CN111995860A - Graphene-reinforced waterborne polyurethane high-barrier material and condom - Google Patents

Graphene-reinforced waterborne polyurethane high-barrier material and condom Download PDF

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CN111995860A
CN111995860A CN202010842073.0A CN202010842073A CN111995860A CN 111995860 A CN111995860 A CN 111995860A CN 202010842073 A CN202010842073 A CN 202010842073A CN 111995860 A CN111995860 A CN 111995860A
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graphene
waterborne polyurethane
semi
latex
condom
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CN111995860B (en
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王绪英
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Chongqing Menduo New Material Technology Co ltd
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Chongqing Menduo New Material Technology Co ltd
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F6/00—Contraceptive devices; Pessaries; Applicators therefor
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Abstract

The invention provides a graphene-reinforced waterborne polyurethane high-barrier material and a condom. The high-barrier material adopts the modified graphene oxide to improve the compatibility with polyurethane materials, increases the interaction between the graphene and polyurethane molecular chains, and achieves the purpose of improving the mechanical property and the barrier property of polyurethane; and simultaneously, introducing carbon-carbon double bonds at the tail end of a polyurethane molecular chain, and bonding the carbon-carbon double bonds with the carbon-carbon double bonds on the natural latex molecular chain through free radical reaction, so that the fusion of the interface between the natural latex layer and the graphene/waterborne polyurethane interlayer is realized. The material can be used for manufacturing the graphene/polyurethane/natural latex composite structure condom with good barrier property and low cost.

Description

Graphene-reinforced waterborne polyurethane high-barrier material and condom
Technical Field
The invention relates to the field of high-barrier treatment and sanitary and family planning products, in particular to a preparation method of graphene oxide reinforced waterborne polyurethane applied to an intermediate layer of a latex condom and a product thereof.
Background
The natural latex condom has the advantages of easily available raw materials, simple production and manufacturing process and the like, and is the most widely used sexual life medical and health article for contraception and prevention of venereal disease transmission at present. Natural latex condoms are effective at sequestering sperm, but have the potential risk of sequestering viruses such as hepatitis b and aids in smaller diameter due to the presence of intrinsic pores in the material of about 5 microns. The water-based polyurethane is a green high polymer material, has good film forming compactness, safety, no toxicity and high strength, is widely applied to the medical field, and has thinner condom prepared by taking the water-based polyurethane as a raw material and good virus isolation effect.
Graphene is a novel two-dimensional nano material, and carbon atoms of the graphene form a hexagonal honeycomb structure by using an SP2 hybrid orbit, and the thickness of the graphene is only 0.34 nm. The graphene is the thinnest material and the toughest material, has excellent thermal conductivity and compactness, and researches prove that the compact structure of the graphene can prevent most substances from penetrating and only protons can pass through the regular hexagonal pore diameter, so that the graphene is an ideal material for preparing the high-barrier condom. Because the chemical bonding reaction between the graphene and the natural latex molecules is difficult to occur, the graphene and the natural latex molecules can not be directly blended to obtain an ideal compact structure. Many reports prove that the graphene can be compounded with the waterborne polyurethane in a chemical bonding mode, so that the strength and the puncture resistance of the waterborne polyurethane film can be improved, and the transparency of the waterborne polyurethane film can be maintained. The condom directly prepared by the graphene/waterborne polyurethane composite material has high cost and great difficulty in application and popularization.
The method is a good method for obtaining the condom with high barrier property and low cost by taking the graphene/waterborne polyurethane composite material as the middle interlayer and taking the natural latex as the cladding layers at the two sides to form the sandwich structure composite film.
In the prior art, the graphene condom is prepared by arranging graphene serving as an interlayer between polymer layers, but the graphene serving as the interlayer has poor dispersibility and poor interface compatibility between a graphene layer and the polymer layers, so that the condom performance is unstable. Therefore, for preparing the natural latex condom with the graphene/waterborne polyurethane composite as the interlayer, the molecular structure of the required waterborne polyurethane emulsion and the preparation method thereof need to be designed and improved in a targeted manner, so that the dispersion performance of the graphene in the waterborne polyurethane and the compatibility and the bonding force between the waterborne polyurethane interlayer and the natural latex layer are improved.
Disclosure of Invention
The invention aims to provide a graphene-reinforced waterborne polyurethane high-barrier material, which is characterized by comprising the following components in parts by weight: has a multi-layer structure; in the multilayer structure, each layer is formed by drying semi-vulcanized natural rubber emulsion or graphene/waterborne polyurethane emulsion.
Further, the multilayer structure is formed by drying the graphene/waterborne polyurethane emulsion to form an intermediate layer; after the semi-vulcanized natural rubber emulsion is dried, coating layers on two sides of the middle interlayer are formed; the graphene/waterborne polyurethane emulsion is an emulsion formed by modifying graphene oxide to improve the compatibility with a polyurethane material and increase the interaction between graphene and a polyurethane molecular chain; meanwhile, carbon-carbon double bonds are introduced at the tail end of a polyurethane molecular chain, so that the carbon-carbon double bonds are bonded with the carbon-carbon double bonds on the natural latex molecular chain through free radical reaction, and the fusion of the interface between the natural latex layer and the graphene/waterborne polyurethane interlayer is realized.
A method for improving the barrier property of a natural latex condom without increasing the thickness of the condom is obtained by the following method:
1) isocyanate functionalization of graphene oxide
1.1) mixing weighed graphene oxide, diisocyanate and N, N-Dimethylformamide (DMF) to obtain a mixed solution A;
the weight portion ratio of the raw materials is as follows:
1-10 parts of graphene oxide
1-10 parts of diisocyanate
100-1000 parts of N, N-dimethylformamide
1.2) fully reacting the mixed solution A obtained in the step 1.1) to obtain a product A;
1.3) washing the product A obtained in the step 1.1) to obtain a product B;
1.4) drying the product B to obtain a product C, namely, isocyanate functionalized graphene oxide (GONCO);
2) preparation of graphene/waterborne polyurethane emulsion
The components are prepared according to the following parts by weight:
Figure BDA0002641791480000021
5-10 parts of front chain extender
0.6-2.5 parts of vinyl end-capping agent
0.1-2 parts of post chain extender
0.05 to 0.1 portion of catalyst
The preparation method comprises the following steps:
2.1) adding GONCO and polyether polyol A into a reactor; when the polyester polyol B is selected, the polyester polyol B is added at the same time; vacuumizing at the temperature of 100-120 ℃ for removing water;
2.2) adding diisocyanate and a catalyst, and reacting for 1-3h at 70-80 ℃;
2.3) adding a chain extender to react for 1-3h at the temperature of 70-80 ℃;
2.4) adding a vinyl end-capping agent to react for 1 to 3 hours at the temperature of between 80 and 90 ℃;
2.5) adding a neutralizing agent to react for 0.5 to 1 hour at the temperature of between 25 and 50 ℃ to ensure that the pH value of a reaction system is more than 7.5;
2.6) adding deionized water under high-speed stirring for emulsification for 0.5-2h, adding a rear chain extender and stirring for 1h to obtain the graphene/waterborne polyurethane emulsion.
3) Obtaining semi-vulcanized natural rubber emulsion
Taking natural latex as a raw material, adding a stabilizer, a surfactant and sulfur for reaction to obtain semi-vulcanized natural rubber emulsion;
4) obtaining a high barrier material having a multilayer structure; each layer in the multilayer structure is formed by drying semi-vulcanized natural rubber emulsion or graphene/waterborne polyurethane emulsion.
Further, in the step 1.2), carrying out ultrasonic treatment on the mixed solution A obtained in the step 1.1), reacting at 80-90 ℃ after the ultrasonic treatment, and cooling to room temperature after 24-48 h to obtain a product A; the ultrasonic treatment time is 30-60 min;
further, in the step 1.3), after the product A is subjected to centrifugal treatment, washing with diethyl ether to obtain a product B;
further, in the step 1.4), the product B is placed at 60 ℃ for vacuum drying, and the product C is obtained after 12-48 hours.
Further, in the step 2), the polyether polyol A is selected from one or more of polypropylene oxide (PPG) or polytetrahydrofuran ether glycol (PTMEG), and the molecular weight of the polyether polyol A is 1000-3000.
Further, in the step 2), the polyester polyol B is selected from one or more of polyethylene glycol adipate, neopentyl glycol succinate, polybutylene isophthalate or neopentyl glycol isophthalate, and the molecular weight of the polyester polyol B is 1000-3000.
Further, in the step 2), the diisocyanate is selected from one of diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), Toluene Diisocyanate (TDI), Hexamethylene Diisocyanate (HDI), and xylylene diisocyanate.
Further, in the step 2), the front chain extender comprises a front chain extender containing a hydrophilic group and a front chain extender containing no hydrophilic group. Further, the hydrophilic group-containing pre-chain extender is selected from dimethylolpropionic acid (DMPA), dimethylolbutyric acid (DMBA), dihydroxy half-ester, N-methyldiethanolamine. The pre-chain extender without hydrophilic groups is selected from the group consisting of ethylene glycol, diethylene glycol (DEG), Trimethylolpropane (TMP).
Further, in the step 2), the vinyl-terminated agent is selected from one or more of 1, 2-dimethylolethylene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and 3-buten-1-ol.
Further, in the step 2), the rear chain extender is one or more selected from ethylenediamine, hexamethylenediamine, Diethylenetriamine (DTA), isophoronediamine and polyetheramine, and the molecular weight of the polyetheramine is 200-1000.
Further, in the step 2), the catalyst is selected from one of organic bismuth and organic tin, such as bismuth carboxylate and dibutyltin Dilaurate (DBTL).
Further, the semi-vulcanized natural rubber emulsion is prepared in the step 3); taking natural latex with solid content of 50-60% as 100 phr; ammonia water as stabilizer in 0.2-1 phr; the surfactant is peregal O, and the dosage is 0.2 to 1.5 phr; the accelerator is zinc diethyldithiocarbamate, the dosage is 0.4 to 1.2phr, the anti-aging agent is 2, 6-di-tert-butyl-4-methylphenol, the dosage is 0.8 to 1.5 phr; the dosage of the sulfur powder is 1 to 2 phr; the vulcanizing activator is zinc oxide, and the dosage is 1 to 3 phr.
The preparation method comprises the following steps:
3.1) adding a stabilizer and a surfactant into the natural latex in a continuous stirring state, wherein the stirring speed is 120-200rpm, and the stirring time is 10-20 min; adding accelerator, antioxidant, sulfur powder and vulcanization activator, and continuously stirring for 10-20min to obtain latex mixed solution;
3.2) carrying out pre-vulcanization treatment on the latex mixed solution: the latex mixed solution is put into a water bath with the temperature of 50-60 ℃ and stirred at the stirring speed of 120-200rpm for 4-5h to prepare the semi-vulcanized natural latex.
Further, in the step 4), 4.1) immersing the mold into the semi-vulcanized natural rubber emulsion obtained in the step 3) firstly, taking out and drying, and 4.2) immersing the dried mold into the graphene/waterborne polyurethane emulsion obtained in the step 2) again, taking out and drying; 4.3) immersing the dried mould into the semi-vulcanized natural rubber emulsion obtained in the step 3) again, taking out, drying and demoulding to obtain the high-barrier material with the sandwich structure of the natural rubber latex layer/graphene-polyurethane layer/natural rubber latex layer on the surface of the mould. Further, the steps 4.2-4.3 can be repeated for a plurality of times to obtain the multilayer material.
Further, it is characterized in that: and repeating the step 4.2-4.3 for a plurality of times to obtain the multilayer material.
The invention also provides a high-barrier natural latex condom which is made of the graphene reinforced waterborne polyurethane high-barrier material.
Further, the preparation method comprises the following steps of adopting the graphene/waterborne polyurethane emulsion and semi-vulcanized natural rubber latex:
A) introducing nitrogen into the graphene/waterborne polyurethane emulsion for 30-60min, and standing at room temperature for later use;
B) standing the semi-vulcanized natural latex for 12-24h, centrifuging at high speed, filtering to obtain refined semi-vulcanized natural latex, and standing at room temperature for later use;
C) cleaning the condom core mould with deionized water, immersing the dried condom core mould into refined semi-vulcanized natural latex at normal temperature for 30-50s, taking out and drying at 90-110 ℃;
D) then, immersing the condom core mould treated in the previous step into the graphene/waterborne polyurethane emulsion for 30-50s at normal temperature, taking out and drying at 90-110 ℃;
E) then immersing the condom core mould treated in the previous step into the refined semi-vulcanized natural latex at normal temperature for 30-50s, taking out and drying at 90-110 ℃;
F) and finally, curling the thin film on the surface of the condom core mould treated in the previous step, demoulding and drying to obtain the finished condom product.
According to the invention, the compatibility of the graphene oxide with a polyurethane material is improved by adopting in-situ chemical grafting modification, the interaction between the graphene and a polyurethane molecular chain is increased, and the purpose of improving the mechanical property and the barrier property of the polyurethane is achieved; and simultaneously, introducing carbon-carbon double bonds at the tail end of a polyurethane molecular chain, bonding the carbon-carbon double bonds with the carbon-carbon double bonds on the natural latex molecular chain through free radical reaction, realizing the fusion of the interface between the natural latex layer and the graphene/waterborne polyurethane interlayer, and finally obtaining the graphene/polyurethane/natural latex composite structure condom with good barrier property and low cost.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a scanning electron microscope image of a graphene/polyurethane composite layer
As can be seen from the scanning electron microscope image of the graphene/polyurethane composite material layer, the microstructure of the composite material is compact, and no obvious holes exist, which indicates that the wettability of a polyurethane molecular chain on the surface of graphene is good, and the bonding degree of graphene and a polyurethane interface is high.
Detailed Description
The present invention is further illustrated by the following examples, but it should not be construed that the scope of the above-described subject matter is limited to the following examples. Various substitutions and alterations can be made without departing from the technical idea of the invention and the scope of the invention is covered by the present invention according to the common technical knowledge and the conventional means in the field.
Example 1:
a graphene-reinforced waterborne polyurethane high-barrier material is characterized by being obtained by the following method:
1) isocyanate functionalization of graphene oxide
1.1) dissolving 100mg of graphene oxide in 100ml of DMF, adding 100mg of TDI, and mixing to obtain a mixed solution A;
1.2) carrying out ultrasonic dispersion on the mixed solution A obtained in the step 1.1) for 30min, reacting at 80 ℃ for 24h, cooling to room temperature,
1.3) centrifuging the product, and washing with diethyl ether for 3 times to obtain a product B;
1.4) drying the product B at 60 ℃ for 12h to obtain the isocyanate functionalized graphene oxide (GONCO).
2) Preparing a graphene/waterborne polyurethane emulsion:
2.1) weighing 5.2g of GONCO and 80g of polypropylene oxide polyol (polyether polyol A) with the average molecular weight of 2000, and vacuumizing for 1h at 110 ℃;
2.2) cooling to 70 ℃, adding 30.5g of diphenylmethane diisocyanate (diisocyanate) and 0.08g of bismuth carboxylate (catalyst), and reacting at the rotating speed of 150rpm for 1 h;
2.3) adding 8g of dimethylolbutyric acid (hydrophilic group-containing chain extender) and 0.5g of ethylene glycol (hydrophilic group-free chain extender) to react for 3 hours at 70 ℃;
2.4) 2.68g of pentaerythritol triacrylate (vinyl blocking agent) are added, the temperature is raised to 80 ℃ and stirring is continued for 2 h.
2.5) cooling the reactant to 50 ℃, adding 60g of acetone (solvent to reduce the viscosity of the system) and 6.0g of triethylamine (neutralizing agent), and stirring at the rotating speed of 200rpm for 40 min;
2.6) adding 410g of deionized water, increasing the rotating speed to 800rpm, emulsifying for 60min, then adding 0.6g of hexamethylenediamine (rear chain extender), and stirring for 60min at the rotating speed of 600rpm to obtain the graphene/waterborne polyurethane emulsion.
3) Preparation of semi-vulcanized Natural rubber emulsion
In the embodiment, natural latex can be used as a raw material, and a stabilizer, a surfactant and sulfur are added for reaction to obtain semi-vulcanized natural rubber emulsion;
the preparation method comprises the following steps:
100phr of natural latex with 50 percent of solid content; ammonia water as stabilizer in 0.3 phr; the surfactant is peregal O, and the dosage is 0.2 phr; the accelerator is zinc diethyldithiocarbamate, the dosage is 0.6phr, the anti-aging agent is 2, 6-di-tert-butyl-4-methylphenol, the dosage is 0.8 phr; the dosage of the sulfur powder is 1 phr; the vulcanization activator was zinc oxide in an amount of 1 phr.
3.1) adding a stabilizer and a surfactant into the natural latex in a continuous stirring state, wherein the stirring speed is 160rpm, and the stirring time is 10 min; adding accelerator, anti-aging agent, sulfur powder and vulcanization activator, and continuously stirring for 10min to obtain latex mixed solution;
3.2) carrying out pre-vulcanization treatment on the latex mixed solution: namely, the latex mixed solution is put into a water bath with the temperature of 60 ℃ and stirred at the stirring speed of 160rpm for 5 hours to prepare the semi-vulcanized natural latex.
Preferably, after the semi-vulcanized latex is left standing at room temperature for 12 hours, it is subjected to high-speed centrifugation and filtered to obtain a refined semi-vulcanized latex.
4) Immersing the mould into the semi-vulcanized natural rubber emulsion obtained in the step 3), taking out and drying,
then, immersing the dried mould into the graphene/waterborne polyurethane emulsion obtained in the step 2), taking out and drying;
and finally, immersing the dried mould into the semi-vulcanized natural rubber emulsion obtained in the step 3), taking out, drying and demoulding to obtain the high-barrier material with the sandwich structure of the natural rubber latex layer/the graphene-polyurethane layer/the natural rubber latex layer on the surface of the mould.
The high-barrier material of the embodiment can be applied to manufacturing high-barrier condoms; namely, the semi-vulcanized natural rubber emulsion or the graphene/waterborne polyurethane emulsion prepared in the steps 2) and 3) is adopted as a raw material, and the method comprises the following steps:
A) introducing nitrogen into the graphene/waterborne polyurethane emulsion for 30-60min, and standing at room temperature for later use;
B) standing the semi-vulcanized natural rubber emulsion for 12h, centrifuging at high speed, filtering to obtain refined semi-vulcanized natural rubber latex, and standing at room temperature for later use;
C) soaking a dried condom core mold which is cleaned by deionized water into refined semi-vulcanized natural latex at normal temperature for 30-50s, lifting to form a film, and heating in a drying tunnel at 90-110 ℃ for about 5 minutes;
D) then, immersing the condom core mould processed in the previous step into the graphene/waterborne polyurethane emulsion for 30-50s at normal temperature, lifting and forming a film, and then heating the film in a drying tunnel at 90-110 ℃ for about 5 minutes;
E) then the condom core mould processed by the previous step is immersed into the refined semi-vulcanized natural latex for 30 to 50 seconds at normal temperature, is pulled to form a film, is heated in a drying tunnel at the temperature of between 90 and 110 ℃ for about 8 minutes,
F) and finally, curling the thin film on the surface of the condom core mould treated in the previous step, demoulding and drying to obtain the finished condom product.
And (3) testing: the high-barrier natural latex condom film thickness is 0.04mm, the tensile strength is 46N, and the elongation at break is 530%. The barrier performance of the high-barrier natural latex condom and the barrier performance of the conventional natural latex condom are tested by adopting a weight reduction method (refer to the standard GB1037-88 plastic film and sheet water vapor permeability test method cup method), wherein the water vapor permeability WVT (unit is g/m)2Day) at a given temperature, relative humidity, a given vapor pressure difference and a given thickness of 1m2The smaller the amount of water vapor that the sample of (a) transmits in 24 hours, the better the barrier properties of the film. The WVT value of the natural latex condom with the thickness of 0.048mm is 1.6g/m2Day; the WVT value of the high-barrier condom with the graphene/polyurethane layer thickness of about 0.010mm and the total thickness of 0.04mm is 0.23g/m2·day。
Example 2:
a graphene-reinforced waterborne polyurethane high-barrier material is characterized by being obtained by the following method:
1) isocyanate functionalization of graphene oxide
1.1) dissolving 120mg of graphene oxide in 100ml of DMF, adding 100mg of TDI, and mixing to obtain a mixed solution A;
1.2) carrying out ultrasonic dispersion on the mixed solution A obtained in the step 1.1) for 30min, reacting at 80 ℃ for 24h, cooling to room temperature,
1.3) centrifuging the product, and washing with diethyl ether for 3 times to obtain a product B;
1.4) drying the product B at 60 ℃ for 12h to obtain the isocyanate functionalized graphene oxide (GONCO).
2) Preparing a graphene/waterborne polyurethane emulsion:
2.1) weighing 7.0g of GONCO and 80g of polypropylene oxide polyol (polyether polyol A) with the average molecular weight of 2000, and vacuumizing for 1h at 110 ℃;
2.2) cooling to 70 ℃, adding 29g of isophorone diisocyanate (diisocyanate) and 0.12g of bismuth carboxylate (catalyst), and reacting for 1h at the rotating speed of 150 rpm;
2.3) adding 7.5g dimethylolpropionic acid (hydrophilic group-containing chain extender) and 2g diethylene glycol (hydrophilic group-free chain extender) and reacting for 3h at 70 ℃;
2.4) 2.3g of 2-hydroxyethyl acrylate (vinyl blocking agent) are added, the temperature is raised to 85 ℃ and stirring is continued for 2 h.
2.5) cooling the reactant to 50 ℃, adding 80g of acetone and 6.2g of triethylamine, and stirring at the rotation speed of 200rpm for 40 min;
2.6) adding 400g of deionized water, increasing the rotating speed to 800rpm, emulsifying for 60min, then adding 0.5g of hexamethylenediamine (rear chain extender), and stirring for 60min at the rotating speed of 600rpm to obtain the graphene/waterborne polyurethane emulsion.
3) Preparation of semi-vulcanized Natural rubber emulsion
In the embodiment, natural latex can be used as a raw material, and a stabilizer, a surfactant and sulfur are added for reaction to obtain semi-vulcanized natural rubber emulsion;
the preparation method comprises the following steps:
100phr of natural latex with 50 percent of solid content; ammonia water as stabilizer in 0.3 phr; the surfactant is peregal O, and the dosage is 0.2 phr; the accelerator is zinc diethyldithiocarbamate, the dosage is 0.6phr, the anti-aging agent is 2, 6-di-tert-butyl-4-methylphenol, the dosage is 0.8 phr; the dosage of the sulfur powder is 1 phr; the vulcanization activator was zinc oxide in an amount of 1 phr.
3.1) adding a stabilizer and a surfactant into the natural latex in a continuous stirring state, wherein the stirring speed is 160rpm, and the stirring time is 10 min; adding accelerator, anti-aging agent, sulfur powder and vulcanization activator, and continuously stirring for 10min to obtain latex mixed solution;
3.2) carrying out pre-vulcanization treatment on the latex mixed solution: namely, the latex mixed solution is put into a water bath with the temperature of 60 ℃ and stirred at the stirring speed of 160rpm for 5 hours to prepare the semi-vulcanized natural latex.
Preferably, after the semi-vulcanized latex is left standing at room temperature for 12 hours, it is subjected to high-speed centrifugation and filtered to obtain a refined semi-vulcanized latex.
4) Immersing the mould into the semi-vulcanized natural rubber emulsion obtained in the step 3), taking out and drying,
then, immersing the dried mould into the graphene/waterborne polyurethane emulsion obtained in the step 2), taking out and drying;
and finally, immersing the dried mould into the semi-vulcanized natural rubber emulsion obtained in the step 3), taking out, drying and demoulding to obtain the high-barrier material with the sandwich structure of the natural rubber latex layer/the graphene-polyurethane layer/the natural rubber latex layer on the surface of the mould.
The high-barrier material of the embodiment can be applied to manufacturing high-barrier condoms; namely, the semi-vulcanized natural rubber emulsion or the graphene/waterborne polyurethane emulsion prepared in the steps 2) and 3) is adopted as a raw material, and the method comprises the following steps:
A) introducing nitrogen into the graphene/waterborne polyurethane emulsion for 30-60min, and standing at room temperature for later use;
B) standing the semi-vulcanized natural rubber emulsion for 12h, centrifuging at high speed, filtering to obtain refined semi-vulcanized natural rubber latex, and standing at room temperature for later use;
C) soaking a dried condom core mold which is cleaned by deionized water into refined semi-vulcanized natural latex at normal temperature for 30-50s, lifting to form a film, and heating in a drying tunnel at 90-110 ℃ for about 5 minutes;
D) then, immersing the condom core mould processed in the previous step into the graphene/waterborne polyurethane emulsion for 30-50s at normal temperature, lifting and forming a film, and then heating the film in a drying tunnel at 90-110 ℃ for about 5 minutes;
E) then the condom core mould processed by the previous step is immersed into the refined semi-vulcanized natural latex for 30 to 50 seconds at normal temperature, is pulled to form a film, is heated in a drying tunnel at the temperature of between 90 and 110 ℃ for about 8 minutes,
F) and finally, curling the thin film on the surface of the condom core mould treated in the previous step, demoulding and drying to obtain the finished condom product.
And (3) testing: the high-barrier natural latex condom film thickness is 0.04mm, the tensile strength is 38N, and the elongation at break is 543 percent. The high-barrier natural latex condom was tested according to the test method in example 1, and the WVT value of the high-barrier condom with the graphene/polyurethane layer thickness of about 0.012mm and the total thickness of 0.042mm was 0.16g/m2·day。
Example 3:
a graphene-reinforced waterborne polyurethane high-barrier material is characterized by being obtained by the following method:
1) isocyanate functionalization of graphene oxide
1.1) taking 150mg of graphene oxide to dissolve in 100ml of DMF, and adding 100mg of TDI to obtain a mixed solution A;
1.2) carrying out ultrasonic dispersion on the mixed solution A obtained in the step 1.1) for 30min, reacting at 80 ℃ for 24h, cooling to room temperature,
1.3) centrifuging the product, and washing with diethyl ether for 3 times to obtain a product B;
1.4) drying the product B at 60 ℃ for 12h to obtain the isocyanate functionalized graphene oxide (GONCO).
2) Preparing a graphene/waterborne polyurethane emulsion:
2.1) weighing 6.0g of GONCO, 80g of polypropylene oxide polyol (polyether polyol A) with average molecular weight of 2000 and 20g of neopentyl glycol succinate polyol (polyester polyol B) with average molecular weight of 1000, and vacuumizing for 1h at 110 ℃;
2.2) cooling to 70 ℃, adding 29g of hexamethylene diisocyanate (diisocyanate) and 0.1g of bismuth carboxylate (catalyst), and reacting for 1h at the rotating speed of 150 rpm;
2.3) adding 6.8g of dimethylolpropionic acid (hydrophilic group-containing chain extender) and 2g of diethylene glycol (hydrophilic group-free chain extender) and reacting at 70 ℃ for 3 h;
2.4) 1.32g of 1, 2-dimethylolethylene (vinyl blocking agent) are added, the temperature is raised to 85 ℃ and stirring is carried out for 2 h.
2.5) cooling the reactant to 50 ℃, adding 100g of acetone and 5.65g of triethylamine, and stirring at the rotation speed of 200rpm for 40 min;
2.6) adding 500g of deionized water, increasing the rotating speed to 800rpm, emulsifying for 60min, then adding 1g of triethylene diamine (rear chain extender), and stirring for 60min at the rotating speed of 600rpm to obtain the graphene/waterborne polyurethane emulsion.
3) Preparation of semi-vulcanized Natural rubber emulsion
In the embodiment, natural latex can be used as a raw material, and a stabilizer, a surfactant and sulfur are added for reaction to obtain semi-vulcanized natural rubber emulsion;
the preparation method comprises the following steps:
100phr of natural latex with 50 percent of solid content; ammonia water as stabilizer in 0.3 phr; the surfactant is peregal O, and the dosage is 0.2 phr; the accelerator is zinc diethyldithiocarbamate, the dosage is 0.6phr, the anti-aging agent is 2, 6-di-tert-butyl-4-methylphenol, the dosage is 0.8 phr; the dosage of the sulfur powder is 1 phr; the vulcanization activator was zinc oxide in an amount of 1 phr.
3.1) adding a stabilizer and a surfactant into the natural latex in a continuous stirring state, wherein the stirring speed is 160rpm, and the stirring time is 10 min; adding accelerator, anti-aging agent, sulfur powder and vulcanization activator, and continuously stirring for 10min to obtain latex mixed solution;
3.2) carrying out pre-vulcanization treatment on the latex mixed solution: namely, the latex mixed solution is put into a water bath with the temperature of 60 ℃ and stirred at the stirring speed of 160rpm for 5 hours to prepare the semi-vulcanized natural latex.
Preferably, after the semi-vulcanized latex is left standing at room temperature for 12 hours, it is subjected to high-speed centrifugation and filtered to obtain a refined semi-vulcanized latex.
4) Immersing the mould into the semi-vulcanized natural rubber emulsion obtained in the step 3), taking out and drying,
then, immersing the dried mould into the graphene/waterborne polyurethane emulsion obtained in the step 2), taking out and drying;
and finally, immersing the dried mould into the semi-vulcanized natural rubber emulsion obtained in the step 3), taking out, drying and demoulding to obtain the high-barrier material with the sandwich structure of the natural rubber latex layer/the graphene-polyurethane layer/the natural rubber latex layer on the surface of the mould.
The high-barrier material of the embodiment can be applied to manufacturing high-barrier condoms; namely, the semi-vulcanized natural rubber emulsion or the graphene/waterborne polyurethane emulsion prepared in the steps 2) and 3) is adopted as a raw material, and the method comprises the following steps:
A) introducing nitrogen into the graphene/waterborne polyurethane emulsion for 30-60min, and standing at room temperature for later use;
B) standing the semi-vulcanized natural rubber emulsion for 12h, centrifuging at high speed, filtering to obtain refined semi-vulcanized natural rubber latex, and standing at room temperature for later use;
C) soaking a dried condom core mold which is cleaned by deionized water into refined semi-vulcanized natural latex at normal temperature for 30-50s, lifting to form a film, and heating in a drying tunnel at 90-110 ℃ for about 5 minutes;
D) then, immersing the condom core mould processed in the previous step into the graphene/waterborne polyurethane emulsion for 30-50s at normal temperature, lifting and forming a film, and then heating the film in a drying tunnel at 90-110 ℃ for about 5 minutes;
E) then the condom core mould processed by the previous step is immersed into the refined semi-vulcanized natural latex for 30 to 50 seconds at normal temperature, is pulled to form a film, is heated in a drying tunnel at the temperature of between 90 and 110 ℃ for about 8 minutes,
F) and finally, curling the thin film on the surface of the condom core mould treated in the previous step, demoulding and drying to obtain the finished condom product.
And (3) testing: the high-barrier natural latex condom film thickness is tested to be 0.042mm, the tensile strength is 36N, and the elongation at break is testedThe rate was 520%. The high barrier natural latex condom was tested according to the test method in example 1, with a graphene/polyurethane layer thickness of about 0.015mm and a total thickness of 0.042mm, and the high barrier condom had a WVT of 0.10g/m2·day。
Example 4:
a graphene-reinforced waterborne polyurethane high-barrier material is characterized by being obtained by the following method:
1) isocyanate functionalization of graphene oxide
1.1) taking 150mg of graphene oxide, dissolving the graphene oxide in 100ml of DMF, and adding 200mg of TDI for mixing to obtain a mixed solution A;
1.2) carrying out ultrasonic dispersion on the mixed solution A obtained in the step 1.1) for 30min, reacting at 80 ℃ for 24h, cooling to room temperature,
1.3) centrifuging the product, and washing with diethyl ether for 3 times to obtain a product B;
1.4) drying the product B at 60 ℃ for 12h to obtain the isocyanate functionalized graphene oxide (GONCO).
2) Preparing a graphene/waterborne polyurethane emulsion:
2.1) 3.0g of GONCO and 10g of polypropylene oxide polyol (polyether polyol A) having an average molecular weight of 2000 and 90g of neopentyl glycol adipate polyol (polyester polyol B) having an average molecular weight of 2000 are weighed out and evacuated at 110 ℃ for 1 hour;
2.2) cooling to 70 ℃, adding 26g of hexamethylene diisocyanate (diisocyanate) and 0.1g of bismuth carboxylate (catalyst), and reacting for 1h at the rotating speed of 150 rpm;
2.3) adding 6g of dimethylolpropionic acid (hydrophilic group-containing chain extender) and 4g of N-methyldiethanolamine (hydrophilic group-free chain extender) to react for 3 hours at 70 ℃;
2.4) 1.8g of pentaerythritol diacrylate (vinyl blocking agent) are added, the temperature is raised to 80 ℃ and stirring is continued for 3 h.
2.5) cooling the reactant to 50 ℃, adding 80g of acetone and 5.0g of triethylamine, and stirring at the rotation speed of 200rpm for 40 min;
2.6) adding 450g of deionized water, increasing the rotating speed to 800rpm, emulsifying for 60min, then adding 2.6g of isophorone diamine (rear chain extender), and stirring for 60min at the rotating speed of 600rpm to obtain the graphene/waterborne polyurethane emulsion.
3) Preparation of semi-vulcanized Natural rubber emulsion
In the embodiment, natural latex can be used as a raw material, and a stabilizer, a surfactant and sulfur are added for reaction to obtain semi-vulcanized natural rubber emulsion;
the preparation method comprises the following steps:
100phr of natural latex with 50 percent of solid content; ammonia water as stabilizer in 0.3 phr; the surfactant is peregal O, and the dosage is 0.2 phr; the accelerator is zinc diethyldithiocarbamate, the dosage is 0.6phr, the anti-aging agent is 2, 6-di-tert-butyl-4-methylphenol, the dosage is 0.8 phr; the dosage of the sulfur powder is 1 phr; the vulcanization activator was zinc oxide in an amount of 1 phr.
3.1) adding a stabilizer and a surfactant into the natural latex in a continuous stirring state, wherein the stirring speed is 160rpm, and the stirring time is 10 min; adding accelerator, anti-aging agent, sulfur powder and vulcanization activator, and continuously stirring for 10min to obtain latex mixed solution;
3.2) carrying out pre-vulcanization treatment on the latex mixed solution: namely, the latex mixed solution is put into a water bath with the temperature of 60 ℃ and stirred at the stirring speed of 160rpm for 5 hours to prepare the semi-vulcanized natural latex.
Preferably, after the semi-vulcanized latex is left standing at room temperature for 12 hours, it is subjected to high-speed centrifugation and filtered to obtain a refined semi-vulcanized latex.
4) Immersing the mould into the semi-vulcanized natural rubber emulsion obtained in the step 3), taking out and drying,
then, immersing the dried mould into the graphene/waterborne polyurethane emulsion obtained in the step 2), taking out and drying;
and finally, immersing the dried mould into the semi-vulcanized natural rubber emulsion obtained in the step 3), taking out, drying and demoulding to obtain the high-barrier material with the sandwich structure of the natural rubber latex layer/the graphene-polyurethane layer/the natural rubber latex layer on the surface of the mould.
The high-barrier material of the embodiment can be applied to manufacturing high-barrier condoms; namely, the semi-vulcanized natural rubber emulsion or the graphene/waterborne polyurethane emulsion prepared in the steps 2) and 3) is adopted as a raw material, and the method comprises the following steps:
A) introducing nitrogen into the graphene/waterborne polyurethane emulsion for 30-60min, and standing at room temperature for later use;
B) standing the semi-vulcanized natural rubber emulsion for 12h, centrifuging at high speed, filtering to obtain refined semi-vulcanized natural rubber latex, and standing at room temperature for later use;
C) soaking a dried condom core mold which is cleaned by deionized water into refined semi-vulcanized natural latex at normal temperature for 30-50s, lifting to form a film, and heating in a drying tunnel at 90-110 ℃ for about 5 minutes;
D) then, immersing the condom core mould processed in the previous step into the graphene/waterborne polyurethane emulsion for 30-50s at normal temperature, lifting and forming a film, and then heating the film in a drying tunnel at 90-110 ℃ for about 5 minutes;
E) then the condom core mould processed by the previous step is immersed into the refined semi-vulcanized natural latex for 30 to 50 seconds at normal temperature, is pulled to form a film, is heated in a drying tunnel at the temperature of between 90 and 110 ℃ for about 8 minutes,
F) and finally, curling the thin film on the surface of the condom core mould treated in the previous step, demoulding and drying to obtain the finished condom product.
And (3) testing: the high-barrier natural latex condom film thickness is 0.04mm, the tensile strength is 40N, and the elongation at break is 546%. The barrier performance of the high-barrier natural latex condom and the barrier performance of the conventional natural latex condom are tested by adopting a weight reduction method (refer to the standard GB1037-88 plastic film and sheet water vapor permeability test method cup method), wherein the water vapor permeability WVT (unit is g/m)2Day) at a given temperature, relative humidity, a given vapor pressure difference and a given thickness of 1m2The smaller the amount of water vapor that the sample of (a) transmits in 24 hours, the better the barrier properties of the film. The WVT value of the natural latex condom with the thickness of 0.048mm is 1.6g/m2Day; the WVT value of the high-barrier condom with the graphene/polyurethane layer thickness of about 0.010mm and the total thickness of 0.04mm is 0.33g/m2·day。

Claims (10)

1. A graphene-reinforced waterborne polyurethane high-barrier material is characterized in that: having the multilayer structure; in the multilayer structure, each layer is formed by drying semi-vulcanized natural rubber emulsion or graphene/waterborne polyurethane emulsion.
2. The graphene-reinforced waterborne polyurethane high-barrier material according to claim 1, wherein the graphene-reinforced waterborne polyurethane high-barrier material is characterized in that:
the multilayer structure is formed by drying a graphene/waterborne polyurethane emulsion to form an intermediate layer; after the semi-vulcanized natural rubber emulsion is dried, coating layers on two sides of the middle interlayer are formed;
the graphene/waterborne polyurethane emulsion is an emulsion formed by modifying graphene oxide to improve the compatibility with a polyurethane material and increase the interaction between graphene and a polyurethane molecular chain; meanwhile, carbon-carbon double bonds are introduced at the tail end of a polyurethane molecular chain, so that the carbon-carbon double bonds are bonded with the carbon-carbon double bonds on the natural latex molecular chain through free radical reaction, and the fusion of the interface between the natural latex layer and the graphene/waterborne polyurethane interlayer is realized.
3. A preparation method of a graphene-reinforced waterborne polyurethane high-barrier material is characterized by comprising the following steps:
1) isocyanate functionalization of graphene oxide
1.1) mixing weighed graphene oxide, diisocyanate and N, N-Dimethylformamide (DMF) to obtain a mixed solution A;
1.2) fully reacting the mixed solution A obtained in the step 1.1) to obtain a product A;
1.3) washing the product A obtained in the step 1.1) to obtain a product B;
1.4) drying the product B to obtain a product C, namely, isocyanate functionalized graphene oxide (GONCO);
2) preparation of graphene/waterborne polyurethane emulsion
The components are prepared according to the following parts by weight:
Figure FDA0002641791470000011
the preparation method comprises the following steps:
2.1) adding GONCO and polyether polyol A into a reactor; when the polyester polyol B is selected, the polyester polyol B is added at the same time;
2.2) adding diisocyanate and a catalyst for reaction;
2.3) adding a chain extender for reaction;
2.4) adding a vinyl end-capping agent for reaction;
2.5) adding a neutralizing agent for reaction;
and 2.6) adding deionized water for emulsification under high-speed stirring, adding a rear chain extender, and stirring to obtain the graphene/waterborne polyurethane emulsion.
3) Obtaining semi-vulcanized natural rubber emulsion
Taking natural latex as a raw material, adding a stabilizer, a surfactant and sulfur for reaction to obtain semi-vulcanized natural rubber emulsion;
4) obtaining a high barrier material having a multilayer structure; each layer in the multilayer structure is formed by drying semi-vulcanized natural rubber emulsion or graphene/waterborne polyurethane emulsion.
4. The preparation method of the graphene-reinforced waterborne polyurethane high-barrier material according to claim 3, wherein the preparation method comprises the following steps:
in the step 1.2), carrying out ultrasonic treatment on the mixed solution A obtained in the step 1.1), and carrying out reaction after the ultrasonic treatment to obtain a product A;
in the step 1.3), after the product A is subjected to centrifugal treatment, ether is used for cleaning to obtain a product B;
in step 1.4), the product B is dried to obtain a product C.
5. The preparation method of the graphene-reinforced waterborne polyurethane high-barrier material according to claim 3, wherein the preparation method comprises the following steps:
in the step 2), the step (c) is carried out,
the polyether polyol A is selected from one or more of polypropylene oxide or polytetrahydrofuran ether glycol, and the molecular weight of the polyether polyol A is 1000-3000.
The polyester polyol B is selected from one or more of polyethylene glycol adipate, neopentyl glycol polysuccinate, polybutylene succinate, polybutylene isophthalate or neopentyl glycol polysuccinate, and the molecular weight of the polyester polyol B is 1000-3000.
The diisocyanate is selected from one of diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), Toluene Diisocyanate (TDI) Hexamethylene Diisocyanate (HDI) and xylylene diisocyanate.
The pre-chain extender comprises a pre-chain extender containing a hydrophilic group and a pre-chain extender containing no hydrophilic group.
The vinyl blocking agent is selected from one or more of 1, 2-dimethylolethylene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and 3-buten-1-ol.
The post-chain extender is one or more selected from ethylenediamine, hexamethylenediamine, Diethylenetriamine (DTA), isophoronediamine and polyetheramine, and the molecular weight of the polyetheramine is 200-1000.
The catalyst is selected from one of organic bismuth or organic tin, such as bismuth carboxylate and dibutyltin Dilaurate (DBTL).
6. The preparation method of the graphene-reinforced waterborne polyurethane high-barrier material according to claim 5, wherein the preparation method comprises the following steps:
the hydrophilic group-containing pre-chain extender is selected from dimethylolpropionic acid (DMPA), dimethylolbutyric acid (DMBA), dihydroxy half ester, and N-methyldiethanolamine.
The pre-chain extender without hydrophilic groups is selected from the group consisting of ethylene glycol, diethylene glycol (DEG), Trimethylolpropane (TMP).
The organic bismuth is selected from bismuth carboxylates.
The organotin is selected from dibutyltin Dilaurate (DBTL).
7. The preparation method of the graphene-reinforced waterborne polyurethane high-barrier material according to claim 3, wherein the preparation method comprises the following steps: the semi-vulcanized natural rubber emulsion is prepared in the step 3); the preparation method comprises the following steps:
3.1) adding a stabilizer and a surfactant into the natural latex in a continuous stirring state and then stirring; adding a promoter, an anti-aging agent, sulfur powder and a vulcanization activator, and continuously stirring to obtain a latex mixed solution;
3.2) carrying out pre-vulcanization treatment on the latex mixed solution: the latex mixed solution is put into a water bath with the temperature of 50-60 ℃ and stirred at the stirring speed of 120-200rpm for 4-5h to prepare the semi-vulcanized natural latex.
8. The preparation method of the graphene-reinforced waterborne polyurethane high-barrier material according to claim 3, wherein the preparation method comprises the following steps:
in the step 4):
4.1) immersing the mould into the semi-vulcanized natural rubber emulsion obtained in the step 3), taking out and drying,
4.2) immersing the dried mould into the graphene/waterborne polyurethane emulsion obtained in the step 2), taking out and drying;
4.3) immersing the dried mould into the semi-vulcanized natural rubber emulsion obtained in the step 3) again, taking out, drying and demoulding to obtain the high-barrier material with the sandwich structure of the natural rubber latex layer/graphene-polyurethane layer/natural rubber latex layer on the surface of the mould.
And repeating the step 4.2-4.3 for a plurality of times to obtain the multilayer material.
9. A high resistant separates type natural latex condom which characterized in that: the graphene reinforced waterborne polyurethane high-barrier material is manufactured by adopting any one of claims 1 to 7.
10. The high-barrier natural latex condom of claim 8, wherein: the preparation method comprises the following steps of adopting the graphene/waterborne polyurethane emulsion and the semi-vulcanized natural latex:
A) introducing nitrogen into the graphene/waterborne polyurethane emulsion, and placing the graphene/waterborne polyurethane emulsion in a room-temperature environment for later use;
B) standing the semi-vulcanized natural latex, performing high-speed centrifugal treatment on the semi-vulcanized natural latex, filtering to obtain refined semi-vulcanized natural latex, and standing at room temperature for later use;
C) cleaning the condom core mould with deionized water, soaking the dried condom core mould into refined semi-vulcanized natural latex at normal temperature, taking out and drying;
D) then, immersing the condom core mould treated in the previous step into graphene/waterborne polyurethane emulsion at normal temperature, taking out and drying;
E) then the condom core mould processed by the previous step is immersed into the refined semi-vulcanized natural latex at normal temperature, and is taken out and dried;
F) and finally, curling the thin film on the surface of the condom core mould treated in the previous step, demoulding and drying to obtain the finished condom product.
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