and the hydrogen ions removed from the alcohol has a good effect of regulating the pH value of the polyurethane, and improves the mechanical properties of the polyurethane synthetic leather.

[0013] The acid value regulator for waterborne polyurethane of the present invention is prepared by reacting alcohols and M2 (SO4) under the catalytic action of a surfactant. nIt is prepared by solid phase synthesis reaction at room temperature of XH2O. Its process is simple and easy, has no pollution to the environment, embodies the advantages of green production, and has low production cost.

[0014] The acid value regulator for waterborne polyurethane of the present invention is simple to use and does not require other treatment. It can be directly dissolved in DMF and a small amount of water and then added to the polyurethane resin to adjust the pH value of the polyurethane processing system. DETAILED DESCRIPTION

[0015] In order to make the purpose, technical solution and advantages of the present invention clearer, the technical solution of the present invention will be clearly and completely described below in conjunction with the specific embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention. Example 1

[0016] An acid value regulator composition for waterborne polyurethane includes alcohol substances, M2 (SO4) n ·XH2O and catalyst, the alcohol and M2(SO4) n The molar mass ratio of XH2O is 2:1, and the mass of the catalyst is alcohol and M2 (SO4) n 0.5% of the total mass of XH2O, where M is a high-valent metal element, 2≤n≤7, n is a natural number, and X is a natural number.

[0017] Furthermore, the alcohol substance in the acid value regulator composition for water-based polyurethane of this embodiment is 1,3-propylene glycol.

[0018] Furthermore, the M2 (SO4) in the acid value regulator composition for water-based polyurethane of this embodiment n In XH2O, M is Zr.

[0019] Furthermore, the catalyst in the acid value regulator composition for waterborne polyurethane of this embodiment is sodium benzenesulfonate and isomers of its homologues.

[0020] According to the above formula, a method for preparing an acid value regulator for waterborne polyurethane in this embodiment comprises the following steps: Step 1, accurately weighing an alcohol substance, M2(SO4)n·XH2O and a catalyst and placing them in a reactor to obtain a mixture; Step 2: Grind the mixture in step 1 for 10 minutes and then dissolve it with DMF and a small amount of water to obtain the acid value regulator for waterborne polyurethane.

[0021] The acid value regulator for water-based polyurethane of this embodiment is used to adjust the pH value in water-based polyurethane.

[0022] Furthermore, the application of the acid value regulator for waterborne polyurethane in this embodiment includes the following steps: adding 0.5-4 wt % of the acid value regulator for waterborne polyurethane into the waterborne polyurethane and stirring at 2000 rpm for 7.5 min to obtain a waterborne polyurethane slurry. Example 2

[0023] An acid value regulator composition for waterborne polyurethane includes alcohol substances, M2 (SO4) n ·XH2O and catalyst, the alcohol and M2(SO4) n The molar mass ratio of XH2O is 3:2, and the mass of the catalyst is alcohol and M2 (SO4) n 0.5% of the total mass of XH2O, where M is a high-valent metal element, 2≤n≤7, n is a natural number, and X is a natural number.

[0024] Furthermore, the alcohol substance in the acid value regulator composition for water-based polyurethane of this embodiment is 1,3-propylene glycol.

[0025] Furthermore, the M2 (SO4) in the acid value regulator composition for water-based polyurethane of this embodiment n In XH2O, M is Zr.

[0026] Furthermore, the catalyst in the acid value regulator composition for waterborne polyurethane of this embodiment is sodium benzenesulfonate and isomers of its homologues.

[0027] According to the above formula, a method for preparing an acid value regulator for waterborne polyurethane in this embodiment comprises the following steps: Step 1, accurately weighing an alcohol substance, M2(SO4)n·XH2O and a catalyst and placing them in a reactor to obtain a mixture; Step 2: Grind the mixture in step 1 for 8 minutes and then dissolve it with DMF and a small amount of water to obtain the acid value regulator for waterborne polyurethane.

[0028] The acid value regulator for water-based polyurethane of this embodiment is used to adjust the pH value in water-based polyurethane.

[0029] Furthermore, the application of the acid value regulator for waterborne polyurethane in this embodiment includes the following steps: adding 0.5-4 wt % of the acid value regulator for waterborne polyurethane into the waterborne polyurethane and stirring at 2000 rpm for 5 min to obtain a waterborne polyurethane slurry. Example 3

[0030] An acid value regulator composition for waterborne polyurethane includes alcohol substances, M2 (SO4) n·XH2O and catalyst, the alcohol and M2(SO4) n The molar mass ratio of XH2O is 3:2, and the mass of the catalyst is alcohol and M2 (SO4) n 0.5% of the total mass of XH2O, where M is a high-valent metal element, 2≤n≤7, n is a natural number, and X is a natural number.

[0031] Furthermore, the alcohol substance in the acid value regulator composition for water-based polyurethane of this embodiment is 1,3-propylene glycol.

[0032] Furthermore, the M2 (SO4) in the acid value regulator composition for water-based polyurethane of this embodiment n In XH2O, M is Al.

[0033] Furthermore, the catalyst in the acid value regulator composition for waterborne polyurethane of this embodiment is sodium benzenesulfonate and isomers of its homologues.

[0034] According to the above formula, a method for preparing an acid value regulator for waterborne polyurethane in this embodiment comprises the following steps: Step 1, accurately weighing an alcohol substance, M2(SO4)n·XH2O and a catalyst and placing them in a reactor to obtain a mixture; Step 2: Grind the mixture in step 1 for 12 minutes and then dissolve it with DMF and a small amount of water to obtain the acid value regulator for waterborne polyurethane.

[0035] The acid value regulator for water-based polyurethane of this embodiment is used to adjust the pH value in water-based polyurethane.

[0036] Furthermore, the application of the acid value regulator for waterborne polyurethane in this embodiment includes the following steps: adding 0.5-4 wt % of the acid value regulator for waterborne polyurethane into the waterborne polyurethane and stirring at 2000 rpm for 10 min to obtain a waterborne polyurethane slurry. Example 4

[0037] An acid value regulator composition for waterborne polyurethane includes alcohol substances, M2 (SO4) n ·XH2O and catalyst, the alcohol and M2(SO4) n The molar mass ratio of XH2O is 2:1, and the mass of the catalyst is alcohol and M2 (SO4) n 0.5% of the total mass of XH2O, where M is a high-valent metal element, 2≤n≤7, n is a natural number, and X is a natural number.

[0038] Furthermore, the alcohol substance in the acid value regulator composition for water-based polyurethane of this embodiment is 1,4-butanediol.

[0039] Furthermore, the M2 (SO4) in the acid value regulator composition for water-based polyurethane of this embodiment n In XH2O, M is Zr.

[0040] Furthermore, the catalyst in the acid value regulator composition for waterborne polyurethane of this embodiment is sodium benzenesulfonate and isomers of its homologues.

[0041] According to the above formula, a method for preparing an acid value regulator for waterborne polyurethane in this embodiment comprises the following steps: Step 1, accurately weighing an alcohol substance, M2(SO4)n·XH2O and a catalyst and placing them in a reactor to obtain a mixture; Step 2: Grind the mixture in step 1 for 10 minutes and then dissolve it with DMF and a small amount of water to obtain the acid value regulator for waterborne polyurethane.

[0042] The acid value regulator for water-based polyurethane of this embodiment is used to adjust the pH value in water-based polyurethane.

[0043] Furthermore, the application of the acid value regulator for waterborne polyurethane in this embodiment includes the following steps: adding 0.5-4 wt % of the acid value regulator for waterborne polyurethane into the waterborne polyurethane and stirring at 2000 rpm for 7.5 min to obtain a waterborne polyurethane slurry. Example 5

[0044] An acid value regulator composition for waterborne polyurethane includes alcohol substances, M2 (SO4) n ·XH2O and catalyst, the alcohol and M2(SO4) n The molar mass ratio of XH2O is 3:2, and the mass of the catalyst is alcohol and M2 (SO4) n 0.5% of the total mass of XH2O, where M is a high-valent metal element, 2≤n≤7, n is a natural number, and X is a natural number.

[0045] Furthermore, the alcohol substance in the acid value regulator composition for water-based polyurethane of this embodiment is 1,4-butanediol.

[0046] Furthermore, the M2 (SO4) in the acid value regulator composition for water-based polyurethane of this embodiment n In XH2O, M is Fe.

[0047] Furthermore, the catalyst in the acid value regulator composition for waterborne polyurethane of this embodiment is sodium benzenesulfonate and isomers of its homologues.

[0048] According to the above formula, a method for preparing an acid value regulator for waterborne polyurethane in this embodiment comprises the following steps: Step 1, accurately weighing an alcohol substance, M2(SO4)n·XH2O and a catalyst and placing them in a reactor to obtain a mixture; Step 2: Grind the mixture in step 1 for 8-12 minutes and then dissolve it with DMF and a small amount of water to obtain the acid value regulator for waterborne polyurethane.

[0049] The acid value regulator for water-based polyurethane of this embodiment is used to adjust the pH value in water-based polyurethane.

[0050] Furthermore, the application of the acid value regulator for waterborne polyurethane in this embodiment includes the following steps: adding 0.5-4 wt % of the acid value regulator for waterborne polyurethane into the waterborne polyurethane and stirring at 2000 rpm for 5 min to obtain a waterborne polyurethane slurry. Example 6

[0051] An acid value regulator composition for waterborne polyurethane includes alcohol substances, M2 (SO4) n ·XH2O and catalyst, the alcohol and M2(SO4) n The molar mass ratio of XH2O is 3:2, and the mass of the catalyst is alcohol and M2 (SO4) n 0.5% of the total mass of XH2O, where M is a high-valent metal element, 2≤n≤7, n is a natural number, and X is a natural number.

[0052] Furthermore, the alcohol substance in the acid value regulator composition for water-based polyurethane of this embodiment is any one of 1,3-propylene glycol and 1,4-butylene glycol.

[0053] Furthermore, the M2 (SO4) in the acid value regulator composition for water-based polyurethane of this embodiment n In XH2O, M is Al.

[0054] Furthermore, the catalyst in the acid value regulator composition for waterborne polyurethane of this embodiment is sodium benzenesulfonate and isomers of its homologues.

[0055] According to the above formula, a method for preparing an acid value regulator for waterborne polyurethane in this embodiment comprises the following steps: Step 1, accurately weighing an alcohol substance, M2(SO4)n·XH2O and a catalyst and placing them in a reactor to obtain a mixture; Step 2: Grind the mixture in step 1 for 8-12 minutes and then dissolve it with DMF and a small amount of water to obtain the acid value regulator for waterborne polyurethane.

[0056] The acid value regulator for water-based polyurethane of this embodiment is used to adjust the pH value in water-based polyurethane.

[0057] Furthermore, the application of the acid value regulator for waterborne polyurethane in this embodiment includes the following steps: adding 0.5-4 wt % of the acid value regulator for waterborne polyurethane into the waterborne polyurethane and stirring at 2000 rpm for 10 min to obtain a waterborne polyurethane slurry.

[0058] Test example In the fixed modulus polyurethane preparation formula (polyurethane 100 parts, DMF 100, calcium powder 50, wood powder 25, colorant 2), 0.5-4% of acid value regulator (calculated as sulfate) was added to make bass, and the results of acid value and peel strength test were shown in Table 1. Among them, pH>7.5 was unqualified.

[0059] Table 1

[0060] From the above table, it can be seen that the acid value regulator product obtained by this method improves the mechanical properties of polyurethane processing and can meet the national standards for polyurethane plastic products. All raw materials can be used without waste, which is green and environmentally friendly. The acid value regulator product has good compatibility with polyurethane.

[0061] The above description is only an embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent substitution, improvement, etc. made within the spirit and principle of the present invention should be included in the scope of the claims of the present invention.

Claims

1. An acid value regulator composition for waterborne polyurethane, characterized in that: Including alcohols, M2 (SO4) n ·XH2O and catalyst, the alcohol and M2(SO4) n The molar mass ratio of XH2O is (2-3): (1-2), and the mass of the catalyst is alcohol and M2 (SO4) n 0.1-5% of the total mass of XH2O, wherein M is a high-valent metal element, 2≤n≤7, n is a natural number, and X is a natural number.

2. The acid value regulator composition for waterborne polyurethane according to claim 1, characterized in that: The alcohol substance is any one of C2-C16 diols and their isomers, triols, tetraols and pentaols.

3. The acid value regulator composition for waterborne polyurethane according to claim 2, characterized in that: The C2-C16 diol is any one of 1,3-propylene glycol and 1,4-butylene glycol.

4. The acid value regulator composition for waterborne polyurethane according to claim 1, characterized in that: The M2 (SO4) n In XH2O, M is any one of Al, Zr, Fe, Ti, Sn, Ce, Sb, Bi, La and Mn.

5. The acid value regulator composition for waterborne polyurethane according to claim 4, characterized in that: The M2 (SO4) n In XH2O, M is any one of Al, Zr and Fe.

6. The acid value regulator composition for waterborne polyurethane according to claim 1, characterized in that: The catalyst is sodium benzenesulfonate and isomers of its homologues.

7. A method for preparing an acid value regulator for waterborne polyurethane, characterized in that: The following steps are involved: Step 1, accurately weighing an alcohol substance, M2(SO4)n·XH2O and a catalyst and placing them in a reactor to obtain a mixture; Step 2: Grind the mixture in step 1 for 8-12 minutes and then dissolve it with DMF and a small amount of water to obtain the acid value regulator for waterborne polyurethane.

8. An application of an acid value regulator for waterborne polyurethane, characterized in that: Used to adjust the pH in waterborne polyurethane.

9. The use of an acid value regulator for waterborne polyurethane according to claim 8, characterized in that: The method comprises the following steps: adding DMF, calcium powder, wood powder, colorant and 0.5-4 wt% of an acid value regulator for water-based polyurethane into water-based polyurethane, and stirring at a speed of 2000 rpm for 5-10 minutes to obtain water-based polyurethane slurry.

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