Modified organic silicon leveling agent containing bio-based polyurethane and preparation method of modified organic silicon leveling agent

Abstract

The invention relates to a preparation method of a bio-based polyurethane-containing modified organic silicon flatting agent, which comprises the following steps: reacting a T-type organic silicon monomer, benzene ring-containing polyester polyol and bio-based diisocyanate to obtain an isocyanate-terminated prepolymer, and then carrying out chain extension reaction by using bio-based dihydric alcohol to obtain the bio-based polyurethane-containing modified organic silicon flatting agent. The bio-based polyurethane modified flatting agent with certain viscosity is obtained; according to the invention, the organic silicon leveling agent is modified by bio-based polyurethane, so that an organic silicon chain segment extends towards the outer side, the surface is endowed with good hand feeling, wear resistance and other properties, the compatibility of organic silicon and a polyurethane system can be effectively improved, the polyurethane resin system is transparent and uniform, and good leveling property is obtained.

Description

Technical Field

[0001] The invention belongs to the field of fine chemicals and relates to a leveling agent and a preparation method thereof, in particular to a bio-based polyurethane-modified organic silicon leveling agent and a preparation method thereof. Background Art

[0002] Leveling agents are usually used in coatings, synthetic leather and other fields to effectively reduce the surface energy of resins and improve the leveling and uniformity of resins. In the field of synthetic leather, polyurethane resins are widely used, especially in dry and wet synthetic leathers, because of their good film-forming properties. Considering the cost issues and the requirements for resin strength, most polyurethane resins in dry and wet synthetic leathers are synthesized by polyester polyol reactions; in order to improve the feel, wear resistance, and anti-sticking requirements of synthetic leather, a certain amount of silicone additives will be added in the synthetic leather processing process by physical mixing. Due to the poor compatibility of silicone and polyester resins, simple mixing can easily cause silicone additives to float on the surface of the resin system and fail to be effectively dispersed in the system, resulting in problems such as reduced gloss, whitening, and reduced skin-friendly feel on the surface of the finished product, which seriously affects the downstream processing of the finished product. At the same time, most of the leveling agents on the market are based on compounds synthesized from petrochemical raw materials. Focusing on the concepts of green, environmental protection, and low carbon, the development of bio-based leveling agents urgently needs to be studied and created. Summary of the invention

[0003] The purpose of the present invention is to solve the above problems and provide a method for preparing a bio-based polyurethane modified organic silicon leveling agent.

[0004] Another object of the present invention is to provide a bio-based polyurethane modified silicone leveling agent in order to solve the above problems.

[0005] The present invention creatively proposes a method for preparing a bio-based polyurethane-modified organosilicon leveling agent, comprising the following steps:

[0006] The T-type silicone monomer, the benzene ring-containing polyester polyol and the bio-based diisocyanate are reacted to obtain a terminal isocyanate prepolymer, and then the bio-based diol is used for chain extension reaction to obtain a bio-based polyurethane-modified leveling agent with a certain viscosity;

[0007] The structural formula of the T-type organosilicon monomer is as follows:

[0008]

[0009] In the above-mentioned method for preparing a bio-based polyurethane-modified organosilicon leveling agent, an organic bismuth catalyst is added during the reaction of T-shaped organosilicon monomer, benzene ring-containing polyester polyol and bio-based diisocyanate;

[0010] In the above-mentioned method for preparing a bio-based polyurethane-modified organosilicon leveling agent, the mass of the organic bismuth catalyst is 0.05-0.4% of the mass of the benzene ring-containing polyester polyol.

[0011] In the above-mentioned method for preparing a bio-based polyurethane-modified organosilicon leveling agent, the T-type organosilicon monomer and the benzene ring-containing polyester polyol are first heated to 100-110° C. in a reaction container, vacuum dehydrated for 1-2 hours, then cooled to 50-60° C., bio-based diisocyanate is added, stirred continuously, and under the protection of an inert gas atmosphere, the organic bismuth catalyst is added for catalysis, and the temperature is raised to 75-80° C. for reaction for 2-3 hours;

[0012] After the reaction is completed, the temperature is lowered to 50-60°C and stirred continuously. Under the protection of an inert gas atmosphere, bio-based diol is added and the temperature is raised to 75-80°C for reaction for 1-2 hours to obtain a bio-based polyurethane-modified leveling agent with a certain viscosity.

[0013] In the above-mentioned method for preparing a bio-based polyurethane-modified silicone leveling agent, the molar ratio of the T-shaped silicone monomer, the benzene ring-containing polyester polyol, the bio-based diisocyanate and the bio-based diol is 1-1.4:0.6-1:1.8-2.2:1-1.5.

[0014] In the above-mentioned method for preparing a bio-based polyurethane-modified organosilicon leveling agent, the average molecular weight of the T-type organosilicon monomer is 1000-2000.

[0015] In the above-mentioned method for preparing a bio-based polyurethane-modified organosilicon leveling agent, the benzene ring-containing polyester polyol includes at least one of polyethylene isophthalate diol and poly(1,6-hexanediol isophthalate diol).

[0016] In the above-mentioned method for preparing a bio-based polyurethane-modified organosilicon leveling agent, the bio-based diisocyanate includes pentamethylene diisocyanate.

[0017] In the above-mentioned method for preparing a bio-based polyurethane-modified organosilicon leveling agent, the bio-based diol includes at least one of 1,3-propylene glycol, 1,4-butanediol, and 1,2-pentanediol.

[0018] The present invention creatively proposes a bio-based polyurethane-modified organic silicon leveling agent, which is prepared by the above method.

[0019] The present invention uses bio-based polyurethane to modify the organosilicon leveling agent so that the organosilicon chain segments extend outward, giving the surface good hand feel, wear resistance and other properties. The benzene ring and the carbonyl group are affinity with the polyurethane resin through chemical bonds, i.e., the large π bond of the benzene ring, or van der Waals forces based on the "like dissolves like" principle. Compared with physical mixing, the compatibility of the organosilicon and the polyurethane system can be effectively improved, and the polyurethane resin system is transparent and uniform, and good leveling properties are obtained.

[0020] The invention relates to a bio-based polyurethane-modified organic silicon leveling agent which can be used for improving the processing and finishing of dry and wet synthetic leather.

[0021] Compared with the prior art, the invention has a simple structure, simple synthesis operation, material selection and recycling, significant effect, and is green and environmentally friendly. DETAILED DESCRIPTION

[0022] Further described by the following specific examples;

[0023] The present invention will be further described below in conjunction with specific examples, and it should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope limited by the appended claims of the application.

[0024] Example 1

[0025] 150g of T-type silicone monomer 8822 selected from Guangzhou Siloke Polymer Co., Ltd. and 100g of benzene ring-containing polyester polyol PD-110LV with a molecular weight of 1000 were first heated to 100°C in a reaction container, vacuum dehydrated for 1 hour, then cooled to 50-60°C, 36g of pentamethylene diisocyanate was added, and stirring was continued. Under the protection of nitrogen atmosphere, 0.2g of organic bismuth catalyst was added for catalysis, and the temperature was raised to 75-80°C for reaction for 2 hours;

[0026] After the reaction is completed, the temperature is lowered to 50-60° C. and stirring is continued. Under the protection of nitrogen atmosphere, 7.6 g of 1,3-propylene glycol is added, and the temperature is raised to 75-80° C. for reaction for 1 hour to obtain a bio-based polyurethane modified leveling agent.

[0027] Example 2

[0028] 150g of T-type silicone monomer 8822 selected from Guangzhou Siloke Polymer Co., Ltd. and 160g of benzene ring-containing polyester polyol PD-70LV with a molecular weight of 1600 were first heated to 100°C in a reaction container, vacuum dehydrated for 1 hour, then cooled to 50-60°C, 38g of pentamethylene diisocyanate was added, and stirring was continued. Under the protection of nitrogen atmosphere, 0.2g of organic bismuth catalyst was added for catalysis, and the temperature was raised to 75-80°C for reaction for 2 hours;

[0029] After the reaction is completed, the temperature is lowered to 50-60° C. and stirring is continued. Under the protection of nitrogen atmosphere, 7.6 g of 1,3-propylene glycol is added, and the temperature is raised to 75-80° C. for reaction for 1 hour to obtain a bio-based polyurethane modified leveling agent.

[0030] Example 3

[0031] 150g of T-type silicone monomer 8822 selected from Guangzhou Siloke Polymer Co., Ltd. and 200g of benzene ring-containing polyester polyol PD-56LV with a molecular weight of 2000 were first heated to 100°C in a reaction container, vacuum dehydrated for 1 hour, then cooled to 50-60°C, 38g of pentamethylene diisocyanate was added, and stirring was continued. Under the protection of nitrogen atmosphere, 0.2g of organic bismuth catalyst was added for catalysis, and the temperature was raised to 75-80°C for reaction for 3 hours;

[0032] After the reaction is completed, the temperature is lowered to 50-60°C and stirred continuously. Under the protection of nitrogen atmosphere, 7.6 g of 1,3-propylene glycol is added and the temperature is raised to 75-80°C for reaction for 2 hours to obtain a bio-based polyurethane-modified leveling agent with a certain viscosity.

[0033] Example 4

[0034] 200g of T-type silicone monomer 8822 selected from Guangzhou Siloke Polymer Co., Ltd. and 100g of benzene ring-containing polyester polyol PD-110LV with a molecular weight of 1000 were first heated to 100°C in a reaction container, vacuum dehydrated for 1 hour, then cooled to 50-60°C, 38g of pentamethylene diisocyanate was added, and stirring was continued. Under the protection of nitrogen atmosphere, 0.2g of organic bismuth catalyst was added for catalysis, and the temperature was raised to 75-80°C for reaction for 3 hours;

[0035] After the reaction is completed, the temperature is lowered to 50-60°C and stirred continuously. Under the protection of nitrogen atmosphere, 10.4 g of 1,2-pentanediol is added and the temperature is raised to 75-80°C for reaction for 2 hours to obtain a bio-based polyurethane-modified leveling agent with a certain viscosity.

[0036] Example 5

[0037] 200g of T-type silicone monomer 8822 selected from Guangzhou Siloke Polymer Co., Ltd. and 160g of benzene ring-containing polyester polyol PD-70LV with a molecular weight of 1600 were first heated to 100°C in a reaction container, vacuum dehydrated for 1 hour, then cooled to 50-60°C, 38g of pentamethylene diisocyanate was added, and stirring was continued. Under the protection of nitrogen atmosphere, 0.2g of organic bismuth catalyst was added for catalysis, and the temperature was raised to 75-80°C for reaction for 3 hours;

[0038] After the reaction is completed, the temperature is lowered to 50-60°C and stirred continuously. Under the protection of nitrogen atmosphere, 10.4 g of 1,2-pentanediol is added and the temperature is raised to 75-80°C for reaction for 2 hours to obtain a bio-based polyurethane-modified leveling agent with a certain viscosity.

[0039] Comparative Example

[0040] (1) 150 g of T-type silicone monomer 8822, 100 g of benzene ring-containing polyester polyol PD-110LV with a molecular weight of 1000 and 7.6 g of 1,3-propylene glycol were added to a reaction vessel, and the temperature was raised to 50-60° C. and stirred continuously and fully under nitrogen atmosphere protection;

[0041] (2) cooling to room temperature to obtain the product of the comparative example;

[0042] Performance Comparison

[0043] The products obtained in Examples 1 to 5 and the comparative example were added to the polyurethane resin in an amount of 1 wt % of the polyurethane resin. After stirring evenly, the transparency and leveling performance of the polyurethane resin mixed system were compared. The results are shown in Table 1:

[0044] Table 1 Experimental results of various embodiments and comparative examples

[0045]

[0046] As can be seen from the above table, the comparative example is a mixture of various unreacted monomers, which is added to the polyurethane resin and shows that the transparency and leveling are worse than those of the blank polyurethane resin; Examples 1-5 are uniform substances bridged by chemical reactions of silicone monomers, benzene ring-containing polyester polyols, bio-based isocyanates, and bio-based small molecule alcohols. After comparison, they all have better performance than the blank polyurethane resin and the comparative example.

[0047] The unmodified control ratio cannot fuse the silicone monomer with the polyurethane resin. After the modification reaction technology, the compatibility of the polyurethane resin can be effectively improved, the processing effect of the polyurethane resin can be solved, abnormal phenomena such as stratification and whitening can be prevented, and the surface coating appearance of the synthetic leather can be improved; at the same time, the selection of raw materials conforms to the environmental protection concept of green chemical industry and low-carbon chemical industry, and promotes the sustainable development of synthetic leather processing technology.

[0048] The specific embodiments described herein are merely examples of the spirit of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in similar ways, but they will not deviate from the spirit of the present invention or exceed the scope defined by the appended claims.

[0049] Although the terms such as T-type silicone monomer, benzene ring-containing polyester polyol, bio-based diisocyanate, isocyanate-terminated prepolymer, bio-based diol, and organic bismuth catalyst are frequently used in this article, these terms are used only to more conveniently describe and explain the essence of the present invention, and interpreting them as any additional limitations is contrary to the spirit of the present invention.

Claims

1. A method for preparing a bio-based polyurethane-modified organosilicon leveling agent, characterized in that: The following steps are involved: The T-type silicone monomer, the benzene ring-containing polyester polyol and the bio-based diisocyanate are reacted to obtain a terminal isocyanate prepolymer, and then a bio-based diol is used for chain extension reaction to obtain a bio-based polyurethane-modified leveling agent; The structural formula of the T-type organosilicon monomer is as follows:

2. The method for preparing a bio-based polyurethane-modified organosilicon leveling agent according to claim 1, characterized in that: An organic bismuth catalyst is added during the reaction of T-type silicone monomer, benzene ring-containing polyester polyol and bio-based diisocyanate.

3. The method for preparing a bio-based polyurethane-modified organosilicon leveling agent according to claim 2, characterized in that: The mass of the organic bismuth catalyst is 0.05-0.4% of the mass of the benzene ring-containing polyester polyol.

4. The method for preparing a bio-based polyurethane-modified organosilicon leveling agent according to claim 1, characterized in that: The T-type silicone monomer and the benzene ring-containing polyester polyol are first heated to 100-110° C. in a reaction container, vacuum-dehydrated, then cooled to 50-60° C., bio-based diisocyanate is added, stirred continuously, and under the protection of an inert gas atmosphere, the organic bismuth catalyst is added for catalysis, and the temperature is raised to 75-80° C. for reaction; After the reaction is completed, the temperature is lowered to 50-60°C and stirred continuously. Under the protection of an inert gas atmosphere, bio-based diol is added and the temperature is raised to 75-80°C for reaction to obtain a bio-based polyurethane-modified leveling agent with a certain viscosity.

5. The method for preparing a bio-based polyurethane-modified organosilicon leveling agent according to claim 4, characterized in that: The molar ratio of the T-shaped silicone monomer, the benzene ring-containing polyester polyol, the bio-based diisocyanate and the bio-based diol is 1-1.4:0.6-1:1.8-2.2:1-1.

5.

6. The method for preparing a bio-based polyurethane-modified organosilicon leveling agent according to claim 1, characterized in that: The average molecular weight of the T-type silicone monomer is 1000-2000.

7. The method for preparing a bio-based polyurethane-modified organosilicon leveling agent according to claim 1, characterized in that: The benzene ring-containing polyester polyol includes at least one of polyethylene isophthalate diol and polyhexanediol isophthalate diol.

8. The method for preparing a bio-based polyurethane-modified organosilicon leveling agent according to claim 1, characterized in that: The bio-based diisocyanate includes pentamethylene diisocyanate.

9. The method for preparing a bio-based polyurethane-modified organosilicon leveling agent according to claim 1, characterized in that: The bio-based diol includes at least one of 1,3-propylene glycol, 1,4-butanediol, and 1,2-pentanediol.

10. A bio-based polyurethane-modified organosilicon leveling agent prepared by the method according to any one of claims 1 to 9.

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