CN115746780B - Polyamide hot melt adhesive and preparation method and application thereof - Google Patents
Polyamide hot melt adhesive and preparation method and application thereof Download PDFInfo
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- CN115746780B CN115746780B CN202211481364.7A CN202211481364A CN115746780B CN 115746780 B CN115746780 B CN 115746780B CN 202211481364 A CN202211481364 A CN 202211481364A CN 115746780 B CN115746780 B CN 115746780B
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Abstract
The application relates to a polyamide hot melt adhesive, which comprises the following raw materials in parts by mass: 600 to 700 parts of dibasic acid, 20 to 80 parts of diamine, 100 to 500 parts of polyether amine, 10 to 50 parts of sulfamic acid, 10 to 50 parts of silicone oil, 20 to 200 parts of resin, 10 to 40 parts of antioxidant, 2 to 20 parts of catalyst and 10 to 40 parts of colorant. The polyamide hot melt adhesive greatly improves the adhesive force, hardness value and rebound resilience of the hot melt adhesive, can be suitable for an injection molding process, and has better encapsulation and protection effects on sensitive electronic components.
Description
Technical Field
The application relates to the technical field of adhesives, in particular to a polyamide hot melt adhesive and a preparation method and application thereof.
Background
The low pressure injection molding polyamide is a kind of polyamide hot melt adhesive, which is molten and applied with certain pressure to form. The polyamide hot melt adhesive has the characteristics of excellent heat resistance, cold resistance, electrical property, oil resistance, chemical resistance, no smell, no toxicity, quick solidification and the like, and has been widely applied to the field of manufacturing of automobile electronic parts, and related subdivision products comprise grommets, sensors, microswitches, plugs of automobile wire harnesses, other electronic part encapsulation protection products with higher requirements on shock resistance, moisture resistance, oil resistance, chemical corrosion resistance and the like.
The traditional polyamide hot melt adhesive is widely used because of the simple operation and use method, good low-temperature flexibility, no toxicity, environmental protection and the like. However, the traditional polyamide hot melt adhesive has weak adhesion, low hardness and poor rebound resilience, and is easy to damage electronic elements when being used for encapsulating and protecting sensitive elements in the fields of automobiles and the like.
Disclosure of Invention
Based on this, it is necessary to provide a polyamide hot melt adhesive capable of improving adhesion, hardness and rebound resilience, and a preparation method and application thereof.
The embodiment of the application provides a polyamide hot melt adhesive, which comprises the following raw materials in parts by mass:
in one embodiment, the dibasic acid comprises one or more of azelaic acid, sebacic acid, dodecanedioic acid, tridecanedioic acid, heneicosanoic acid, shanzoic acid, linoleic acid, and dimer acid;
optionally, the dimer acid comprises one or more of dimer oleic acid, dimer elaidic acid, tall oil dimer acid, and dimer ricinoleic acid.
In one embodiment, the diamine comprises one or more of diethylene diamine, ethylene diamine, hexamethylene diamine, pentane diamine, 1, 3-m-phenylene diamine, di-t-butyl ethylene diamine, and 2-methyl pentane diamine.
In one embodiment, the polyetheramine comprises an amine terminated polyetheramine;
optionally, the molecular weight of the amino-terminated polyether amine is 100Da to 2000Da;
further alternatively, the amine-terminated polyetheramine comprises one or more of polyetheramine D-400, polyetheramine D-230, polyetheramine D-2000, and polyetheramine FL-1000.
In one embodiment, the sulfamic acid comprises one or more of 2-naphthylamine-3, 6, 8-trisulfonic acid, 7-amino-1, 3, 5-naphthalene trisulfonic acid, 8-aminonaphthalene-1, 3, 6-trisulfonic acid, 4-amino-1 naphthalene sulfonic acid, 3-aminopropanesulfonic acid, and 8-amino-2 naphthalene sulfonic acid.
In one embodiment, the silicone oil comprises hydroxyl-terminated silicone oil;
optionally, the hydroxyl-terminated silicone oil has a chemical formula:
HO-Si(CH 3 ) 2 O-[Si(CH 3 ) 2 O] n -Si(CH 3 ) 2 -OH，n＝5～20；
further alternatively, n=5 to 15.
In one embodiment, the resin comprises one or more of polyurethane resin, phenolic resin, polyvinyl chloride resin, polyester resin, polyamide resin, and rosin resin.
An embodiment of the present application further provides a method for preparing a polyamide hot melt adhesive, including the following steps:
the components of the raw materials for preparing the polyamide hot melt adhesive described in any of the above examples are mixed and reacted.
In one embodiment, the steps of mixing the components in the raw materials for preparing the polyamide hot melt adhesive and reacting include:
mixing the dibasic acid, the diamine, the polyether amine and the antioxidant, controlling the temperature at a first reaction temperature, and performing a first reaction;
then adding the catalyst into the materials after the first reaction, controlling the temperature at a second reaction temperature, and carrying out a second reaction;
controlling the temperature at a third reaction temperature, and adding the resin into the material after the second reaction to perform the third reaction;
controlling the temperature at a fourth reaction temperature, and adding sulfamic acid, silicone oil and colorant into the material after the third reaction to perform a fourth reaction;
optionally, the first reaction temperature is 80-140 ℃;
optionally, the second reaction temperature is 160 ℃ to 210 ℃;
optionally, the third reaction temperature is 230 ℃ to 250 ℃;
optionally, the fourth reaction temperature is 170 ℃ to 200 ℃.
An embodiment of the present application further provides an application of the polyamide hot melt adhesive in any one of the above embodiments in an injection molding process.
The polyamide hot melt adhesive is prepared by adopting specific raw materials and specific parts by mass through mutual matching, and the molecular structure of the polyamide can be changed by introducing resin, sulfamic acid and silicone oil into the raw materials of the polyamide hot melt adhesive, so that the adhesive force, the hardness value and the rebound resilience of the hot melt adhesive are greatly improved, the process can be applied to an injection molding process, and the encapsulation and protection effects on sensitive electronic components are better by adopting the process.
Detailed Description
In order that the present application may be understood, a more complete description of the present application will be provided below in connection with the examples. This application may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used in the description of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
In the present application, the technical features described in an open manner include a closed technical scheme composed of the listed features, and also include an open technical scheme including the listed features.
The embodiment of the application provides a polyamide hot melt adhesive, which comprises the following raw materials in parts by mass:
the polyamide hot melt adhesive is prepared by adopting specific raw materials and specific parts by mass through mutual matching, and the molecular structure of the polyamide can be changed by introducing resin, sulfamic acid and silicone oil into the raw materials of the polyamide hot melt adhesive, so that the adhesive force, the hardness value and the rebound resilience of the hot melt adhesive are greatly improved, the process can be applied to an injection molding process, and the encapsulation and protection effects on sensitive electronic components are better by adopting the process.
In one embodiment, the preparation raw materials of the polyamide hot melt adhesive comprise the following components in parts by mass:
in one embodiment, the diacid may include, for example, but not limited to, one or more of azelaic acid, sebacic acid, dodecanedioic acid, tridecanedioic acid, heneicosanoic acid, shanzoic acid, linoleic acid, and dimer acid.
Alternatively, the dimer acid may include, for example, but not limited to, one or more of dimerized oleic acid, dimerized elaidic acid, tall oil dimer acid, and dimerized ricinoleic acid.
In one embodiment, the diamine may include, for example, but is not limited to, one or more of diethylene diamine, ethylene diamine, hexamethylene diamine, pentane diamine, 1, 3-m-phenylene diamine, di-t-butyl ethylene diamine, and 2-methyl pentane diamine.
In one embodiment, the polyetheramine may, for example, but not limited to, comprise an amine terminated polyetheramine.
Alternatively, the molecular weight of the amine-terminated polyetheramine is 100Da to 2000Da. It is understood that the molecular weight of the amine-terminated polyetheramine can be, for example, but not limited to, 100Da, 200Da, 230Da, 400Da, 600Da, 800Da, 1000Da, 1200Da, 1400Da, 1600Da, 1800Da, 2000Da, and the like.
Alternatively, the amine-terminated polyetheramine may include, for example, but not limited to, one or more of polyetheramine D-400, polyetheramine D-230, polyetheramine D-2000, and polyetheramine FL-1000.
In one embodiment, sulfamic acid may include, for example, but not limited to, one or more of 2-naphthylamine-3, 6, 8-trisulfonic acid, 7-amino-1, 3, 5-naphthalenetrisulfonic acid, 8-aminonaphthalene-1, 3, 6-trisulfonic acid, 4-amino-1-naphthalenesulfonic acid, 3-aminopropanesulfonic acid, and 8-amino-2-naphthalenesulfonic acid.
In one embodiment, the silicone oil may include, for example, but is not limited to, hydroxyl-terminated silicone oil.
Optionally, the hydroxyl-terminated silicone oil has the formula:
HO-Si(CH 3 ) 2 O-[Si(CH 3 ) 2 O] n -Si(CH 3 ) 2 -OH, n=5-20. It is understood that n may be, for example, but not limited to, equal to 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, etc. Further, n=5 to 15.
In one embodiment, the resin may include, for example, but not limited to, one or more of polyurethane resin, phenolic resin, polyvinyl chloride resin, polyester resin, polyamide resin, and rosin resin.
In one embodiment, the antioxidants may include, for example, but not limited to, one or more of antioxidant 1010, antioxidant 1098, antioxidant 168, and antioxidant 1076.
Alternatively, the antioxidant may be, for example, but not limited to, antioxidant 1010.
In one embodiment, the catalyst may include, for example, but not limited to, one or more of glacial acetic acid, propionic acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.
In one embodiment, the colorant may include, for example, but not limited to, one or more of carbon black, iron oxide black, copper chrome black, iron chrome black, aniline black, antimony sulfide, and cobalt black.
In one embodiment, the antioxidant is added in an amount of 1.8 to 5 percent of the total mass of the raw materials. It is understood that the amount of antioxidant added may be, for example, but not limited to, 1.8%, 1.9%, 2%, 2.1%, 2.8%, 3%, 3.5%, 3.8%, 4%, 4.5%, 5% and the like, based on the total mass of the raw materials. It will be appreciated that the proportion of the antioxidant added to the total mass of the raw materials is achieved under the condition that the above-mentioned ranges of the parts by mass of the oxidizing agent in the raw materials for preparation are satisfied.
In one embodiment, the catalyst is added in an amount of 0.2 to 0.5% of the total mass of the feedstock. It will be appreciated that the catalyst may be added in an amount of, for example, but not limited to, 0.2%, 0.3%, 0.4%, 0.5% and the like based on the total mass of the feedstock. It will be appreciated that the ratio of the catalyst to the total mass of the raw materials is achieved under the condition that the above-mentioned ranges of the parts by mass of the catalyst in the raw materials are satisfied.
In one embodiment, the colorant is added in an amount of 1% to 5% of the total mass of the feedstock. It will be appreciated that the colorant may be added in an amount of, for example, but not limited to, 1%, 1.2%, 1.5%, 2%, 3%, 4%, 5% and the like, based on the total mass of the raw materials. It will be appreciated that the proportion of the colorant added here to the total mass of the raw materials is achieved under the condition that the above-mentioned ranges of the parts by mass of the colorant in the raw materials for preparation are satisfied.
An embodiment of the present application further provides a method for preparing a polyamide hot melt adhesive, including the following steps:
the components in the raw materials for preparing the polyamide hot melt adhesive in any of the above examples are mixed and reacted.
In one embodiment, the steps of mixing the components in the preparation raw materials of the polyamide hot melt adhesive and reacting include the steps S110 to S140:
step S110: mixing dibasic acid, diamine, polyether amine and antioxidant, controlling the temperature at a first reaction temperature, and performing a first reaction.
Optionally, the first reaction is carried out under a protective gas atmosphere. It is understood that the shielding gas may be, for example, but not limited to, any of nitrogen, helium, argon, and the like.
Alternatively, the first reaction temperature is 80 ℃ to 140 ℃. It is understood that the first reaction temperature may be, for example, but not limited to, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, and the like. Further, the first reaction temperature is 100 ℃ to 130 ℃.
Alternatively, the reaction time of the first reaction is 1 to 2 hours. It is understood that the reaction time of the first reaction may be, for example, but not limited to, 1h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.7h, 1.8h, 1.9h, 2h, and the like.
Step S120: then adding a catalyst into the material after the first reaction, controlling the temperature at a second reaction temperature, and carrying out a second reaction.
Optionally, the second reaction is carried out under a protective gas atmosphere. It is understood that the shielding gas may be, for example, but not limited to, any of nitrogen, helium, argon, and the like.
Alternatively, the second reaction temperature is 160℃to 210 ℃. It is understood that the second reaction temperature may be, for example, but not limited to 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, and the like. Further, the second reaction temperature is 180 ℃ to 200 ℃.
Alternatively, the reaction pressure of the second reaction is 1.3MPa to 1.5MPa. It is understood that the reaction pressure of the second reaction may be, for example, but not limited to, 1.3MPa, 1.35MPa, 1.4MPa, 1.45MPa, 1.5MPa, and the like.
Alternatively, the reaction time of the second reaction is 0.5h to 1h. It is understood that the reaction time of the second reaction may be, for example, but not limited to, 0.5h, 0.6h, 0.7h, 0.8h, 0.9h, 1h, and the like.
Step S130: and controlling the temperature at a third reaction temperature, and adding resin into the material after the second reaction to perform the third reaction.
Optionally, the third reaction is carried out under a protective gas atmosphere. It is understood that the shielding gas may be, for example, but not limited to, any of nitrogen, helium, argon, and the like.
Optionally, the third reaction temperature is 230 ℃ to 250 ℃. It is understood that the third reaction temperature may be, for example, but not limited to, 230 ℃, 235 ℃, 240 ℃, 245 ℃, 250 ℃, and the like.
Alternatively, the reaction pressure of the third reaction is 1.3MPa to 1.5MPa. It is understood that the reaction pressure of the third reaction may be, for example, but not limited to, 1.3MPa, 1.35MPa, 1.4MPa, 1.45MPa, 1.5MPa, and the like.
Alternatively, the reaction time of the third reaction is 1h to 1.5h. It is understood that the reaction time of the third reaction may be, for example, but not limited to, 1h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, and the like.
Step S140: and controlling the temperature at a fourth reaction temperature, and adding sulfamic acid, silicone oil and a colorant into the material after the third reaction to perform the fourth reaction.
Optionally, the fourth reaction is carried out under a protective gas atmosphere. It is understood that the shielding gas may be, for example, but not limited to, any of nitrogen, helium, argon, and the like.
Optionally, the fourth reaction temperature is 170 ℃ to 200 ℃. It is understood that the fourth reaction temperature may be, for example, but not limited to, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, and the like. Further, the fourth reaction temperature is 180-190 ℃.
Alternatively, the reaction time of the fourth reaction is 1h to 1.5h. It is understood that the reaction time of the fourth reaction may be, for example, but not limited to, 1h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, and the like.
An embodiment of the present application further provides an application of the polyamide hot melt adhesive in any one of the above embodiments in an injection molding process.
The method adopts the specific raw materials and the specific mass parts to mutually cooperate to prepare the polyamide hot melt adhesive, resin, sulfamic acid and silicone oil are introduced into a reaction system as raw materials, and the molecular structure of the polyamide is changed by a specific multi-step polymerization reaction method, so that the adhesive force, the hardness value and the rebound resilience of the hot melt adhesive are greatly improved, the hot melt adhesive can be suitable for an injection molding process, and the encapsulation and protection effects on sensitive electronic components are better by adopting the process.
An embodiment of the present application further provides an application of the polyamide hot melt adhesive in the above embodiment in an injection molding process. Further, the polyamide hot melt adhesive can be applied to, for example, but not limited to, a low pressure injection molding process, wherein the low pressure injection molding process can be performed with a very low injection pressure, and the injection pressure can be 5kgf/cm, for example 2 ～40kgf/cm 2 . It can be appreciated that the polyamide hot melt adhesive provided in any embodiment can be used for manufacturing grommet, sensor, micro switch, plug of automobile wire harness and other sensitive electronic components such as electronic components encapsulation protection products with high requirements on shock resistance, moisture resistance, oil resistance, chemical corrosion resistance and the like by adopting a low-pressure injection molding process.
The polyamide hot melt adhesive of the present application, and the preparation method and application thereof are described in further detail with reference to specific examples and comparative examples. It will be appreciated that in the specific examples, all materials are commercially available unless otherwise specified.
Wherein, partial sources of raw materials are shown in the following table 1.
TABLE 1 partial sources of raw materials
Example 1
Step one: the raw materials were weighed as follows in table 2:
TABLE 2 reaction starting materials for example 1
Step two: under the protection of nitrogen, dimer acid Prpol 1013, azelaic acid, ethylenediamine, polyether amine D-230 and antioxidant 1010 are added into a glass reactor with a temperature control device, a mechanical stirring device and a speed regulating device and a capacity of 2L, stirring is started, the temperature is gradually increased to 100 ℃, and the reaction is kept at 100 ℃ for 2h;
then adding phosphoric acid into a glass reactor, heating to 190 ℃, keeping the pressure at 1.3-1.5 MPa, and keeping the temperature at 190 ℃ for reaction for 1h;
then raising the temperature to 240 ℃, adding phenolic resin and polyester resin into a glass reactor, keeping the pressure between 1.3MPa and 1.5MPa, and keeping the temperature at 240 ℃ for reaction for 1h;
finally, the temperature is reduced to 190 ℃, and then 2-naphthylamine-3, 6, 8-trisulfonic acid, hydroxyl-terminated silicone oil and carbon black color master batch are added into a glass reactor, and the reaction is continued for 1h at the temperature of 190 ℃.
Example 2
Step one: the raw materials were weighed according to the following Table 3
TABLE 3 reaction starting materials for example 2
Step two: under the protection of nitrogen, dimer acid Prpol 1013, sebacic acid, hexamethylenediamine, polyether amine D-400 and antioxidant 1010 are added into a glass reactor with a temperature control device, a mechanical stirring device and a speed regulating device and the capacity of 2L, stirring is started, the temperature is gradually increased to 100 ℃, and the reaction is kept at 100 ℃ for 2h;
then adding hydrofluoric acid into a glass reactor, heating to 190 ℃, keeping the pressure at 1.3-1.5 MPa, and keeping the temperature at 190 ℃ for reaction for 1h;
then raising the temperature to 240 ℃, adding phenolic resin and polyurethane resin into a glass reactor, keeping the pressure between 1.3MPa and 1.5MPa, and keeping the temperature at 240 ℃ for reaction for 1h;
finally, the temperature is reduced to 190 ℃, and then 2-naphthylamine-3, 6, 8-trisulfonic acid, hydroxyl-terminated silicone oil and carbon black color master batch are added into a glass reactor, and the reaction is continued for 1h at the temperature of 190 ℃.
Example 3
Step one: the raw materials were weighed as follows in table 4:
TABLE 4 reaction starting materials for example 3
Step two: under the protection of nitrogen, dimer acid pripol 1017, dodecanedioic acid, dodecanediamine, polyether amine D-230 and antioxidant 1010 are added into a glass reactor with a temperature control device, a mechanical stirring and speed regulating device and a capacity of 2L, stirring is started, the temperature is gradually increased to 100 ℃, and the temperature is kept at 100 ℃ for 2h of reaction;
then adding glacial acetic acid into the glass reactor, heating to 190 ℃, keeping the pressure at 1.3-1.5 MPa, and keeping the temperature at 190 ℃ for reaction for 1h;
then the temperature is raised to 240 ℃, rosin resin and polyurethane resin are added into a glass reactor, the pressure is kept between 1.3MPa and 1.5MPa, and the temperature is kept at 240 ℃ for reaction for 1 hour;
finally, the temperature is reduced to 190 ℃, and then 7-amino-1, 3, 5-naphthalene trisulfonic acid, hydroxyl-terminated silicone oil and carbon black color master batch are added into a glass reactor, and the reaction is continued for 1h at the temperature of 190 ℃.
Example 4
Step one: the raw materials were weighed as follows in table 5:
TABLE 5 reaction starting materials for example 4
Step two: under the protection of nitrogen, dimer acid pripol 1022, sebacic acid, pentanediamine, polyether amine D-2000 and antioxidant 1010 are added into a glass reactor with a temperature control device, a mechanical stirring device and a speed regulating device and the capacity of 2L, stirring is started, the temperature is gradually increased to 100 ℃, and the reaction is kept at 100 ℃ for 2h;
then adding sulfuric acid into a glass reactor, heating to 190 ℃, keeping the pressure at 1.3-1.5 MPa, and keeping the temperature at 190 ℃ for reaction for 1h;
then the temperature is raised to 240 ℃, rosin resin and phenolic resin are added into a glass reactor, the pressure is kept between 1.3MPa and 1.5MPa, and the temperature is kept at 240 ℃ for reaction for 1 hour;
finally, the temperature is reduced to 190 ℃, and then 8-aminonaphthalene-1, 3, 6-trisulfonic acid, hydroxyl-terminated silicone oil and carbon black masterbatch are added into a glass reactor, and the reaction is continued for 1h at the temperature of 190 ℃.
Comparative example 1
Step one: the raw materials were weighed as follows in table 6:
TABLE 6 reaction starting materials for comparative example 1
Step two: under the protection of nitrogen, dimer acid pripol 1017, azelaic acid, ethylenediamine, polyether amine D-230 and antioxidant 1010 are added into a glass reactor with a temperature control device, a mechanical stirring device and a speed regulating device and a capacity of 2L, stirring is started, the temperature is gradually increased to 100 ℃, and the reaction is kept at 100 ℃ for 2h;
then adding phosphoric acid into a glass reactor, heating to 190 ℃, keeping the pressure at 1.3-1.5 MPa, and keeping the temperature at 190 ℃ for reaction for 1h;
the temperature is kept at 190 ℃, then 2-naphthylamine-3, 6, 8-trisulfonic acid, hydroxyl-terminated silicone oil and carbon black masterbatch are added into a glass reactor, and the reaction is continued for 1h at 190 ℃.
Comparative example 2
Step one: the raw materials were weighed as follows in table 7:
TABLE 7 reaction starting materials for comparative example 2
Step two: under the protection of nitrogen, dimer acid Prpol 1013, azelaic acid, ethylenediamine, polyether amine D-230 and antioxidant 1010 are added into a glass reactor with a temperature control device, a mechanical stirring device and a speed regulating device and a capacity of 2L, stirring is started, the temperature is gradually increased to 100 ℃, and the reaction is kept at 100 ℃ for 2h;
then adding phosphoric acid into a glass reactor, heating to 190 ℃, keeping the pressure at 1.3-1.5 MPa, and keeping the temperature at 190 ℃ for reaction for 1h;
then raising the temperature to 240 ℃, adding phenolic resin and polyester resin into a glass reactor, keeping the pressure between 1.3MPa and 1.5MPa, and keeping the temperature at 240 ℃ for reaction for 1h;
finally, the temperature is reduced to 190 ℃, then carbon black masterbatch is added into the reaction system, and the reaction is continued for 1h at 190 ℃.
Comparative example 3
Step one: the raw materials were weighed as follows in table 8:
TABLE 8 reaction starting materials for comparative example 3
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Step two: under the protection of nitrogen, dimer acid pripol 1022, azelaic acid, ethylenediamine, polyether amine D-230 and antioxidant 1010 are added into a glass reactor with a temperature control device, a mechanical stirring device and a speed regulating device and a capacity of 2L, stirring is started, the temperature is gradually increased to 100 ℃, and the reaction is kept at 100 ℃ for 2h;
then adding phosphoric acid into a glass reactor, heating to 190 ℃, keeping the pressure at 1.3-1.5 MPa, and keeping the temperature at 190 ℃ for reaction for 1h;
the temperature was maintained at 190℃and then a carbon black masterbatch was added to the glass reactor, and the reaction was continued at 190℃for 1 hour.
The polyamide hot melt adhesives prepared in examples 1 to 4 and comparative examples 1 to 3 were subjected to performance test, and the test results are shown in tables 9 and 10 below.
Table 9 comparative tests of the Properties of the Polyamide Hot melt adhesives of examples 1 to 4
TABLE 10 comparative polyamide Hot melt adhesive Performance test of example 1 and comparative examples 1-3
As can be seen from Table 9, the rebound resilience of the polyamide hot melt adhesives prepared in examples 1 to 4 can reach more than 40%, and the rebound resilience performance is good; the softening point is above 165 ℃, the melt viscosity (190 ℃) is 2500-4000 CP, and the adhesive property is excellent; the Shore hardness can reach more than 88A, and the hardness is high; the PET has high peel strength and PET/PET tensile shear strength, and strong cohesiveness.
As can be seen from table 10, the polyamide hot melt adhesive prepared in example 1 was more excellent in all of the properties such as shore hardness, tensile strength, rebound resilience, peel strength, tensile shear strength, etc., as compared with comparative examples 1 to 3.
The technical features of the above embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The foregoing embodiments represent only a few embodiments of the present application, which are described in some detail and are not to be construed as limiting the scope of the invention. It should be noted that it would be obvious to those skilled in the art that various modifications and improvements could be made without departing from the inventive concept of the present application, which would be within the scope of the present application. Accordingly, the scope of protection of the present application is to be determined by the claims appended hereto.
Claims (13)
1. The polyamide hot melt adhesive is characterized by comprising the following raw materials in parts by mass:
600-700 parts of dibasic acid,
20-80 parts of diamine,
100-500 parts of polyether amine,
10 to 50 parts of sulfamic acid,
10-50 parts of silicone oil,
20-200 parts of resin,
10-40 parts of antioxidant,
2-20 parts of catalyst
10-40 parts of a colorant;
the resin includes one or more of polyurethane resin, phenolic resin, polyvinyl chloride resin, polyester resin, polyamide resin, and rosin resin.
2. The polyamide hot melt adhesive of claim 1 wherein the diacid comprises one or more of azelaic acid, sebacic acid, dodecanedioic acid, tridecanedioic acid, heneicosanoic acid, shan acid, linoleic acid, and dimer acid.
3. The polyamide hot melt adhesive of claim 2, wherein the dimer acid comprises one or more of dimer oleic acid, dimer elaidic acid, tall oil dimer acid, and dimer ricinoleic acid.
4. The polyamide hot melt adhesive of claim 1, wherein the diamine comprises one or more of diethylene diamine, ethylene diamine, hexamethylene diamine, pentane diamine, 1, 3-m-phenylene diamine, di-t-butyl ethylene diamine, and 2-methyl pentane diamine.
5. The polyamide hot melt adhesive of claim 1, wherein the polyetheramine comprises an amine-terminated polyetheramine; the molecular weight of the amine-terminated polyether amine is 100 Da-2000 Da.
6. The polyamide hot melt adhesive of claim 5, wherein the amine-terminated polyetheramine comprises one or more of polyetheramine D-400, polyetheramine D-230, polyetheramine D-2000, and polyetheramine FL-1000.
7. The polyamide hot melt adhesive of any one of claims 1-6, wherein the sulfamic acid comprises one or more of 2-naphthylamine-3, 6, 8-trisulfonic acid, 7-amino-1, 3, 5-naphthalene trisulfonic acid, 8-aminonaphthalene-1, 3, 6-trisulfonic acid, 4-amino-1 naphthalene sulfonic acid, 3-aminopropanesulfonic acid, and 8-amino-2 naphthalene sulfonic acid.
8. The polyamide hot melt adhesive according to any one of claims 1 to 6, wherein the silicone oil comprises hydroxyl-terminated silicone oil;
the chemical formula of the hydroxyl-terminated silicone oil is as follows:
HO-Si(CH 3 ) 2 O-[Si(CH 3 ) 2 O] n -Si(CH 3 ) 2 -OH，n=5~20。
9. the polyamide hot melt adhesive of claim 8, wherein n = 5-15.
10. The polyamide hot melt adhesive of any one of claims 1-6, wherein the antioxidant comprises one or more of antioxidant 1010, antioxidant 1098, antioxidant 168, and antioxidant 1076; and/or
The catalyst comprises one or more of glacial acetic acid, propionic acid, sulfuric acid, hydrofluoric acid and phosphoric acid; and/or
The colorant comprises one or more of carbon black, iron oxide black, copper chromium black, iron chromium black, aniline black, antimony sulfide and cobalt black.
11. The preparation method of the polyamide hot melt adhesive is characterized by comprising the following steps:
mixing and reacting the components in the raw materials for preparing the polyamide hot melt adhesive according to any one of claims 1 to 10.
12. The method of producing a polyamide hot melt adhesive according to claim 11, wherein the step of mixing each of the components in the raw materials for producing the polyamide hot melt adhesive and reacting comprises:
mixing the dibasic acid, the diamine, the polyether amine and the antioxidant, controlling the temperature at a first reaction temperature, and performing a first reaction;
then adding the catalyst into the materials after the first reaction, controlling the temperature at a second reaction temperature, and carrying out a second reaction;
controlling the temperature at a third reaction temperature, and adding the resin into the material after the second reaction to perform the third reaction;
controlling the temperature at a fourth reaction temperature, and adding sulfamic acid, silicone oil and colorant into the material after the third reaction to perform a fourth reaction;
the first reaction temperature is 80-140 ℃;
the second reaction temperature is 160-210 ℃;
the third reaction temperature is 230-250 ℃;
the fourth reaction temperature is 170-200 ℃.
13. Use of a polyamide hot melt adhesive according to any one of claims 1 to 10 in an injection moulding process.
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| CN101962526A (en) * | 2010-09-30 | 2011-02-02 | 烟台德邦电子材料有限公司 | Low-viscosity dimer acid type polyamine hot melt adhesive and preparation method thereof |
| CN107353867A (en) * | 2017-07-11 | 2017-11-17 | 南通协鑫热熔胶有限公司 | A kind of organosilicon end capping polyamide hot and preparation method thereof |
| EP3763769A1 (en) * | 2020-11-09 | 2021-01-13 | Wenzhou University | Method for preparing copolyamide resin and copolyamide hot-melt yarn |
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| CN101962526A (en) * | 2010-09-30 | 2011-02-02 | 烟台德邦电子材料有限公司 | Low-viscosity dimer acid type polyamine hot melt adhesive and preparation method thereof |
| CN107353867A (en) * | 2017-07-11 | 2017-11-17 | 南通协鑫热熔胶有限公司 | A kind of organosilicon end capping polyamide hot and preparation method thereof |
| EP3763769A1 (en) * | 2020-11-09 | 2021-01-13 | Wenzhou University | Method for preparing copolyamide resin and copolyamide hot-melt yarn |
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