CN118530457B - A carrier material with sustained-release function and its preparation method and application - Google Patents

Abstract

The present invention belongs to the technical field of carrier materials, and in particular, relates to a carrier material with a sustained-release function, a preparation method thereof and an application thereof. The carrier material with a sustained-release function is prepared from the following components by weight: 100 parts of silicate, 5 to 10 parts of acid solution, 3 to 10 parts of organosilicon monomer, and 3 to 5 parts of terminal amino polyether. The carrier material of the present invention is porous and can be used as a sustained-release functional carrier. The polycondensation reaction of the silanol produced by the hydrolysis of silicate forms a mesoporous material with silicon as a skeleton, thereby having a sustained-release effect; the long-term effect of the functional additive can be improved, and the slow release of sensitive coating components can be controlled by the protective effect of the mesopores; the pore size is adjustable, and the slow-release speed is adjustable: by adjusting the hydrophilicity and hydrophobicity of the polyether, that is, adjusting the amount of water combined with the polyether, thereby adjusting the pore size, and then adjusting the speed of the release of the functional substance; through inorganic-organic hybridization, the compatibility with the coating functional additive is good.

Description

A carrier material with sustained-release function and its preparation method and application

Technical Field

The present invention belongs to the technical field of carrier materials, and in particular relates to a carrier material with a sustained-release function and a preparation method and application thereof.

Background Art

In the chemical industry, functional additives play an important role to meet the diverse needs of various fields. For example, commonly used functional additives such as antifouling agents, defoaming agents, and corrosion inhibitors can play functional roles such as antifouling, defoaming, and corrosion inhibition. However, the action time of these functional additives is limited, that is to say, the long-term effectiveness of these functional additives needs to be improved. However, in the field of shipbuilding, the long-term effectiveness of antifouling is required to be relatively high, and the heavy corrosion protection field also has high requirements for the long-term effectiveness of anticorrosion. The long-term effectiveness of functional additives is related to the storage period and cost-effectiveness of the coating. Therefore, from the perspective of long-term effectiveness, it is particularly important to improve the long-term effectiveness of functional additives.

Summary of the invention

In view of the above deficiencies in the prior art, the object of the present invention is to provide a carrier material with sustained-release function and a preparation method and application thereof.

To achieve the above objectives, the technical solutions adopted are:

One of the purposes of the present invention is to provide a carrier material with a sustained-release function, comprising one or more of the following structures:

Wherein, R is a C ₄ ~C ₁₀ aliphatic epoxy group, R' is an aliphatic polyether group, and n≥1.

further,

;

Among them, 1≤x≤30, 1≤y≤10.

Going further, x=19, y=3.

Furthermore, the carrier material is prepared from the following components in parts by weight: 100 parts of silicate, 5-10 parts of acid solution, 3-10 parts of organosilicon monomer, and 3-5 parts of amino-terminated polyether.

The second object of the present invention is to provide a method for preparing the above-mentioned carrier material, comprising the following steps:

(1) Preparation of silica sol: Silicate ester is placed in a reaction vessel, and an acid solution is added under stirring. After hydrolysis, a transparent solution is obtained. After the alcohol by-products are removed by filtration, a silicate hydrolyzate is obtained. The hydrolyzate contains both the orthosilicic acid generated by the first step of the reaction, which contains four silanol groups, and the high-polymerized silicic acid formed by the continued condensation reaction, which is the silica sol.

The mechanism is:

Step 1: Hydrolysis reaction

;

Step 2: Condensation reaction

;

(2) Hybridization modification of silica sol: premix part of the silicate hydrolyzate obtained in step (1) with an organosilicon monomer to obtain a premix of silicate hydrolyzate and organosilicon monomer with a silicate hydrolyzate content of 2-10%, heat the remaining silicate hydrolyzate in step (1) to 40-60° C., dropwise add the premix under stirring, and react for 4-6 hours to complete the hybridization modification of silica sol, thereby obtaining a hybrid modified silica sol;

The reactions involved include:

Hydrolysis of silicone monomer:

;

Taking 3-(2,3-epoxypropoxy)propyltrimethoxysilane as an example, R ₁ is -CH ₃ , R ₂ is -OCH ₃ , and R ₂ ' is -OH;

Coupling agent polycondensation:

;

;

The coupling agent reacts with the hydroxyl groups on the surface of silica sol particles:

;

(3) Hydrophilic modification of hybrid silica sol: slowly drop a terminal amine polyether containing 10-50 wt% of an organosilicon monomer into the hybrid modified silica sol in step (2) under stirring. After the dropwise addition is completed, the reaction temperature and reaction time are controlled under stirring to obtain a hydrophilic modified hybrid silica sol, which is a carrier material with a sustained release function. The reaction mechanism is an amidation condensation reaction of silanol and amine groups, and a polyether is introduced into the side chain. Taking JEFFAMINE® M-1000 polyetheramine as an example:

;

Furthermore, the silicate is ethyl orthosilicate, and the acid solution is a hydrochloric acid aqueous solution or a sulfuric acid aqueous solution.

Furthermore, the organosilicon monomer in steps (2) and (3) is a silane coupling agent containing an epoxy functional group.

Furthermore, the organic silicon monomers in steps (2) and (3) are each independently selected from at least one of 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 3-(2,3-epoxypropoxy)propylmethyldimethoxysilane and 3-(2,3-epoxypropoxy)propylmethyldiethoxysilane.

Furthermore, the reaction time of step (3) is 2-2.5 h, and the reaction temperature is 50-55 °C.

Furthermore, the amine-terminated polyether is M600 or M1000.

The third object of the present invention is to provide an application of the above-mentioned carrier material in the field of coatings.

The invention provides a composite material with a sustained-release function, comprising a carrier material with a sustained-release function and a functional auxiliary agent, wherein the mass ratio of the functional auxiliary agent to the carrier material with a sustained-release function is 1:0.5-4.

The method for preparing the sustained-release functional composite material comprises the following steps:

Under stirring, add the functional auxiliary agent that needs to be sustained-released to the carrier material with sustained-release function, then adjust the pH value to neutral with an alkaline solution to form a gel; crush the wet gel, place it in a 60-80°C oven for drying, and pass it through a 1000-1250 mesh sieve after crushing to obtain a 1000-1250 mesh sustained-release functional composite material.

Furthermore, the functional auxiliary agent is one of an antifouling agent and a defoaming agent.

Furthermore, the alkaline solution is an aqueous ammonia solution or an aqueous sodium hydroxide solution.

The present invention also provides a slow-release antifouling composition, which comprises the following components in parts by weight: 15-18 parts of acrylic copolymer, 9-13 parts of rosin resin, 0.5-1 part of polyamide wax, 40-50 parts of cuprous oxide, 4-6 parts of zinc oxide, 7-9 parts of iron oxide red powder, 13-15 parts of solvent, and 4-6 parts of a composite of an antifouling agent and a carrier material with a slow-release function.

Furthermore, the sustained-release antifouling composition comprises the following components in parts by weight: 15 parts of acrylic copolymer, 10 parts of rosin resin, 1 part of polyamide wax, 40 parts of cuprous oxide, 4 parts of zinc oxide, 9 parts of iron oxide red powder, 15 parts of solvent, and 6 parts of a composite of an antifouling agent and a carrier material having a sustained-release function.

Furthermore, in the composite of the antifouling agent and the carrier material with a sustained-release function, the mass ratio of the antifouling agent to the carrier material with a sustained-release function is 1:0.5-2.

Furthermore, the solvent is at least one of xylene and butyl acetate.

The present invention also provides a slow-release anti-rust composition, which comprises the following components in parts by weight: 40-50 parts of an aqueous epoxy dispersion, 0.5-2 parts of fumed silica, 14-18 parts of barium sulfate, 3-5 parts of talc, 0.5-1 part of a dispersant, 0.5-1 part of a defoamer, 15-18 parts of deionized water, 8-10 parts of a composite of a rust inhibitor and a slow-release carrier, and 12-15 parts of a polyamine curing agent.

Furthermore, the slow-release anti-rust composition comprises the following components by weight: 40 parts of aqueous epoxy dispersion, 0.5 parts of fumed silica, 15 parts of barium sulfate, 5 parts of talc, 1 part of dispersant, 1 part of defoamer, 18 parts of deionized water, 10 parts of a complex of a rust inhibitor and a slow-release carrier, and 15 parts of a polyamine curing agent.

Furthermore, the rust inhibitor and the sustained-release carrier composite is obtained by compounding the rust inhibitor and the carrier material with sustained-release function in a mass ratio of 1:0.5-4.

Compared with the prior art, the present invention has the following beneficial effects:

1. Porous, can be used as a sustained-release functional carrier, through the polycondensation reaction of silanol produced by silicate hydrolysis, to form a mesoporous material with silicon as the skeleton, thus having a sustained-release effect.

2. It can improve the long-term effectiveness of functional additives and control the slow release of sensitive coating components through the protective effect of mesopores.

3. Adjustable pore size and adjustable sustained release speed: By adjusting the hydrophilicity and hydrophobicity of the polyether, that is, adjusting the amount of water bound to the polyether, the pore size is adjusted, and then the speed of release of the functional substance is adjusted.

4. Inorganic-organic hybridization, good compatibility with coating functional additives: Contains organic ingredients, which can be well compatible with organic film-forming resins and play a better role.

DETAILED DESCRIPTION

The present invention is described below in conjunction with examples, which are only used to explain the present invention and are not used to limit the scope of the present invention.

"Parts" in all examples are parts by weight.

1. Carrier material

Example 1

(1) Place 100 parts of tetraethyl orthosilicate in a reaction kettle, add 5 parts of a 5% sulfuric acid aqueous solution under stirring, stir at 100 r/min for 25 min, hydrolyze to obtain a transparent silica sol solution, remove the alcohol by-product by suction, and obtain a silicate hydrolyzate;

(2) Premixing part of the silicate hydrolyzate obtained in step (1) with 3-(2,3-epoxypropoxy)propyltrimethoxysilane to obtain a premix of silicate hydrolyzate and 3-(2,3-epoxypropoxy)propyltrimethoxysilane with a silicate hydrolyzate content of 5%, heating the remaining silicate hydrolyzate in step (1) to 50° C., adding 5 parts of the premix at a speed of 150 r/min, and reacting for 4 hours to obtain a hybrid modified silica sol;

(3) At a speed of 200 r/min, 3 parts of terminal amino polyether (M-1000) containing 10 wt% of 3-(2,3-epoxypropoxy)propyltrimethoxysilane were slowly added dropwise to the above hybrid modified silica sol. After the addition was completed, the mixture was reacted for 2 h under stirring and heat preservation. The temperature was controlled at 50-55 °C during the whole process to obtain a hydrophilic modified hybrid silica sol, which is a carrier material with sustained release function.

Example 2

(1) Place 100 parts of tetraethyl orthosilicate in a reaction kettle, add 5 parts of a 5% sulfuric acid aqueous solution under stirring, stir at 100 r/min for 25 min, hydrolyze to obtain a transparent silica sol solution, remove the alcohol by-product by suction, and obtain a silicate hydrolyzate;

(2) Premixing part of the silicate hydrolyzate obtained in step (1) with 3-(2,3-epoxypropoxy)propyltrimethoxysilane to obtain a premix of silicate hydrolyzate and 3-(2,3-epoxypropoxy)propyltrimethoxysilane with a silicate hydrolyzate content of 5%, heating the remaining silicate hydrolyzate in step (1) to 50° C., adding 5 parts of the premix at a speed of 150 r/min, and reacting for 4 hours to obtain a hybrid modified silica sol;

(3) At a speed of 200 r/min, 5 parts of terminal amino polyether (M-1000) containing 10 wt% of 3-(2,3-epoxypropoxy)propyltrimethoxysilane were slowly added dropwise to the above hybrid modified silica sol. After the addition was completed, the mixture was reacted for 2 h under stirring and heat preservation. The temperature was controlled at 50-55 °C during the whole process to obtain a hydrophilic modified hybrid silica sol, which is a carrier material with sustained release function.

Example 3

(1) Place 100 parts of tetraethyl orthosilicate in a reaction kettle, add 5 parts of a 5% sulfuric acid aqueous solution under stirring, stir at 100 r/min for 25 min, hydrolyze to obtain a transparent silica sol solution, remove the alcohol by-product by suction, and obtain a silicate hydrolyzate;

(2) Premixing part of the silicate hydrolyzate obtained in step (1) with 3-(2,3-epoxypropoxy)propyltrimethoxysilane to obtain a premix of silicate hydrolyzate and 3-(2,3-epoxypropoxy)propyltrimethoxysilane with a silicate hydrolyzate content of 5%, heating the remaining silicate hydrolyzate in step (1) to 50° C., adding 5 parts of the premix at a speed of 150 r/min, and reacting for 4 hours to obtain a hybrid modified silica sol;

(3) At a speed of 200 r/min, 3 parts of terminal amino polyether (M-600) containing 10 wt% of 3-(2,3-epoxypropoxy)propyltrimethoxysilane were slowly added dropwise to the above hybrid modified silica sol. After the addition was completed, the mixture was reacted for 2 h under stirring and heat preservation. The temperature was controlled at 50-55 °C during the whole process to obtain a hydrophilic modified hybrid silica sol, which is a carrier material with sustained release function.

test

The pore size test of the carrier materials prepared in the above Examples 1-3 was carried out using a nitrogen adsorption/desorption method. The test results are shown in Table 1.

Table 1. Pore size test results of carrier materials of Examples 1-3

It can be seen from the data in Table 1 that M1000 in the embodiment is a hydrophilic polyether, which combines more with water and has a small pore size, and the pore size becomes smaller as the addition amount increases; M600 is a hydrophobic polyether, which combines less with water and has a larger pore size.

2. Sustained-release functional composite materials

Under stirring, a functional auxiliary agent requiring sustained release is added to the carrier material with sustained release function prepared in Example 1, wherein the mass ratio of the functional auxiliary agent to the carrier material is 1:0.5-4, and then the pH value is adjusted to neutral with an alkaline solution to form a gel; the wet gel is crushed and placed in a 60-80°C oven for drying, and after crushing, it is passed through a 1000-1250 mesh sieve to obtain a 1000-1250 mesh composite material with sustained release function.

The alkaline solution may be an aqueous ammonia solution or an aqueous calcium hydroxide solution.

1. Slow-release antifouling composition

Sustained-release performance test Firstly, the sustained-release antifouling composition is taken as an example to verify the sustained-release performance of the carrier material with sustained-release function prepared by the present invention.

Example 4

Under stirring, the antifouling agent to be sustained-released is added to the carrier material with sustained-release function prepared in Example 1, the mass ratio of the antifouling agent to the carrier material with sustained-release function obtained in Example 1 is 1:1, and then the pH value is adjusted to neutral with an alkaline solution (aqueous ammonia solution) to form a gel; the wet gel is crushed and placed in an oven at 60-80° C. for drying, and after crushing, it is passed through a 1250-mesh sieve to obtain a 1250-mesh antifouling agent and a sustained-release carrier complex of Example 1, and other components are combined according to the formula in Table 2 to obtain a sustained-release antifouling composition.

Example 5

The only difference between Example 5 and Example 4 is that the mass ratio of the antifouling agent to the carrier material with sustained-release function obtained in Example 1 is 1:0.5, and the rest is the same as Example 4.

Example 6

The only difference between Example 6 and Example 4 is that the mass ratio of the antifouling agent to the carrier material with sustained-release function obtained in Example 1 is 1:2, and the rest is the same as Example 4.

Comparative Example 1

The difference between Comparative Example 1 and Example 4 is that an antifouling agent is used instead of the complex of the antifouling agent and the sustained-release carrier of Example 1.

Comparative Example 2

The only difference between Comparative Example 2 and Example 4 is that the mass ratio of the antifouling agent to the carrier material with sustained-release function obtained in Example 1 is 1:5, and the rest is the same as Example 4.

Comparative Example 3

The only difference between Comparative Example 3 and Example 4 is that the mass ratio of the antifouling agent to the carrier material with sustained-release function obtained in Example 1 is 1:0.2, and the rest is the same as Example 4.

Table 2. Formulas of the sustained-release antifouling compositions obtained in Examples 4 to 6 and Comparative Examples 1 to 3

The slow-release antifouling compositions obtained in Examples 4 to 6 and Comparative Examples 1 to 3 were subjected to performance tests, and the results are shown in Table 3.

Table 3. Performance test data of the sustained-release antifouling composition obtained in Examples 4 to 6 and Comparative Examples 1 to 3

It is obvious from the comparative experiment that fixing the antifouling agent in the above carrier, compared with the method of simply adding the antifouling agent, significantly enhances the antifouling effect when the amount of antifouling agent used is reduced, and also greatly reduces the pollution of the antifouling agent to the marine environment. And through comparative experiments, the optimal ratio of antifouling agent and carrier material was studied.

2. Slow-release anti-rust composition

Example 7

Under stirring, a rust inhibitor to be sustained-released is added to the carrier material with sustained-release function prepared in Example 1, the mass ratio of the rust inhibitor to the carrier material with sustained-release function obtained in Example 1 is 1:1, and then the pH value is adjusted to neutral with an alkaline solution (aqueous ammonia solution) to form a gel; the wet gel is crushed and placed in an oven at 60-80° C. for drying, and after crushing, it is passed through a 1250-mesh sieve to obtain a 1250-mesh rust inhibitor and a sustained-release carrier complex of Example 1, and other components are combined according to the formula in Table 4 to obtain a sustained-release rust-proof composition.

Example 8

The only difference between Example 8 and Example 7 is that the mass ratio of the rust inhibitor to the carrier material with sustained-release function obtained in Example 1 is 1:4, and the rest is the same as Example 7.

Example 9

The only difference between Example 9 and Example 7 is that the mass ratio of the rust inhibitor to the carrier material with sustained-release function obtained in Example 1 is 3:2, and the rest is the same as Example 7.

Comparative Example 4

The difference between Comparative Example 4 and Example 7 is that a rust inhibitor is used instead of the complex of the rust inhibitor and the sustained-release carrier of Example 1.

Comparative Example 5

The only difference between Comparative Example 5 and Example 7 is that the mass ratio of the rust inhibitor to the carrier material with sustained-release function obtained in Example 1 is 1:5, and the rest is the same as Example 7.

Comparative Example 6

The only difference between Comparative Example 6 and Example 7 is that the mass ratio of the rust inhibitor to the carrier material with sustained-release function obtained in Example 1 is 1:0.2, and the rest is the same as Example 7.

Table 4. Formulas of the sustained-release antirust compositions obtained in Examples 7 to 9 and Comparative Examples 4 to 6

The slow-release antirust compositions obtained in Examples 7 to 9 and Comparative Examples 4 to 6 were subjected to performance tests, and the results are shown in Table 5.

Table 5. Performance test results of the slow-release antirust compositions obtained in Examples 7 to 9 and Comparative Examples 4 to 6

It is obvious from the comparative experiments that fixing the rust inhibitor in the above-mentioned carrier, compared with the method of simply adding the rust inhibitor, significantly enhances the anti-rust effect when the amount of rust inhibitor used is reduced, and also greatly reduces the pollution of the antifouling agent to the marine environment. Through comparative experiments, the optimal ratio of rust inhibitor to carrier material is studied.

The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (8)

1. A carrier material with sustained release function, characterized by comprising one or more of the following structures: Wherein, R is a C ₄ ~C ₁₀ aliphatic epoxy group, R' is an aliphatic polyether group, and n≥1; The method for preparing the carrier material with sustained-release function comprises the following steps: (1) Preparation of silica sol: Silicate ester is placed in a reaction vessel, and an acid solution is added under stirring to obtain a transparent solution through hydrolysis. After removing the alcohol by-product by suction filtration, a silicate hydrolyzate is obtained; (2) Hybridization modification of silica sol: premix part of the silicate hydrolyzate obtained in step (1) with a silane coupling agent containing an epoxy functional group to obtain a silicate hydrolyzate-silane coupling agent premix containing 2 to 10% of the silicate hydrolyzate content; heat the remaining silicate hydrolyzate in step (1) to 40 to 60° C., dropwise add the premix under stirring, and react for 4 to 6 hours to complete the hybridization modification of the silica sol, thereby obtaining a hybrid modified silica sol; (3) Hydrophilic modification of hybrid silica sol: 10-50 wt% of terminal amino polyether containing epoxy functional group is slowly added dropwise to the hybrid modified silica sol in step (2) under stirring. After the addition is completed, the reaction temperature and reaction time are controlled under stirring to obtain a hydrophilic modified hybrid silica sol, which is a carrier material with sustained release function. 2. The carrier material with sustained release function according to claim 1, characterized in that: ; Among them, 1≤x≤30, 1≤y≤10. 3. The carrier material with sustained-release function according to claim 1 is characterized in that it is prepared from the following components in parts by weight: 100 parts of silicate, 5-10 parts of acid solution, 3-10 parts of silane coupling agent containing epoxy functional group, and 3-5 parts of terminal amino polyether. 4. A method for preparing a carrier material with sustained-release function according to any one of claims 1 to 3, characterized in that it comprises the following steps: (1) Preparation of silica sol: Silicate ester is placed in a reaction vessel, and an acid solution is added under stirring to obtain a transparent solution through hydrolysis. After removing the alcohol by-product by suction filtration, a silicate hydrolyzate is obtained; (2) Hybridization modification of silica sol: premix part of the silicate hydrolyzate obtained in step (1) with a silane coupling agent containing an epoxy functional group to obtain a silicate hydrolyzate-epoxy functional group-containing silane coupling agent premix containing 2-10% of the silicate hydrolyzate content; heat the remaining silicate hydrolyzate in step (1) to 40-60° C., dropwise add the premix under stirring, and react for 4-6 hours to complete the hybridization modification of the silica sol, thereby obtaining a hybrid modified silica sol; (3) Hydrophilic modification of hybrid silica sol: 10-50 wt% of terminal amino polyether containing epoxy functional group is slowly added dropwise to the hybrid modified silica sol in step (2) under stirring. After the addition is completed, the reaction temperature and reaction time are controlled under stirring to obtain a hydrophilic modified hybrid silica sol, which is a carrier material with sustained release function. 5 . The method for preparing a carrier material with a sustained-release function according to claim 4 , wherein the silicate is tetraethyl orthosilicate, and the acid solution is a hydrochloric acid aqueous solution or a sulfuric acid aqueous solution. 6. The method for preparing a carrier material with a sustained-release function according to claim 4, characterized in that the epoxy-functional silane coupling agents in steps (2) and (3) are each independently selected from at least one of 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 3-(2,3-epoxypropoxy)propylmethyldimethoxysilane, and 3-(2,3-epoxypropoxy)propylmethyldiethoxysilane. 7. The method for preparing a carrier material with sustained-release function according to claim 4, characterized in that the reaction time in step (3) is 2-2.5 h, and the reaction temperature is 50-55°C. 8. Use of the carrier material with sustained release function as claimed in any one of claims 1 to 3 in the field of coatings.