CN115353842A - Flame-retardant EVA (ethylene-vinyl acetate) foaming hot melt adhesive and preparation method thereof - Google Patents
Flame-retardant EVA (ethylene-vinyl acetate) foaming hot melt adhesive and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a flame-retardant EVA (ethylene vinyl acetate) foaming hot melt adhesive and a preparation method thereof, and relates to the technical field of hot melt adhesives, wherein the flame-retardant EVA foaming hot melt adhesive is prepared from the following raw materials: graft copolymer of EVA and 2-bromoacrylic acid tert-butyl ester, rosin resin, antioxidant, flame retardant, foaming agent, crosslinking agent, carbon black and filler; the graft copolymer of the EVA and the tert-butyl 2-bromoacrylate is obtained by the melt grafting reaction of the EVA and the tert-butyl 2-bromoacrylate; the flame-retardant EVA foaming hot melt adhesive disclosed by the invention is excellent in oxidation resistance, and can solve the problem of old thermal oxidation deterioration of raw material resin in the processing and using processes, and prolong the service life of the material; the foaming is uniform, the size of the microcells after foaming is between 0.5 and 2mm, the bonding strength after foaming is high, the flame retardant property is excellent, and the requirement of practical use can be met.
Description
Technical Field
The invention relates to the technical field of hot melt adhesives, in particular to a flame-retardant EVA foaming hot melt adhesive and a preparation method thereof.
Background
Foaming hot melt adhesive belongs to one kind of hot melt adhesive, when the hot melt adhesive heating melts, adds the foamer that has the foaming function wherein, and the mixing is even can obtain foaming hot melt adhesive, and foaming hot melt adhesive can prevent that the temperature sensing material from warping, can seal the part that the clearance is big. In the prior art, hot melt adhesive foaming mainly comprises physical foaming and chemical foaming, and physical foaming is as in patent CN109468106A, which discloses a preparation method of a foaming hot melt adhesive, wherein gases such as nitrogen, carbon dioxide and the like are compressed into liquid to be internally mixed with the hot melt adhesive to obtain the foaming hot melt adhesive. Chemical foaming, such as CN 110951417A, discloses a foaming hot melt adhesive prepared by mixing polyolefin resin with a foaming agent, and utilizes the chemical reaction of the foaming agent to generate gas; however, this method requires deep embrittlement of polyethylene wax and C5 petroleum resin, and melting with other raw materials after pulverization, which greatly affects the adhesive strength of the polyolefin resin itself.
In addition, the existing foaming hot melt adhesive has the following problems in use, such as uneven foaming effect, low bonding strength and poor flame retardant property after foaming, and the requirement of practical use cannot be met.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a flame-retardant EVA foaming hot melt adhesive and a preparation method thereof.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the flame-retardant EVA foaming hot melt adhesive is prepared from the following raw materials in parts by weight: 50-70 parts of graft copolymer of EVA and tert-butyl 2-bromoacrylate, 1-12 parts of rosin resin, 0.1-1 part of antioxidant, 10-20 parts of flame retardant, 5-10 parts of foaming agent, 0.1-1 part of crosslinking agent azobisisobutyronitrile, 0.5-1 part of carbon black and 5-10 parts of filler;
the graft copolymer of the EVA and the tert-butyl 2-bromoacrylate is obtained by the melt grafting reaction of the EVA and the tert-butyl 2-bromoacrylate;
the antioxidant is antioxidant 264 or antioxidant 1010;
the foaming agent is one or two of azodicarbonamide, sodium bicarbonate, ammonium bicarbonate and foaming microspheres;
the flame retardant is one or two of pentaerythritol, melamine and modified ammonium polyphosphate;
the filler is hollow glass beads;
the modified ammonium polyphosphate is prepared by the following steps:
adding an ethanol solution into a reaction kettle, adding ammonium polyphosphate into the reaction kettle, stirring to form a suspension, adding calcium chloride and manganese chloride into the suspension, starting stirring to react for 4-6 hours, adding 4-hydroxyethyl piperazine ethanesulfonic acid, an ammonia water solution and dopamine into the reaction kettle, reacting for 20-24 hours under stirring, filtering to obtain a filter cake, and drying the filter cake to obtain modified ammonium polyphosphate;
the mass concentration of the ethanol solution is 5-10%; the mass concentration of the ammonia water solution is 18-22%;
wherein the mass ratio of the ethanol solution, the ammonium polyphosphate, the calcium chloride, the manganese chloride, the 4-hydroxyethyl piperazine ethanesulfonic acid, the ammonia water solution and the dopamine is 90-110: 10: 0.2-0.3: 0.2-0.4: 1.5-1.7: 0.8-1: 0.8-1.2.
Preferably, the graft copolymer of EVA and tert-butyl 2-bromoacrylate is prepared by the following steps:
adding EVA resin and tert-butyl 2-bromoacrylate into a reaction kettle, stirring and heating to 85-90 ℃ under the protection of nitrogen, adding benzoyl peroxide into the reaction kettle, heating to 105-110 ℃, and reacting for 30-60 minutes to obtain a graft copolymer of EVA and tert-butyl 2-bromoacrylate;
the mass ratio of the EVA resin, the tert-butyl 2-bromoacrylate and the benzoyl peroxide is 10: 1-4: 0.01-0.03.
Preferably, the flame retardant is obtained by mixing pentaerythritol and modified ammonium polyphosphate.
Preferably, the foaming agent is azodicarbonamide or/and foaming microspheres.
Preferably, the hollow glass beads have a particle size of 2 to 100 μm and a density of 0.3 to 0.5g/cm 3 。
The invention also comprises a preparation method of the flame-retardant EVA foaming hot melt adhesive, which comprises the following steps:
(1) melting: adding 50-70 parts by weight of graft copolymer of EVA and tert-butyl 2-bromoacrylate, 1-12 parts by weight of rosin resin, 0.1-1 part by weight of antioxidant and 0.5-1 part by weight of carbon black into a reaction kettle at the temperature of 130-140 ℃ under the protection of nitrogen, starting stirring to melt all raw materials in the reaction kettle, melting the melted raw materials together, adding 10-20 parts by weight of flame retardant and 5-10 parts by weight of filler into the mixture, and continuously stirring until the mixture is uniformly mixed to obtain a mixture;
(2) cooling the mixture obtained in the step (1) to 110-120 ℃, adding 5-10 parts of foaming agent and 0.1-1 part of azodiisobutyronitrile serving as a crosslinking agent, and quickly stirring and uniformly mixing to obtain a colloid;
(3) taking the colloid obtained in the step (2) out of the reaction kettle, pouring the colloid into a mold, manufacturing the colloid into different shapes by using different molds, wrapping the produced colloid with a plastic film, and storing the wrapped colloid in a cool and dry place to obtain the flame-retardant EVA foaming hot melt adhesive;
the antioxidant is antioxidant 264 and antioxidant 1010;
the foaming agent is one or two of azodicarbonamide, sodium bicarbonate, ammonium bicarbonate and foaming microspheres;
the flame retardant is one or two of pentaerythritol, melamine and modified ammonium polyphosphate;
the filler is hollow glass beads.
Compared with the prior art, the invention has the following advantages:
the flame-retardant EVA foaming hot melt adhesive is prepared by mixing a graft copolymer of EVA and tert-butyl 2-bromoacrylate, rosin resin, an antioxidant, a flame retardant, a foaming agent and the like, has an excellent antioxidant effect, can solve the problem of old thermal oxidation deterioration of raw material resin in the processing and using processes, and prolongs the service life of the material; the adopted hollow glass microspheres are light in weight and low in heat conductivity coefficient, and can achieve effective flame-retardant and heat-insulating effects; the flame-retardant EVA foaming hot melt adhesive disclosed by the invention is uniform in foaming, the size of a micropore after foaming is 0.5-2 mm, the bonding strength after foaming is high, the flame-retardant property is excellent, and the requirements of practical use can be met.
Drawings
Fig. 1 is a structure diagram of a fine pore of the flame retardant EVA foamed hot melt adhesive obtained in example 11 after foaming.
Detailed Description
The invention aims to provide a flame-retardant EVA foaming hot melt adhesive and a preparation method thereof, and the flame-retardant EVA foaming hot melt adhesive is realized by the following technical scheme:
the flame-retardant EVA foaming hot melt adhesive comprises the following raw materials in parts by weight: 50-70 parts of graft copolymer of EVA and tert-butyl 2-bromoacrylate, 1-12 parts of rosin resin, 0.1-1 part of antioxidant, 10-20 parts of flame retardant, 5-10 parts of foaming agent, 0.1-1 part of crosslinking agent azodiisobutyronitrile, 0.5-1 part of carbon black and 5-10 parts of filler;
the graft copolymer of the EVA and the tert-butyl 2-bromoacrylate is obtained by the melt grafting reaction of the EVA and the tert-butyl 2-bromoacrylate;
the antioxidant is antioxidant 264 or antioxidant 1010;
the foaming agent is one or two of azodicarbonamide, sodium bicarbonate, ammonium bicarbonate and foaming microspheres; wherein azodicarbonamide, sodium bicarbonate and ammonium bicarbonate belong to chemical foaming agents, foaming microbeads belong to physical foaming agents,
the flame retardant is one or two of pentaerythritol, melamine and modified ammonium polyphosphate;
the filler is hollow glass beads;
the modified ammonium polyphosphate is prepared by the following steps:
adding an ethanol solution into a reaction kettle, adding ammonium polyphosphate into the reaction kettle, stirring to form a suspension, adding calcium chloride and manganese chloride into the suspension, starting stirring to react for 4-6 hours, adding 4-hydroxyethyl piperazine ethanesulfonic acid, an ammonia water solution and dopamine into the reaction kettle, reacting for 20-24 hours under stirring, filtering to obtain a filter cake, and drying the filter cake to obtain modified ammonium polyphosphate;
the mass concentration of the ethanol solution is 5-10%; the mass concentration of the ammonia water solution is 18-22%;
wherein the mass ratio of the ethanol solution, the ammonium polyphosphate, the calcium chloride, the manganese chloride, the 4-hydroxyethyl piperazine ethanesulfonic acid, the ammonia water solution and the dopamine is 90-110: 10: 0.2-0.3: 0.2-0.4: 1.5-1.7: 0.8-1: 0.8-1.2.
Preferably, the graft copolymer of EVA and tert-butyl 2-bromoacrylate is prepared by the following steps:
adding EVA resin and tert-butyl 2-bromoacrylate into a reaction kettle, stirring and heating to 85-90 ℃ under the protection of nitrogen, adding benzoyl peroxide into the reaction kettle, heating to 105-110 ℃, and reacting for 30-60 minutes to obtain a graft copolymer of EVA and tert-butyl 2-bromoacrylate;
the mass ratio of the EVA resin to the tert-butyl 2-bromoacrylate to the benzoyl peroxide is 10: 1-4: 0.01-0.03.
Because the EVA resin has the defects and shortcomings of poor adhesion, poor material compatibility, high brittleness at low temperature, poor adhesive property and the like, the EVA resin needs to be modified to show better performance. The existing grafting of EVA and acrylic acid substances mostly adopts a solution method or an emulsion method, a solvent or a dispersing agent participates in the reaction process, the process is complex, pollution is easily caused, and the existence of the solvent toluene influences the meeting probability of the active points of the EVA resin and butyl acrylate, so that the grafting rate is influenced.
The preferable scheme adopts a melt grafting method to prepare the graft reaction of the EVA and the acrylic substance, no solvent is involved, the operation is simple, only molten EVA resin, an initiator and 2-bromoacrylic acid tert-butyl ester are needed in the whole process, the meeting probability of the active point of the EVA resin and the monomer is greatly increased, and the grafting rate is improved; a melt grafting method is utilized to connect a monomer containing functional groups such as hydroxyl, carboxyl, anhydride, isocyanate and the like to an EVA copolymer main chain, so that the EVA copolymer is endowed with reaction activity, functionality and polarity, and a tert-butyl 2-bromoacrylate monomer with flame retardant property is grafted to the EVA copolymer main chain, so that the graft copolymer of EVA and tert-butyl 2-bromoacrylate has certain flame retardant property.
Preferably, the flame retardant is obtained by mixing pentaerythritol and modified ammonium polyphosphate.
Preferably, the foaming agent is azodicarbonamide or/and foaming microspheres.
Preferably, the hollow glass microspheres have the particle size of 2-100 mu m and the density of 0.3-0.5 g/cm 3 。
The invention also comprises a preparation method of the flame-retardant EVA foaming hot melt adhesive, which comprises the following steps:
(1) melting: adding 50-70 parts by weight of graft copolymer of EVA and tert-butyl 2-bromoacrylate, 1-12 parts by weight of rosin resin, 0.1-1 part by weight of antioxidant and 0.5-1 part by weight of carbon black into a reaction kettle at the temperature of 130-140 ℃ under the protection of nitrogen, starting stirring to melt all raw materials in the reaction kettle, melting the melted raw materials together, adding 10-20 parts by weight of flame retardant and 5-10 parts by weight of filler into the mixture, and continuously stirring until the mixture is uniformly mixed to obtain a mixture;
(2) cooling the mixture obtained in the step (1) to 110-120 ℃, adding 5-10 parts of foaming agent and 0.1-1 part of azodiisobutyronitrile serving as a crosslinking agent, and quickly stirring and uniformly mixing to obtain a colloid;
(3) taking the colloid obtained in the step (2) out of the reaction kettle, pouring the colloid into a mold, manufacturing the colloid into different shapes by using different molds, wrapping the produced colloid by using a plastic film, and storing the wrapped colloid in a cool and dry place to obtain the flame-retardant EVA foaming hot melt adhesive;
the antioxidant is antioxidant 264 and antioxidant 1010;
the foaming agent is one or two of azodicarbonamide, sodium bicarbonate, ammonium bicarbonate and foaming microspheres;
the flame retardant is one or two of pentaerythritol, melamine and modified ammonium polyphosphate;
the filler is hollow glass beads.
The EVA in the application is ethylene-vinyl acetate copolymer;
the foaming microspheres adopted by the invention are high molecular particles with a core-shell structure, the shell is thermoplastic polymer, the core is gas, the particle size is 10-45 mu m at room temperature, and the high-temperature expansion is multiplied to the original value, so that the foaming effect is achieved, the existing foaming microspheres (expansion microspheres) in the market can be selected, and the foaming microspheres in the embodiment of the invention are American clocell 190DU20 type foaming plastic microspheres.
The invention is further described with reference to specific examples.
Example 1
The modified ammonium polyphosphate is prepared by the following steps:
b is to beAdding the alcoholic solution into a reaction kettle, adding ammonium polyphosphate into the alcoholic solution, stirring to form a suspension, adding calcium chloride and manganese chloride into the suspension, starting stirring to react H 1 H, adding 4-hydroxyethyl piperazine ethanesulfonic acid, ammonia water solution and dopamine into the reaction kettle, and reacting under stirring 2 And filtering to obtain a filter cake, and drying the filter cake to obtain the modified ammonium polyphosphate.
The addition amounts of the ethanol solution, the ammonium polyphosphate, the calcium chloride, the manganese chloride, the 4-hydroxyethyl piperazine ethanesulfonic acid, the ammonia water solution and the dopamine, and the mass concentration parameters of the ethanol solution and the ammonia water solution are set to obtain a series of modified ammonium polyphosphate products, wherein the addition parameters of the materials and the corresponding example labels are shown in table 1.
TABLE 1 modified ammonium polyphosphate product preparation Process the addition parameters of the materials and the corresponding example designations
The modified ammonium polyphosphate is obtained by modifying dopamine, calcium chloride and manganese chloride, wherein dopamine is self-polymerized in an alkaline aqueous solution to form polydopamine, firstly, the ammonium polyphosphate, the calcium chloride and the manganese chloride form a chelate, then 4-hydroxyethyl piperazine ethanesulfonic acid forms an active site on the ammonium polyphosphate, and finally, the polydopamine is connected to the ammonium polyphosphate through the active site to modify the ammonium polyphosphate.
On the other hand, the surface of the polydopamine has a large number of functional groups such as amino groups, hydroxyl groups and the like, so that abundant metal chelating sites can be provided, the polydopamine chelated by calcium ions and manganese ions has strong catalytic carbonization capacity, and a more compact carbon layer can be obtained to inhibit the transfer of energy and oxygen to the polymer, so that the flame retardant property of the polymer is effectively improved.
The modified ammonium polyphosphates obtained in examples 1-1 to 1-4 were mixed to homogeneity and used in the following examples.
Example 2
The flame-retardant EVA foaming hot melt adhesive is prepared from the following raw materials: 50kg of graft copolymer of EVA and tert-butyl 2-bromoacrylate, 1kg of rosin resin, 0.1kg of antioxidant, 10kg of flame retardant, 5kg of foaming agent, 0.1kg of crosslinking agent azobisisobutyronitrile, 0.5kg of carbon black and 5kg of filler; the graft copolymer of the EVA and the tert-butyl 2-bromoacrylate is obtained by the melt grafting reaction of the EVA and the tert-butyl 2-bromoacrylate;
the antioxidant is antioxidant 264;
the foaming agent is azodicarbonamide;
the flame retardant is pentaerythritol;
the filler is hollow glass beads.
Example 3
The flame-retardant EVA foaming hot melt adhesive is prepared from the following raw materials: 70kg of graft copolymer of EVA and tert-butyl 2-bromoacrylate, 12kg of rosin resin, 1kg of antioxidant, 20kg of flame retardant, 10kg of foaming agent, 1kg of crosslinking agent azobisisobutyronitrile, 1kg of carbon black and 10kg of filler;
the graft copolymer of EVA and tert-butyl 2-bromoacrylate is obtained by melt grafting reaction of EVA and tert-butyl 2-bromoacrylate, and is specifically prepared according to the following steps:
adding 70kg of EVA resin and 7kg of tert-butyl 2-bromoacrylate into a reaction kettle, stirring and heating to 85 ℃ under the protection of nitrogen, adding 0.07kg of benzoyl peroxide into the reaction kettle, heating to 105 ℃, and reacting for 30 minutes to obtain a graft copolymer of EVA and tert-butyl 2-bromoacrylate;
the antioxidant is 1010;
the foaming agent is sodium bicarbonate;
the flame retardant is melamine;
the filler is hollow glass beads.
Example 4
The flame-retardant EVA foaming hot melt adhesive is prepared from the following raw materials: 55kg of graft copolymer of EVA and tert-butyl 2-bromoacrylate, 4kg of rosin resin, 0.2kg of antioxidant, 12kg of flame retardant, 6kg of foaming agent, 0.8kg of crosslinking agent azobisisobutyronitrile, 0.6kg of carbon black and 6kg of filler;
the graft copolymer of EVA and tert-butyl 2-bromoacrylate is obtained by melt grafting reaction of EVA and tert-butyl 2-bromoacrylate, and is specifically prepared according to the following steps:
adding 40kg of EVA resin and 16911 kg of tert-butyl 2-bromoacrylate into a reaction kettle, stirring and heating to 90 ℃ under the protection of nitrogen, adding 0.12kg of benzoyl peroxide into the reaction kettle, heating to 110 ℃, and reacting for 60 minutes to obtain a graft copolymer of EVA and tert-butyl 2-bromoacrylate;
the antioxidant is antioxidant 264;
the foaming agent is ammonium bicarbonate;
the flame retardant is modified ammonium polyphosphate;
the filler is hollow glass beads; the particle size of the hollow glass beads is 2-5 mu m, and the density is 0.3g/cm;
the graft copolymer of EVA and tert-butyl 2-bromoacrylate is obtained by melt grafting reaction of EVA and tert-butyl 2-bromoacrylate, and is prepared according to the following steps:
adding EVA resin and tert-butyl 2-bromoacrylate into a reaction kettle, stirring and heating to 85 ℃ under the protection of nitrogen, adding benzoyl peroxide into the reaction kettle, heating to 105 ℃, and reacting for 30 minutes to obtain the graft copolymer of EVA and tert-butyl 2-bromoacrylate.
Example 5
The flame-retardant EVA foaming hot melt adhesive is prepared from the following raw materials: 68kg of graft copolymer of EVA and tert-butyl 2-bromoacrylate, 10kg of rosin resin, 0.8kg of antioxidant, 18kg of flame retardant, 9kg of foaming agent, 0.4kg of crosslinking agent azobisisobutyronitrile, 0.8kg of carbon black and 9kg of filler;
the graft copolymer of the EVA and the tert-butyl 2-bromoacrylate is obtained by the melt grafting reaction of the EVA and the tert-butyl 2-bromoacrylate; the preparation method comprises the following steps:
adding 60kg of EVA resin and 12kg of tert-butyl 2-bromoacrylate into a reaction kettle, stirring and heating to 86 ℃ under the protection of nitrogen, adding 0.12kg of benzoyl peroxide into the reaction kettle, heating to 108 ℃, and reacting for 40 minutes to obtain a graft copolymer of EVA and tert-butyl 2-bromoacrylate;
the antioxidant is 1010;
the foaming agent is foaming microspheres;
the flame retardant is obtained by mixing modified ammonium polyphosphate and melamine according to the mass ratio of 1: 1;
the filler is hollow glass beads; the hollow glass microspheres have the particle size of 95-100 mu m and the density of 0.5g/cm 3 。
Example 6
The flame-retardant EVA foaming hot melt adhesive is prepared from the following raw materials: 55kg of graft copolymer of EVA and tert-butyl 2-bromoacrylate, 6kg of rosin resin, 0.5kg of antioxidant, 15kg of flame retardant, 8kg of foaming agent, 0.6kg of crosslinking agent azobisisobutyronitrile, 0.7kg of carbon black and 8kg of filler;
the graft copolymer of EVA and tert-butyl 2-bromoacrylate is obtained by melt grafting reaction of EVA and tert-butyl 2-bromoacrylate, and is prepared according to the following steps:
adding 50kg of EVA resin and 15kg of tert-butyl 2-bromoacrylate into a reaction kettle, stirring and heating to 88 ℃ under the protection of nitrogen, adding 0.1kg of benzoyl peroxide into the reaction kettle, heating to 108 ℃, and reacting for 50 minutes to obtain a graft copolymer of EVA and tert-butyl 2-bromoacrylate;
the antioxidant is antioxidant 264;
the foaming agent is obtained by mixing azodicarbonamide and foaming microspheres according to the mass ratio of 3: 1;
the flame retardant is obtained by mixing pentaerythritol and modified ammonium polyphosphate according to the mass ratio of 2: 1;
the filler is hollow glass beads; the hollow glass beads have the particle size of 50-55 mu m and the density of 0.4g/cm 3 。
Example 7
The preparation method of the flame retardant EVA foaming hot melt adhesive of embodiment 2 comprises the following steps:
(1) melting: adding 50kg of graft copolymer of EVA and tert-butyl 2-bromoacrylate, 1kg of rosin resin, 0.1kg of antioxidant and 0.5kg of carbon black into a reaction kettle at the temperature of 130 ℃ under the protection of nitrogen by weight parts, starting stirring to heat and melt all raw materials in the reaction kettle, melting the melted raw materials together, adding 10kg of flame retardant and 5kg of filler into the mixture, and continuously stirring until the mixture is uniformly mixed to obtain a mixture;
(2) cooling the mixture obtained in the step (1) to 110 ℃, adding 5kg of foaming agent and 0.1kg of azodiisobutyronitrile serving as crosslinking agent, and rapidly stirring and uniformly mixing to obtain colloid;
(3) taking the colloid obtained in the step (2) out of the reaction kettle, pouring the colloid into a mold, manufacturing the colloid into different shapes by using different molds, wrapping the produced colloid by using a plastic film, and storing the wrapped colloid in a cool and dry place to obtain the flame-retardant EVA foaming hot melt adhesive;
the graft copolymer of the EVA and the tert-butyl 2-bromoacrylate is obtained by the melt grafting reaction of the EVA and the tert-butyl 2-bromoacrylate;
the antioxidant is antioxidant 264;
the foaming agent is azodicarbonamide;
the flame retardant is pentaerythritol;
the filler is hollow glass beads.
Example 8
The preparation method of the flame retardant EVA foaming hot melt adhesive of embodiment 3 comprises the following steps:
(1) melting: adding 70kg of graft copolymer of EVA and tert-butyl 2-bromoacrylate, 12kg of rosin resin, 1kg of antioxidant and 1kg of carbon black into a reaction kettle at the temperature of 140 ℃ under the protection of nitrogen by weight parts, starting stirring to heat and melt all raw materials in the reaction kettle, melting the melted raw materials together, adding 20kg of flame retardant and 10kg of filler into the mixture, and continuously stirring until the mixture is uniformly mixed to obtain a mixture;
(2) cooling the mixture obtained in the step (1) to 120 ℃, adding 10kg of foaming agent and 1kg of azodiisobutyronitrile serving as a crosslinking agent, and quickly stirring and uniformly mixing to obtain a colloid;
(3) taking the colloid obtained in the step (2) out of the reaction kettle, pouring the colloid into a mold, manufacturing the colloid into different shapes by using different molds, wrapping the produced colloid with a plastic film, and storing the wrapped colloid in a cool and dry place to obtain the flame-retardant EVA foaming hot melt adhesive;
the graft copolymer of the EVA and the tert-butyl 2-bromoacrylate is obtained by the melt grafting reaction of the EVA and the tert-butyl 2-bromoacrylate;
the antioxidant is 1010;
the foaming agent is sodium bicarbonate;
the flame retardant is melamine;
the filler is hollow glass beads.
Example 9
The preparation method of the flame retardant EVA foaming hot melt adhesive of embodiment 4 comprises the following steps:
(1) melting: adding 55kg of graft copolymer of EVA and tert-butyl 2-bromoacrylate, 4kg of rosin resin, 0.2kg of antioxidant and 0.6kg of carbon black into a reaction kettle at the temperature of 132 ℃ under the protection of nitrogen by weight parts, starting stirring to heat and melt all raw materials in the reaction kettle, melting the melted raw materials together, adding 12kg of flame retardant and 6kg of filler into the mixture, and continuously stirring until the mixture is uniformly mixed to obtain a mixture;
(2) cooling the mixture obtained in the step (1) to 112 ℃, adding 6kg of foaming agent and 0.8kg of azodiisobutyronitrile serving as crosslinking agent, and rapidly stirring and uniformly mixing to obtain colloid;
(3) taking the colloid obtained in the step (2) out of the reaction kettle, pouring the colloid into a mold, manufacturing the colloid into different shapes by using different molds, wrapping the produced colloid with a plastic film, and storing the wrapped colloid in a cool and dry place to obtain the flame-retardant EVA foaming hot melt adhesive;
the antioxidant is antioxidant 264;
the foaming agent is ammonium bicarbonate;
the flame retardant is modified ammonium polyphosphate;
the filler is hollow glass microspheres, the particle size of the hollow glass microspheres is 2-5 mu m, and the density is 0.3g/cm 3 。
Example 10
The preparation method of the flame retardant EVA foaming hot melt adhesive of embodiment 5 comprises the following steps:
(1) melting: adding 68kg of graft copolymer of EVA and tert-butyl 2-bromoacrylate, 10kg of rosin resin, 0.8kg of antioxidant and 0.8kg of carbon black into a reaction kettle at the temperature of 138 ℃ under the protection of nitrogen by weight parts, starting stirring to heat and melt all raw materials in the reaction kettle, melting the melted raw materials together, adding 18kg of flame retardant and 9kg of filler into the mixture, and continuously stirring until the mixture is uniformly mixed to obtain a mixture;
(2) cooling the mixture obtained in the step (1) to 118 ℃, adding 9kg of foaming agent and 0.4kg of azodiisobutyronitrile serving as a crosslinking agent, and quickly stirring and uniformly mixing to obtain a colloid;
(3) taking the colloid obtained in the step (2) out of the reaction kettle, pouring the colloid into a mold, manufacturing the colloid into different shapes by using different molds, wrapping the produced colloid with a plastic film, and storing the wrapped colloid in a cool and dry place to obtain the flame-retardant EVA foaming hot melt adhesive;
the antioxidant is 1010;
the foaming agent is foaming microspheres;
the flame retardant is obtained by mixing modified ammonium polyphosphate and melamine according to the mass ratio of 1: 1;
the filler is hollow glass beads; the hollow glass beads have the particle size of 95-100 mu m and the density of 0.5g/cm 3 。
Example 11
The preparation method of the flame retardant EVA foaming hot melt adhesive of embodiment 6 comprises the following steps:
(1) melting: adding 55kg of graft copolymer of EVA and tert-butyl 2-bromoacrylate, 6kg of rosin resin, 0.5kg of antioxidant and 0.7kg of carbon black into a reaction kettle at the temperature of 135 ℃ under the protection of nitrogen by weight parts, starting stirring to heat and melt all raw materials in the reaction kettle, melting the melted raw materials together, adding 15kg of flame retardant and 8kg of filler into the mixture, and continuously stirring until the mixture is uniformly mixed to obtain a mixture;
(2) cooling the mixture obtained in the step (1) to 115 ℃, adding 8kg of foaming agent and 0.6kg of azodiisobutyronitrile serving as crosslinking agent, and rapidly stirring and uniformly mixing to obtain colloid;
(3) taking the colloid obtained in the step (2) out of the reaction kettle, pouring the colloid into a mold, manufacturing the colloid into different shapes by using different molds, wrapping the produced colloid by using a plastic film, and storing the wrapped colloid in a cool and dry place to obtain the flame-retardant EVA foaming hot melt adhesive;
the antioxidant is antioxidant 264;
the foaming agent is obtained by mixing azodicarbonamide and foaming microspheres according to the mass ratio of 3: 1;
the flame retardant is obtained by mixing pentaerythritol and modified ammonium polyphosphate according to the mass ratio of 2: 1;
the filler is hollow glass beads; the hollow glass beads have the particle size of 50-55 mu m and the density of 0.4g/cm 3 。
The foaming temperature of the flame-retardant EVA foaming hot melt adhesive is 150-160 ℃. The pore structure of the flame-retardant EVA foaming hot melt adhesive obtained in example 11 after foaming is shown in FIG. 1, and it can be seen that the pores after foaming are uniformly distributed, and the size of the pores is about 0.5-2 mm.
The flame-retardant EVA foaming hot melt adhesives obtained in examples 7 to 11 were subjected to a performance test, and the results are shown in Table 2, wherein the detection standard of peel strength is GB/T2790-1995, the detection standard of foaming ratio is GB/T6343-2009, and the detection standard of flame retardant grade is fire retardant grade UL 94.
Table 2 results of performance tests on flame retardant EVA foamed hot melt adhesive obtained in examples 7 to 11
The density comparison before and after foaming can characterize the foaming times of the material, the smaller the density under the same mass is, the larger the product volume is, the larger the foaming times are, taking example 7 as an example, the density of the unfoamed hot melt adhesive is 1.21g/cm 3 Density after foamingIt became 0.23g/cm 3 It was found that the foamed hot melt adhesive had a volume after foaming of about 5.26 times that of the unfoamed hot melt adhesive.
The use of different foaming agents has an influence on the initial foaming temperature (use temperature) of the foaming hot melt adhesive and the size and structure of the foaming pores. The foaming temperature of the foaming agents such as sodium bicarbonate and ammonium bicarbonate is low, partial bubbles can be generated in the process of preparing the colloid, and the use temperature of the hot melt adhesive is also low, so that the density of the hot melt adhesive before foaming is low, and the peel strength of the hot melt adhesive is low during use; the gas forming amount of the ammonium bicarbonate is large, the foaming is not uniform in the using process, and a small amount of broken bubbles of the bubbles affect the peeling strength of the ammonium bicarbonate; the azodicarbonamide and the foaming micro-beads belong to high-temperature foaming, the foaming agent can be foamed only by heating to a specific temperature range when in use, generally the temperature is 150-160 ℃, the temperature is not too high, and the foam is easily broken when the temperature is too high, so that the peeling strength of the hot melt adhesive is influenced.
Since the effects of peel strength and flame retardant rating are optimal in example 11, comparative experiments were designed based on example 11 below to explore the effect of various flame retardants on the flame retardant properties of the foamed hot melt adhesive of the present invention.
The following comparative examples were the same as example 11 in terms of the components and production parameters, except that the type of the flame retardant used was different, and the reference numerals of the comparative examples, the selection of the type of the flame retardant and the fire-proof rating were as shown in Table 3.
TABLE 3 selection of flame retardant type and reference numerals for comparative examples
The results in table 3 show that the modified ammonium polyphosphate has the most excellent flame retardant property, but the modified ammonium polyphosphate is expensive in cost due to the self-made requirement, and in order to reduce the cost, the modified ammonium polyphosphate can be used by being compounded with pentaerythritol and melamine in production, the addition amount of the modified ammonium polyphosphate is generally more than 20%, namely the V-0 level can be reached, and the flame retardant effect is achieved while the production cost is reduced.
Claims (6)
1. The utility model provides a fire-retardant type EVA foaming hot melt adhesive which characterized in that: the composite material comprises the following raw materials in parts by weight: 50-70 parts of graft copolymer of EVA and tert-butyl 2-bromoacrylate, 1-12 parts of rosin resin, 0.1-1 part of antioxidant, 10-20 parts of flame retardant, 5-10 parts of foaming agent, 0.1-1 part of crosslinking agent azobisisobutyronitrile, 0.5-1 part of carbon black and 5-10 parts of filler;
the graft copolymer of the EVA and the tert-butyl 2-bromoacrylate is obtained by the melt grafting reaction of the EVA and the tert-butyl 2-bromoacrylate;
the antioxidant is antioxidant 264 or antioxidant 1010;
the foaming agent is one or two of azodicarbonamide, sodium bicarbonate, ammonium bicarbonate and foaming microspheres;
the flame retardant is one or two of pentaerythritol, melamine and modified ammonium polyphosphate;
the filler is hollow glass beads;
the modified ammonium polyphosphate is prepared by the following steps:
adding an ethanol solution into a reaction kettle, adding ammonium polyphosphate into the reaction kettle, stirring to form a suspension, adding calcium chloride and manganese chloride into the suspension, starting stirring to react for 4-6 hours, adding 4-hydroxyethyl piperazine ethanesulfonic acid, an ammonia water solution and dopamine into the reaction kettle, reacting for 20-24 hours under stirring, filtering to obtain a filter cake, and drying the filter cake to obtain modified ammonium polyphosphate;
the mass concentration of the ethanol solution is 5-10%; the mass concentration of the ammonia water solution is 18-22%;
wherein the mass ratio of the ethanol solution, the ammonium polyphosphate, the calcium chloride, the manganese chloride, the 4-hydroxyethyl piperazine ethanesulfonic acid, the ammonia water solution and the dopamine is 90-110: 10: 0.2-0.3: 0.2-0.4: 1.5-1.7: 0.8-1: 0.8-1.2.
2. The flame-retardant EVA foaming hot melt adhesive according to claim 1, characterized in that: the graft copolymer of EVA and tert-butyl 2-bromoacrylate is prepared according to the following steps:
adding EVA resin and tert-butyl 2-bromoacrylate into a reaction kettle, stirring and heating to 85-90 ℃ under the protection of nitrogen, adding benzoyl peroxide into the reaction kettle, heating to 105-110 ℃, and reacting for 30-60 minutes to obtain a graft copolymer of EVA and tert-butyl 2-bromoacrylate;
the mass ratio of the EVA resin to the tert-butyl 2-bromoacrylate to the benzoyl peroxide is 10: 1-4: 0.01-0.03.
3. The flame-retardant EVA foaming hot melt adhesive according to claim 1, characterized in that: the flame retardant is obtained by mixing pentaerythritol and modified ammonium polyphosphate.
4. The flame-retardant EVA foaming hot melt adhesive according to claim 1, characterized in that: the foaming agent is azodicarbonamide or/and foaming microspheres.
5. The flame-retardant EVA foaming hot melt adhesive according to claim 1, characterized in that: the hollow glass microballoons have the particle size of 2-100 mu m and the density of 0.3-0.5 g/cm 3 。
6. The preparation method of the flame-retardant EVA foaming hot melt adhesive of claim 1, which is characterized by comprising the following steps: the method comprises the following steps:
(1) melting: adding 50-70 parts by weight of graft copolymer of EVA and tert-butyl 2-bromoacrylate, 1-12 parts by weight of rosin resin, 0.1-1 part by weight of antioxidant and 0.5-1 part by weight of carbon black into a reaction kettle at the temperature of 130-140 ℃ under the protection of nitrogen, starting stirring to melt all raw materials in the reaction kettle, melting the melted raw materials together, adding 10-20 parts by weight of flame retardant and 5-10 parts by weight of filler into the mixture, and continuously stirring until the mixture is uniformly mixed to obtain a mixture;
(2) cooling the mixture obtained in the step (1) to 110-120 ℃, adding 5-10 parts of foaming agent and 0.1-1 part of azodiisobutyronitrile serving as cross-linking agent, and rapidly stirring and uniformly mixing to obtain colloid;
(3) taking the colloid obtained in the step (2) out of the reaction kettle, pouring the colloid into a mold, manufacturing the colloid into different shapes by using different molds, wrapping the produced colloid with a plastic film, and storing the wrapped colloid in a cool and dry place to obtain the flame-retardant EVA foaming hot melt adhesive;
the antioxidant is antioxidant 264 and antioxidant 1010;
the foaming agent is one or two of azodicarbonamide, sodium bicarbonate, ammonium bicarbonate and foaming microspheres;
the flame retardant is one or two of pentaerythritol, melamine and modified ammonium polyphosphate;
the filler is hollow glass beads.
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