CN113667447A - 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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- CN113667447A CN113667447A CN202111135734.7A CN202111135734A CN113667447A CN 113667447 A CN113667447 A CN 113667447A CN 202111135734 A CN202111135734 A CN 202111135734A CN 113667447 A CN113667447 A CN 113667447A
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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
- C09J177/00—Adhesives based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Adhesives based on derivatives of such polymers
- C09J177/06—Polyamides derived from polyamines and polycarboxylic acids
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
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Abstract
The invention relates to a polyamide hot melt adhesive and a preparation method and application thereof, wherein the polyamide hot melt adhesive comprises the following raw materials: dibasic acid, diamine, catalyst and heat conducting seed crystal; the dibasic acid comprises a combination of dimer acid and other dibasic acids; the mass percent of the heat-conducting crystal seeds is 1-2.1% based on 100% of the total mass of the raw materials for preparing the polyamide hot melt adhesive. The polyamide hot melt adhesive disclosed by the invention is high in crystallization rate, has the advantages of low viscosity, good wettability, oil resistance and insulation, is high in solidification rate, can improve the product forming rate, and further improves the production efficiency of an injection molding process pair.
Description
Technical Field
The invention relates to the technical field of polymer materials, in particular to a polyamide hot melt adhesive and a preparation method and application thereof.
Background
The dimer acid type polyamide hot melt adhesive is prepared by condensing dimer acid and diamine or polyamine, has good adhesion to various base materials, has the advantages of narrow melting point range, good wettability, no toxicity, oil resistance, good chemical resistance, excellent wear resistance, high adhesion to polar materials, good low-temperature flexibility and the like, can be used in the field of low-pressure injection molding, and is particularly suitable for packaging in some electronic industries sensitive to temperature and pressure.
CN103555263A discloses a preparation method of dimer acid type copolymerized polyamide hot melt adhesive, which takes dimer acid, dibasic acid and diamine as raw materials, and generates dimer acid type polyamide hot melt adhesive through a polycondensation reaction by adding a molecular regulator, and comprises the following steps: 1 weight part of dimer acid, 0.01 to 0.03 weight part of dibasic acid and 0.005 to 0.012 weight part of molecular weight regulator are put into a reactor, 0.05 to 0.1 weight part of ethylenediamine and 0.05 to 0.09 weight part of diamine are added when the temperature of the reactor rises to 90 to 150 ℃, the temperature is increased to 230 ℃ and 250 ℃ within 2 hours, the temperature is kept at 160 ℃ and 260 ℃, the reaction is carried out for 1 to 5 hours, the reaction is carried out for 1 to 2.5 hours by vacuumizing, the pressure in the reactor is reduced to normal pressure, and the product is discharged. The dimer acid type copolyamide hot melt adhesive disclosed by the invention can be widely applied to the shoe making or electronic industry, has the characteristics of high temperature resistance, small water absorption and environmental friendliness, and has the advantages of simple preparation method, stable production, low cost and renewable raw material resources.
CN102220105A discloses a dimer acid type polyamide hot melt adhesive and a preparation method thereof, wherein the disclosed polyamide hot melt adhesive contains an N-alkyl substituted diamine structure, and consists of 50 mol percent of component A and 50 mol percent of component B, the component A comprises 60-90 mol percent of unsaturated aliphatic dimer acid and 10-40 mol percent of aliphatic dicarboxylic acid, and the component B comprises 60-90 mol percent of N-alkyl substituted aliphatic diamine, 10-30 mol percent of aliphatic diamine and 0-10 mol percent of heterocyclic diamine. The polyamide hot melt adhesive disclosed by the invention has the advantages of high softening point, excellent low temperature resistance, high elongation, low high-temperature melt viscosity, higher tensile strength and shear strength, suitability for a low-pressure injection molding process and high bonding reliability, and is particularly suitable for bonding polar high polymer materials.
At present, the common dimer acid type polyamide hot melt adhesive can basically meet the use requirements, but still has the defect of low solidification speed, and has certain influence on the production efficiency of an injection molding process.
In conclusion, it is important to develop a dimer acid type polyamide hot melt adhesive which has the advantages of low viscosity, good wettability, oil resistance, insulation and the like, and also has a relatively high solidification rate.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a polyamide hot melt adhesive and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a polyamide hot melt adhesive, which comprises the following raw materials in parts by weight: dibasic acid, diamine, catalyst and heat conducting seed crystal;
the dibasic acid comprises a combination of dimer acid and other dibasic acids;
the mass percentage of the heat-conducting seed crystal is 1 to 2.1 percent, such as 1.1 percent, 1.2 percent, 1.3 percent, 1.4 percent, 1.5 percent, 1.6 percent, 1.7 percent, 1.8 percent, 1.9 percent and the like, based on the total mass of the raw materials for preparing the polyamide hot melt adhesive being 100 percent.
The raw materials for preparing the polyamide hot melt adhesive comprise the heat-conducting crystal seeds in a specific proportion, the heat-conducting crystal seeds play a key role in the rapid forming of the polyamide hot melt adhesive, the crystal seeds can be provided for the polyamide molecule crystallization process, and meanwhile, the polyamide hot melt adhesive has good heat-conducting property, can rapidly reduce the temperature of the material and further accelerate the rapid solidification of the hot melt adhesive. The occupation ratio of the heat-conducting crystal seeds is too small, the promotion effect on improving the polyamide crystallization rate is weak, and meanwhile, the heat-conducting effect is not enough; the proportion of the heat-conducting seed crystal is too large, which increases the viscosity of the product and influences the flowability and the wettability of the product.
Preferably, the thermally conductive seeds comprise any one or a combination of at least two of mica, calcium carbonate, calcium sulfate, talc, barium sulfate, boron nitride, or alumina, with typical but non-limiting combinations including: a combination of mica and calcium carbonate, a combination of calcium sulfate, talc powder and barium sulfate, a combination of talc powder, barium sulfate, boron nitride and alumina, etc., and boron nitride is more preferable.
The reason why the heat conducting seed crystal is preferably boron nitride is that the material has very high heat conductivity coefficient and dispersibility, and the boron nitride is inert and not easy to decompose and does not influence the bulk performance of the polyamide.
Preferably, the molar ratio of the diacid to diamine is (0.8-1):1, where 0.8-1 can be 0.82, 0.84, 0.86, 0.88, 0.9, 0.92, 0.94, 0.96, 0.98, etc.
Preferably, the mole percentage of dimer acid is 60% to 80%, such as 62%, 64%, 66%, 68%, 70%, 72%, 74%, 76%, 78%, etc., based on 100% total moles of the diacid.
Preferably, the other dibasic acids include C4-C18 dibasic acids.
The "C4-C18" in the invention means that the number of main chain carbon atoms is 4-18, and C4-C18 can be C5, C6, C8, C10, C12, C14, C16 and the like.
Preferably, the C4-C18 dibasic acid comprises any one of adipic acid, azelaic acid, sebacic acid, or dodecanedioic acid, or a combination of at least two thereof, wherein typical but non-limiting combinations include: combinations of adipic acid and azelaic acid, combinations of azelaic acid, sebacic acid, and dodecanedioic acid, combinations of adipic acid, azelaic acid, sebacic acid, and dodecanedioic acid, and the like.
Preferably, the diamine comprises any one or a combination of at least two of ethylenediamine, 1, 2-propylenediamine, 1, 3-propylenediamine, 1, 4-butylenediamine, pentylenediamine, hexylenediamine, piperazine, a dimer amine, a polyether amine, a xylene diamine, or p-phenylenediamine, wherein typical but non-limiting combinations include: combinations of ethylenediamine and 1, 2-propylenediamine, combinations of 1, 3-propylenediamine, 1, 4-butylenediamine and pentylenediamine, combinations of 1, 2-propylenediamine, 1, 3-propylenediamine, 1, 4-butylenediamine, pentylenediamine and hexylenediamine, combinations of hexylenediamine, piperazine, diethylenediamine, polyetheramine, xylylenediamine and p-phenylenediamine, and the like.
Preferably, the weight percentage of the catalyst is 0.1-0.2%, such as 0.12%, 0.14%, 0.16%, 0.18% and the like, based on 100% of the total mass of the raw materials for preparing the polyamide hot melt adhesive.
Preferably, the catalyst comprises any one of, or a combination of at least two of, phosphoric acid, hypophosphorous acid, p-toluenesulfonic acid, or sodium bisulfate, with typical but non-limiting combinations comprising: combinations of phosphoric acid and hypophosphorous acid, combinations of hypophosphorous acid, p-toluenesulfonic acid, and sodium bisulfate, combinations of phosphoric acid, hypophosphorous acid, p-toluenesulfonic acid, and sodium bisulfate, and the like.
Preferably, the raw materials for preparing the polyamide hot melt adhesive also comprise an antioxidant.
Preferably, the weight percentage of the antioxidant is 0.1-0.2%, such as 0.12%, 0.14%, 0.16%, 0.18% and the like, based on 100% of the total mass of the raw materials for preparing the polyamide hot melt adhesive.
Preferably, the antioxidant comprises pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010), tris (2, 4-di-tert-butylphenyl) phosphite, N, N-bis- [3- (3, 5-di-tert-butyl-4-hydroxyphenyl ] propionyl hexamethylenediamine, 1, 2-bis (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid) hydrazine, or a combination of at least two thereof, wherein typical but non-limiting combinations include a combination of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and tris (2, 4-di-tert-butylphenyl) phosphite, a combination of N, N-bis- [3- (3, a combination of 5-di-t-butyl-4-hydroxyphenyl ] propionylhexamethylenediamine and 1, 2-bis (3, 5-di-t-butyl-4-hydroxy-phenylpropionic acid) hydrazine, pentaerythritol tetrakis [ β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], tris (2, 4-di-t-butylphenyl) phosphite, a combination of N, N-bis- [3- (3, 5-di-t-butyl-4-hydroxyphenyl ] propionylhexamethylenediamine and 1, 2-bis (3, 5-di-t-butyl-4-hydroxy-phenylpropionic acid) hydrazine, and the like.
In a second aspect, the present invention provides a preparation method of the polyamide hot melt adhesive, wherein the preparation method comprises the following steps:
mixing dibasic acid, diamine, a catalyst and heat-conducting seed crystals, and carrying out polycondensation reaction to obtain the polyamide hot melt adhesive;
the dibasic acid comprises a combination of dimer acid and other dibasic acids;
the mass percentage of the heat-conducting seed crystal is 1-2%, such as 1.2%, 1.4%, 1.6%, 1.8% and the like, based on 100% of the total mass of the raw materials for preparing the polyamide hot melt adhesive.
Preferably, the polycondensation reaction is carried out under stirring conditions.
Preferably, the preparation method specifically comprises: dividing diamine into two parts, then mixing dimer acid, other dibasic acid, antioxidant, first diamine and heat-conducting seed crystal, heating for the first time, then adding second diamine into the mixed solution, heating for the second time, preserving heat, and finally vacuumizing to obtain the polyamide hot melt adhesive.
Preferably, the first diamine comprises a polyetheramine.
Preferably, the first heating is to 100-.
Preferably, the second heating is to 220-250 deg.C, such as 210 deg.C, 220 deg.C, 230 deg.C, 240 deg.C, etc., and more preferably 240 deg.C.
Preferably, the incubation time is 0.5-2h, such as 0.6h, 0.8h, 1.0h, 1.2h, 1.4h, 1.6h, 1.8h, etc., more preferably 1 h.
Preferably, the time for evacuation is 2-5h, such as 2.5h, 3h, 3.5h, 4h, 4.5h, etc., and further preferably 3 h.
As a preferred technical scheme, the preparation method comprises the following steps:
dividing diamine into two parts, mixing dimer acid, other dibasic acid, antioxidant, first diamine and heat conducting seed crystal, heating to 150 ℃ for the first time, adding second diamine into the mixed solution, heating to 250 ℃ for the second time, preserving heat for 0.5-2h, and finally vacuumizing for 2-5h to obtain the polyamide hot melt adhesive.
In a third aspect, the invention provides the application of the polyamide hot melt adhesive in the first aspect in the electronic industry.
Compared with the prior art, the invention has the following beneficial effects:
the polyamide hot melt adhesive disclosed by the invention is high in crystallization rate, has the advantages of low viscosity, good wettability, oil resistance and insulation, is high in solidification rate, can improve the product forming rate, and further improves the production efficiency of an injection molding process pair. The melt viscosity of the invention is below 3300cp, and the softening point is below 175.8 ℃; the breaking strength is more than 6.8MPa, and the breaking elongation is more than 568.1 percent; the setting time is below 2.8 s.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a polyamide hot melt adhesive, and the preparation raw materials of the polyamide hot melt adhesive comprise the following components: dibasic acid, diamine, a catalyst, an antioxidant and a heat conducting seed crystal;
the total mass of the raw materials for preparing the polyamide hot melt adhesive is 100 percent:
catalyst: 0.4 percent of phosphoric acid by mass;
antioxidant: 1.6 percent of antioxidant 1010;
heat conduction seed crystal: 2.1 percent by mass of boron nitride;
the balance of dibasic acid and diamine, and the molar ratio of the dibasic acid to the diamine is 1: 1;
the dibasic acid comprises dimer acid and sebacic acid, and the mole ratio of the dimer acid in the dibasic acid is 70%;
the dimer acid is purchased from Dahurian company and has the brand number of 1013;
the diamine is polyether amine D2000 and ethylenediamine;
the polyether amine D2000 is purchased from Henschel under the trademark D2000, and the mass percentage of the polyether amine D2000 in the diamine is 66.8%.
The preparation method of the polyamide hot melt adhesive comprises the following steps:
dividing diamine into two parts, then mixing diacid, an antioxidant, polyetheramine D2000 and heat-conducting seed crystals, heating to 130 ℃ for the first time, then adding ethylenediamine into the mixed solution, heating to 240 ℃ for the second time, preserving heat for 1h, vacuumizing for 3h, then relieving vacuum by using nitrogen, discharging on a polytetrafluoroethylene plate while hot, and obtaining a yellow film, namely the polyamide hot melt adhesive.
Example 2
The embodiment provides a polyamide hot melt adhesive, and the preparation raw materials of the polyamide hot melt adhesive comprise the following components: dibasic acids (dimer acid and other dibasic acids), diamine, a catalyst, an antioxidant and a heat-conducting seed crystal;
the total mass of the raw materials for preparing the polyamide hot melt adhesive is 100 percent:
catalyst: 0.05 percent of p-toluenesulfonic acid and 0.05 percent of sodium bisulfate in percentage by mass;
antioxidant: 2 percent of 1, 2-bis (3, 5-di-tert-butyl-4-hydroxy-phenyl propionic acid) hydrazine;
heat conduction seed crystal: 0.75 percent of boron nitride and 0.25 percent of calcium carbonate respectively in percentage by mass;
the balance of dibasic acid and diamine, and the molar ratio of the dibasic acid to the diamine is 0.8: 1;
the dibasic acid comprises dimer acid and other dibasic acids, and the mole ratio of the dimer acid in the dibasic acid is 60%;
the dimer acid is purchased from Dahurian company and has the brand number of 1013;
the other dibasic acids are adipic acid, adipic acid and azelaic acid in equal molar numbers;
the diamine is 1, 2-propane diamine, 1, 3-propane diamine, 1, 4-butane diamine, xylene diamine, diamine and polyether amine D400 with equal mole number;
wherein, the diamine is purchased from Dahurian company and has the trade name of 1073; polyetheramine D400 was purchased from hensman under the designation D400.
The preparation method of the polyamide hot melt adhesive comprises the following steps:
mixing dibasic acid, an antioxidant, 1/3 parts by mass of diamine and heat-conducting seed crystals, heating to 150 ℃ for the first time, adding the rest 2/3 parts by mass of diamine into the mixed solution, heating to 220 ℃ for the second time, preserving heat for 0.5h, vacuumizing for 2h, removing vacuum by using nitrogen, discharging on a polytetrafluoroethylene plate while the mixture is hot, and obtaining a yellow film, namely the polyamide hot melt adhesive.
Example 3
The embodiment provides a polyamide hot melt adhesive, and the preparation raw materials of the polyamide hot melt adhesive comprise the following components: dibasic acids (dimer acid and other dibasic acids), diamine, a catalyst, an antioxidant and a heat-conducting seed crystal;
the total mass of the raw materials for preparing the polyamide hot melt adhesive is 100 percent:
catalyst: 0.2 percent of hypophosphorous acid by mass percent;
antioxidant: 0.07 percent of phosphorous acid tri (2, 4-di-tert-butyl phenyl) ester and 0.03 percent of N, N-bis- [3- (3, 5-di-tert-butyl-4-hydroxyphenyl ] propionyl hexamethylene diamine;
heat conduction seed crystal: the mass percentages of the components are respectively 1.6 percent of boron nitride, 0.1 percent of calcium sulfate, 0.1 percent of talcum powder, 0.1 percent of barium sulfate and 0.1 percent of alumina;
the balance of dibasic acid and diamine, and the molar ratio of the dibasic acid to the diamine is 1: 1;
the dibasic acid comprises dimer acid and other dibasic acids, and the mole ratio of the dimer acid in the dibasic acid is 80%;
the dimer acid is purchased from Dahurian company and has the brand number of 1013;
the other dibasic acids are sebacic acid and dodecanedioic acid with equal mole numbers;
the diamine is pentamethylene diamine, hexamethylene diamine, piperazine, polyether amine D230 and p-phenylenediamine with equal mole number;
polyetheramine D230 is available from Henschel under the designation D230.
The preparation method of the polyamide hot melt adhesive comprises the following steps:
mixing dibasic acid, an antioxidant, polyetheramine D230, p-phenylenediamine and heat-conducting seed crystals, heating to 100 ℃ for the first time, adding pentanediamine, hexamethylenediamine and piperazine into the mixed solution, heating to 250 ℃ for the second time, preserving heat for 0.5h, vacuumizing for 5h, removing vacuum by using nitrogen, discharging on a polytetrafluoroethylene plate while the material is hot, and obtaining a yellow film, namely the polyamide hot melt adhesive.
Example 4
Example 4 example 1 differs in that the mass percentage of the thermally conductive seed crystal is 1%, and the rest is the same as example 1.
Example 5
The difference between this example and example 1 is that the heat conductive seed crystal is replaced by equal mass mica with boron nitride, and the rest is the same as example 1.
Comparative example 1
This comparative example differs from example 1 in that no thermally conductive seed crystal was added, and the rest was the same as example 1.
Comparative examples 2 to 3
Comparative examples 2 to 3 are different from example 1 in that the mass percentages of the thermally conductive seed crystals are 0.5% (example 4) and 2.5% (example 5), respectively, and the rest is the same as example 1.
Performance testing
The polyamide hot melt adhesives described in examples 1 to 5 and comparative examples 1 to 3 were subjected to the following tests:
(1) melt viscosity: the procedure was followed in accordance with ASTM D3236 Standard test method for apparent viscosity of Hot melt adhesives and coating materials.
(2) Softening point: the ring and ball method for measuring the softening point of the hot melt adhesive is adopted according to GB/T15332.
(3) Hardness: method for testing press-in hardness of vulcanized rubber or thermoplastic rubber of GB/T531.1 Shore durometer.
(4) Breaking strength: according to the measurement of the tensile stress strain performance of GB/T528 vulcanized rubber or thermoplastic rubber.
(5) Elongation at break: according to the measurement of the tensile stress strain performance of GB/T528 vulcanized rubber or thermoplastic rubber.
(6) Setting time (mold opening time):
the test results are summarized in table 1.
TABLE 1
As can be seen from the analysis of the data in Table 1, in each example, the melt viscosity of the invention is below 3300cp, which ensures excellent injection molding performance and fluidity, and the softening point is below 175.8 ℃; the breaking strength is more than 6.8MPa, the breaking elongation is more than 568.1%, the mechanical property is higher, but the solidification time is less than 2.8s, and the processing time is shortened; therefore, the polyamide hot melt adhesive disclosed by the invention has the advantages of high crystallization rate, low viscosity, good wettability, oil resistance and insulation, and high solidification rate, can improve the product forming rate, and further improves the production efficiency of an injection molding process pair.
As can be seen from the analysis of comparative example 1 and example 1, the performance of comparative example 1 is inferior to that of example 1, and the fact that the addition of the heat-conducting seed crystal during the preparation is beneficial to the improvement of the performance of the polyamide hot melt adhesive is proved.
As can be seen from the analysis of comparative examples 2-3 and examples 1 and 4, the setting time of comparative example 2 is significantly longer, while the setting time of comparative example 3 is faster, but the shortening degree is very limited compared with that of example 1, and at the same time, the melt viscosity is increased greatly, which increases the difficulty of injection molding, therefore, the performance of comparative examples 2-3 is inferior to that of examples 1 and 4, which proves that the performance of the polyamide hot melt adhesive formed by the heat-conducting seed crystal in the range of 1% -2.1% in the raw materials for preparation is better.
As can be seen from the analysis of example 6 and example 1, the performance of example 6 is inferior to that of example 1, and the performance of the polyamide hot melt adhesive formed by boron nitride selected by the heat-conducting seed crystal is proved to be better.
The present invention is illustrated in detail by the examples described above, but the present invention is not limited to the details described above, i.e., it is not intended that the present invention be implemented by relying on the details described above. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The polyamide hot melt adhesive is characterized by comprising the following raw materials in parts by weight: dibasic acid, diamine, catalyst and heat conducting seed crystal;
the dibasic acid comprises a combination of dimer acid and other dibasic acids;
the mass percent of the heat-conducting crystal seeds is 1-2.1% based on 100% of the total mass of the raw materials for preparing the polyamide hot melt adhesive.
2. The polyamide hot melt adhesive of claim 1, wherein the thermally conductive seed crystals comprise any one of mica, calcium carbonate, calcium sulfate, talc, barium sulfate, boron nitride or alumina, or a combination of at least two thereof.
3. The polyamide hot melt adhesive according to claim 1 or 2, characterized in that the molar ratio of the dibasic acid to the diamine is (0.8-1): 1;
preferably, the mole percentage of the dimer acid is 60% to 80% based on 100% of the total moles of the dibasic acid.
4. The polyamide hot melt adhesive of any one of claims 1 to 3, wherein the other dibasic acids comprise C4-C18 dibasic acids;
preferably, the C4-C18 dibasic acid comprises any one or a combination of at least two of adipic acid, azelaic acid, sebacic acid, or dodecanedioic acid;
preferably, the diamine comprises any one or a combination of at least two of ethylenediamine, 1, 2-propanediamine, 1, 3-propanediamine, 1, 4-butanediamine, pentanediamine, hexanediamine, piperazine, dimer amine, polyether amine, xylene diamine, or p-phenylenediamine.
5. The polyamide hot melt adhesive according to any one of claims 1 to 4, wherein the weight percentage of the catalyst is 0.1 to 0.2 percent, based on 100 percent of the total mass of the raw materials for preparing the polyamide hot melt adhesive;
preferably, the catalyst comprises any one of phosphoric acid, hypophosphorous acid, p-toluenesulfonic acid or sodium bisulfate or a combination of at least two thereof.
6. The polyamide hot melt adhesive according to any one of claims 1 to 5, wherein the raw materials for preparing the polyamide hot melt adhesive further comprise an antioxidant;
preferably, the weight percentage of the antioxidant is 0.1-0.2% based on 100% of the total mass of the raw materials for preparing the polyamide hot melt adhesive;
preferably, the antioxidant comprises any one of or a combination of at least two of pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], tris (2, 4-di-tert-butylphenyl) phosphite, N-bis- [3- (3, 5-di-tert-butyl-4-hydroxyphenyl ] propionyl hexamethylenediamine, and 1, 2-bis (3, 5-di-tert-butyl-4-hydroxy-phenylpropionic acid) hydrazine.
7. A preparation method of the polyamide hot melt adhesive as claimed in any one of claims 1 to 6, characterized by comprising the following steps:
mixing dibasic acid, diamine, a catalyst and heat-conducting seed crystals, and carrying out polycondensation reaction to obtain the polyamide hot melt adhesive;
the dibasic acid comprises a combination of dimer acid and other dibasic acids;
the mass percent of the heat-conducting crystal seeds is 1-2% based on 100% of the total mass of the raw materials for preparing the polyamide hot melt adhesive.
8. The production method according to claim 7, wherein the polycondensation reaction is carried out under stirring conditions;
preferably, the preparation method specifically comprises: dividing diamine into two parts, then mixing dimer acid, other dibasic acid, an antioxidant, first diamine and heat-conducting seed crystal, heating for the first time, then adding second diamine into the mixed solution, heating for the second time, preserving heat, and finally vacuumizing to obtain the polyamide hot melt adhesive;
preferably, the first diamine comprises a polyetheramine;
preferably, the first heating is performed to 100-;
preferably, the second heating is performed to 220-;
preferably, the heat preservation time is 0.5-2 h;
preferably, the vacuumizing time is 2-5 h.
9. The method according to claim 7 or 8, characterized in that it comprises the steps of:
dividing diamine into two parts, mixing dimer acid, other dibasic acid, antioxidant, first diamine and heat conducting seed crystal, heating to 150 ℃ for the first time, adding second diamine into the mixed solution, heating to 250 ℃ for the second time, preserving heat for 0.5-2h, and finally vacuumizing for 2-5h to obtain the polyamide hot melt adhesive.
10. Use of the polyamide hot melt adhesive according to any one of claims 1 to 6 in the electronics industry.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114619627A (en) * | 2022-05-17 | 2022-06-14 | 烟台万华聚氨酯合成材料有限公司 | Glue supply device for low-pressure injection molding equipment |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105670550A (en) * | 2016-03-31 | 2016-06-15 | 东莞新能源科技有限公司 | Heat-conducting adhesive and secondary battery containing heat-conducting adhesive |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105670550A (en) * | 2016-03-31 | 2016-06-15 | 东莞新能源科技有限公司 | Heat-conducting adhesive and secondary battery containing heat-conducting adhesive |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114619627A (en) * | 2022-05-17 | 2022-06-14 | 烟台万华聚氨酯合成材料有限公司 | Glue supply device for low-pressure injection molding equipment |
| CN114619627B (en) * | 2022-05-17 | 2022-07-29 | 烟台万华聚氨酯合成材料有限公司 | Glue supply device for low-pressure injection molding equipment |
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