CN112409557B - Vegetable oil-based polyurethane film and preparation thereof - Google Patents
Vegetable oil-based polyurethane film and preparation thereof Download PDFInfo
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- CN112409557B CN112409557B CN202011334312.8A CN202011334312A CN112409557B CN 112409557 B CN112409557 B CN 112409557B CN 202011334312 A CN202011334312 A CN 202011334312A CN 112409557 B CN112409557 B CN 112409557B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
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- Polyurethanes Or Polyureas (AREA)
Abstract
A vegetable oil-based polyurethane film and its preparation are provided. The preparation method comprises the following steps: preparing hydroxylated epoxidized soybean oil from epoxidized soybean oil, polyethylene glycol and concentrated sulfuric acid; according to a certain proportion, diisocyanate and hydroxylated epoxidized soybean oil are added with a catalyst, heated by using an oil bath, vegetable oil-based polyurethane is prepared under the atmosphere of nitrogen protection, and a polytetrafluoroethylene plate is used for tape casting and film forming. The polyurethane film has good hydrophobicity, toughness and ductility, and meanwhile, the vegetable oil-based raw material is used for overcoming the difficulties of difficult degradation of materials and the like.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a plant oil-based polyurethane film and a preparation method thereof.
Background
As the application of polymer films in packaging field is becoming wider, the requirements on film properties are becoming stricter, and polyurethane has good comprehensive properties compared with other films with single properties. Polyurethane is an emerging organic polymer material, and even has the name of 'fifth large plastic' in the field of polymer materials, and is widely applied to various fields of national economy due to the excellent performance. The application fields of the product relate to light industry, chemical industry, electronics, textile, medical treatment, construction, building materials, automobiles, national defense, aerospace, aviation and the like. Polyurethane products are also growing in china. Compared with other polymer films, the polyurethane film has excellent tension, tensile force, toughness, ageing resistance, wear resistance, impact resistance and the like. The processing technology is simple, and the cost can be reduced. Polyurethanes are generally synthesized from polyols and diisocyanates by polyaddition. The hydroxyl-terminated polyester and hydroxyl-terminated polyether of the traditional synthetic polyurethane are mainly from petrochemical resource routes, and petrochemical resources are easy to be in shortage, so that the substitution of the polyester and polyether polyol by the bio-based polyol becomes a research hot spot.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a novel polyurethane film with high performance and exquisite appearance. The plant oil-based polyurethane film with good mechanical property, attractive appearance and good hydrophobicity is prepared by comparing and researching the existing polyurethane synthetic material, and the method for preparing the film is also provided.
The aim of the invention is achieved by the following scheme:
a vegetable oil-based polyurethane film comprising the steps of:
(1) Preparation of hydroxylated epoxy vegetable oil: a 250ml round bottom three-neck flask respectively connected with a mechanical stirrer, a condenser and a nitrogen inlet and outlet is used as a hydroxylation reaction container, polyethylene glycol, epoxy vegetable oil and a catalyst are added into the hydroxylation reaction container according to a certain proportion for reaction, and the whole reaction process is heated in an oil bath;
(2) Preparing a vegetable oil-based polyurethane film: adding hydroxylated epoxy vegetable oil, diisocyanate and catalyst into a reactor according to a certain proportion, reacting for 15-30min in an oil bath at 70-90 ℃, pouring into a beaker, adding an organic solvent for dissolution, pouring the dissolved solution onto a tetrafluoroethylene plate, and drying the solvent in an oven at 30-70 ℃ to obtain the vegetable oil-based polyurethane film.
The method comprises the steps of (1) heating, adding a proper amount of sodium carbonate solution to terminate the reaction, and further comprises the steps of separation and purification, wherein the steps of separation and purification are as follows: and cooling the mixture to room temperature, extracting the unreacted polyethylene glycol with deionized water, separating the solution, drying the organic layer to remove water, and performing rotary evaporation to obtain the light yellow viscous liquid hydroxylated epoxy vegetable oil.
In the step (1), the mixture is heated to 100-120 ℃ and the reaction time is 2-3 h.
The epoxidized vegetable oil in the step (1) is epoxidized soybean oil.
The polyethylene glycol in the step (1) is one of polyethylene glycol 200, polyethylene glycol 400 and polyethylene glycol 600.
The mol ratio of the polyethylene glycol to the epoxy vegetable oil in the step (1) is 1.6:1-3:1.
The catalyst in the step (1) is concentrated sulfuric acid, and the dosage of the catalyst is 0.3-0.5% of the total weight of the hydroxylated epoxidized vegetable oil reaction.
The diisocyanate in the step (2) is isophorone diisocyanate, and the dosage of the diisocyanate is 30-39.16% of the total mass of the film forming material.
The dosage of the hydroxylated epoxy vegetable oil in the step (2) is 60.68-69.83% of the total mass of the film forming substance.
The catalyst in the step (2) is dibutyl tin dilaurate, and the dosage of the dibutyl tin dilaurate is 0.13-0.17% of the total mass of the film forming substance.
The organic solvent in the step (2) is N, N-dimethylformamide, and a proper amount of organic solvent can be added when the viscosity is excessive in the reaction process.
The reaction process of step (1) and step (2) must be carried out under nitrogen atmosphere.
The invention has the advantages and positive effects that:
(1) Opens up a new application field for natural materials, improves the use value of the natural materials, and greatly relieves the pressure of petrochemical industry on the other hand.
(2) The polyurethane film prepared by the invention has good aesthetic property.
(3) The polyurethane film prepared by the invention has good hydrophobicity.
(4) The polyurethane film prepared by the invention has good toughness and ductility.
Detailed Description
The invention will now be described in further detail by way of specific examples, which are given by way of illustration only and not by way of limitation, with reference to the accompanying drawings.
Example 1
In this example, we have taken the formulation in table 1 for experimental study:
table 1 vegetable oil based polyurethane film formulations
(1) Preparation of hydroxylated epoxy vegetable oil: a250 ml round bottom three-neck flask respectively connected with a mechanical stirrer, a condenser and a nitrogen inlet and outlet is used as a hydroxylation reaction container, the reaction is added according to the mol ratio of polyethylene glycol 600 to epoxidized soybean oil of 1.66:1, the dosage of concentrated sulfuric acid is 0.5 percent of the total weight of the hydroxylation epoxidized vegetable oil, the whole reaction process is carried out under the nitrogen environment, 10ml of 0.1mol/l sodium carbonate solution is added after the oil bath is heated for 3 hours at 100 ℃ to terminate the reaction, the mixture is cooled to room temperature, the unreacted complete polyethylene glycol is extracted by deionized water, liquid separation is carried out, and the organic layer is dried and dehydrated, and then rotary evaporation is carried out, thus obtaining the light yellow viscous liquid hydroxylation epoxidized vegetable oil.
(2) Preparing a vegetable oil-based polyurethane film: hydroxylated epoxy vegetable oil, isophorone diisocyanate, dibutyltin dilaurate were added to the reactor according to the formulation in Table 1, reacted in an oil bath at 80℃and 5ml of N, N-dimethylformamide were added when a large number of bubbles had occurred.
(3) Film formation
Pouring polyurethane prepolymer into a beaker, pouring N, N-dimethylformamide, dissolving the prepolymer in a solvent at 40 ℃ under magnetic stirring, pouring the dissolved product into a polytetrafluoroethylene plate, and drying in a 50 ℃ oven to form a film.
(4) Performance testing
(1) Mechanical properties
The films were tested for tensile strength and elongation at break by preparing a spline according to astm d-882 test standard. The test results are shown in Table 6.
(2) Contact angle of water
Sample bars were prepared according to GB/T30693-2014 test standard to test the water contact angle of the films. The test results are shown in Table 6.
Example 2
In this example, we have taken the formulation in table 2 for experimental study:
table 2 vegetable oil based polyurethane film formulations
Other steps are the same as those of embodiment 1.
Performance testing
(1) Mechanical properties
The films were tested for tensile strength and elongation at break by preparing a spline according to astm d-882 test standard. The test results are shown in Table 6.
(2) Contact angle of water
Sample bars were prepared according to GB/T30693-2014 test standard to test the water contact angle of the films. The test results are shown in Table 6.
Example 3
In this example, we have taken the formulation in table 3 for experimental study:
table 3 vegetable oil based polyurethane film formulations
The other steps are the same as those of embodiment examples 1 to 2.
Performance testing
(1) Mechanical properties
The films were tested for tensile strength and elongation at break by preparing a spline according to astm d-882 test standard. The test results are shown in Table 6.
(2) Contact angle of water
Sample bars were prepared according to GB/T30693-2014 test standard to test the water contact angle of the films. The test results are shown in Table 6.
Example 4
In this example, we have taken the formulation in table 4 for experimental study:
table 4 vegetable oil based polyurethane film formulations
The other steps are the same as those of embodiment examples 1 to 3.
Performance testing
(1) Mechanical properties
The films were tested for tensile strength and elongation at break by preparing a spline according to astm d-882 test standard. The test results are shown in Table 6.
(2) Contact angle of water
Sample bars were prepared according to GB/T30693-2014 test standard to test the water contact angle of the films. The test results are shown in Table 6.
Example 5
In this example, we have taken the formulation in table 5 for experimental study:
table 5 vegetable oil based polyurethane film formulations
The other steps are the same as those of embodiment examples 1 to 4.
Performance testing
(1) Mechanical properties
The films were tested for tensile strength and elongation at break by preparing a spline according to astm d-882 test standard. The test results are shown in Table 6.
(2) Contact angle of water
Sample bars were prepared according to GB/T30693-2014 test standard to test the water contact angle of the films. The test results are shown in Table 6.
Table 6 examples one to five obtained final product test results
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that it will be apparent to those skilled in the art that variations and modifications can be made without departing from the scope of the invention.
Drawings
FIG. 1 is a flow chart of the method of the present invention.
Claims (2)
1. The preparation method of the vegetable oil-based polyurethane film is characterized by comprising the following steps of:
(1) Preparation of hydroxylated epoxy vegetable oil: a 250ml round bottom three-neck flask which is respectively connected with a mechanical stirrer, a condenser and a nitrogen inlet and outlet is adopted as a hydroxylation reaction vessel, polyethylene glycol, epoxy vegetable oil and a catalyst are added for reaction, and the whole reaction process is heated to 100-120 ℃ in an oil bath, and the reaction time is 2-3 h; the mol ratio of the polyethylene glycol to the epoxy vegetable oil is 1.6:1-3:1;
the catalyst in the step (1) is concentrated sulfuric acid, and the dosage of the catalyst is 0.3-0.5% of the total weight of the hydroxylated epoxidized vegetable oil reaction;
the epoxidized vegetable oil in the step (1) is epoxidized soybean oil;
the polyethylene glycol in the step (1) is polyethylene glycol 600;
(2) Preparing a vegetable oil-based polyurethane film: adding hydroxylated epoxy vegetable oil, diisocyanate and a catalyst into a reactor, reacting for 15-30min in an oil bath at 70-90 ℃, pouring into a beaker, adding an organic solvent for dissolution, pouring the dissolved solution onto a tetrafluoroethylene plate, and placing into a baking oven at 30-70 ℃ to dry the solvent, thus obtaining the vegetable oil-based polyurethane film; the total mass of the film forming material is 64.05%, the total mass of the film forming material is 35.81% and the total mass of the film forming material is 35.14% respectively, the total mass of the film forming material is 62.32%, the total mass of the film forming material is 37.53%, the total mass of the film forming material is 0.15%, the total mass of the film forming material is 60.70%, the total mass of the film forming material is 39.16%, and the total mass of the film forming material is 0.14%;
the diisocyanate in the step (2) is isophorone diisocyanate;
the catalyst in the step (2) is dibutyl tin dilaurate; the organic solvent in the step (2) is N, N-dimethylformamide, and a proper amount of organic solvent can be added when the viscosity is excessive in the reaction process; the reaction process in the step (1) and the step (2) must be carried out under a nitrogen atmosphere.
2. The vegetable oil-based polyurethane film of claim 1, wherein the reaction is terminated by adding an appropriate amount of sodium carbonate solution after heating in step (1), and further comprising a separation and purification step.
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| CN102206154A (en) * | 2011-03-11 | 2011-10-05 | 清华大学 | Vegetable oil polyol and preparation method thereof |
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| TR201611717A2 (en) * | 2016-08-19 | 2016-10-21 | Form Suenger Ve Yatak Sanayi Ticaret Anonim Sirketi | COTTON OIL BASED SPONGE |
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