Polyvinyl alcohol composition, preparation method thereof, and polyvinyl alcohol medical catheter containing thereof

Abstract

The present application discloses a polyvinyl alcohol composition, as well as a preparation method and polyvinyl alcohol medical catheter containing thereof, wherein raw materials include the following components: 60-90 parts of polyvinyl alcohol; 0.1-3 parts of glutaraldehyde; and the polyvinyl alcohol composition is made by mixing the polyvinyl alcohol in molten state with the glutaraldehyde in an acidic environment.

Claims

1. A polyvinyl alcohol composition, wherein raw materials of the polyvinyl alcohol composition comprise the following components in parts by weight: 60-90 parts of polyvinyl alcohol; and 0.1-3 parts of glutaraldehyde; and the polyvinyl alcohol composition is made by mixing the polyvinyl alcohol in molten state with the glutaraldehyde in an acidic environment.

2. The polyvinyl alcohol composition according to claim 1, wherein the raw materials of the polyvinyl alcohol composition further comprise 4-10 parts of urea by weight.

3. The polyvinyl alcohol composition according to claim 2, wherein the raw materials of the polyvinyl alcohol composition further comprise 5-15 parts of glycerol and 2-10 parts of calcium chloride by weight.

4. The polyvinyl alcohol composition according to claim 3, wherein the raw materials of the polyvinyl alcohol composition comprise the following components in parts by weight: 76-85 parts of polyvinyl alcohol; 5.4-6.5 parts of urea; 8-11 parts of glycerol; 3-5 parts of calcium chloride; 0.4-0.6 part of glutaraldehyde; 0.1-2 parts of acid; wherein the acid is one of a 10-98 mass % sulfuric acid aqueous solution, an aliphatic carboxylic acid, pyrophosphoric acid, and disulfuric acid.

5. The polyvinyl alcohol composition according to claim 1, wherein a polymerization degree of the polyvinyl alcohol is 300-7,000, and an alcoholysis degree of the polyvinyl alcohol is 50-99%.

6. A preparation method of the polyvinyl alcohol composition according to claim 1, comprising: step 1: mixing polyvinyl alcohol with the acid, heating at a heating temperature of 140-220° C. to melt the polyvinyl alcohol to obtain an acidic polyvinyl alcohol material, and then pelletizing the acidic polyvinyl alcohol material at 140-220° C. to provide pellets; step 2: uniformly mixing the pellets with glutaraldehyde at 140-220° C. to obtain an intermediate material of the polyvinyl alcohol composition; step 3: soaking the intermediate material of the polyvinyl alcohol composition in a 5-10 mass % sodium hydroxide solution for 24-48 hours; and step 4: taking the intermediate material of the polyvinyl alcohol composition out of the sodium hydroxide solution and washing with deionized water to obtain the polyvinyl alcohol composition.

7. The preparation method of the polyvinyl alcohol composition according to claim 6, wherein in step 1, 4-10 parts of urea, 5-15 parts of glycerol, and 2-10 parts of calcium chloride are added to the mixture of the polyvinyl alcohol and the acid before heating.

8. A polyvinyl alcohol medical catheter, wherein the polyvinyl alcohol medical catheter is made from the polyvinyl alcohol composition of claim 4, and a surface of the polyvinyl alcohol medical catheter is coated with a coating comprising vinyl pyrrolidone, 2-hydroxyl-4′-(2-hydroxyethoxy)-2-methylpropiophenone, N,N′-methylenebisacrylamide, and ethanol at a mass ratio of vinyl pyrrolidone,2-hydroxyl-4′-(2-hydroxyethoxy)-2-methylpropiophenone,N,N′-methylenebisacrylamide and ethanol of 3:1:0.04:95.96.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows DSC test results of examples 1-5 and comparative examples 1-4.

DETAILED DESCRIPTION

Example 1

(2) A polyvinyl alcohol composition having the components of the raw materials shown in table 1 was prepared, in which the acid is aliphatic carboxylic acid, the polymerization degree of the polyvinyl alcohol is 7,000, and the alcoholysis degree is 99%.

(3) The polyvinyl alcohol composition was prepared as follows: step 1: polyvinyl alcohol, glycerol, calcium chloride, and the acid were mixed, extruded with an extruder, and pelletized with a pelletizer to obtain an acidic polyvinyl alcohol material, in which the extruder is a twin screw extruder, the length diameter ratio is 40-60:1, and the temperature inside the extruder is 160-220° C.

(4) Step 2: glutaraldehyde and the acidic polyvinyl alcohol material obtained in step 1 were mixed and extruded with an extruder to obtain an intermediate material of the polyvinyl alcohol composition, in which the temperature inside the extruder is 160-220° C.

(5) Step 3: the intermediate material of the polyvinyl alcohol composition from step 2 was cooled and then soaked in a 5 mass % sodium hydroxide solution for 24-48 hours.

(6) Step 4: the intermediate material of the polyvinyl alcohol composition was taken out of the sodium hydroxide solution and washed with deionized water to obtain the polyvinyl alcohol composition.

Example 2

(7) A polyvinyl alcohol composition having the components of the raw materials shown in table 1 was prepared, in which the acid is pyrophosphoric acid, the polymerization degree of the polyvinyl alcohol is 6,000, and the alcoholysis degree is 80%.

(8) The polyvinyl alcohol composition was prepared as follows: step 1: the polyvinyl alcohol, urea, glycerol, calcium chloride, and the acid were mixed, extruded with an extruder, and pelletized with a pelletizer to obtain an acidic polyvinyl alcohol material, in which the extruder is a twin screw extruder, the length diameter ratio is 40-60:1, and the temperature inside the extruder is 150-180° C.

(9) Step 2: glutaraldehyde and the acidic polyvinyl alcohol material obtained in step 1 were mixed and extruded with an extruder to obtain an intermediate material of the polyvinyl alcohol composition, in which the temperature inside the extruder is 150-180° C.

(10) Step 3: the intermediate material of the polyvinyl alcohol composition from step 2 was cooled and then soaked in a 8 mass % sodium hydroxide solution for 24-48 hours.

(11) Step 4: the intermediate material of the polyvinyl alcohol composition was taken out of the sodium hydroxide solution and washed with deionized water to obtain the polyvinyl alcohol composition.

Example 3

(12) A polyvinyl alcohol composition having components of the raw materials of the polyvinyl alcohol composition shown in table 1 was prepared, in which the acid is disulfuric acid, the polymerization degree of the polyvinyl alcohol is 4,000, and the alcoholysis degree is 70%.

Example 4

(13) A polyvinyl alcohol composition having the components of the raw materials shown in table 1 was prepared, in which the acid is 10 mass % sulfuric acid aqueous solution, the polymerization degree of the polyvinyl alcohol is 2,000, and the alcoholysis degree is 50%.

(14) The polyvinyl alcohol composition was prepared as follows: step 1: the polyvinyl alcohol, urea, glycerol, calcium chloride, and the acid were mixed, extruded with an extruder, and pelletized with a pelletizer to obtain an acidic polyvinyl alcohol material, in which the extruder is a twin screw extruder, the length diameter ratio is 40-60:1, and the temperature inside the extruder is 140-160° C.

(15) Step 2: glutaraldehyde and the acidic polyvinyl alcohol material obtained in step 1 were mixed and extruded with an extruder to obtain an intermediate material of the polyvinyl alcohol composition, in which the temperature inside the extruder is 140-160° C.

(16) Step 3: the intermediate material of the polyvinyl alcohol composition from step 2 was cooled and then soaked in a 10 mass % sodium hydroxide solution for 24-48 hours.

(17) Step 4, the intermediate material of the polyvinyl alcohol composition was taken out of the sodium hydroxide solution and washed with deionized water to obtain the polyvinyl alcohol composition.

Example 5

(18) A polyvinyl alcohol composition was prepared, differing from example 4 in that, the components of the raw materials of the polyvinyl alcohol are as shown in table 1, in which the acid is a 98 mass % sulfuric acid aqueous solution. The polymerization degree of the polyethylene is 300, and the alcoholysis degree is 50%. In preparing the polyethylene composition, the temperature inside the extruder in step 1 is 140-220° C., and the temperature inside the extruder in step 2 is 140-220° C.

Example 6

(19) A polyvinyl alcohol medical catheter made of a polyvinyl alcohol composition was prepared. The raw materials of the polyvinyl alcohol composition include the components as shown in table 1, in which the acid is a 60 mass % sulfuric acid aqueous solution, the polymerization degree of the polyvinyl alcohol is 300-7,000, and the degree of alcoholysis is 50-99%. The material of the polyvinyl alcohol medical catheter is the polyvinyl alcohol composition, and it's surface is coated with a coating, and the raw materials of the coating included vinyl pyrrolidone, 2-hydroxyl-4′-(2-hydroxyethoxy)-2-methylpropiophenone, N,N′-methylenebisacrylamide, and ethanol.

(20) The polyvinyl alcohol medical catheter was prepared as follows: step 1: polyvinyl alcohol, glycerol, calcium chloride, the acid, and urea were mixed, extruded with an extruder, and pelletized to obtain an acidic polyvinyl alcohol material, wherein the extruder is a twin screw extruder, the length diameter ratio of the screw is 40-60:1, and the temperature inside the extruder is 140-220° C.

(21) Step 2: glutaraldehyde and the acidic polyvinyl alcohol material obtained in step (1) were mixed and extruded with an extruder to obtain a polyvinyl alcohol pipe, wherein the temperature inside the extruder is 140-220° C.

(22) Step 3: the polyvinyl alcohol pipe was cooled and then soaked in a 5-10 mass % sodium hydroxide solution for 24-48 hours.

(23) Step 4: the polyvinyl alcohol pipes was taken out of the sodium hydroxide solution, washed with deionized water, and cut into a polyvinyl alcohol catheter.

(24) Step 5: the polyvinyl alcohol catheter was coated with a mixed solution and treated with ultraviolet radiation to obtain a polyvinyl alcohol catheter with coating on the surface, in which the mixed solution include vinyl pyrrolidone, 2-hydroxyl-4′-(2-hydroxyethoxy)-2-methylpropiophenone, N,N′-methylenebisacrylamide, and ethanol, where the mass ratio of the components of the mixed solution was: vinyl pyrrolidone:2-hydroxyl-4′-(2-hydroxyethoxy)-2-methylpropiophenone:N,N′-methylenebisacrylamide:ethanol=3:1:0.04:95.96. The range of the ultraviolet wavelength during the treatment with ultraviolet radiation is 365-370 nm.

(25) Step 6: the polyvinyl alcohol catheter with coating on the surface was soaked in an aqueous Artemisia capillaris water-soluble antibacterial solution.

(26) Step 7: the polyvinyl alcohol catheter soaked in the aqueous Artemisia capillaris water-soluble antibacterial solution was taken out and sterilized with radiation, wherein cobalt 60 is used for the sterilization with radiation, and the radiant quantity is 0.5-1.5 KGy.

(27) Wherein, each of the 100 ml of the aqueous Artemisia capillaris water-soluble antibacterial solution was prepared as follows: a: 10 g of material, that is, a whole plant of the Artemisia capillaris, was weighed and added into an Erlenmeyer flask; b: adding water: 150 g of distilled water was added into the Erlenmeyer flask; c: leaching: the Erlenmeyer flask was thermostatically treated at 60° C. for 80 minutes; d: bringing to volume: the mixture in the Erlenmeyer flask was poured into a volumetric flask through a funnel, then water was added into the volumetric flask to the volume of 500 mL, and the mixture was shaked multiple times and let stand for 10 minutes; e, filtering: the mixture was filtered with a funnel to obtain 100 mL of filtrate, i.e., the aqueous Artemisia capillaris water-soluble antibacterial solution.

(28) Step 8: the polyvinyl alcohol catheter subjected to sterilization with radiation was sealed and packaged to obtain a finished product of the polyvinyl alcohol medical catheter.

Example 7

(29) A sealing gasket was made from any of the polyvinyl alcohol compositions of examples 1-5. The polyvinyl alcohol composition was injected by using a plastic injection molding machine into a mold so as to be shaped into a sealing gasket. Since the polyvinyl alcohol has the water absorbency, the sealing gasket swells after absorption of water, which increases the sealing property of the sealing gasket.

Example 8

(30) A desiccant was made from any of the polyvinyl alcohol compositions of examples 1-5. The preparation method was as follows: the polyvinyl alcohol composition was cut into pieces to obtain a desiccant. The polyvinyl alcohol in the desiccant has water absorbency, so that it absorbs water and provides a good drying effect.

Example 9

(31) An oil pipe was made from any of the polyvinyl alcohol compositions of examples 1-5. The preparation method of the oil pipe was as follows: step 1: the polyvinyl alcohol, glycerol, calcium chloride, the acid, and urea are mixed, extruded with an extruder, and pelletized to obtain an acidic polyvinyl alcohol material, wherein the extruder is a twin screw extruder, the length diameter ratio of the screw is 40-60:1, and the temperature inside the extruder is 140-220° C.

(32) Step 2: glutaraldehyde and the acidic polyvinyl alcohol material obtained in step 1) were mixed and extruded with an extruder to obtain a polyvinyl alcohol pipe, wherein the temperature inside the extruder is 140-220° C.

(33) Step 3: the polyvinyl alcohol pipes were cooled and then soaked in a 5-10 mass % sodium hydroxide solution for 24-48 hours.

(34) Step 4: the polyvinyl alcohol pipe was taken out of the sodium hydroxide solution, washed with deionized water, and cut into an oil pipe. The oil pipe obtained has the advantages of good air barrier property and smooth inner wall.

Example 10

(35) A handbag was made from any of the polyvinyl alcohol compositions of examples 1-5, wherein the handbag was made by a blow molding process. The handbag as obtained is susceptible to degradation in the environment after usage.

Example 11

(36) An insole was made from any of the polyvinyl alcohol compositions of examples 1-5, in which the polyvinyl alcohol composition was injected into a mold by a plastic injection molding machine to be shaped into an insole. The raw materials of the insole contain the polyvinyl alcohol having water absorbency, therefore the insole has the ability of absorbing sweat.

Example 12

(37) A flowerpot was made by mixing any of the polyvinyl alcohol compositions of examples 1-5 with a fertilizer. During the manufacturing the polyvinyl alcohol composition was heated to 140-220° C. The fertilizer was added and stirred until becoming homogeneous, and the mixture was poured into a mold so as to be cooled and shaped into a flowerpot. During using the flowerpot, the polyvinyl alcohol was continuously degraded, and thus the fertilizer contained in the flowerpot was continuously released to provide nutrients for the plant in the flowerpot.

Example 13

(38) A packaging bag was made from any of the polyvinyl alcohol compositions of examples 1-5, in which the packaging bag was made by a blow molding process. The packaging bag thus obtained is susceptible to degradation in the environment after use.

Comparative Example 1

(39) A polyvinyl alcohol with a polymerization degree of 300-7000 and an alcoholysis degree of 50%-99%.

Comparative Example 2

(40) A polyvinyl alcohol composition with the components of the raw materials shown in table 1, in which the polymerization degree of the polyvinyl alcohol is 300-7000, and the alcoholysis degree is 50%-99%.

(41) The polyvinyl alcohol composition was prepared as follows: step 1: the polyvinyl alcohol, glycerol, and calcium chloride were mixed, extruded with an extruder, and pelletized with a pelletizer to obtain a polyvinyl alcohol material, wherein the extruder is a twin screw extruder, the length diameter ratio is 40-60:1, and the temperature inside the extruder is 140-220° C.

(42) Step 2: glutaraldehyde and the polyvinyl alcohol material obtained in step 1 were mixed and extruded with an extruder to obtain a polyvinyl alcohol composition, in which the temperature inside the extruder was 140-220° C.

Comparative Example 3

(43) A polyvinyl alcohol composition with the components of the raw materials as shown in table 1, in which the polymerization degree of the polyvinyl alcohol is 3007000, and the alcoholysis degree is 50%-99%.

(44) The polyvinyl alcohol composition was prepared as follows: the polyvinyl alcohol, glycerol, and calcium chloride were mixed, extruded with an extruder, and pelletized with a pelletizer to obtain an acidic polyvinyl alcohol material, wherein the extruder is a twin screw extruder, the length diameter ratio is 40-60:1, and the temperature inside the extruder is 140-220° C. The acidic polyvinyl alcohol material was pelletized to provide a polyvinyl alcohol composition.

Comparative Example 4

(45) A polyvinyl alcohol composition with the components of the raw materials as shown in table 1, in which the polymerization degree of the polyvinyl alcohol is 3007000, and the alcoholysis degree is 50%-99%.

(46) The polyvinyl alcohol composition was prepared as follows: the polyvinyl alcohol, urea, glycerol, and calcium chloride were mixed, extruded with an extruder, and pelletized with a pelletizer to obtain an acidic polyvinyl alcohol composition, in which the extruder is a twin screw extruder, the length diameter ratio is 40-60:1, and the temperature inside the extruder is 140-220° C. The acidic polyvinyl alcohol composition was pelletized to obtain the polyvinyl alcohol composition.

(47) TABLE-US-00001 TABLE 1 Polyvinyl Calcium Glutaral- alcohol Urea Glycerol chloride dehyde Acid (Kg) (Kg) (Kg) (Kg) (Kg) (Kg) Example 1 76 0 8 3 0.4 0.1 Example 2 76 5.4 8 3 0.4 0.1 Example 3 85 6.5 11 5 0.6 0.6 Example 4 60 10 5 10 0.1 1 Example 5 90 4 15 2 3 2 Example 6 85 6.5 11 5 0.6 0.6 Comparative 76 0 8 3 0.4 0 Example 2 Comparative 76 0 8 3 0 0 Example 3 Comparative 76 5.4 8 3 0 0 Example 4

(48) The polyvinyl alcohol composition was test regarding the melting temperature: The polyvinyl alcohol compositions of examples 1-5 and comparative examples 1-4 and the polyvinyl alcohol of comparative example 1 were subjected to a DSC test, that is, Differential Scanning Calorimetry test, respectively. The test results are shown in FIG. 1, wherein curve 1 is the test result of example 1, curve 2 is the test result of example 2, curve 3 is the test result of example 3, curve 4 is the test result of example 4, curve 5 is the test result of example 5, curve 6 is the test result of comparative example 1, curve 7 is the test result of comparative example 3, curve 8 is the test result of comparative example 4, and curve 9 is the test result of comparative example 2. The results of FIG. 1 show that all the melting points of the polyvinyl alcohol composition of examples 1-6 are apparently lower than the melting points of the polyvinyl alcohol of comparative example 1 and the polyvinyl alcohol composition of comparative examples 2-4.