CN114163740A - Method for improving hydrophilicity of polyolefin elastomer - Google Patents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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Abstract
The invention discloses a method for improving the hydrophilicity of a polyolefin elastomer, which comprises the following steps: adding chitosan into acetic acid water solution to prepare chitosan solution; adding dodecanal and tetrabutylammonium bromide into the chitosan solution, heating, stirring, adjusting the pH value with alkali liquor, and adding sodium borohydride; then adjusting the solution to be weakly acidic, adding dodecanal, adjusting the pH value with alkaline solution, and adding sodium borohydride; then adjusting the pH value with alkali liquor, washing the precipitated product with distilled water to be neutral, washing with acetone for several times, and drying to obtain N, N-didodecyl chitosan; dissolving N, N-didodecyl chitosan in tetrahydrofuran to obtain a solution A; dissolving a polyolefin elastomer in tetrahydrofuran to obtain a solution B; and mixing the solution A and the solution B, pouring the mixed solution into a mold, and airing to obtain the N, N-didodecyl chitosan modified polyolefin elastomer composite material. The method of the present invention can effectively improve the hydrophilicity of the polyolefin elastomer.
Description
Technical Field
The present invention relates to a method for improving the hydrophilicity of a polyolefin elastomer.
Background
The polyolefin elastomer is a high polymer material with high yield and wide application because of rich raw materials, low price, easy processing and forming and excellent comprehensive performance, and can be applied to the fields of medical gloves, medical catheters and the like. However, the polyolefin elastomer has a relatively hydrophobic surface, and the comfort of the polyolefin elastomer is greatly influenced when the polyolefin elastomer is used for a human body. Therefore, it is of great importance to increase the hydrophilicity of polyolefin elastomers.
Disclosure of Invention
The object of the present invention is to provide a method for improving the hydrophilicity of a polyolefin elastomer, which method is capable of improving the hydrophilicity of a polyolefin elastomer.
The invention is realized by adopting the following technical scheme:
a method of improving the hydrophilicity of a polyolefin elastomer comprising the steps of:
a method for improving the hydrophilicity of a polyolefin elastomer comprises the following specific steps:
1) adding chitosan powder into 2-5% acetic acid water solution, stirring for 0.5-1 h to obtain chitosan solution with the concentration of 2-5%;
2) heating the chitosan solution in the step 1) to 40-60 ℃, and adding dodecanal and tetrabutylammonium bromide; then heating to 90-100 ℃, stirring for 8-12 hours, adjusting the pH to 7.0-8.0 by using KOH, NaOH or LiOH solution, adding sodium borohydride, and continuously heating and stirring for 2-3 hours;
3) adjusting the pH value of the solution obtained in the step 2) to 4.5-6.2 by using glacial acetic acid, adding dodecanal again, stirring for 8-12 hours at 90-100 ℃, adjusting the pH value to 7.0-8.0 by using KOH, NaOH or LiOH solution, adding sodium borohydride, and continuously heating and stirring for 2-3 hours; after the second reduction reaction is finished, regulating the pH value to 9.0-10.0 by using KOH, NaOH or LiOH solution, washing the precipitated product to be neutral by using distilled water, and washing the product for several times by using acetone; putting the product in a vacuum drying oven, and drying to constant weight to obtain N, N-didodecyl chitosan;
4) adding N, N-didodecyl chitosan into tetrahydrofuran solvent, heating to 50-65 ℃, stirring for 2-5 hours to obtain 1-2% N, N-didodecyl chitosan solution, and marking as solution A;
5) adding a polyolefin elastomer into a tetrahydrofuran solvent, heating to 50-65 ℃, stirring for 4-6 hours to prepare 1-2% of polyolefin elastomer solution, and marking as solution B;
6) mixing the solution A and the solution B according to different proportions to prepare an N, N-didodecyl chitosan-polyolefin elastomer mixed solution;
7) and (3) pouring the mixed solution obtained in the step 6) into a mold, and then putting the mold in a fume hood for airing to obtain the N, N-didodecyl chitosan modified polyolefin elastomer composite material.
In the above technical solution, the polyolefin elastomer is a copolymer obtained by polymerizing ethylene and propylene under the catalysis of a metallocene catalyst, wherein the content of an ethylene structural unit in the copolymer is 60% to 80%, the content of a propylene structural unit in the copolymer is 20% to 40%, and the polyolefin elastomer can be dissolved in a tetrahydrofuran solvent.
Furthermore, the mass percentage of the N, N-didodecyl chitosan in the N, N-didodecyl chitosan-polyolefin elastomer composite material is 10-30%.
Further, in the step 2), the feeding ratio of the dodecanal, the tetrabutylammonium bromide and the sodium borohydride to the chitosan is 2.8-11.2 mL: 1-2 g: 0.8-2 g: 2g of the total weight.
Further, in the step 3), the feeding ratio of the dodecanal to the sodium borohydride to the chitosan is 2.8-11.2 mL: 0.8-2 g: 2g of the total weight.
The invention principle of the invention is as follows:
chitosan is a natural polysaccharide, contains a large amount of hydroxyl and amino functional groups on a molecular chain, has good hydrophilicity, is non-toxic, non-irritant and non-allergenic, and is widely applied to the fields of medicine, daily chemicals, food, environmental protection, textile, agriculture and the like. According to the invention, the molecular compatibility of chitosan and the polyolefin elastomer is improved by carrying out double dodecyl modification on the chitosan, so that the hydrophilicity and the human body affinity of the polyolefin elastomer are improved, and the application prospect of the polyolefin elastomer in the field of biomedicine is expanded.
The invention has the beneficial effects that:
the surface of the polyolefin elastomer is relatively hydrophobic, and the contact angle reaches 110.1 degrees, so that the comfort of human body use is influenced. The chitosan is a natural polysaccharide, contains a large amount of hydroxyl and amino functional groups on a molecular chain, and has good hydrophilicity. However, chitosan and polyolefin elastomer have poor molecular compatibility, and the polyolefin elastomer cannot be modified with chitosan by a direct blending method. The invention improves the molecular compatibility of chitosan and polyolefin elastomer by carrying out double dodecyl modification on the chitosan, thereby improving the hydrophilicity of the polyolefin elastomer, reducing the contact angle of the modified polyolefin elastomer to 97.6 degrees, and having good application prospect in the fields of medical catheters, medical gloves and the like.
Drawings
FIG. 1 photograph of contact angles before and after modification of polyolefin elastomer: a) a polyolefin elastomer before modification; b-d) is modified polyolefin elastomer, and the mass percentages of the N, N-didodecyl chitosan are respectively 10%, 20% and 30%.
Detailed Description
The invention is further illustrated by the following specific examples.
Example 1:
1) adding 2g of chitosan powder into 100mL of 2% acetic acid aqueous solution, and stirring for 0.5 hour to obtain a chitosan solution, wherein the concentration of the chitosan solution is 2%;
2) heating the chitosan solution in the step 1) to 40 ℃, and adding 2.8mL of dodecanal and 1g of tetrabutylammonium bromide; then heating to 90 ℃, stirring for 8 hours, adjusting the pH value to 7.0 by using a KOH solution, adding 0.8g of sodium borohydride, and continuously heating and stirring for 2 hours;
3) adjusting the pH of the solution in the step 2) to 4.5 by using glacial acetic acid, adding 2.8mL of dodecanal again, stirring for 8 hours at 90 ℃, adjusting the pH to 7.0 by using a KOH solution, adding 0.8g of sodium borohydride, and continuing to heat and stir for 2 hours; after the second reduction reaction is finished, regulating the pH value to 9.0 by using a KOH solution, washing a precipitated product to be neutral by using distilled water, and washing the product for several times by using acetone; putting the product in a vacuum drying oven, and drying to constant weight to obtain N, N-didodecyl chitosan;
4) adding N, N-didodecyl chitosan into tetrahydrofuran solvent, heating to 50 ℃, stirring for 2 hours to obtain 1% N, N-didodecyl chitosan solution, and marking as solution A;
5) adding a polyolefin elastomer into a tetrahydrofuran solvent, heating to 50 ℃, and stirring for 4 hours to prepare a 1% polyolefin elastomer solution, which is marked as solution B;
6) mixing the solution A and the solution B according to the volume ratio of 1:9 to prepare an N, N-didodecyl chitosan-polyolefin elastomer mixed solution;
7) and (3) pouring the mixed solution obtained in the step 6) into a mold, and then putting the mold in a fume hood for airing to obtain the N, N-didodecyl chitosan modified polyolefin elastomer composite material.
The polyolefin elastomer had an ethylene structural unit content of 60% and a propylene structural unit content of 40%. The N, N-didodecyl chitosan has good molecular compatibility with the polyolefin elastomer, the mass percentage of the N, N-didodecyl chitosan in the N, N-didodecyl chitosan-polyolefin elastomer composite material is 10%, the contact angle of the modified polyolefin elastomer is 103.5 degrees, and the hydrophilicity of the polyolefin elastomer is improved.
Example 2:
1) adding 2g of chitosan powder into 50mL of 4% acetic acid aqueous solution, and stirring for 45 minutes to prepare a chitosan solution, wherein the concentration of the chitosan solution is 4%;
2) heating the chitosan solution in the step 1) to 50 ℃, and adding 8.4mL of dodecanal and 1.5g of tetrabutylammonium bromide; then heating to 95 ℃, stirring for 10 hours, adjusting the pH value to 7.5 by using NaOH solution, adding 1g of sodium borohydride, and continuously heating and stirring for 2.5 hours;
3) adjusting the pH of the solution in the step 2) to 5.5 by using glacial acetic acid, adding 8.4mL of dodecanal again, stirring at 95 ℃ for 10 hours, adjusting the pH to 7.5 by using a NaOH solution, adding 1g of sodium borohydride, and continuing to heat and stir for 2.5 hours; after the second reduction reaction is finished, adjusting the pH value to 9.5 by using NaOH solution, washing the precipitated product to be neutral by using distilled water, and washing the product for several times by using acetone; putting the product in a vacuum drying oven, and drying to constant weight to obtain N, N-didodecyl chitosan;
4) adding N, N-didodecyl chitosan into tetrahydrofuran solvent, heating to 55 ℃, stirring for 3 hours to obtain 1.5% N, N-didodecyl chitosan solution, and marking as solution A;
5) adding a polyolefin elastomer into a tetrahydrofuran solvent, heating to 55 ℃, stirring for 5 hours to prepare a 1.5% polyolefin elastomer solution, and marking as a solution B;
6) mixing the solution A and the solution B according to the volume ratio of 2:8 to prepare an N, N-didodecyl chitosan-polyolefin elastomer mixed solution;
7) and (3) pouring the mixed solution obtained in the step 6) into a mold, and then putting the mold in a fume hood for airing to obtain the N, N-didodecyl chitosan modified polyolefin elastomer composite material.
The polyolefin elastomer had an ethylene structural unit content of 70% and a propylene structural unit content of 30%. The N, N-didodecyl chitosan has good molecular compatibility with the polyolefin elastomer, the mass percentage of the N, N-didodecyl chitosan in the N, N-didodecyl chitosan-polyolefin elastomer composite material is 20%, the contact angle of the modified polyolefin elastomer is 101.3 degrees, and the hydrophilicity of the polyolefin elastomer is improved.
Example 3:
1) adding 2g of chitosan powder into 40mL of 5% acetic acid aqueous solution, and stirring for 1 hour to prepare a chitosan solution, wherein the concentration of the chitosan solution is 5%;
2) heating the chitosan solution in the step 1) to 60 ℃, and adding 11.2mL of dodecanal and 2g of tetrabutylammonium bromide; then heating to 100 ℃, stirring for 12 hours, adjusting the pH to 8.0 by using LiOH solution, adding 1.4g of sodium borohydride, and continuously heating and stirring for 3 hours;
3) adjusting the pH value of the solution obtained in the step 2) to 6.2 by using glacial acetic acid, adding 11.2mL of dodecanal again, stirring at 100 ℃ for 12 hours, adjusting the pH value to 8.0 by using a LiOH solution, adding 1.4g of sodium borohydride, and continuing heating and stirring for 3 hours; after the second reduction reaction is finished, adjusting the pH value to 10.0 by using LiOH solution, washing the precipitated product to be neutral by using distilled water, and washing the product for several times by using acetone; putting the product in a vacuum drying oven, and drying to constant weight to obtain N, N-didodecyl chitosan;
4) adding N, N-didodecyl chitosan into tetrahydrofuran solvent, heating to 65 ℃, stirring for 5 hours to obtain 2% N, N-didodecyl chitosan solution, and marking as solution A;
5) adding a polyolefin elastomer into a tetrahydrofuran solvent, heating to 65 ℃, and stirring for 6 hours to prepare a 2% polyolefin elastomer solution, which is marked as solution B;
6) mixing the solution A and the solution B according to the volume ratio of 3:7 to prepare an N, N-didodecyl chitosan-polyolefin elastomer mixed solution;
7) and (3) pouring the mixed solution obtained in the step 6) into a mold, and then putting the mold in a fume hood for airing to obtain the N, N-didodecyl chitosan modified polyolefin elastomer composite material.
The polyolefin elastomer had an ethylene structural unit content of 80% and a propylene structural unit content of 20%. The N, N-didodecyl chitosan has good molecular compatibility with the polyolefin elastomer, the mass percentage of the N, N-didodecyl chitosan in the N, N-didodecyl chitosan-polyolefin elastomer composite material is 30%, the contact angle of the modified polyolefin elastomer is 97.6 degrees, and the hydrophilicity of the polyolefin elastomer is improved.
Claims (5)
1. A method for improving the hydrophilicity of a polyolefin elastomer is characterized by comprising the following specific steps:
1) adding chitosan powder into 2-5% acetic acid water solution, stirring for 0.5-1 h to obtain chitosan solution with the concentration of 2-5%;
2) heating the chitosan solution in the step 1) to 40-60 ℃, and adding dodecanal and tetrabutylammonium bromide; then heating to 90-100 ℃, stirring for 8-12 hours, adjusting the pH to 7.0-8.0 by using KOH, NaOH or LiOH solution, adding sodium borohydride, and continuously heating and stirring for 2-3 hours;
3) adjusting the pH value of the solution obtained in the step 2) to 4.5-6.2 by using glacial acetic acid, adding dodecanal again, stirring for 8-12 hours at 90-100 ℃, adjusting the pH value to 7.0-8.0 by using KOH, NaOH or LiOH solution, adding sodium borohydride, and continuously heating and stirring for 2-3 hours; after the second reduction reaction is finished, regulating the pH value to 9.0-10.0 by using KOH, NaOH or LiOH solution, washing the precipitated product to be neutral by using distilled water, and washing the product for several times by using acetone; putting the product in a vacuum drying oven, and drying to constant weight to obtain N, N-didodecyl chitosan;
4) adding N, N-didodecyl chitosan into tetrahydrofuran solvent, heating to 50-65 ℃, stirring for 2-5 hours to obtain 1-2% N, N-didodecyl chitosan solution, and marking as solution A;
5) adding a polyolefin elastomer into a tetrahydrofuran solvent, heating to 50-65 ℃, stirring for 4-6 hours to prepare 1-2% of polyolefin elastomer solution, and marking as solution B;
6) mixing the solution A and the solution B according to different proportions to prepare an N, N-didodecyl chitosan-polyolefin elastomer mixed solution;
7) and (3) pouring the mixed solution obtained in the step 6) into a mold, and then putting the mold in a fume hood for airing to obtain the N, N-didodecyl chitosan modified polyolefin elastomer composite material.
2. The method of claim 1, wherein the polyolefin elastomer is a copolymer obtained by polymerizing ethylene and propylene under the catalysis of metallocene catalyst, the content of ethylene structural units in the copolymer is 60% to 80%, the content of propylene structural units in the copolymer is 20% to 40%, and the polyolefin elastomer is soluble in tetrahydrofuran solvent.
3. The method for improving the hydrophilicity of polyolefin elastomer as claimed in claim 1, wherein the mass percentage of N, N-didodecyl chitosan in the N, N-didodecyl chitosan-polyolefin elastomer composite material is 10% -30%.
4. The method for improving the hydrophilicity of the polyolefin elastomer as claimed in claim 1, wherein in the step 2), the charge ratio of the dodecanal, the tetrabutylammonium bromide and the sodium borohydride to the chitosan is 2.8-11.2 mL: 1-2 g: 0.8-2 g: 2g of the total weight.
5. The method for improving the hydrophilicity of the polyolefin elastomer as claimed in claim 1, wherein in the step 3), the charge ratio of the dodecanal and the sodium borohydride to the chitosan is 2.8-11.2 mL: 0.8-2 g: 2g of the total weight.
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| JPH1017699A (en) * | 1996-07-03 | 1998-01-20 | Asahi Chem Ind Co Ltd | Moisture and water-absorbing molding and its production |
| CN1803852A (en) * | 2005-12-21 | 2006-07-19 | 华侨大学 | Method for preparing organic solvent soluble amphiphilic N,N-dilong chain alkyl chitosan |
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| CN109232913A (en) * | 2018-07-12 | 2019-01-18 | 廊坊市思丁生物科技发展有限公司 | EP rubbers-chitosan quaternary ammonium salt composite material preparation method and applications |
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