CN114773532A - Organic silicon modified starch emulsion and preparation method thereof - Google Patents
Organic silicon modified starch emulsion and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of new materials, and particularly relates to an organic silicon modified starch emulsion and a preparation method thereof, wherein the organic silicon modified starch emulsion is prepared from the following raw materials in parts by weight: 25-35 parts of oxidized starch, 1-5 parts of inorganic catalyst, 10-15 parts of vinyl ether, 0.5-1.5 parts of peroxide initiator, 10-20 parts of comonomer, 0.5-0.6 part of preservative, 2-6 parts of stabilizer and 30-40 parts of solvent. The invention combines the advantages of acrylic ester, organic silicon and starch emulsion, ensures the film forming property, the caking property and the anti-shearing capacity of the emulsion, improves the properties of heat resistance, water resistance and shearing force of the starch, has good dispersion force and binding force, strong caking force, good emulsibility, difficult putrefaction and mildew and stable chemical performance. And the film forming property is superior to that of the original starch and the modified starch, so that a tough, continuous and uniform film can be formed, and the film has good air permeability and good adhesive force.
Description
Technical Field
The invention belongs to the technical field of new materials, and particularly relates to an organic silicon modified starch emulsion and a preparation method thereof.
Background
The starch is a renewable natural resource, has wide sources, good cohesiveness and biodegradability and wide application range. The starch has new characteristics after being modified, can be used as a base material to prepare adhesives and is applied to various fields. The adhesive produced by using starch and derivatives thereof as base materials has good leveling property, brushing property and anti-settling property, and has the advantages of no formaldehyde, no harm to human bodies and the like. And the production process is simple, the product price is low, and the adhesive is a green environment-friendly adhesive and conforms to the environmental protection policy promoted by various countries in the world. At present, starch derivatives mainly comprise oxidized starch and crosslinked starch, but due to the hydrophilicity and degradability of the starch, the water resistance, mildew resistance, coating film strength and other aspects of the starch-based adhesive need to be further improved. In addition, most of the traditional water-based polymer adhesives such as isocyanate adhesives, urea-formaldehyde resin adhesives and the like adopt synthetic resin as a main raw material, so that the adhesives have the defects of high cost, release of other harmful substances and the like. Therefore, the development of the aqueous environment-friendly starch emulsion has wide market prospect.
Disclosure of Invention
The invention aims to provide an organosilicon modified starch emulsion aiming at the defects of starch in the aspects of water resistance, mildew resistance, coating film strength and the like, and further improve the heat resistance, water resistance and chemical stability of the starch.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
an organic silicon modified starch emulsion is composed of the following raw materials in parts by weight:
25-35 parts of oxidized starch, 1-5 parts of inorganic catalyst, 10-15 parts of vinyl ether, 0.5-1.5 parts of peroxide initiator, 10-20 parts of comonomer, 0.5-0.6 part of preservative, 2-6 parts of stabilizer and 30-40 parts of solvent.
Preferably, the inorganic catalyst is mercury sulfate.
Preferably, the vinyl ether is selected from one of vinyl ethyl ether, divinyl ether, vinyl diglycol ether, 4-hydroxybutyl vinyl ether and 4-vinylbenzyl glycidyl ether.
Preferably, the peroxide initiator is selected from one of ammonium persulfate, potassium persulfate or sodium persulfate.
Preferably, the comonomer is selected from one of vinyl siloxane, triisopropyl silicon-based acrylate or fluorine-containing acrylate.
Preferably, the preservative is edible sodium benzoate.
Preferably, the stabilizer is hydroxypropyl carboxymethyl cellulose or polyvinyl alcohol.
Preferably, the solvent is selected from one of a DMSO/TBAF mixture or an ethyl acetate/TBAF mixture.
Based on one general inventive concept, another object of the present invention is to provide a method for preparing the above-mentioned silicone modified starch emulsion, comprising the steps of:
(1) preparation of vinyl etherified starch
Uniformly mixing the oxidized starch, the vinyl ether and the solvent in parts by weight, dropwise adding an inorganic catalyst, heating to 40-200 ℃, refluxing, carrying out an ether exchange reaction for 2-12 h, then quenching with a saturated sodium carbonate aqueous solution, carrying out extraction separation, and removing the solvent in vacuum to obtain vinyl etherified starch;
(2) preparation of organosilicon modified starch emulsion
Preparing 20-25 wt% solution of vinyl etherified starch, adding 0.5-0.8 part of peroxide initiator, pre-initiating reaction at room temperature for 30-60 min, and adjusting pH to 6.8-7.2 to obtain self-emulsifying etherified starch emulsion; and then slowly adding the comonomer in parts by weight within 30-50 min for copolymerization reaction, adjusting the pH to 4.5-5.5, performing heat preservation reaction at the temperature of 55-65 ℃ for 1.5h, then adding the rest 0-1.0 part of peroxide initiator, continuing the heat preservation reaction at the temperature of 55-65 ℃ for 1.5h, adding a stabilizer and a preservative, adjusting the pH to 6.8-7.2, and filtering to obtain the organic silicon modified starch emulsion.
The organosilicon modified starch emulsion prepared by the invention has uniform particle size distribution, the PDI index is between 0.28 and 0.32, the particle diameter of the emulsion is in the range of 90nm-120nm, the particle size is smaller, the penetration is facilitated, the storage stability of the emulsion is excellent, the soaking water absorption of the emulsion film approaches 0 wt%, and the surface free energy of the emulsion film is obviously reduced (from 28.1mN/m-36.5mN/m to 25.2mN/m-26.3 mN/m).
Compared with the traditional preparation method of modified starch, the preparation method of the invention firstly carries out multiple treatments such as vinyl etherification, copolymerization and the like on oxidized starch, adopts the oxidized starch as a framework, carries out etherification reaction firstly, introduces vinyl groups, then carries out emulsion copolymerization reaction with vinyl siloxane and silicon-containing or fluorine-containing acrylate monomers, introduces organic silicon groups and acrylic ester on the starch framework, combines the advantages of the acrylic ester, organic silicon and starch emulsion, ensures the film forming property, the caking property and the shear resistance of the emulsion, improves the properties of the starch such as heat resistance, water resistance and shear force, has good dispersion force and binding force, strong adhesive force, good emulsibility, difficult putrefaction and mildew, and stable chemical performance. And the film forming property is superior to that of the original starch and the modified starch, so that a tough, continuous and uniform film can be formed, and the film has good air permeability and good adhesive force. In order to improve the crosslinking degree and stability of the emulsion, the invention adds the stabilizing agents of hydroxypropyl carboxymethyl cellulose and polyvinyl alcohol, which can also be complexed with hydroxyl in starch molecules to form hydrogen bonds to generate crosslinking and form a multinuclear complex with a net structure, thereby increasing the water resistance and stability of the starch emulsion, improving the initial adhesion strength of the modified starch emulsion, and being widely applied to the fields of coating, papermaking and the like. The method has the characteristics of simple and convenient operation, no environmental pollution, easy industrialization and the like, and can generate great ecological environmental benefit and social and economic benefit after popularization and application.
Detailed Description
The present invention will be further described with reference to specific embodiments for the purpose of making the objects, technical solutions and advantages of the present invention more apparent, but the present invention is not limited to these examples. It should be noted that, without conflict, any combination between the embodiments or technical features described below may form a new embodiment. In the invention, all parts and percentages are mass units, and the adopted equipment, raw materials and the like can be purchased from the market or are commonly used in the field. The methods in the following examples are all conventional in the art unless otherwise specified.
As used herein, the terms "comprises," "comprising," "includes," "including," "contains," "containing," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of values, with a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range.
Example 1
An organosilicon modified starch emulsion is composed of the following raw materials in parts by weight:
30 parts of oxidized starch (the content of carboxyl group/aldehyde group is 0.5mol/mol), 3 parts of inorganic catalyst, 12.5 parts of vinyl ether, 1.0 part of peroxide initiator, 15 parts of comonomer, 0.55 part of preservative, 4 parts of stabilizer and 35 parts of solvent;
the inorganic catalyst is mercuric sulfate, the vinyl ether is vinyl diglycol ether, the peroxide initiator is ammonium persulfate, the comonomer is vinyl siloxane, and the preservative is edible sodium benzoate; the stabilizer is hydroxypropyl carboxymethyl cellulose, and the solvent is a DMSO/TBAF mixture.
The preparation method of the organic silicon modified starch emulsion comprises the following steps:
(1) preparation of vinyl etherified starch
Uniformly mixing the oxidized starch, the vinyl ether and the solvent in parts by weight, dropwise adding an inorganic catalyst, heating to 120 ℃, refluxing, carrying out an ether exchange reaction for 7 hours, then quenching with a saturated sodium carbonate aqueous solution, carrying out extraction separation, and removing the solvent in vacuum to obtain vinyl etherified starch;
(2) preparation of organosilicon modified starch emulsion
Preparing vinyl etherified starch into a 22.5% wt solution, adding 0.6 part of peroxide initiator, pre-initiating reaction at room temperature for 45min, and adjusting the pH value to 7.0 to obtain a self-emulsifying etherified starch emulsion; and then slowly adding the comonomer in parts by weight within 40min for copolymerization reaction, adjusting the pH value to 5.0, carrying out heat preservation reaction at the temperature of 60 ℃ for 1.5h, then adding the rest 0.4 part of peroxide initiator, continuing the heat preservation reaction at the temperature of 60 ℃ for 1.5h, then adding a stabilizer and a preservative, adjusting the pH value to 7.0, and filtering to obtain the organic silicon modified starch emulsion.
The static contact angle of the organosilicon modified starch emulsion film to deionized water in the embodiment is 100.9 degrees, the static contact angle to hexadecane is 0 degree, the surface free energy is 25.2mN/m, and the soaking water absorption rate approaches to 0 wt%.
Example 2
An organic silicon modified starch emulsion is composed of the following raw materials in parts by weight:
35 parts of oxidized starch (the content of carboxyl group/aldehyde group is 0.6mol/mol), 1 part of inorganic catalyst, 15 parts of vinyl ether, 0.5 part of peroxide initiator, 20 parts of comonomer, 0.5 part of preservative, 6 parts of stabilizer and 30 parts of solvent;
the inorganic catalyst is mercuric sulfate, the vinyl ether is vinyl ethyl ether, the peroxide initiator is potassium persulfate, the comonomer is triisopropyl silicon-based acrylate, the preservative is edible sodium benzoate, the stabilizer is 1799 type polyvinyl alcohol (the polymerization degree is 1700, the hydrolysis degree is 88-99%), and the solvent is an ethyl acetate/TBAF mixture.
The preparation method of the organic silicon modified starch emulsion comprises the following steps:
(1) preparation of vinyl etherified starch
Uniformly mixing the oxidized starch, the vinyl ether and the solvent in parts by weight, dropwise adding an inorganic catalyst, heating to 180 ℃, refluxing, carrying out an ether exchange reaction for 4 hours, then quenching with a saturated sodium carbonate aqueous solution, carrying out extraction separation, and removing the solvent in vacuum to obtain vinyl etherified starch;
(2) preparation of organosilicon modified starch emulsion
Preparing vinyl etherified starch into a 25% wt solution, adding 0.5 part of peroxide initiator, pre-initiating reaction at room temperature for 60min, and adjusting the pH value to 6.8 to obtain a self-emulsifying etherified starch emulsion; and then slowly adding the comonomer in parts by weight within 50min for copolymerization reaction, adjusting the pH value to 4.5, carrying out heat preservation reaction at the temperature of 65 ℃ for 1.5h, then adding the rest 0.5 part of peroxide initiator, continuing the heat preservation reaction at the temperature of 65 ℃ for 1.5h, then adding a stabilizer and a preservative, adjusting the pH value to 6.8, and filtering to obtain the organic silicon modified starch emulsion.
In the embodiment, the static contact angle of the organosilicon modified starch emulsion film to deionized water is 100.8 degrees, the static contact angle to hexadecane is 0 degree, the surface free energy is 25.9mN/m, and the soaking water absorption rate approaches to 0 wt%.
Example 3
An organic silicon modified starch emulsion is composed of the following raw materials in parts by weight:
25 parts of oxidized starch (the content of carboxyl group/aldehyde group is 0.4mol/mol), 5 parts of inorganic catalyst, 10 parts of vinyl ether, 1.5 parts of peroxide initiator, 10 parts of comonomer, 0.6 part of preservative, 2 parts of stabilizer and 40 parts of solvent.
The inorganic catalyst is mercury sulfate, the vinyl ether is 4-vinylbenzyl glycidyl ether, the peroxide initiator is sodium persulfate, the comonomer is fluorine-containing acrylate, the preservative is edible sodium benzoate, the stabilizer is 1788 type polyvinyl alcohol (the polymerization degree is 1700, the hydrolysis degree is 88% -99%), and the solvent is a DMSO/TBAF mixture.
The preparation method of the organic silicon modified starch emulsion comprises the following steps:
(1) preparation of vinyl etherified starch
Uniformly mixing the oxidized starch, the vinyl ether and the solvent in parts by weight, dropwise adding an inorganic catalyst, heating to 50 ℃, refluxing, carrying out an ether exchange reaction for 12 hours, then quenching with a saturated sodium carbonate aqueous solution, carrying out extraction separation, and removing the solvent in vacuum to obtain vinyl etherified starch;
(2) preparation of organosilicon modified starch emulsion
Preparing 20 wt% solution of vinyl etherified starch, adding 0.8 part of peroxide initiator, pre-initiating reaction at room temperature for 30min, and adjusting the pH value to 7.2 to obtain self-emulsifying etherified starch emulsion; and then slowly adding the comonomer in parts by weight within 30min for copolymerization reaction, adjusting the pH value to 5.5, carrying out heat preservation reaction at the temperature of 55 ℃ for 1.5h, then adding the rest 0.2 part of peroxide initiator, continuing the heat preservation reaction at the temperature of 55 ℃ for 1.5h, then adding a stabilizer and a preservative, adjusting the pH value to 7.2, and filtering to obtain the organic silicon modified starch emulsion.
The static contact angle of the organosilicon modified starch emulsion film to deionized water in the embodiment is 100.7 degrees, the static contact angle to hexadecane is 0 degree, the surface free energy is 26.3mN/m, and the soaking water absorption rate approaches to 0 wt%.
Comparative example 1
The procedure of example 1 was repeated except that starch having an oxidation degree (carboxyl group content/aldehyde group content) of 0.3mol/mol was used as the starting material.
The static contact angle of the organosilicon modified starch emulsion film in the comparative example to deionized water is 60.2 degrees, the static contact angle to hexadecane is 0.2 degrees, the surface free energy is 38.6mN/m, and the soaking water absorption approaches to 0.5 wt%.
Comparative example 2
The procedure of example 1 was repeated except that the starting material was starch having an oxidation degree (carboxyl group content/aldehyde group content) of 0.6 mol/mol.
The static contact angle of the organosilicon modified starch emulsion film to deionized water in the comparative example is 58.6 degrees, the static contact angle to hexadecane is 0.1 degree, the surface free energy is 36.9mN/m, and the soaking water absorption rate approaches to 0.2 wt%.
Comparative example 3
The same as in example 1 except that the inorganic catalyst was not contained.
The static contact angle of the organosilicon modified starch emulsion film in the comparative example to deionized water is 62.8 degrees, the static contact angle to hexadecane is 0.1 degree, the surface free energy is 39.1mN/m, and the soaking water absorption approaches to 0.3 wt%.
Comparative example 4
Hydroxypropyl carboxymethyl cellulose as a component was not contained, and the rest was the same as in example 1.
The static contact angle of the organosilicon modified starch emulsion film to deionized water in the comparative example is 58.4 degrees, the static contact angle to hexadecane is 0.1 degree, the surface free energy is 38.9mN/m, and the soaking water absorption rate approaches to 0.1% wt.
Comparative example 5
The same procedure as in example 1 was repeated except that the polyvinyl alcohol type 1788 was not contained.
In the comparative example, the static contact angle of the organosilicon modified starch emulsion film to deionized water is 59.2 degrees, the static contact angle to hexadecane is 0.1 degree, the surface free energy is 37.3mN/m, and the soaking water absorption rate approaches to 0.1% wt.
Comparative example 6
The components hydroxypropyl carboxymethylcellulose and 1788 type polyvinyl alcohol are not included, the rest being the same as in example 1.
The static contact angle of the organosilicon modified starch emulsion film in the comparative example to deionized water is 56.3 degrees, the static contact angle to hexadecane is 0.2 degrees, the surface free energy is 39.8mN/m, and the soaking water absorption approaches to 0.3 wt%.
Comparative example 7
The method comprises the steps of selecting starch with the degree of oxidation (carboxyl content/aldehyde group content) of 0.4mol/mol as a raw material from oxidized starch prepared by a nitric acid oxidation method, adding 40% of oxidized starch milk and 20% of polyvinyl alcohol solution into a 500ml four-neck flask with a stirrer and a thermometer respectively to enable the weight ratio of the oxidized starch to the polyvinyl alcohol in the solution to be 0.2, adding 10% of hydrochloric acid to adjust the pH of the solution to be 2.5, heating the solution to 65 ℃ and carrying out crosslinking reaction for 2 hours. Adding vinyl trimethoxy siloxane monomer accounting for 4 percent of the weight of the polyvinyl alcohol, uniformly stirring for 30 minutes, dropwise adding 3 percent potassium persulfate solution to initiate reaction, and reacting for 5 hours at the temperature of 60-80 ℃ to obtain the organosilicon modified oxidized starch emulsion.
The static contact angle of the organosilicon modified starch emulsion film to deionized water in the comparative example is 60.9 degrees, the static contact angle to hexadecane is 0.1 degrees, the surface free energy is 38.2mN/m, and the soaking water absorption rate approaches to 0.1% wt.
Test example 1
The organosilicon modified starch emulsions prepared in examples 1-3 and comparative examples 1-7 were subjected to performance tests in accordance with the GB/T9755-2001 synthetic resin emulsion exterior wall coating standards, and the water resistance and alkali resistance of the emulsions were tested in accordance with GB/T1733 and GB/T9265, and the performance measured in accordance with the standards is shown in Table 1 below.
TABLE 1 results of measuring Properties of examples 1 to 3 and comparative examples 1 to 7
The above embodiments are merely preferred embodiments of the present invention, and any simple modifications, alterations and substitutions made to the above embodiments according to the technical essence of the present invention are within the scope of the technical solution of the present invention.
Claims (9)
1. The organic silicon modified starch emulsion is characterized by comprising the following raw materials in parts by weight:
25-35 parts of oxidized starch, 1-5 parts of inorganic catalyst, 10-15 parts of vinyl ether, 0.5-1.5 parts of peroxide initiator, 10-20 parts of comonomer, 0.5-0.6 part of preservative, 2-6 parts of stabilizer and 30-40 parts of solvent.
2. The emulsion of claim 1, wherein the inorganic catalyst is mercuric sulfate.
3. The silicone-modified starch emulsion of claim 1 wherein the vinyl ether is selected from the group consisting of vinyl ethyl ether, divinyl ether, vinyl diglycol ether, 4-hydroxybutyl vinyl ether, and 4-vinylbenzyl glycidyl ether.
4. The emulsion of claim 1, wherein the peroxide initiator is selected from the group consisting of ammonium persulfate, potassium persulfate, and sodium persulfate.
5. The emulsion of claim 1, wherein the comonomer is selected from the group consisting of vinyl siloxane, triisopropyl silicon acrylate, and fluorine-containing acrylate.
6. The emulsion of claim 1, wherein the preservative is edible sodium benzoate.
7. The silicone-modified starch emulsion of claim 1 wherein the stabilizer is hydroxypropyl carboxymethyl cellulose or polyvinyl alcohol.
8. The emulsion of claim 1, wherein the solvent is selected from the group consisting of a DMSO/TBAF mixture and an ethyl acetate/TBAF mixture.
9. The method for preparing the organosilicon modified starch emulsion of any one of claims 1-8, comprising the steps of:
(1) preparation of vinyl etherified starch
Uniformly mixing the oxidized starch, the vinyl ether and the solvent in parts by weight, dropwise adding an inorganic catalyst, heating to 40-200 ℃, refluxing, carrying out an ether exchange reaction for 2-12 h, then quenching with a saturated sodium carbonate aqueous solution, carrying out extraction separation, and removing the solvent in vacuum to obtain vinyl etherified starch;
(2) preparation of organosilicon modified starch emulsion
Preparing 20-25 wt% solution of vinyl etherified starch, adding 0.5-0.8 part of peroxide initiator, pre-initiating reaction at room temperature for 30-60 min, and adjusting pH to 6.8-7.2 to obtain self-emulsifying etherified starch emulsion; and then slowly adding the comonomer in parts by weight within 30-50 min for copolymerization reaction, adjusting the pH to 4.5-5.5, performing heat preservation reaction at the temperature of 55-65 ℃ for 1.5h, then adding the rest 0-1.0 part of peroxide initiator, continuing the heat preservation reaction at the temperature of 55-65 ℃ for 1.5h, adding a stabilizer and a preservative, adjusting the pH to 6.8-7.2, and filtering to obtain the organic silicon modified starch emulsion.
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