CN112029262A - Boron nitride reinforced waterborne polyurethane high-thermal-conductivity high-barrier material and condom - Google Patents

Boron nitride reinforced waterborne polyurethane high-thermal-conductivity high-barrier material and condom Download PDF

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CN112029262A
CN112029262A CN202010842596.5A CN202010842596A CN112029262A CN 112029262 A CN112029262 A CN 112029262A CN 202010842596 A CN202010842596 A CN 202010842596A CN 112029262 A CN112029262 A CN 112029262A
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boron nitride
waterborne polyurethane
condom
barrier material
polyurethane emulsion
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王绪英
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GUILIN HENGBAO HEALTH PROTECTION 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
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    • A61F6/02—Contraceptive devices; Pessaries; Applicators therefor for use by males
    • A61F6/04—Condoms, sheaths or the like, e.g. combined with devices protecting against contagion
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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Abstract

The invention provides a boron nitride reinforced waterborne polyurethane high-barrier material and a condom. The compatibility of boron nitride and polyurethane materials is improved, the interaction between the boron nitride and polyurethane molecular chains is increased, and the aims of improving the mechanical property and the barrier property of polyurethane are fulfilled; meanwhile, the boron nitride/waterborne polyurethane composite material is used as a middle interlayer, and the waterborne polyurethane emulsion is used as coating layers on two sides to form a sandwich structure composite film, so that the thickness and the production cost of the condom can be further reduced. Finally, the condom with the boron nitride/polyurethane composite structure, which has high strength, good barrier property and low cost, is obtained.

Description

Boron nitride reinforced waterborne polyurethane high-thermal-conductivity high-barrier material and condom
Technical Field
The invention relates to the field of sanitary and family planning products, in particular to a boron nitride reinforced waterborne polyurethane high-thermal-conductivity high-barrier material and a condom.
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 isolating sperm, but the presence of intrinsic pores of about 5 microns in material presents a potential risk for blocking viruses such as hepatitis b and aids, which are smaller in diameter. The water-based polyurethane is a green high polymer material, has good film forming compactness, is safe and nontoxic, and has been widely applied to the medical field, the condom prepared by taking the water-based polyurethane as a raw material is thinner, and the virus isolation effect is better, but the prepared ultrathin water-based polyurethane condom has the problems of insufficient strength and generally unavailable blasting test standard. Compared with the commonly used method for reinforcing the water-based polyurethane material, the method mainly comprises the steps of increasing the crosslinking degree, modifying silane, reinforcing graphene and the like, but the methods have various problems and disadvantages, for example, the increase of the crosslinking degree can cause the condom to be hardened and the elongation at break to be reduced; silane modification is easy to occur, and poor compatibility affects molecular weight and distribution thereof; although the strength can be effectively improved by adding the graphene, the product is brown or dark black, and the appearance quality of the condom is seriously influenced.
Boron nitride is a crystal composed of nitrogen atoms and boron atoms. Boron nitride has four different variants, and when nitrogen atoms and boron atoms are hybridized in an SP2 mode, because the bond angle is 120 degrees, a plane hexagonal network structure similar to graphite is formed after bonding, namely the hexagonal boron nitride with one of the four structures. The hexagonal boron nitride has a graphite-like structure, is white in appearance, is very stable in air, can resist 2270K high temperature, is sublimated at 3270K, and has light color, good heat insulation property, thermal conductivity and chemical stability. In addition, the compact structure of the boron nitride prevents most substances from penetrating through, has extremely excellent barrier property, and meanwhile, the boron nitride is white in appearance, and is almost colorless and transparent with a film material prepared by compounding with polyurethane, so that the boron nitride is an ideal additive material for preparing the high-thermal-conductivity and high-barrier condom.
The method is a good method for obtaining the condom with high barrier property, high strength and low cost by taking the boron nitride/waterborne polyurethane composite material as the middle interlayer and the waterborne polyurethane emulsion as the cladding layers at the two sides to form the sandwich structure composite film.
An effective method for preparing the boron nitride/waterborne polyurethane composite material is an in-situ polymerization method, wherein covalent functionalized groups are introduced on the surface of boron nitride in a covalent bonding mode, and then the in-situ polymerization method is adopted for polymerization reaction. The method can effectively eliminate the interface repulsive force of the inorganic filler and the organic matrix, improve the dispersibility of the boron nitride filler in the aqueous polyurethane matrix and enhance the compatibility of the boron nitride and the aqueous polyurethane resin.
Disclosure of Invention
The invention aims to provide a boron nitride reinforced waterborne polyurethane high-heat-conduction and high-barrier material which is characterized by having a multilayer structure; in the multilayer structure, each layer is formed by drying boron nitride/aqueous polyurethane emulsion or aqueous polyurethane emulsion.
Further, the multilayer structure is formed by drying boron nitride/waterborne polyurethane emulsion to form an intermediate interlayer; after the aqueous polyurethane emulsion is dried, coating layers on two sides of the middle interlayer are formed;
the boron nitride/waterborne polyurethane emulsion is obtained by modifying boron nitride to improve the compatibility of the boron nitride and a polyurethane material.
The preparation method of the high-barrier material comprises the following steps:
1) surface functional modification of boron nitride
In a reactor, dispersing boron nitride in a solvent, adding a silane coupling agent for reaction to prepare surface modified boron nitride dispersion liquid (BNNTs);
2) preparation of sandwich layer boron nitride/waterborne polyurethane composite emulsion
The proportion ranges of the components are as follows:
2-6 parts of BNNTs dispersion liquid (with the concentration of 10-30%)
Figure BDA0002641978360000021
The preparation method comprises the following steps:
2.1) adding polyether glycol 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 BNNTs, diisocyanate and a catalyst, and reacting for 1-3h at the temperature of 80-90 ℃;
2.3) adding a chain extender to react for 1-3h at the temperature of 80-90 ℃;
2.4) adding a neutralizing agent to react for 0.5 to 1 hour at room temperature, so that the pH value of the reaction system is more than 7.5;
2.5) adding deionized water for emulsification under high-speed stirring, adding a rear chain extender, and stirring for 1h to obtain the boron nitride/waterborne polyurethane emulsion.
3) Preparation of coating layer aqueous polyurethane emulsion
The proportion ranges of the components are as follows:
Figure BDA0002641978360000031
the preparation method comprises the following steps:
3.1) adding polyether glycol 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;
3.2) adding diisocyanate and a catalyst, and reacting for 1-3h at the temperature of 80-90 ℃;
3.3) adding a chain extender to react for 1-3h at the temperature of 80-90 ℃;
3.4) adding a neutralizing agent to react for 0.5 to 1 hour at room temperature, so that the pH value of the reaction system is more than 7.5;
3.5) adding deionized water for emulsification under high-speed stirring, adding a rear chain extender, and stirring for 1h to obtain the waterborne polyurethane emulsion.
4) Preparing a high-barrier material:
obtaining a high barrier material having a multilayer structure; each layer in the multilayer structure is formed by the aqueous polyurethane emulsion obtained in step 3) or the boron nitride/aqueous polyurethane emulsion obtained in step 2).
Further, in the step 1), the raw materials are as follows:
10-20 parts of boron nitride
Solvent 200-500 parts
1-10 parts of silane coupling agent
0.01-0.1 part of water
In the step 1), the solvent is dimethylformamide
In the step 1), the silane coupling agent is selected from: 3-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-diethylenetriaminopropylmethyldimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane or 3-mercaptopropyltrimethoxysilane
Adding 10-20 parts of boron nitride sheet into a reactor, adding 200-500 parts of solvent dimethylformamide, carrying out ultrasonic dispersion for 3-5h, heating to 60-80 ℃, adding 1-10 parts of silane coupling agent and 0.01-0.1 part of water, and heating for 5-8 h. Centrifuging to remove supernatant, washing the lower solid with dimethylformamide for 2-3 times, stirring, centrifuging to obtain viscous semi-dry substance, and regulating with dimethylformamide to solid content of 20-30% to obtain surface modified boron nitride dispersion (BNNTs).
Further, in the step 1), the boron nitride raw material is a boron nitride nanosheet; the boron nitride nanosheet is hexagonal boron nitride, D50 is 5-30 mu m, and the number of layers is 1-20.
In the step 1), the solvent is dimethylformamide
In the step 1), the silane coupling agent is selected from: 3-Aminopropyltriethoxysilane (NH)2(CH2)3Si(OC2H5)3) Gamma-aminopropyltrimethoxysilane (H)2N(CH2)3Si(OCH3)3) Gamma-diethylenetriaminepropylmethyldimethoxysilane (CH)3(CH3O)2SiCH2CH2CH2N(CH2CH2NH2)2) N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane (NH)2(CH2)2NH(CH2)3Si(OCH3)3) 3-mercaptopropyltriethoxysilane (HS (CH)2)Si(OC2H5)3) Or 3-mercaptopropyltrimethoxysilane (HS (CH)2)3Si(OCH3)3)。
Further, in the steps 2) and 3): the diisocyanate is selected from: one of diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), Toluene Diisocyanate (TDI), Hexamethylene Diisocyanate (HDI), and xylylene diisocyanate.
Further, 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 is 1000-3000.
Further, the polyester polyol B is selected from: one or more of polyethylene glycol adipate, neopentyl glycol succinate, polybutylene isophthalate or neopentyl glycol isophthalate, wherein the molecular weight of the polyester polyol is 1000-3000.
Further, the pre-chain extender includes a chain extender containing a hydrophilic group and a chain extender containing no hydrophilic group. Further, in the steps 2) and 3): the chain extender containing hydrophilic groups can be one of dimethylolpropionic acid (DMPA), dimethylolbutyric acid (DMBA), dihydroxy half ester and N-methyldiethanolamine. The chain extender without hydrophilic group can be one of ethylene glycol, diethylene glycol (DEG), Trimethylolpropane (TMP) and Diethylenetriamine (DTA).
Further, the catalyst is one of organic bismuth or organic tin. Further, the organic bismuth catalyst is selected from bismuth carboxylates; the organotin catalyst is selected from dibutyltin Dilaurate (DBTL).
Further, step 4 comprises the following steps:
4.1) immersing the mould into the aqueous polyurethane emulsion obtained in the step 3), taking out and drying;
4.2) immersing the dried mould into the boron nitride/waterborne polyurethane emulsion obtained in the step 2), taking out and drying;
4.3) finally, immersing the dried mould into the aqueous polyurethane emulsion obtained in the step 3), taking out and drying to obtain the material with the composite structure.
Further, repeating the steps 4.2-4.3 for a plurality of times to obtain the multilayer material.
The invention also provides a boron nitride reinforced waterborne polyurethane high-barrier material condom which is made of the high-heat-conductivity and high-barrier material with the sandwich structure of the waterborne polyurethane layer/the boron nitride-polyurethane layer/the waterborne polyurethane layer. When manufacturing, step 4 is the preparation of the condom; the adopted mould is a condom core mould.
The invention has the beneficial effects that: the invention improves the compatibility of boron nitride and polyurethane material, increases the interaction between the boron nitride and polyurethane molecular chain, and achieves the purpose of improving the mechanical property and the barrier property of polyurethane; meanwhile, the boron nitride/waterborne polyurethane composite material is used as a middle interlayer, and the waterborne polyurethane emulsion is used as coating layers on two sides to form a sandwich structure composite film, so that the thickness and the production cost of the condom can be further reduced. Finally, the condom with the boron nitride/polyurethane composite structure, which has high strength, high thermal conductivity, good barrier property and low cost, is obtained.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a scanning electron microscope image of a boron nitride/polyurethane composite layer
As can be seen from the scanning electron microscope image of the boron nitride/polyurethane composite material layer, the microstructure of the composite material is compact without obvious holes, which indicates that the wettability of the polyurethane molecular chain on the surface of the boron nitride is good and the bonding degree of the boron nitride and the 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:
the boron nitride reinforced waterborne polyurethane high-barrier material condom is characterized in that the preparation method comprises the following steps:
1) surface functional modification of boron nitride
Adding 10g of boron nitride nanosheet into a reactor, adding 200g of solvent dimethylformamide, performing ultrasonic dispersion for 3 hours,
2g of 3-aminopropyltriethoxysilane (silane coupling agent) and 0.01g of water were added to the reactor, heated to 70 ℃ and kept warm for 5 hours. Centrifuging to remove supernatant, washing the lower solid with dimethylformamide for 2-3 times, stirring, centrifuging to obtain viscous semi-dry substance, and regulating with dimethylformamide to 20% concentration to obtain surface modified boron nitride dispersion (BNNTs).
2) Preparation of sandwich layer boron nitride/waterborne polyurethane composite emulsion
2.1) 5.2g of BNNTs with a concentration of 20% and 80g of polypropylene oxide polyol with an average molecular weight of 2000 (polyether polyol A) were added to the reactor, a vacuum was applied at 110 ℃ for 1h,
2.2) cooling to 70 ℃, adding 30.5g of diphenylmethane diisocyanate (diisocyanate) and 0.08g of bismuth carboxylate, and reacting for 1h at the rotating speed of 150 rpm;
2.3) adding 8g of dimethylolbutyric acid (chain pre-extender) and 0.5g of ethylene glycol (chain pre-extender) to react for 3 hours at 70 ℃; the temperature is increased to 80 ℃ and the mixture is stirred for 2 hours.
2.4) 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;
2.5) adding 410g of deionized water, increasing the rotating speed to 800rpm, emulsifying for 60min, then adding 0.6g of hexamethylene diamine (rear chain extender), and stirring for 60min at the rotating speed of 600rpm to finally obtain the boron nitride/waterborne polyurethane emulsion.
3) Preparation of sandwich layer boron nitride/waterborne polyurethane composite emulsion
3.1) adding 80g of polypropylene oxide polyol (polyether polyol A) with the average molecular weight of 2000 into a reactor, vacuumizing for 1h at 110 ℃, and cooling to 70 ℃;
3.2) adding 30.5g of diphenylmethane diisocyanate (diisocyanate) and 0.08g of bismuth carboxylate, and reacting at the rotating speed of 150rpm for 1 h;
3.3) adding 8g of dimethylolbutyric acid (chain extender) and 0.5g of ethylene glycol (chain extender) and reacting for 3h at 70 ℃; the temperature is increased to 80 ℃, and the mixture is stirred for 2 hours.
3.4) 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;
3.5) adding 410g of deionized water, increasing the rotating speed to 800rpm, emulsifying for 60min, then adding 0.6g of hexamethylene diamine (rear chain extender), and stirring for 60min at the rotating speed of 600rpm to finally obtain the waterborne polyurethane emulsion.
4) High-strength, high-thermal conductivity and high-barrier condom molding, namely dipping and film forming are carried out by using a cleaned condom core mold:
4.1) firstly immersing a core mould into the waterborne polyurethane emulsion obtained in the step 3, and heating the core mould in a drying tunnel at the temperature of 90-110 ℃ for about 5 minutes after the core mould is pulled to form a film;
4.2) then immersing the core mould into the boron nitride/polyurethane emulsion obtained in the step 2, lifting and forming a film, and then heating the film in a drying tunnel at the temperature of 90-110 ℃ for about 5 minutes;
4.3) immersing the core mould into the waterborne polyurethane emulsion obtained in the step 3, and heating the core mould in a drying tunnel at the temperature of 90-110 ℃ for about 8 minutes after the core mould is pulled to form a film. Finally, the polyurethane condom with ultra-thin type, high strength, high thermal conductivity and high resistance and water resistance is obtained through the processes of curling, demoulding and drying.
Example 2
The boron nitride reinforced waterborne polyurethane high-barrier material condom is characterized in that the preparation method comprises the following steps:
1) surface functional modification of boron nitride
Adding 15g of boron nitride nanosheets into a reactor, adding 400g of solvent dimethylformamide, and performing ultrasonic dispersion for 4 hours;
5g of N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane and 0.02g of water were added to the reactor and heated to 80 ℃ and the temperature was maintained for 5 h. Centrifuging to remove supernatant, washing the lower solid with dimethylformamide for 2-3 times, stirring, centrifuging to obtain viscous semi-dry substance, and regulating with dimethylformamide to 25% concentration to obtain surface modified boron nitride dispersion (BNNTs).
2) Preparation of sandwich layer boron nitride/waterborne polyurethane composite emulsion
2.1) 6.2g of BNNTs with a concentration of 25% and 80g of polypropylene oxide polyol (polyether polyol A) with an average molecular weight of 2000 are added into the reactor, and the reactor is evacuated for 1h at 110 ℃;
2.2) cooling to 70 ℃, adding 29g of isophorone diisocyanate (diisocyanate) and 0.12g of bismuth carboxylate, stirring at the rotating speed of 150rpm, and reacting for 1 h;
2.3) adding 7.5g dimethylolpropionic acid (chain extender) and 2g diethylene glycol (chain extender) and reacting for 3h at 70 ℃; the temperature is raised to 85 ℃ and the mixture is stirred for 2 hours.
2.4) cooling the reactant to 50 ℃, adding 80g of acetone (solvent to reduce the viscosity of the system) and 6.2g of triethylamine (neutralizing agent), and stirring at the rotating speed of 200rpm for 40 min;
2.5) adding 400g of deionized water, increasing the rotating speed to 800rpm, emulsifying for 60min, then adding 0.5g of hexamethylene diamine (rear chain extender), and stirring for 60min at the rotating speed of 600rpm to finally obtain the boron nitride/waterborne polyurethane emulsion.
3) Preparation of sandwich layer boron nitride/waterborne polyurethane composite emulsion
3.1) adding 80g of polypropylene oxide polyol with average molecular weight of 2000 into a reactor, vacuumizing for 1h at 110 ℃, cooling to 70 DEG C
3.2) adding 29g of isophorone diisocyanate and 0.12g of bismuth carboxylate, stirring at the rotating speed of 150rpm, and reacting for 1 h;
3.3) adding 7.5g dimethylolpropionic acid (pre-chain extender) and 2g diethylene glycol (pre-chain extender) to react for 3h at 70 ℃; the temperature is raised to 85 ℃ and the mixture is stirred for 2 hours.
3.4) cooling the reactant to 50 ℃, adding 80g of acetone (solvent to reduce the viscosity of the system) and 6.2g of triethylamine (neutralizing agent), and stirring at the rotating speed of 200rpm for 40 min;
3.5) adding 400g of deionized water, increasing the rotating speed to 800rpm, emulsifying for 60min, then adding 0.5g of hexamethylene diamine (rear chain extender), and stirring for 60min at the rotating speed of 600rpm to finally obtain the waterborne polyurethane emulsion.
4) And forming the high-strength and high-barrier condom, namely dipping the condom into a film by using a cleaned condom core mold:
4.1) firstly immersing the core mould into the waterborne polyurethane emulsion in the step 3, and heating the core mould in a drying tunnel at the temperature of 90-110 ℃ for about 5 minutes after the core mould is pulled to form a film;
4.2) immersing the core mould into the boron nitride/polyurethane emulsion obtained in the step 2, lifting to form a film, and heating in a drying tunnel at the temperature of 90-110 ℃ for about 5 minutes;
4.3) immersing the core mould into the aqueous polyurethane emulsion obtained in the step 3, lifting and drawing the core mould into a film, heating the film in a drying tunnel at 90-110 ℃ for about 8 minutes, and finally performing processes of curling, demoulding and drying to obtain the ultrathin high-strength high-resistance water-proof polyurethane condom.
Example 3
The boron nitride reinforced waterborne polyurethane high-barrier material condom is characterized in that the preparation method comprises the following steps:
1) surface functional modification of boron nitride
Adding 20g of boron nitride nanosheets into a reactor, adding 500g of solvent dimethylformamide, and performing ultrasonic dispersion for 4 hours;
8g of 3-mercaptopropyltriethoxysilane and 0.05g of water were added and heated to 80 ℃ and incubated for 5 h. Centrifuging to remove supernatant, washing the lower solid with dimethylformamide for 2-3 times, stirring, centrifuging to obtain viscous semi-dry substance, and regulating with dimethylformamide to 30% to obtain surface modified boron nitride dispersion (BNNTs).
2) Preparation of sandwich layer boron nitride/waterborne polyurethane composite emulsion
2.1) adding 7.0g of 30% BNNTs, 80g of polypropylene oxide polyol (polyether polyol A) having an average molecular weight of 2000 and 20g of neopentyl glycol succinate polyol (polyester polyol B) having an average molecular weight of 1000 into the reactor, and evacuating at 110 ℃ for 1 hour;
2.2) cooling to 70 ℃, adding 29g of hexamethylene diisocyanate and 0.1g of bismuth carboxylate, stirring at the rotating speed of 150rpm, and reacting for 1 h;
2.3) adding 6.8g dimethylolpropionic acid (pre-chain extender) and 2g diethylene glycol (pre-chain extender) to react for 3h at 70 ℃; the temperature is increased to 85 ℃ and the mixture is stirred for 2 h.
2.4) 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;
2.5) 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 finally obtain the boron nitride/waterborne polyurethane emulsion.
3) Preparation of sandwich layer boron nitride/waterborne polyurethane composite emulsion
3.1) adding 80g of polypropylene oxide polyol (polyether polyol A) with the average molecular weight of 2000 and 20g of neopentyl glycol succinate polyol (polyester polyol B) with the average molecular weight of 1000 into a reactor, vacuumizing for 1h at 110 ℃, and cooling to 70 ℃;
3.2) adding 29g of hexamethylene diisocyanate and 0.1g of bismuth carboxylate, stirring at the rotating speed of 150rpm, and reacting for 1 h;
3.3) adding 6.8g dimethylolpropionic acid (pre-chain extender) and 2g diethylene glycol (pre-chain extender) to react for 3h at 70 ℃; the temperature is increased to 85 ℃ and the mixture is stirred for 2 h.
3.4) cooling the reactant to 50 ℃, adding 100g of acetone (solvent to reduce the viscosity of the system) and 5.65g of triethylamine (neutralizing agent), and stirring at the rotating speed of 200rpm for 40 min;
3.5) adding 500g of deionized water, increasing the rotating speed to 800rpm, emulsifying for 60min, adding 1g of post-chain-extended triethylene diamine, and stirring for 60min at the rotating speed of 600rpm to finally obtain the aqueous polyurethane emulsion.
4) And forming the condom with high strength, high thermal conductivity and high barrier, namely dipping and film forming by using a cleaned condom core mould:
4.1) firstly immersing the core mould into the waterborne polyurethane emulsion in the step 3, and heating the core mould in a drying tunnel at the temperature of 90-110 ℃ for about 5 minutes after the core mould is pulled to form a film;
4.2) immersing the core mould into the boron nitride/polyurethane emulsion obtained in the step 2, lifting to form a film, and heating in a drying tunnel at the temperature of 90-110 ℃ for about 5 minutes;
4.3) immersing the core mould into the aqueous polyurethane emulsion obtained in the step 3, lifting and drawing the core mould into a film, heating the film in a drying tunnel at 90-110 ℃ for about 8 minutes, and finally performing processes of curling, demoulding and drying to obtain the ultrathin polyurethane condom with high strength, high thermal conductivity and high resistance to water.
Comparative example 1:
1. preparing the aqueous polyurethane emulsion:
weighing 80g of polypropylene oxide polyol with the average molecular weight of 2000 and 20g of neopentyl glycol succinate polyol with the average molecular weight of 1000, vacuumizing for 1h at 110 ℃, cooling to 70 ℃, adding 29g of hexamethylene diisocyanate and 0.1g of bismuth carboxylate, stirring at the rotating speed of 150rpm, and reacting for 1 h; then adding 6.8g of dimethylolpropionic acid as a front chain extender and 2g of diethylene glycol to react for 3 hours at 70 ℃; the temperature is increased to 85 ℃ and the mixture is stirred for 2 h. 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; and then adding 500g of deionized water, increasing the rotating speed to 800rpm, emulsifying for 60min, adding 1g of post-chain-extended triethylene diamine, and stirring for 60min at the rotating speed of 600rpm to finally obtain the waterborne polyurethane emulsion.
2. Forming the high-strength and high-barrier condom: dipping into film by using a cleaned condom core mould. Firstly, immersing a core mold into the waterborne polyurethane emulsion in the step 1, lifting and forming a film, and then heating the film in a drying tunnel at the temperature of 90-110 ℃ for about 5 minutes; then, the core mould is immersed into the boron nitride/polyurethane emulsion obtained in the step 1, and after being lifted to form a film, the film is heated in a drying tunnel at the temperature of 90-110 ℃ for about 5 minutes; and (2) immersing the core mold into the aqueous polyurethane emulsion obtained in the step (1), pulling the core mold into a film, heating the film in a drying tunnel at the temperature of 90-110 ℃ for about 8 minutes, and finally performing processes of edge curling, demolding and drying to obtain the ultrathin polyurethane condom with high strength, high thermal conductivity and high resistance to water.
Specific examples condom performance test data are shown in the following table:
Figure BDA0002641978360000101
note: the WVT value is the water vapor transmission rate, which characterizes the barrier properties of the condom, with a smaller value indicating a better barrier property of the film.
As can be seen from the analysis of the data in the table above, the condom material prepared by the method has the advantages of ultra-thinness, high strength, high thermal conductivity and high barrier property, and is greatly superior to the performance of condoms prepared by common waterborne polyurethane materials.

Claims (10)

1. A boron nitride reinforced waterborne polyurethane high-heat-conduction and high-barrier material is characterized by having the multilayer structure; in the multilayer structure, each layer is formed by drying boron nitride/aqueous polyurethane emulsion or aqueous polyurethane emulsion.
2. The boron nitride-reinforced waterborne polyurethane high-thermal-conductivity high-barrier material as claimed in claim 1, wherein: the multilayer structure is formed by drying boron nitride/waterborne polyurethane emulsion to form an intermediate interlayer; after the aqueous polyurethane emulsion is dried, coating layers on two sides of the middle interlayer are formed;
the boron nitride/waterborne polyurethane emulsion is obtained by modifying boron nitride to improve the compatibility of the boron nitride and a polyurethane material.
3. A preparation method of a boron nitride reinforced waterborne polyurethane high-thermal-conductivity high-barrier material is characterized by comprising the following steps:
1) surface functional modification of boron nitride
In a reactor, dispersing boron nitride in a solvent, adding a silane coupling agent for reaction to prepare surface modified boron nitride dispersion liquid (BNNTs);
2) preparation of sandwich layer boron nitride/waterborne polyurethane composite emulsion
The proportion ranges of the components are as follows:
Figure FDA0002641978350000011
the preparation method comprises the following steps:
2.1) adding polyether glycol A into a reactor; when the polyester polyol B is selected, the polyester polyol B is added at the same time;
2.2) adding BNNTs, diisocyanate and a catalyst for reaction;
2.3) adding a chain extender for reaction;
2.4) adding a neutralizing agent for reaction;
2.5) adding deionized water for emulsification under high-speed stirring, and adding a rear chain extender to obtain the boron nitride/waterborne polyurethane emulsion.
3) Preparation of coating layer aqueous polyurethane emulsion
The proportion ranges of the components are as follows:
Figure FDA0002641978350000012
Figure FDA0002641978350000021
the preparation method comprises the following steps:
3.1) adding polyether glycol A into a reactor; when the polyester polyol B is selected, the polyester polyol B is added at the same time;
3.2) adding diisocyanate and a catalyst for reaction;
3.3) adding a chain extender for reaction;
3.4) adding a neutralizing agent for reaction;
3.5) emulsifying under the stirring condition, and adding a rear chain extender for reaction to obtain the waterborne polyurethane emulsion.
4) Preparing a high-barrier material:
obtaining a high barrier material having a multilayer structure; each layer in the multilayer structure is formed by the aqueous polyurethane emulsion obtained in step 3) or the boron nitride/aqueous polyurethane emulsion obtained in step 2).
4. The preparation method of the boron nitride reinforced waterborne polyurethane high-thermal-conductivity high-barrier material according to claim 3, wherein in the step 1), the raw materials are prepared in the following ratio:
10-20 parts of boron nitride
Solvent 200-500 parts
1-10 parts of silane coupling agent
0.01-0.1 part of water.
5. The preparation method of the boron nitride-reinforced aqueous polyurethane high-thermal-conductivity high-barrier material according to claim 3 or 4, wherein in the steps 2) and 3):
the diisocyanate is selected from: one of diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), Toluene Diisocyanate (TDI), Hexamethylene Diisocyanate (HDI), and xylylene diisocyanate.
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 is 1000-3000.
The polyester polyol B is selected from: one or more of polyethylene glycol adipate, neopentyl glycol succinate, polybutylene isophthalate or neopentyl glycol isophthalate, wherein the molecular weight of the polyester polyol is 1000-3000.
The pre-chain extender includes a chain extender containing a hydrophilic group and a chain extender containing no hydrophilic group.
The catalyst is one of organic bismuth or organic tin.
6. The boron nitride-reinforced aqueous polyurethane high-thermal-conductivity high-barrier material according to claim 4 or 5, wherein in the steps 2) and 3):
the chain extender containing hydrophilic groups can be one of dimethylolpropionic acid (DMPA), dimethylolbutyric acid (DMBA), dihydroxy half ester and N-methyldiethanolamine.
The chain extender without hydrophilic group can be one of ethylene glycol, diethylene glycol (DEG), Trimethylolpropane (TMP) and Diethylenetriamine (DTA).
The organic bismuth catalyst is selected from bismuth carboxylate;
the organotin catalyst is selected from dibutyltin Dilaurate (DBTL).
7. The boron nitride-reinforced waterborne polyurethane high-thermal-conductivity high-barrier material as claimed in claim 3 or 5, wherein: the step 4 comprises the following steps:
4.1) immersing the mould into the aqueous polyurethane emulsion obtained in the step 3), taking out and drying;
4.2) immersing the dried mould into the boron nitride/waterborne polyurethane emulsion obtained in the step 2), taking out and drying;
4.3) finally, immersing the dried mould into the aqueous polyurethane emulsion obtained in the step 3), taking out and drying to obtain the material with the composite structure.
8. The boron nitride-reinforced waterborne polyurethane high-thermal-conductivity high-barrier material according to claim 7, wherein: and repeating the step 4.2-4.3 for a plurality of times to obtain the multilayer material.
9. The boron nitride reinforced waterborne polyurethane condom with the high heat conduction and the high barrier material is characterized in that: the material is manufactured by adopting the material of any one of claims 1 to 7.
10. The condom of claim 8, wherein the condom is prepared from the boron nitride-reinforced waterborne polyurethane high-thermal-conductivity high-barrier material, and is characterized in that: when the material of any one of claims 1 to 5 is used for manufacturing, the step 4 is the preparation of the condom; the adopted mould is a condom core mould.
CN202010842596.5A 2020-04-15 2020-08-20 Boron nitride reinforced waterborne polyurethane high-thermal-conductivity high-barrier material and condom Pending CN112029262A (en)

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