Organic silicon modified bio-based water-based self-extinction resin as well as preparation method and application thereof

Abstract

The invention relates to the technical field of matting resin, in particular to organic silicon modified bio-based water-based self-matting resin and a preparation method and application thereof.The organic silicon modified bio-based water-based self-matting resin is prepared from, by weight, 150-800 parts of bio-based polyol, 15-25 parts of hydroxypropyl-terminated polydimethylsiloxane, 100-350 parts of isocyanate, 15-50 parts of a hydrophilic chain extender and 10-30 parts of a small molecule alcohol chain extender, the preparation method comprises the following steps: adding 10-80 parts of a micromolecular amine chain extender, 10-40 parts of a salt-forming agent, 0.5-2 parts of a catalyst and 700-3000 parts of water; by optimizing the selection and matching of the raw materials in the system and controlling the addition amount, the solvent resistance, stability and application effect of the product are effectively improved while the self-extinction effect is ensured, and the actual application requirements are better met.

Description

Technical Field

[0001] This invention relates to the field of matting resin technology, specifically to an organosilicon-modified bio-based waterborne self-matting resin, its preparation method, and its application. Background Technology

[0002] Waterborne polyurethane is widely used in coatings, adhesives, and leather finishing due to its advantages such as environmental friendliness, safety, and adjustable performance. However, traditional waterborne polyurethane still has several problems in high-end decorative applications: to achieve a matte effect, matting agents are usually added, which can easily lead to decreased transparency, rough feel, and poor gloss stability; its comprehensive performance, such as wear resistance, water resistance, and weather resistance, needs further improvement; some formulations contain sulfur impurities, which can easily cause oxidation and discoloration of the metal layer in subsequent high-temperature processes such as hot stamping, affecting the decorative effect; and it has a high dependence on petroleum-based raw materials, which is not in line with the trend of sustainable development. Currently available acrylic resins or ordinary waterborne polyurethane products often cannot simultaneously achieve matting, high toughness, workability, and subsequent processing stability. For example, Chinese patent (authorization announcement number CN 110183611 B) discloses a waterborne polyurethane self-matting resin and its preparation method, as well as a printing paste, which mainly obtains a low-gloss, solvent-free, and flexurally resistant printing paste by optimizing the system, but the toughness, stability, and application performance of the product need further improvement. Summary of the Invention

[0003] To address the aforementioned issues, this invention provides an organosilicon-modified bio-based waterborne self-matting resin. By optimizing the selection and combination of raw materials in the system and controlling their addition amounts, the self-matting effect is ensured while effectively improving the product's solvent resistance, stability, and application performance, thus better meeting practical application needs.

[0004] This invention provides an organosilicon-modified bio-based waterborne self-matting resin, comprising the following components by weight: 150-800 parts of bio-based polyol, 15-25 parts of hydroxypropyl-terminated polydimethylsiloxane, 100-350 parts of isocyanate, 15-50 parts of hydrophilic chain extender, 10-30 parts of small molecule alcohol chain extender, 10-80 parts of small molecule amine chain extender, 10-40 parts of salt-forming agent, 0.5-2 parts of catalyst, and 700-3000 parts of water.

[0005] In one embodiment, the organosilicon-modified bio-based waterborne self-matting resin comprises, by weight, the following components: 500-600 parts of bio-based polyol, 18-20 parts of hydroxypropyl-terminated polydimethylsiloxane, 250-300 parts of isocyanate, 30-35 parts of hydrophilic chain extender, 15-20 parts of small molecule alcohol chain extender, 40-50 parts of small molecule amine chain extender, 15-20 parts of salt-forming agent, 0.8-1 part of catalyst, and 2800-2954 parts of water.

[0006] In one embodiment, the bio-based polyol includes at least one of castor oil polyol, soybean oil polyol, cashew nut shell oil polyol, or polylactic acid polyol.

[0007] In one embodiment, the bio-based polyol has a weight-average molecular weight of 600 to 3000.

[0008] In one embodiment, the bio-based polyol has a weight-average molecular weight of 1000-2000.

[0009] In one embodiment, the bio-based polyol is polylactic acid polyol, the polylactic acid polyol has a weight-average molecular weight of 2000, is model PLA 2000, and is sourced from Anhui Fengyuan Group Co., Ltd.

[0010] In one embodiment, the hydroxypropyl-terminated polydimethylsiloxane has a viscosity of 50-120 cSt at 25°C.

[0011] In one embodiment, the hydroxypropyl-terminated polydimethylsiloxane is designated SS2119 and is sourced from Hubei Shishun Biotechnology Co., Ltd.

[0012] In one embodiment, the isocyanate comprises isophorone diisocyanate (IPDI).

[0013] In one embodiment, the hydrophilic chain extender includes at least one of a carboxylic acid hydrophilic chain extender or a sulfonic acid hydrophilic chain extender.

[0014] In one embodiment, the carboxylic acid hydrophilic chain extender includes at least one of 2,2-dimethylolpropionic acid or 2,2-dimethylolbutyric acid.

[0015] In one embodiment, the sulfonic acid hydrophilic chain extender includes sodium ethylenediamine ethanesulfonate.

[0016] In one embodiment, the small molecule alcohol chain extender includes at least one of polytetrahydrofurandiol, 1,4-butanediol, or neopentyl glycol.

[0017] In one embodiment, the small molecule amine chain extender includes at least one of ethylenediamine, hexamethylenediamine, or isophoronediamine.

[0018] In one embodiment, the salt-forming agent includes triethylamine or N,N-dimethylethanolamine.

[0019] In one embodiment, the catalyst comprises organic bismuth.

[0020] In one embodiment, the organic bismuth comprises bismuth isooctanoate.

[0021] This invention utilizes polylactic acid polyol with a weight-average molecular weight of 1000-2000 as the main soft segment. Its long-chain structure, after amine chain extension, helps to form a large-particle-size and uniformly distributed emulsion. During film formation, the large-particle latex particles stack on the film surface to form a micro-rough structure, which diffuses light, thereby achieving a stable bulk matting effect. Furthermore, the gloss is insensitive to film thickness and application dilution.

[0022] Furthermore, this invention modifies the product by introducing hydroxypropyl-terminated polydimethylsiloxane, combined with specific isocyanates, hydrophilic chain extenders, small molecule alcohol chain extenders, and small molecule amine chain extenders, resulting in a product with excellent durability. The inventors believe the reason may be that the hard segments formed by the chain extension of IPDI with ethylenediamine are rich in urethane bonds and highly polar urea bonds, providing high cohesive energy and mechanical strength. The hydroxypropyl-terminated polydimethylsiloxane is chemically bonded to the polymer chain, and after film formation, it migrates to the surface, forming a low surface energy, highly lubricating organosilicon protective layer. These two elements synergistically impart excellent wear resistance to the coating. The hydrophobicity of the polylactic acid polyol itself, the polymer network structure, and the surface-enriched organosilicon layer together constitute an effective barrier, preventing the penetration and erosion of water molecules and chemical media. The alicyclic structure of IPDI has excellent photostability, and the high bond energy of the organosilicon segments (Si-O bonds) provides resistance to ultraviolet radiation and thermal oxidation, jointly ensuring that the coating does not discolor or chalk over long-term use.

[0023] The main soft segment of the product provided by this invention uses renewable polylactic acid polyol, which reduces the product's carbon footprint. It is a sulfur-free system with excellent environmental friendliness and processing stability, thus expanding the product's application range.

[0024] Another aspect of the present invention provides a method for preparing an organosilicon-modified bio-based waterborne self-matting resin, comprising the following steps: The prepolymer was obtained by vacuum dehydration of bio-based polyol and prepolymerization reaction with hydroxypropyl-terminated polydimethylsiloxane, isocyanate and catalyst. The prepolymer is subjected to a hydrophilic chain extension reaction with a hydrophilic chain extender and a small molecule alcohol chain extender to obtain the reactant; The reactants were neutralized with a salting agent and then dispersed in water. A small molecule amine chain extender was added to carry out a post-chain extension reaction. The resulting product was obtained by vacuum distillation and was an organosilicon-modified bio-based waterborne self-matting resin.

[0025] In one embodiment, the vacuum dehydration treatment conditions include: a temperature of 100-110℃, a vacuum pressure of -0.099~-0.08MPa, a time of 2-3h, and vacuum dehydration treatment until the moisture content is <0.02%.

[0026] In one embodiment, the conditions for the prepolymerization reaction include: inert gas protection, reaction at 70-85°C for 2-3 hours.

[0027] In one embodiment, the conditions for the hydrophilic chain extension reaction include: reacting at 60-65°C for 1-1.5 hours.

[0028] In one embodiment, the conditions for the neutralization reaction include: reacting at 25-30°C for 0.5-1 h.

[0029] In one embodiment, the conditions for the post-chain extension reaction include: reacting at 20-40°C for 0.5-1 h.

[0030] This invention optimizes the formulation and controls the process conditions to obtain a product with moderate viscosity, excellent coating leveling properties, and storage stability.

[0031] The third aspect of this invention provides an application of an organosilicon-modified bio-based waterborne self-matting resin, which is used in the preparation of printing inks, leather finishing agents, wood coatings, plastic coatings, industrial topcoats, and adhesives.

[0032] Beneficial effects 1. This invention provides an organosilicon-modified bio-based waterborne self-matting resin. By optimizing the selection and combination of raw materials in the system and controlling the amount added, the self-matting effect is guaranteed while effectively improving the solvent resistance, stability and application effect of the product, thus better meeting the needs of practical applications.

[0033] 2. This invention uses polylactic acid polyol with a weight-average molecular weight of 1000-2000 as the main soft segment. Its long-chain structure, after amine chain extension, helps to form a large-particle-size and uniformly distributed emulsion. During film formation, the large-particle latex particles stack on the film surface to form a micro-rough structure, which produces diffuse reflection of light, thereby achieving a stable bulk matting effect. Moreover, the gloss is not sensitive to film thickness and dilution during application.

[0034] 3. This invention modifies the product by introducing hydroxypropyl-terminated polydimethylsiloxane, and combines it with specific isocyanates, hydrophilic chain extenders, small molecule alcohol chain extenders and small molecule amine chain extenders, so that the provided product has excellent durability.

[0035] 4. The main soft segment of the product provided by this invention uses renewable polylactic acid polyol, which reduces the carbon footprint of the product. It is a sulfur-free system with excellent environmental protection and processing stability, and expands the application range of the product.

[0036] 5. By optimizing the formula and controlling the process conditions, this invention achieves a product with moderate viscosity and excellent coating leveling and storage stability. Detailed Implementation

[0037] Example 1 Example 1 of the present invention provides an organosilicon-modified bio-based waterborne self-matting resin, the formulation of which is shown in Table 1 by weight.

[0038] Table 1

[0039] Example 1 of the present invention provides a method for preparing an organosilicon-modified bio-based waterborne self-matting resin, comprising the following steps: (1) After vacuum dehydration of bio-based polyol, it is prepolymerized with hydroxypropyl-terminated polydimethylsiloxane, isocyanate and catalyst to obtain prepolymer; (2) The prepolymer is subjected to a hydrophilic chain extender and a small molecule alcohol chain extender to obtain the reactants; (3) After neutralizing the reactants with the salting agent, the reactants are dispersed in water, and a small molecule amine chain extender is added to carry out a post-chain extension reaction. The organosilicon-modified bio-based waterborne self-masking resin is obtained by vacuum distillation.

[0040] The conditions for the vacuum dehydration treatment include: a temperature of 110℃, a vacuum pressure of -0.099MPa, a time of 2h, and vacuum dehydration treatment until the moisture content is <0.02%.

[0041] The conditions for the prepolymerization reaction include: inert gas protection, reaction at 80°C for 3 hours.

[0042] The conditions for the hydrophilic chain extension reaction include: reaction at 60°C for 1 hour.

[0043] The conditions for the neutralization reaction include: reaction at 30°C for 0.5 h.

[0044] The conditions for the post-chain extension reaction include: reaction at 30°C for 1 hour.

[0045] Example 2 Example 2 of the present invention provides an organosilicon-modified bio-based waterborne self-masking resin and its preparation method. The specific implementation method is the same as that of Example 1, except that step (1) is replaced by vacuum dehydration of bio-based polyol and reaction with isocyanate and catalyst at 75°C for 2 hours, followed by addition of hydroxypropyl-terminated polydimethylsiloxane and reaction at 75°C for 1 hour to obtain a prepolymer.

[0046] Comparative Example 1 Comparative Example 1 of the present invention provides an organosilicon-modified bio-based waterborne self-matting resin and its preparation method. The specific implementation method is the same as that of Example 1, except that the polylactic acid polyol PLA 2000 is replaced with polytetrahydrofuran ether diol PTMEG-2000.

[0047] Comparative Example 2 Comparative Example 2 of the present invention provides an organosilicon-modified bio-based waterborne self-matting resin and its preparation method. The specific implementation method is the same as that of Example 1, except that the isophorone diisocyanate (300 parts by weight) is replaced with dicyclohexylmethane diisocyanate (350 parts by weight, CAS No. 5124-30-1).

[0048] Comparative Example 3 Comparative Example 3 of the present invention provides an organosilicon-modified bio-based waterborne self-matting resin and its preparation method. The specific implementation method is the same as that of Example 1, except that the polytetrahydrofuran diol is replaced with trimethylolpropane.

[0049] Performance testing The products provided in each embodiment and comparative example were subjected to the tests listed in Table 2, and the test results are shown in Table 3.

[0050] Table 2

[0051] Table 3

[0052] Analysis of the data in Table 3 shows that Examples 1-2 have better overall performance than Comparative Examples 1-3, with Example 1 providing the best overall performance.

Claims

1. A silicone-modified bio-based waterborne self-matting resin, characterized in that, The product comprises, by weight, the following components: 150-800 parts of bio-based polyol, 15-25 parts of hydroxypropyl-terminated polydimethylsiloxane, 100-350 parts of isocyanate, 15-50 parts of hydrophilic chain extender, 10-30 parts of small molecule alcohol chain extender, 10-80 parts of small molecule amine chain extender, 10-40 parts of salt-forming agent, 0.5-2 parts of catalyst, and 700-3000 parts of water; wherein the bio-based polyol includes at least one of castor oil polyol, soybean oil polyol, cashew nut shell oil polyol, or polylactic acid polyol.

2. The waterborne self-matting resin according to claim 1, characterized in that, The weight-average molecular weight of the bio-based polyol is 600-3000.

3. The waterborne self-matting resin according to claim 1, characterized in that, The isocyanate includes isophorone diisocyanate.

4. The waterborne self-matting resin according to claim 1, characterized in that, The small molecule alcohol chain extender includes at least one of polytetrahydrofurandiol, 1,4-butanediol, or neopentyl glycol.

5. The waterborne self-matting resin according to claim 1, characterized in that, The hydrophilic chain extender includes at least one of carboxylic acid hydrophilic chain extenders or sulfonic acid hydrophilic chain extenders.

6. The waterborne self-matting resin according to claim 5, characterized in that, The carboxylic acid hydrophilic chain extender includes at least one of 2,2-dihydroxymethylpropionic acid or 2,2-dihydroxymethylbutyric acid.

7. The waterborne self-matting resin according to claim 1, characterized in that, The small molecule amine chain extender includes at least one of ethylenediamine, hexamethylenediamine, or isophoronediamine.

8. The waterborne self-matting resin according to claim 1, characterized in that, The salt-forming agent includes triethylamine or N,N-dimethylethanolamine.

9. A method for preparing a self-matting resin according to any one of claims 1-8, characterized in that, Includes the following steps: The prepolymer was obtained by vacuum dehydration of bio-based polyol and prepolymerization reaction with hydroxypropyl-terminated polydimethylsiloxane, isocyanate and catalyst. The prepolymer is subjected to a hydrophilic chain extension reaction with a hydrophilic chain extender and a small molecule alcohol chain extender to obtain the reactant; The reactants were neutralized with a salting agent and then dispersed in water. A small molecule amine chain extender was added to carry out a post-chain extension reaction. The resulting product was obtained by vacuum distillation and was an organosilicon-modified bio-based waterborne self-matting resin.

10. An application of the waterborne self-matting resin according to any one of claims 1-8, characterized in that, It is used in the preparation of printing inks, leather finishing agents, wood coatings, plastic coatings, industrial topcoats, and adhesives.

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