阅读说明：本技术 一种适用于酒精体系的增稠聚合物的制备方法 (Preparation method of thickening polymer suitable for alcohol system ) 是由 沈惠 林高宇 于 2020-12-08 设计创作，主要内容包括：本发明属于聚合物领域,为了解决酒精溶液的浓度过高的情况下,凝胶透光率会极速下降的问题,本发明提出了一种适用于酒精体系的增稠聚合物的制备方法,所述方法包括如下步骤：步骤1：将溶剂置于反应容器中,加热至回流温度；步骤2：将部分单体、分散剂、部分交联剂一次性加入到反应容器中,恒温于回流温度；步骤3：将剩余的单体、分散剂、剩余交联剂以滴加的方式加入到反应容器中,引发剂同步滴加进入反应容器；步骤4：一次性加入用于消除溶液中残留单体的引发剂溶液,反应时间0.2-0.8h；步骤5：过滤、干燥得到聚合物粉末。通过该方法制备的增稠聚合物在70％以上的酒精溶液中能够较好的分散形成粘度不低于8000mpa.s、透光率不低于92％(浓度1％)的凝胶溶液。(The invention belongs to the field of polymers, and provides a preparation method of a thickening polymer suitable for an alcohol system in order to solve the problem that the gel transmittance can be reduced extremely quickly under the condition that the concentration of an alcohol solution is too high, wherein the method comprises the following steps: step 1: placing the solvent in a reaction vessel, and heating to reflux temperature; step 2: adding part of monomer, dispersant and part of cross-linking agent into a reaction vessel at one time, and keeping the temperature at the reflux temperature; and step 3: adding the rest of the monomers, the dispersing agent and the rest of the cross-linking agent into a reaction container in a dropwise manner, and synchronously dropwise adding the initiator into the reaction container; and 4, step 4: adding an initiator solution for eliminating residual monomers in the solution at one time, wherein the reaction time is 0.2-0.8 h; and 5: filtering and drying to obtain polymer powder. The thickening polymer prepared by the method can be well dispersed in an alcohol solution with the concentration of more than 70 percent to form a gel solution with the viscosity of not less than 8000mpa.s and the light transmittance of not less than 92 percent (the concentration is 1 percent).)

1. A method for preparing a thickening polymer suitable for use in an alcohol system, the method comprising the steps of:

step 1: placing the solvent in a reaction vessel, and heating to reflux temperature;

step 2: adding part of monomer, dispersant and part of cross-linking agent into a reaction vessel at one time, and keeping the temperature at the reflux temperature;

and step 3: adding the rest of the monomers, the dispersing agent and the rest of the cross-linking agent into a reaction container in a dropwise manner, and synchronously dropwise adding the initiator into the reaction container;

and 4, step 4: adding an initiator solution for eliminating residual monomers in the solution at one time, wherein the reaction time is 0.2-0.8 h;

and 5: filtering and drying to obtain polymer powder;

the monomer comprises acrylic acid, methyl acrylate or ethyl acrylate, methyl methacrylate or ethyl methacrylate, N-dimethylacrylamide or N, N-diethylacrylamide;

the weight ratio of the acrylic acid to the methyl acrylate or the ethyl acrylate to the methyl methacrylate or the ethyl methacrylate to the N, N-dimethylacrylamide or the N, N-diethylacrylamide is 100: 5-10: 3-5: 1-5.

2. The method of claim 1, wherein: the weight ratio of the acrylic acid to the methyl acrylate or the ethyl acrylate to the methyl methacrylate or the ethyl methacrylate to the N, N-dimethyl bisacrylamide or the N, N-diethyl bisacrylamide is 100: 6-8: 3.5-4.5: 2-4.

3. The method of claim 2, wherein: the monomers are acrylic acid, methyl acrylate, methyl methacrylate and N, N-dimethylacrylamide in a weight ratio of 100:8:4: 2.

4. The method of claim 1, wherein: the dispersant is sodium dodecyl benzene sulfonate or sodium dodecyl sulfate.

5. The method of claim 1, wherein: the solvent is a mixture of cyclohexane and ethyl acetate; the weight ratio of the cyclohexane to the ethyl acetate is 2.5-3: 1.

6. The method of claim 1, wherein: the reflux temperature was 75 ± 5 ℃.

7. The method of claim 5, wherein: the initiator is azobisisobutyronitrile or azobisisoheptonitrile, and in step 3, the amount of the initiator is 1.0-1.5% of the weight of the monomer; the amount of initiator used in step 4 is 0.2 to 0.4% by weight based on the weight of the monomers.

8. The method of claim 5, wherein: the crosslinking agent is N, N-methylene bisacrylamide, the crosslinking agent in the step 2 is 0.1-0.2% of the total weight of the monomers, and the crosslinking agent in the step 2 is 0.2-0.4% of the total weight of the monomers.

9. The production method according to any one of claims 1 to 8, characterized in that: the ratio of the monomers in the step 2 to the step 3 is 1-2: 8-9.

Technical Field

The invention relates to the field of polymers, in particular to a preparation method of a thickening polymer suitable for an alcohol system.

Background

Acrylic thickeners are lightly crosslinked acrylic polymers which provide excellent stability and thickening properties to the surfactant system and excellent suspendability even in low viscosity formulations, and insoluble and difficult to stabilize ingredients such as silicones can be co-emulsified and stabilized.

It is widely used in the field of daily chemicals, and is characterized in that:

excellent suspension and thickening performance, and improves the working efficiency of a formulator;

the compatibility is strong, and the product is almost compatible with all nonionic, anionic and amphoteric surfactants and various cationic polymers;

can be used for transparent products, is convenient to use and is an ideal matching of personal cleaning products.

With the wider market of the alcohol gel products in the aspects of personal sterilization, nursing and the like, the development of the thickening agent suitable for the alcohol gel is a matter with wide prospect.

Most of the conventional thickeners for alcohol gels are only suitable for alcohol solutions with a concentration of 60 VOL% or less, and when the concentration of the alcohol solution is too high, the light transmittance of the gel is extremely reduced.

Disclosure of Invention

In order to overcome the defects of the prior art, the invention aims to provide a preparation method of a thickening polymer suitable for an alcohol system, wherein the thickening polymer prepared by the method can be well dispersed in an alcohol solution with the concentration of more than 70% to form a gel solution with the viscosity of not less than 8000mpa.s and the light transmittance of not less than 92% (concentration of 1%).

In order to achieve the purpose, the invention provides the following technical scheme:

a method of preparing a thickening polymer suitable for use in an alcohol system, the method comprising the steps of:

step 1: placing the solvent in a reaction vessel, and heating to reflux temperature;

step 2: adding part of monomer, dispersant and part of cross-linking agent into a reaction vessel at one time, and keeping the temperature at the reflux temperature;

and step 3: adding the rest of the monomers, the dispersing agent and the rest of the cross-linking agent into a reaction container in a dropwise manner, and synchronously dropwise adding the initiator into the reaction container;

and 4, step 4: adding an initiator solution for eliminating residual monomers in the solution at one time, wherein the reaction time is 0.2-0.8 h;

and 5: filtering and drying to obtain polymer powder;

the monomer comprises acrylic acid, methyl acrylate or ethyl acrylate, methyl methacrylate or ethyl methacrylate, N-dimethylacrylamide or N, N-diethylacrylamide;

the weight ratio of the acrylic acid to the methyl acrylate or the ethyl acrylate to the methyl methacrylate or the ethyl methacrylate to the N, N-dimethylacrylamide or the N, N-diethylacrylamide is 100: 5-10: 3-5: 1-5.

Further, the weight ratio of the acrylic acid, the methyl acrylate or the ethyl acrylate, the methyl methacrylate or the ethyl methacrylate, the N, N-dimethylacrylamide or the N, N-diethylacrylamide is 100: 6-8: 3.5-4.5: 2-4.

Further, the monomers are acrylic acid, methyl acrylate, methyl methacrylate and N, N-dimethylacrylamide in a weight ratio of 100:8:4: 2.

Further, the dispersant is sodium dodecyl benzene sulfonate or sodium dodecyl sulfate, and the dispersant is 1 to 1.5 percent of the weight of the monomer.

Further, the solvent is a mixture of cyclohexane and ethyl acetate; the weight ratio of cyclohexane to ethyl acetate is 2.5-3:1, and the solvent is approximately 3-4 times of the weight of the monomer.

Further, the reflux temperature is 75 ± 5 ℃.

Further, the initiator is azobisisobutyronitrile or azobisisoheptonitrile, and in step 3, the amount of the initiator is 1.0-1.5% of the weight of the monomer; the amount of initiator used in step 4 is 0.2 to 0.4% by weight based on the weight of the monomers.

Further, the cross-linking agent is N, N-methylene bisacrylamide, the cross-linking agent in the step 2 is 0.1-0.2% of the total weight of the monomers, and the cross-linking agent in the step 2 is 0.2-0.4% of the total weight of the monomers.

Further, the ratio of the monomers in the step 2 and the step 3 is 1-2:8-9

Compared with the prior art, the invention has the beneficial effects that:

the invention adopts acrylic acid, methyl acrylate or ethyl acrylate, methyl methacrylate or ethyl methacrylate, N-dimethylacrylamide or N, N-diethylacrylamide to form a monomer mixture, and the prepared polymer can adapt to an alcohol solution with the concentration of more than 70 percent, and the light transmittance can reach more than 92 percent.

In the monomers, dialkyl acrylamide has the dual characteristics of hydrophilicity and lipophilicity, acrylic acid is a hydrophilic monomer, methyl acrylate and methyl methacrylate are lipophilic monomers, methyl acrylate or ethyl acrylate is a soft monomer, methyl methacrylate and ethyl methacrylate are soft monomers, and reasonable matching of adding a small amount of hard monomers and soft and hard monomers into a monomer system is helpful for improving the light transmittance of a polymer in an alcohol system, and meanwhile, the hydrophilic monomer has close relation with the maintenance of the viscosity of the system and the maintenance of the light transmittance.

Detailed Description

The technical solution of the present invention will be described in further detail with reference to the following embodiments, but the present invention is not limited thereto.

Example 1

A method of preparing a thickening polymer suitable for use in an alcohol system, the method comprising the steps of:

step 1: placing the solvent in a reaction vessel and heating to reflux temperature;

the solvent is a mixture of cyclohexane and ethyl acetate with the weight ratio of 2.7:1, and the reflux temperature is 70-75 ℃; the total weight of the solvent is 300 g;

step 2: adding part of monomer, dispersant and cross-linking agent (N, N-methylene bisacrylamide, the cross-linking agents of the subsequent examples and the comparative examples are the cross-linking agents) into a reaction vessel at one time, and keeping the temperature at the reflux temperature;

and step 3: adding the rest monomers, the dispersing agent and the cross-linking agent N, N-methylene bisacrylamide into a reaction container in a dropwise manner, and synchronously dropwise adding the initiator into the reaction container; the dripping time is controlled to be 2 hours, and the temperature is kept for 2 hours;

the monomer compositions in the step 2 and the step 3 are the same and are both: acrylic acid, methyl acrylate, methyl methacrylate, N-dimethylacrylamide; the weight ratio is 100:8:4: 2; 20g of monomers in the step 2 and 80g of monomers in the step 3; the proportion of the dispersing agent and the cross-linking agent in the step 2 and the step 3 is distributed with the proportion of the monomers in the step 2 and the step 3; 30g of solvent is used for the initiator solution, and 1.3g of initiator is used in the step 3;

and 4, step 4: adding an initiator solution for eliminating residual monomers in the solution at one time, and reacting for 0.5 h; 20g of solvent is used for the initiator solution, and the amount of the initiator in the step 4 is 0.2 g; the initiators in steps 3 and 4 are all azobisisobutyronitrile.

And 5: carrying out suction filtration at normal pressure and drying in a vacuum drying oven for half a day to obtain polymer powder;

the proportion of the dispersing agent in the step 2 and the step 3 is 2:8, the total amount of the dispersing agent is 0.8g, and the dispersing agent is sodium dodecyl benzene sulfonate.

Example 2

A method of preparing a thickening polymer suitable for use in an alcohol system, the method comprising the steps of:

step 1: placing the solvent in a reaction vessel and heating to reflux temperature;

the solvent is a mixture of cyclohexane and ethyl acetate with the weight ratio of 2.5:1, and the reflux temperature is 70-75 ℃; the total weight of the solvent is 250 g;

step 2: adding part of monomer, dispersant and cross-linking agent into a reaction vessel at one time, and keeping the temperature at the reflux temperature;

and step 3: adding the rest monomers, the dispersing agent and the cross-linking agent into a reaction container in a dropwise manner, and synchronously dropwise adding the initiator into the reaction container; the dripping time is controlled to be 2 hours, and the temperature is kept for 2 hours;

the monomer compositions in the step 2 and the step 3 are the same and are both: acrylic acid, methyl acrylate, methyl methacrylate, N-dimethylacrylamide; the weight ratio is 100:7:5: 1; 10g of monomers in the step 2 and 90g of monomers in the step 3; 30g of solvent is used for the initiator solution, and 1.2g of initiator is used in the step 3; the proportion of the dispersing agent and the cross-linking agent in the step 2 and the step 3 is distributed with the proportion of the monomers in the step 2 and the step 3;

and 4, step 4: adding an initiator solution for eliminating residual monomers in the solution at one time, and reacting for 0.5 h; 20g of solvent is used for the initiator solution, and the amount of the initiator in the step 4 is 0.3 g; the initiators in steps 3 and 4 are all azobisisobutyronitrile.

And 5: carrying out suction filtration at normal pressure and drying in a vacuum drying oven for half a day to obtain polymer powder;

the proportion of the dispersing agent in the step 2 and the step 3 is 1:9, the total amount of the dispersing agent is 1g, and the dispersing agent is sodium dodecyl benzene sulfonate.

Example 3

A method of preparing a thickening polymer suitable for use in an alcohol system, the method comprising the steps of:

step 1: placing the solvent in a reaction vessel and heating to reflux temperature;

the solvent is a mixture of cyclohexane and ethyl acetate in a weight ratio of 3:1, and the reflux temperature is 70-75 ℃; the total weight of the solvent is 350 g;

step 2: adding part of monomer, dispersant and cross-linking agent into a reaction vessel at one time, and keeping the temperature at the reflux temperature;

and step 3: adding the rest monomers, the dispersing agent and the cross-linking agent into a reaction container in a dropwise manner, and synchronously dropwise adding the initiator into the reaction container; the dripping time is controlled to be 2 hours, and the temperature is kept for 2 hours;

the monomer compositions in the step 2 and the step 3 are the same and are both: acrylic acid, methyl acrylate, methyl methacrylate, N-dimethylacrylamide; the weight ratio is 100:6:5: 4; 15g of monomers in the step 2 and 75g of monomers in the step 3; 30g of solvent is used for the initiator solution, and 1.5g of initiator is used in the step 3; the proportion of the dispersing agent and the cross-linking agent in the step 2 and the step 3 is distributed with the proportion of the monomers in the step 2 and the step 3;

and 4, step 4: adding an initiator solution for eliminating residual monomers in the solution at one time, and reacting for 0.5 h; 20g of solvent is used for the initiator solution, and the amount of the initiator in the step 4 is 0.4 g; the initiators in steps 3 and 4 are all azobisisobutyronitrile.

And 5: carrying out suction filtration at normal pressure and drying in a vacuum drying oven for half a day to obtain polymer powder;

the proportion of the dispersing agent in the step 2 and the step 3 is 1.5:8.5, the total amount of the dispersing agent is 1.1g, and the dispersing agent is sodium dodecyl benzene sulfonate.

Example 4

A method of preparing a thickening polymer suitable for use in an alcohol system, the method comprising the steps of:

step 1: placing the solvent in a reaction vessel and heating to reflux temperature;

the solvent is a mixture of cyclohexane and ethyl acetate with the weight ratio of 2.7:1, and the reflux temperature is 70-75 ℃; the total weight of the solvent is 300 g;

step 2: adding part of monomer, dispersant and cross-linking agent into a reaction vessel at one time, and keeping the temperature at the reflux temperature;

and step 3: adding the rest monomers, the dispersing agent and the cross-linking agent into a reaction container in a dropwise manner, and synchronously dropwise adding the initiator into the reaction container; the dripping time is controlled to be 2 hours, and the temperature is kept for 2 hours;

the monomer compositions in the step 2 and the step 3 are the same and are both: acrylic acid, ethyl acrylate, methyl methacrylate, N-diethylacrylamide; the weight ratio is 100:8:4: 2; 20g of monomers in the step 2 and 80g of monomers in the step 3; 30g of solvent is used for the initiator solution, and 1.3g of initiator is used in the step 3; the proportion of the dispersing agent and the cross-linking agent in the step 2 and the step 3 is distributed with the proportion of the monomers in the step 2 and the step 3;

and 4, step 4: adding an initiator solution for eliminating residual monomers in the solution at one time, and reacting for 0.5 h; 20g of solvent is used for the initiator solution, and the amount of the initiator in the step 4 is 0.2 g; the initiators in steps 3 and 4 are all azobisisobutyronitrile.

And 5: carrying out suction filtration at normal pressure and drying in a vacuum drying oven for half a day to obtain polymer powder;

the proportion of the dispersing agent in the step 2 and the step 3 is 2:8, the total amount of the dispersing agent is 0.8g, and the dispersing agent is sodium dodecyl sulfate.

Example 5

A method of preparing a thickening polymer suitable for use in an alcohol system, the method comprising the steps of:

step 1: placing the solvent in a reaction vessel and heating to reflux temperature;

the solvent is a mixture of cyclohexane and ethyl acetate with the weight ratio of 2.7:1, and the reflux temperature is 70-75 ℃; the total weight of the solvent is 300 g;

step 2: adding part of monomer, dispersant and cross-linking agent into a reaction vessel at one time, and keeping the temperature at the reflux temperature;

and step 3: adding the rest monomers, the dispersing agent and the cross-linking agent into a reaction container in a dropwise manner, and synchronously dropwise adding the initiator into the reaction container; the dripping time is controlled to be 2 hours, and the temperature is kept for 2 hours;

the monomer compositions in the step 2 and the step 3 are the same and are both: acrylic acid, methyl acrylate, ethyl methacrylate, N-diethylacrylamide; the weight ratio is 100:8:4: 2; 20g of monomers in the step 2 and 80g of monomers in the step 3; 30g of solvent is used for the initiator solution, and 1.3g of initiator is used in the step 3; the proportion of the dispersing agent and the cross-linking agent in the step 2 and the step 3 is distributed with the proportion of the monomers in the step 2 and the step 3;

and 4, step 4: adding an initiator solution for eliminating residual monomers in the solution at one time, and reacting for 0.5 h; 20g of solvent is used for the initiator solution, and the amount of the initiator in the step 4 is 0.2 g; the initiators in steps 3 and 4 are all azobisisobutyronitrile.

And 5: carrying out suction filtration at normal pressure and drying in a vacuum drying oven for half a day to obtain polymer powder;

the proportion of the dispersing agent in the step 2 and the step 3 is 2:8, the total amount of the dispersing agent is 0.8g, and the dispersing agent is sodium dodecyl sulfate.

Comparative example 1

Analogously to example 1, the points of distinction are: no N, N-dimethylacrylamide was added.

Comparative example 2

Analogously to example 1, the points of distinction are: methyl methacrylate was not added.

Comparative example 3

Analogously to example 1, the points of distinction are: the ratio of the monomers in step 2 and step 3 is 1: 1.

test items

The test items were viscosity and light transmittance were measured with the addition amount of the polymer thickener powder of which ethanol gel (ethanol concentration was 80 vol%) was 1%.

The viscosity was measured as follows: viscosity measured at 20 revolutions per minute with a Brookfield DV-II viscometer;

the light transmittance test instrument is as follows: (model 725 ultraviolet-visible spectrophotometer, Shanghai prism technology Co., Ltd.).

TABLE 1 test results of examples and comparative examples