CN113980621B - High-light-transmittance acid-alkali-resistant hot melt adhesive based on organic silicon-based material modification - Google Patents
High-light-transmittance acid-alkali-resistant hot melt adhesive based on organic silicon-based material modification Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment
- C09J123/28—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
Abstract
The invention discloses a high-light-transmission acid-alkali-resistant hot melt adhesive based on modification of an organic silicon-based material, and relates to the technical field of hot melt adhesives. The invention firstly prepares nano-silica into hollow porous organic silicon microspheres, then reacts with silane coupling agent to prepare modified organic silicon microspheres, chloridizes hot melt resin, then reacts with trifluoromethyl (1, 10-phenanthroline) copper to prepare modified hot melt resin, mixes and stirs the modified hot melt resin, the modified organic silicon microspheres, dispersant, antioxidant and talcum powder in a melting kettle to prepare melting material, and cools and granulates the melting material to prepare the high-light-transmission acid-alkali-resistant hot melt adhesive. The high-light-transmission acid-alkali-resistant hot melt adhesive prepared by the invention has excellent acid-alkali-resistant performance and bonding performance.
Description
Technical Field
The invention relates to the technical field of hot melt adhesives, in particular to a high-light-transmission acid-alkali-resistant hot melt adhesive based on modification of an organic silicon-based material.
Background
The hot melt adhesive is a plastic adhesive, the physical state of which changes along with the change of temperature within a certain temperature range, and the chemical property of which is unchanged, is nontoxic and tasteless, and belongs to an environment-friendly chemical product. The product is solid, so the product is convenient to package, transport and store, and has no solvent, pollution and toxicity; and the production process is simple, the added value is high, the bonding strength is high, the speed is high, and the like. The existing hot melt adhesive has the advantages of high strength, aging resistance, no toxicity, good thermal stability and the like. The product can be used for mutually adhering and bonding objects such as wood, plastics, fibers, fabrics, metal, furniture, lampshades, leather, artware, toy electronics, electrical appliance components, paper products, ceramics, pearl wool packages and the like, and can be widely used in factories and families.
Along with the development of society and technological innovation, various performances of the hot melt adhesive are not improved, and requirements of people on the performances of the hot melt adhesive are higher and higher, so that the hot melt adhesive suitable for severe environments, such as acid and alkali resistance, wear resistance, deformation resistance and the like, needs to be developed, and the prepared hot melt adhesive has excellent acid and alkali resistance and bonding strength.
Disclosure of Invention
The invention aims to provide a high-light-transmission acid-alkali-resistant hot melt adhesive based on modification of an organic silicon-based material, so as to solve the problems in the prior art.
The high-light-transmission acid-alkali-resistant hot melt adhesive based on modification of the organic silicon-based material is characterized by mainly comprising the following components in parts by weight: 80-100 parts of modified hot-melt resin, 10-15 parts of modified organic silicon microspheres, 1-2 parts of dispersing agent, 1-2 parts of antioxidant and 1-2 parts of talcum powder.
Preferably, the modified hot-melt resin is prepared by chlorination of EVA resin and reaction with trifluoromethyl (1, 10-phenanthroline) copper.
Preferably, the trifluoromethyl (1, 10-phenanthroline) copper is prepared by reacting tert-butyl copper with trifluoromethyl trimethyl alkane, and then adding 1, 10-phenanthroline for reaction.
Preferably, the modified organic silicon microspheres are prepared by preparing nano silicon dioxide from tetraethoxysilane, preparing organic silicon microspheres from the nano silicon dioxide, hexadecyl trimethyl ammonium chloride and triethanolamine, etching the organic silicon microspheres by using a sodium hydroxide solution, extracting by using a sodium chloride methanol solution to prepare hollow porous organic silicon microspheres, and modifying the hollow porous organic silicon microspheres by using a silane coupling agent.
As optimization, the preparation method of the high-light-transmission acid-alkali-resistant hot melt adhesive based on modification of the organic silicon-based material mainly comprises the following preparation steps:
(1) Mixing hexadecyl trimethyl ammonium chloride, triethanolamine and pure water according to the mass ratio of 5:1:20, uniformly mixing, stirring for 1-2 h at normal temperature to prepare an organic solution, adding nano-silica into the organic solution with the mass of 3 times that of the nano-silica, stirring for 1-2 h, washing for 3-5 times by using absolute ethyl alcohol after filtering, adding into a sodium hydroxide solution with the mass fraction of 10% and the mass of 10-15 times that of the nano-silica, etching for 30-40 min at the temperature of 20-30 ℃, filtering, and washing for 2-3 times by using pure water. Extracting with 1% sodium chloride methanol solution at 20-30 ℃, washing with pure water and absolute ethyl alcohol for 3-5 times respectively, drying at-10-1 ℃ under the pressure of 5-10 Pa for 6-8 h to prepare the hollow porous organic silicon microspheres, and mixing the hollow porous organic silicon microspheres, the absolute ethyl alcohol and the pure water according to the mass ratio of 1:15:5, uniformly mixing, adding hydrochloric acid to adjust the pH value to 4-5, adding a silane coupling agent with the mass of 0.3-0.5 time that of the hollow porous organic silicon microsphere, stirring and reacting at the temperature of 60-70 ℃ at 800-1000 r/min for 10-12 h, washing with absolute ethyl alcohol for 3-5 times, and drying at the temperature of-10 to-1 ℃ under the pressure of 5-10 Pa for 6-8 h to prepare the modified organic silicon microsphere;
(2) Placing hot-melt resin in a glass tube, introducing chlorine gas at the speed of 3-5 cm/s for 2-3 h at the temperature of 80-90 ℃, cooling to 20-30 ℃, ventilating and extracting chlorine, placing in a ventilation kitchen for 20-24 h to prepare chlorinated hot-melt resin, and mixing the chlorinated hot-melt resin with an acetone solution with the mass fraction of 30% according to the mass ratio of 1:10 to 1:15, adding trifluoromethyl (1, 10-phenanthroline) copper with the mass of 0.5-0.6 time of that of the chlorinated hot-melt resin after uniformly mixing, stirring for 8-12 h at the rotating speed of 2000-3000 r/min under the conditions of 20-30 ℃ and 60W power and ultraviolet irradiation with the wavelength of 365nm, filtering, washing for 3-5 times by using absolute ethyl alcohol, and carrying out vacuum freeze drying for 5-6 h at the temperature of-10-5 ℃ and the pressure of 10Pa to prepare the modified hot-melt resin;
(3) Putting the modified hot-melt resin into a melting kettle, heating to 170-180 ℃, stirring for 10min at 300-500 r/min, then adding modified organic silicon microspheres with the mass of 0.1-0.2 time of that of the modified hot-melt resin, dispersing agents with the mass of 0.01-0.03 time of that of the modified hot-melt resin, antioxidants with the mass of 0.01-0.03 time of that of the modified hot-melt resin and talcum powder with the mass of 0.01-0.03 time of that of the modified hot-melt resin, and continuously stirring for 50-60 min to prepare a melting material;
(4) And (3) placing the molten material in a flat plate mold, cooling to 10-30 ℃ for molding under the pressure of 5-10 MPa in the nitrogen atmosphere, and placing in a granulator for granulation to obtain the high-light-transmission acid-base-resistant hot melt adhesive.
As optimization, the preparation method of the nano silicon dioxide in the step (1) comprises the following steps: ammonia water, absolute ethyl alcohol and pure water with the mass part of 25% are mixed according to the proportion of 3:5:2, adding tetraethoxysilane with the mass of 0.18-0.22 time of that of the absolute ethyl alcohol, reacting for 2-3 hours at the temperature of 20-30 ℃ and the rotating speed of 500-800 r/min, filtering, sequentially washing for 3-5 times by using deionized water and the absolute ethyl alcohol respectively, and drying for 6-8 hours at the temperature of-10-1 ℃ and the pressure of 5-10 Pa to prepare the catalyst.
Preferably, the hot-melt resin in the step (2) is EVA resin.
Preferably, the trifluoromethyl (1, 10-phenanthroline) copper in the step (2) is prepared by mixing copper tert-butoxide, trifluoromethyl trimethyl alkane and absolute ethyl alcohol in a mass ratio of 2:1: 10-1: 1:15, stirring the mixture for 1h at the temperature of 60 ℃ at the rotating speed of 800-1000 r/min, adding 1, 10-phenanthroline with the mass being 2 times that of the fluoromethyl trimethyl alkane, and stirring the mixture for 5min at the temperature of 80 ℃ at the rotating speed of 100-200 r/min to prepare the composite material.
Compared with the prior art, the invention has the following beneficial effects:
the high-light-transmission acid-alkali-resistant hot melt adhesive prepared by the invention is composed of modified hot melt resin, modified organic silicon microspheres, a dispersing agent, an antioxidant and talcum powder.
The modified organosilicon microspheres are prepared by preparing hollow porous organosilicon microspheres from nano-silica and reacting with a silane coupling agent, the hollow porous structure of the modified organosilicon microspheres can absorb modified hot-melt resin, and the modified hot-melt resin is wound on the modified organosilicon microspheres in an inserting manner, so that the bonding is tighter, the mechanical property and the acid and alkali resistance of the material are enhanced, and simultaneously, the modified organosilicon microspheres can react with carboxyl groups on the modified hot-melt resin after being modified by the silane coupling agent, so that a cross-linked network structure is formed, and the modified organosilicon microspheres can be used as a cross-linking center to bind and fix the modified hot-melt resin, so that the mechanical property and the acid and alkali resistance of the material are further enhanced.
Secondly, after the hot-melt resin is chlorinated, the hot-melt resin reacts with trifluoromethyl (1, 10-phenanthroline) copper, trifluoromethyl is introduced, the modified hot-melt resin is prepared, the introduced trifluoromethyl plays a role in shielding and protecting a modified hot-melt resin main body, and the material is hydrophobic, so that the waterproof effect and the acid and alkali resistance are improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In order to more clearly illustrate the method provided by the invention, the following examples are used for detailed description, and the test methods of all indexes of the high-light-transmittance acid-alkali-resistant hot melt adhesive prepared in the following examples are as follows:
acid and alkali resistance: the high-light-transmission acid-alkali-resistant hot melt adhesive obtained in each example and a comparative product are weighed to be the same in mass, placed in an acidic or alkaline solution with the same concentration at 20 ℃ for the same time, taken out, washed, dried and weighed, and the corrosion amount is recorded according to the mass difference between the front and the back.
Adhesion: the high-light-transmission acid-alkali-resistant hot melt adhesive obtained in each embodiment and a comparative product are subjected to the same quality, hot melting is carried out on the same substrate at the same temperature, the drawing heads of the same type are bonded on the substrate for drawing test, and the tensile strength of the drawing heads when the drawing heads are separated from the substrate is recorded.
Example 1
A high-light-transmission acid-alkali-resistant hot melt adhesive based on modification of an organic silicon-based material mainly comprises the following components in parts by weight: 100 parts of modified hot-melt resin, 10 parts of modified organic silicon microspheres, 1 part of dispersing agent, 1 part of antioxidant and 1 part of talcum powder.
A preparation method of a high-light-transmission acid-and-alkali-resistant hot melt adhesive based on modification of an organic silicon-based material mainly comprises the following preparation steps:
(1) Mixing hexadecyl trimethyl ammonium chloride, triethanolamine and pure water according to the mass ratio of 5:1:20, uniformly mixing, stirring at normal temperature for 1h to prepare an organic solution, adding nano silicon dioxide into the organic solution with the mass of 3 times that of the nano silicon dioxide, stirring for 1h, filtering, washing for 3 times by using absolute ethyl alcohol, adding into a sodium hydroxide solution with the mass fraction of 10% and the mass of 10 times that of the nano silicon dioxide, etching at 20 ℃ for 40min, filtering, and washing for 2 times by using pure water. Extracting with 1% sodium chloride methanol solution at 20 ℃, washing with pure water and absolute ethyl alcohol for 3 times respectively, drying at-10 ℃ and 5Pa for 6 hours to obtain hollow porous organic silicon microspheres, and mixing the hollow porous organic silicon microspheres, the absolute ethyl alcohol and the pure water according to a mass ratio of 1:15:5, uniformly mixing, adding hydrochloric acid to adjust the pH value to 4, adding a silane coupling agent with the mass of 0.3 time that of the hollow porous organic silicon microsphere, stirring and reacting at 60 ℃ at 800r/min for 12 hours, washing for 3 times by using absolute ethyl alcohol, and drying at-10 ℃ under the pressure of 5Pa for 8 hours to prepare the modified organic silicon microsphere;
(2) Placing the hot-melt resin in a glass tube, introducing chlorine gas at the speed of 3cm/s for 2h at the temperature of 80 ℃, cooling to 20 ℃, ventilating and chlorine extracting, placing in a ventilation kitchen for 24h to prepare chlorinated hot-melt resin, and mixing the chlorinated hot-melt resin with an acetone solution with the mass fraction of 30% according to the mass ratio of 1:10, adding trifluoromethyl (1, 10-phenanthroline) copper with the mass 0.5 time that of the chlorinated hot-melt resin, stirring at the ultraviolet irradiation condition of 20 ℃,60W power and 365nm wavelength for 12h at the rotating speed of 2000r/min, filtering, washing for 3 times by using absolute ethyl alcohol, and carrying out vacuum freeze drying for 6h at-10 ℃ and under the pressure of 10Pa to prepare the modified hot-melt resin;
(3) Putting the modified hot-melt resin into a melting kettle, heating to 170 ℃, stirring for 10min at 300r/min, then adding modified organic silicon microspheres with the mass of 0.1 time that of the modified hot-melt resin, dispersing agents with the mass of 0.01 time that of the modified hot-melt resin, antioxidants with the mass of 0.01 time that of the modified hot-melt resin and talcum powder with the mass of 0.01 time that of the modified hot-melt resin, and continuously stirring for 60min to obtain a melting material;
(4) And (3) placing the molten material into a flat plate die, cooling to 10 ℃ under the pressure of 5MPa in the nitrogen atmosphere for forming, and placing the molten material into a granulator for granulation to obtain the high-light-transmission acid-base-resistance hot melt adhesive.
Example 2
A high-light-transmission acid-alkali-resistant hot melt adhesive based on modification of an organic silicon-based material mainly comprises the following components in parts by weight: 90 parts of modified hot-melt resin, 12 parts of modified organic silicon microspheres, 1 part of dispersing agent, 1 part of antioxidant and 1 part of talcum powder.
A preparation method of a high-light-transmission acid-and-alkali-resistant hot melt adhesive based on modification of an organic silicon-based material mainly comprises the following preparation steps:
(1) Mixing hexadecyl trimethyl ammonium chloride, triethanolamine and pure water according to the mass ratio of 5:1:20, uniformly mixing, stirring at normal temperature for 1h to prepare an organic solution, adding nano silicon dioxide into the organic solution with the mass of 3 times that of the nano silicon dioxide, stirring for 1h, filtering, washing for 4 times by using absolute ethyl alcohol, adding into a sodium hydroxide solution with the mass fraction of 10% and the mass of 12 times that of the nano silicon dioxide, etching for 35min at 25 ℃, filtering, and washing for 2 times by using pure water. Extracting with 1% sodium chloride methanol solution at 25 ℃, washing with pure water and absolute ethyl alcohol for 4 times respectively, drying at-5 ℃ under the pressure of 8Pa for 7 hours to prepare the hollow porous organic silicon microsphere, wherein the mass ratio of the hollow porous organic silicon microsphere, the absolute ethyl alcohol and the pure water is 1:15:5, uniformly mixing, adding hydrochloric acid to adjust the pH value to 4, adding a silane coupling agent with the mass of 0.4 time that of the hollow porous organic silicon microsphere, stirring and reacting at 65 ℃ for 11h at 900r/min, washing for 4 times by using absolute ethyl alcohol, and drying for 7h at-5 ℃ under the pressure of 8Pa to prepare the modified organic silicon microsphere;
(2) Placing the hot-melt resin in a glass tube, introducing chlorine gas at the speed of 4cm/s for 2h at the temperature of 85 ℃, cooling to 25 ℃, ventilating and chlorine extracting, placing in a ventilation kitchen for 22h to prepare chlorinated hot-melt resin, and mixing the chlorinated hot-melt resin with an acetone solution with the mass fraction of 30% according to the mass ratio of 1:12, adding trifluoromethyl (1, 10-phenanthroline) copper with the mass 0.5 time that of the chlorinated hot-melt resin, stirring at the rotating speed of 2500r/min for 10 hours under the conditions of 25 ℃,60W, power and ultraviolet irradiation with the wavelength of 365nm, filtering, washing for 4 times by using absolute ethyl alcohol, and carrying out vacuum freeze drying for 5 hours at the temperature of-8 ℃ and under the pressure of 10Pa to prepare the modified hot-melt resin;
(3) Putting the modified hot-melt resin into a melting kettle, heating to 175 ℃, stirring for 10min at 400r/min, then adding modified organic silicon microspheres with the mass of 0.1 time that of the modified hot-melt resin, dispersing agents with the mass of 0.02 time that of the modified hot-melt resin, antioxidants with the mass of 0.01 time that of the modified hot-melt resin and talcum powder with the mass of 0.02 time that of the modified hot-melt resin, and continuously stirring for 55min to prepare a melting material;
(4) And (3) placing the molten material into a flat plate die, cooling to 20 ℃ under the pressure of 8MPa in the nitrogen atmosphere for forming, and placing the molten material into a granulator for granulation to obtain the high-light-transmission acid-base-resistance hot melt adhesive.
Example 3
The high-transmittance acid and alkali resistant hot melt adhesive based on modification of the organic silicon-based material mainly comprises the following components in parts by weight: 80 parts of modified hot-melt resin, 15 parts of modified organic silicon microspheres, 2 parts of dispersing agent, 2 parts of antioxidant and 2 parts of talcum powder.
A preparation method of a high-light-transmission acid-and-alkali-resistant hot melt adhesive based on modification of an organic silicon-based material mainly comprises the following preparation steps:
(1) Mixing hexadecyl trimethyl ammonium chloride, triethanolamine and pure water according to the mass ratio of 5:1:20, uniformly mixing, stirring at normal temperature for 2 hours to prepare an organic solution, adding nano silicon dioxide into the organic solution with the mass of 3 times that of the nano silicon dioxide, stirring for 2 hours, filtering, washing for 5 times by using absolute ethyl alcohol, adding into a sodium hydroxide solution with the mass fraction of 10% and the mass of 15 times that of the nano silicon dioxide, etching for 30min at 30 ℃, filtering, and washing for 3 times by using pure water. Extracting with 1% sodium chloride methanol solution at 30 ℃, washing with pure water and absolute ethyl alcohol for 5 times respectively, drying at-1 ℃ under the pressure of 10Pa for 6 hours to prepare the hollow porous organic silicon microsphere, and mixing the hollow porous organic silicon microsphere, the absolute ethyl alcohol and the pure water according to the mass ratio of 1:15:5, uniformly mixing, adding hydrochloric acid to adjust the pH value to 5, adding a silane coupling agent with the mass of 0.5 time that of the hollow porous organic silicon microsphere, stirring and reacting at 70 ℃ for 10 hours at 1000r/min, washing for 5 times by using absolute ethyl alcohol, and drying for 6 hours at-1 ℃ under the pressure of 10Pa to prepare the modified organic silicon microsphere;
(2) Placing the hot-melt resin in a glass tube, introducing chlorine gas at the speed of 5cm/s for 2h at the temperature of 90 ℃, cooling to 30 ℃, ventilating and chlorine extracting, placing in a ventilation kitchen for 20h to prepare chlorinated hot-melt resin, and mixing the chlorinated hot-melt resin with an acetone solution with the mass fraction of 30% according to the mass ratio of 1:15, adding trifluoromethyl (1, 10-phenanthroline) copper with the mass 0.6 time that of the chlorinated hot-melt resin, stirring at the rotating speed of 3000r/min for 8 hours under the conditions of 30 ℃ and 60W power and ultraviolet irradiation with the wavelength of 365nm, filtering, washing for 5 times by using absolute ethyl alcohol, and carrying out vacuum freeze drying for 5 hours at the temperature of-10 ℃ and under the pressure of 10Pa to prepare the modified hot-melt resin;
(3) Putting the modified hot-melt resin into a melting kettle, heating to 180 ℃, stirring for 10min at 500r/min, then adding modified organic silicon microspheres in an amount which is 0.2 times the mass of the modified hot-melt resin, a dispersing agent in an amount which is 0.03 times the mass of the modified hot-melt resin, an antioxidant in an amount which is 0.03 times the mass of the modified hot-melt resin and talcum powder in an amount which is 0.03 times the mass of the modified hot-melt resin, and continuously stirring for 50min to prepare a melting material;
(4) And (3) placing the molten material in a flat plate die, cooling to 30 ℃ under the pressure of 10MPa in the nitrogen atmosphere for forming, and placing in a granulator for granulation to obtain the high-light-transmission acid-base-resistant hot melt adhesive.
Comparative example 1
A high-light-transmission acid-alkali-resistant hot melt adhesive based on modification of an organic silicon-based material mainly comprises the following components in parts by weight: 100 parts of hot-melt resin, 10 parts of modified organic silicon microspheres, 1 part of dispersing agent, 1 part of antioxidant and 1 part of talcum powder.
A preparation method of a high-light-transmission acid-and-alkali-resistant hot melt adhesive based on modification of an organic silicon-based material mainly comprises the following preparation steps:
(1) Mixing hexadecyl trimethyl ammonium chloride, triethanolamine and pure water according to the mass ratio of 5:1:20, uniformly mixing, stirring at normal temperature for 1h to prepare an organic solution, adding nano silicon dioxide into the organic solution with the mass of 3 times that of the nano silicon dioxide, stirring for 1h, filtering, washing for 3 times by using absolute ethyl alcohol, adding into a sodium hydroxide solution with the mass fraction of 10% and the mass of 10 times that of the nano silicon dioxide, etching at 20 ℃ for 40min, filtering, and washing for 2 times by using pure water. Extracting with 1% sodium chloride methanol solution at 20 ℃, washing with pure water and absolute ethyl alcohol for 3 times respectively, drying at-10 ℃ under the pressure of 5Pa for 6h to prepare the hollow porous organic silicon microsphere, and mixing the hollow porous organic silicon microsphere, the absolute ethyl alcohol and the pure water according to the mass ratio of 1:15:5, uniformly mixing, adding hydrochloric acid to adjust the pH value to 4, adding a silane coupling agent with the mass of 0.3 time that of the hollow porous organic silicon microsphere, stirring and reacting at 60 ℃ at 800r/min for 12 hours, washing for 3 times by using absolute ethyl alcohol, and drying at-10 ℃ under the pressure of 5Pa for 8 hours to prepare the modified organic silicon microsphere;
(2) Putting hot-melt resin into a melt kettle, heating to 170 ℃, stirring for 10min at a speed of 300r/min, adding modified organic silicon microspheres with the mass being 0.1 time of that of the hot-melt resin, dispersing agents with the mass being 0.01 time of that of the hot-melt resin, antioxidants with the mass being 0.01 time of that of the hot-melt resin and talcum powder with the mass being 0.01 time of that of the hot-melt resin, and continuously stirring for 60min to prepare a melt;
(3) And (3) placing the molten material in a flat plate die, cooling to 10 ℃ for forming under the pressure of 5MPa in the nitrogen atmosphere, and placing in a granulator for granulation to obtain the high-light-transmission acid-base-resistant hot melt adhesive.
Comparative example 2
A high-light-transmission acid-alkali-resistant hot melt adhesive based on modification of an organic silicon-based material mainly comprises the following components in parts by weight: 100 parts of modified hot-melt resin, 10 parts of hollow porous organic silicon microspheres, 1 part of dispersing agent, 1 part of antioxidant and 1 part of talcum powder.
A preparation method of a high-light-transmission acid-and-alkali-resistant hot melt adhesive based on modification of an organic silicon-based material mainly comprises the following preparation steps:
(1) Mixing hexadecyl trimethyl ammonium chloride, triethanolamine and pure water according to the mass ratio of 5:1:20, uniformly mixing, stirring at normal temperature for 1h to prepare an organic solution, adding nano silicon dioxide into the organic solution with the mass of 3 times that of the nano silicon dioxide, stirring for 1h, filtering, washing for 3 times by using absolute ethyl alcohol, adding into a sodium hydroxide solution with the mass fraction of 10% and the mass of 10 times that of the nano silicon dioxide, etching at 20 ℃ for 40min, filtering, and washing for 2 times by using pure water. Extracting with 1% sodium chloride methanol solution at 20 deg.C, washing with pure water and anhydrous ethanol for 3 times, respectively, drying at-10 deg.C under 5Pa for 6 hr to obtain hollow porous organosilicon microsphere, and mixing the hollow porous organosilicon microsphere with the above extract;
(2) Placing hot-melt resin in a glass tube, introducing chlorine gas at the speed of 3cm/s for 2h at the temperature of 80 ℃, cooling to 20 ℃, ventilating and chlorine extracting, placing in a ventilation kitchen for 24h to prepare chlorinated hot-melt resin, and mixing the chlorinated hot-melt resin with an acetone solution with the mass fraction of 30% according to the mass ratio of 1:10, uniformly mixing, adding trifluoromethyl (1, 10-phenanthroline) copper with the mass 0.5 time of that of the chlorinated hot-melt resin, stirring at the rotating speed of 2000r/min for 12 hours under the conditions of 20 ℃,60W, power and ultraviolet irradiation with the wavelength of 365nm, filtering, washing for 3 times by using absolute ethyl alcohol, and carrying out vacuum freeze drying for 6 hours at the temperature of-10 ℃ and under the pressure of 10Pa to prepare the modified hot-melt resin;
(3) Putting the modified hot-melt resin into a melting kettle, heating to 170 ℃, stirring for 10min at 300r/min, then adding hollow porous organic silicon microspheres with the mass of 0.1 time that of the modified hot-melt resin, a dispersing agent with the mass of 0.01 time that of the modified hot-melt resin, an antioxidant with the mass of 0.01 time that of the modified hot-melt resin and talcum powder with the mass of 0.01 time that of the modified hot-melt resin, and continuously stirring for 60min to obtain a melting material;
(4) And (3) placing the molten material in a flat plate die, cooling to 10 ℃ for forming under the pressure of 5MPa in the nitrogen atmosphere, and placing in a granulator for granulation to obtain the high-light-transmission acid-base-resistant hot melt adhesive.
Comparative example 3
A high-light-transmission acid-alkali-resistant hot melt adhesive based on modification of an organic silicon-based material mainly comprises the following components in parts by weight: 100 parts of modified hot-melt resin, 1 part of dispersing agent, 1 part of antioxidant and 1 part of talcum powder.
A preparation method of a high-light-transmission acid-and-alkali-resistant hot melt adhesive based on modification of an organic silicon-based material mainly comprises the following preparation steps:
(1) Placing the hot-melt resin in a glass tube, introducing chlorine gas at the speed of 3cm/s for 2h at the temperature of 80 ℃, cooling to 20 ℃, ventilating and chlorine extracting, placing in a ventilation kitchen for 24h to prepare chlorinated hot-melt resin, and mixing the chlorinated hot-melt resin with an acetone solution with the mass fraction of 30% according to the mass ratio of 1:10, adding trifluoromethyl (1, 10-phenanthroline) copper with the mass 0.5 time that of the chlorinated hot-melt resin, stirring at the ultraviolet irradiation condition of 20 ℃,60W power and 365nm wavelength for 12h at the rotating speed of 2000r/min, filtering, washing for 3 times by using absolute ethyl alcohol, and carrying out vacuum freeze drying for 6h at-10 ℃ and under the pressure of 10Pa to prepare the modified hot-melt resin;
(2) Placing the modified hot-melt resin into a melting kettle, heating to 170 ℃, stirring for 10min at a speed of 300r/min, then adding a dispersing agent with the mass 0.01 times that of the modified hot-melt resin, an antioxidant with the mass 0.01 times that of the modified hot-melt resin and talcum powder with the mass 0.01 times that of the modified hot-melt resin, and continuously stirring for 60min to obtain a melting material;
(3) And (3) placing the molten material in a flat plate die, cooling to 10 ℃ for forming under the pressure of 5MPa in the nitrogen atmosphere, and placing in a granulator for granulation to obtain the high-light-transmission acid-base-resistant hot melt adhesive.
Examples of effects
The following table 1 shows the results of the acid and alkali resistance and adhesion performance analysis of the highly light-transmitting acid and alkali resistant hot melt adhesives of examples 1 to 3 and comparative examples 1 to 3.
TABLE 1
The comparison of experimental data in table 1 shows that the acid resistance, alkali resistance and adhesion of the material can be obviously improved by modifying the hot-melt resin and adding the modified organic silicon microspheres; compared with the experimental data of examples 1, 2 and 3 and comparative example 1 in table 1, it can be seen that the corrosion amount of examples 1, 2 and 3 is small compared with comparative example 1, which indicates that after the hot-melt resin is modified, the introduced trifluoromethyl plays a role in shielding and protecting the main body of the material, so that the acid and alkali resistance of the material is improved; the experimental data comparison of examples 1, 2 and 3 with comparative example 2 shows that the corrosion amount of examples 1, 2 and 3 with comparative example 2 is small, and the tensile strength is high, which indicates that carboxyl groups on the modified hot-melt resin can be crosslinked on the modified organic silicon microspheres after the hollow porous organic silicon microspheres are modified by the silane coupling agent, so that the modified organic silicon microspheres become central nodes of a crosslinking network, and the acid-base resistance and the adhesion of the material are improved; the comparison example 2 has smaller corrosion amount and larger tensile strength compared with the comparison example 3, which shows that the hollow porous organic silicon microsphere is added, and the modified hot melt resin can be adsorbed and wound on the hollow porous organic silicon microsphere, so that the materials are combined more tightly, and the acid and alkali resistance and the adhesion of the materials are improved.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (5)
1. The high-light-transmission acid-alkali-resistant hot melt adhesive based on modification of the organic silicon-based material is characterized by mainly comprising the following components in parts by weight: 80-100 parts of modified hot-melt resin, 10-15 parts of modified organic silicon microspheres, 1-2 parts of dispersing agent, 1-2 parts of antioxidant and 1-2 parts of talcum powder;
the modified hot-melt resin is prepared by reacting chlorinated EVA resin with trifluoromethyl (1, 10-phenanthroline) copper;
the trifluoromethyl (1, 10-phenanthroline) copper is prepared by reacting tert-butyl copper with trifluoromethyl trimethyl alkane, and then adding 1, 10-phenanthroline for reaction;
the modified organic silicon microspheres are prepared by preparing nano silicon dioxide from ethyl orthosilicate, preparing organic silicon microspheres from the nano silicon dioxide, hexadecyl trimethyl ammonium chloride and triethanolamine, etching the organic silicon microspheres by using a sodium hydroxide solution, extracting by using a sodium chloride methanol solution to prepare hollow porous organic silicon microspheres, and modifying the hollow porous organic silicon microspheres by using a silane coupling agent.
2. A preparation method of a high-light-transmission acid-alkali-resistant hot melt adhesive based on modification of an organic silicon-based material is characterized by mainly comprising the following preparation steps:
(1) Mixing hexadecyl trimethyl ammonium chloride, triethanolamine and pure water according to the mass ratio of 5:1:20, uniformly mixing, stirring for 1-2 h at normal temperature to prepare an organic solution, adding nano-silica into an organic solution with the mass of 3 times that of the nano-silica, stirring for 1-2 h, washing for 3-5 times by using absolute ethyl alcohol after filtering, adding into a sodium hydroxide solution with the mass fraction of 10% and the mass of 10-15 times that of the nano-silica, etching for 30-40 min at the temperature of 20-30 ℃, filtering, washing for 2-3 times by using pure water, extracting by using a 1% sodium chloride methanol solution at the temperature of 20-30 ℃, washing for 3-5 times by using pure water and absolute ethyl alcohol respectively, drying for 6-8 h at the pressure of-10 to-1 ℃ and 5-10 Pa to prepare hollow porous organosilicon microspheres, and mixing the hollow porous organosilicon microspheres with the absolute ethyl alcohol and the pure water according to the mass ratio of 1:15:5, uniformly mixing, adding hydrochloric acid to adjust the pH value to 4-5, adding a silane coupling agent with the mass of 0.3-0.5 time that of the hollow porous organic silicon microsphere, stirring and reacting at the temperature of 60-70 ℃ at 800-1000 r/min for 10-12 h, washing with absolute ethyl alcohol for 3-5 times, and drying at the temperature of-10 to-1 ℃ under the pressure of 5-10 Pa for 6-8 h to prepare the modified organic silicon microsphere;
(2) Placing the hot-melt resin in a glass tube, introducing chlorine gas at the speed of 3-5 cm/s for 2-3 h at the temperature of 80-90 ℃, cooling to 20-30 ℃, ventilating and chlorine extracting, placing in a ventilating kitchen for 20-24 h to prepare chlorinated hot-melt resin, and mixing the chlorinated hot-melt resin with 30 mass percent of acetone solution according to the mass ratio of 1: 10-1: 15, adding trifluoromethyl (1, 10-phenanthroline) copper with the mass of 0.5-0.6 time of that of the chlorinated hot-melt resin after uniformly mixing, stirring for 8-12 h at the rotating speed of 2000-3000 r/min under the conditions of 20-30 ℃ and 60W power and ultraviolet irradiation with the wavelength of 365nm, filtering, washing for 3-5 times by using absolute ethyl alcohol, and carrying out vacuum freeze drying for 5-6 h at the temperature of-10-5 ℃ and the pressure of 10Pa to prepare the modified hot-melt resin;
(3) Putting the modified hot-melt resin into a melting kettle, heating to 170-180 ℃, stirring for 10min at 300-500 r/min, then adding modified organic silicon microspheres with the mass of 0.1-0.2 time of that of the modified hot-melt resin, dispersing agents with the mass of 0.01-0.03 time of that of the modified hot-melt resin, antioxidants with the mass of 0.01-0.03 time of that of the modified hot-melt resin and talcum powder with the mass of 0.01-0.03 time of that of the modified hot-melt resin, and continuously stirring for 50-60 min to prepare a melting material;
(4) And (3) placing the molten material in a flat plate mold, cooling to 10-30 ℃ for molding under the pressure of 5-10 MPa in the nitrogen atmosphere, and placing in a granulator for granulation to obtain the high-light-transmission acid-base-resistant hot melt adhesive.
3. The preparation method of the high-transmittance acid-and-alkali-resistant hot melt adhesive based on modification of the organosilicon-based material according to claim 2, wherein the preparation method of the nano-silica in the step (1) comprises the following steps: ammonia water, absolute ethyl alcohol and pure water with the mass part of 25% are mixed according to the proportion of 3:5:2, adding tetraethoxysilane with the mass of 0.18-0.22 time of that of the absolute ethyl alcohol, reacting for 2-3 hours at the temperature of 20-30 ℃ and the rotating speed of 500-800 r/min, filtering, sequentially washing for 3-5 times by using deionized water and the absolute ethyl alcohol respectively, and drying for 6-8 hours at the temperature of-10-1 ℃ and the pressure of 5-10 Pa to prepare the catalyst.
4. The preparation method of the high-light-transmission acid-alkali-resistant hot melt adhesive based on modification of the organosilicon-based material according to claim 2, wherein the hot melt resin in the step (2) is EVA resin.
5. The preparation method of the high-transmittance acid-and-alkali-resistant hot melt adhesive based on modification of the organosilicon-based material according to claim 2, wherein the trifluoromethyl (1, 10-phenanthroline) copper in the step (2) is prepared from tert-butyl copper, trifluoromethyl trimethyl alkane and absolute ethyl alcohol in a mass ratio of 2:1:10 to 1:1:15, stirring the mixture for 1h at the temperature of 60 ℃ at the rotating speed of 800-1000 r/min, adding 1, 10-phenanthroline with the mass being 2 times that of the fluoromethyl trimethyl alkane, and stirring the mixture for 5min at the temperature of 80 ℃ at the rotating speed of 100-200 r/min to prepare the composite material.
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