CN107266684B - Polyamide-imide resin and resin adhesive and application thereof - Google Patents
Polyamide-imide resin and resin adhesive and application thereof Download PDFInfo
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- CN107266684B CN107266684B CN201610216331.8A CN201610216331A CN107266684B CN 107266684 B CN107266684 B CN 107266684B CN 201610216331 A CN201610216331 A CN 201610216331A CN 107266684 B CN107266684 B CN 107266684B
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
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- C08G73/14—Polyamide-imides
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- 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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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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- C09J11/06—Non-macromolecular additives organic
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- C08L2205/00—Polymer mixtures characterised by other features
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- C09J2409/00—Presence of diene rubber
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- C09J2463/00—Presence of epoxy resin
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- C09J2479/00—Presence of polyamine or polyimide
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Abstract
The invention provides a polyamide-imide resin, wherein the inherent viscosity number of the polyamide-imide resin is 0.6-2 dL/g; the structural unit of the polyamide-imide resin comprises a structural unit M and a structural unit R, wherein the structural unit M and the structural unit R are alternately connected. The invention also provides a resin adhesive which contains epoxy resin, nitrile rubber and the polyamide-imide resin. The invention also provides the use of the polyamide-imide resin as described above and/or the resin adhesive as described above in the preparation of an automotive reinforcing patch. Through the technical scheme, the reinforcing multiplying power of the adhesive resin for reinforcing the automobile is greatly enhanced, and the adhesive resin for reinforcing the automobile has good thermal stability.
Description
Technical Field
The invention relates to the field of polymer chemistry, in particular to a polyamide-imide resin, a resin adhesive and application of the polyamide-imide resin and the resin adhesive.
Background
The light weight of the automobile is an effective way for saving energy and reducing pollution, and if the total mass of the automobile is reduced by ten percent, the oil consumption of one hundred kilometers can be reduced by three to seven percent. At present, the weight reduction of the automobile is mainly realized by the following two methods: one is that materials with high strength and light weight, such as aluminum alloy, magnesium alloy, high-strength steel, engineering plastics and the like, are adopted, but the defect of high cost is caused; secondly, the automobile structure is improved, the material thickness is reduced, the outer plate is thinned, the structural part is hollowed, and the like, but the local rigidity of the automobile body is reduced due to the thinning of the steel plate, and the parts such as the automobile door, the top cover, the side wall and the like are easy to generate noise and resonance in the running process of the automobile; the impact energy absorption becomes small in the event of an accidental collision, and the occupant is easily injured.
Aiming at the adverse effect caused by thinning of the automobile steel plate, one of the remedial measures which can be taken is to apply the composite reinforcing high polymer material as a reinforcing patch of the automobile steel plate. The adhesive resin with the reinforcing function is prepared from nitrile rubber, epoxy resin, polyvinyl chloride resin or vinyl chloride/vinyl acetate copolymer, an auxiliary agent and calcium carbonate, the reinforcing rate of the adhesive resin still needs to be improved, the stability to light and heat is poor, the adhesive resin cannot meet the post-processing use requirement of higher temperature of more than 200 ℃, and the adhesive resin can be decomposed and initiate autocatalytic decomposition under severe use conditions of more than 100 ℃ or long-time sunshine exposure, so that the mechanical property is greatly reduced.
Disclosure of Invention
The invention provides a polyamide-imide resin, a resin adhesive and application of the polyamide-imide resin and the resin adhesive, aiming at overcoming the defects of lower reinforcing multiplying power and poorer thermal stability of the existing adhesive resin for reinforcing automobiles.
In one aspect, the present invention provides a polyamideimide resin, wherein the inherent viscosity of the polyamideimide resin is from 0.6 to 2 dL/g; the structural unit of the polyamide-imide resin comprises a structural unit M and a structural unit R, wherein the structural unit M and the structural unit R are alternately connected, the structural unit M is shown as a formula (1), and the structural unit R is selected from at least one of a formula (2) to a formula (7);
in another aspect, the present invention also provides a method for preparing a polyamideimide resin, wherein the method comprises: diamine is contacted with trimellitic anhydride under the condition of water separation in the presence of an organic solvent to generate amidation reaction; wherein the diamine comprises at least one of 2, 2-bis [4- (4-aminophenoxy) benzene ] propane, 2-bis [4- (3-aminophenoxy) benzene ] propane, 4 '-bis (3-aminophenoxy) diphenyl sulfone, 4' -bis (4-aminophenoxy) biphenyl, 1, 3-bis (4-aminophenoxy) benzene, and diaminodiphenyl ether.
In another aspect, the present invention also provides a resin adhesive, wherein the resin adhesive comprises an epoxy resin, a nitrile rubber and the above polyamideimide resin; wherein, the content of the nitrile rubber is 30-100 parts by weight relative to 100 parts by weight of the epoxy resin; the content of the polyamide-imide resin is 3-25 parts by weight.
In a further aspect, the present invention also provides the use of a polyamideimide resin as described above and/or a resin adhesive as described above for the preparation of an automotive reinforcing patch.
Through the technical scheme, the reinforcing multiplying power of the adhesive resin for reinforcing the automobile is greatly enhanced, and the adhesive resin for reinforcing the automobile has good thermal stability.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
In one aspect, the present invention provides a polyamideimide resin, wherein the inherent viscosity of the polyamideimide resin is from 0.6 to 2.0 dL/g; the structural unit of the polyamide-imide resin comprises a structural unit M and a structural unit R, wherein the structural unit M and the structural unit R are alternately connected, the structural unit M is shown as a formula (1), and the structural unit R is selected from at least one of a formula (2) to a formula (7);
wherein, the group shown in the formula (1) can be taken as a structural unit from left to right and can also be taken as a structural unit from right to left; that is, in the polyamideimide resin, the amino groups at both ends of the phenoxy group-containing diamine may be: simultaneously forming amide bond; simultaneously forming an imide bond; or, respectively, forming an amide bond or an imide bond; preferably, the structural unit of the polyamide-imide resin comprises a structural unit X, wherein the structural unit X is shown as a formula (8);
wherein R is as defined above. Wherein, preferably, R is a group represented by formula (2), formula (3) or formula (4); more preferably, R is a group represented by formula (2).
Among them, the inherent viscosity of the polyamideimide resin of the present invention may be 0.6 to 2.0dL/g, and preferably 0.6 to 1.6 dL/g. Wherein the viscosity value for calculating the intrinsic viscosity is obtained by testing the viscosity value by using a Brookfield rotary viscometer LVDV-II + Pro at a test temperature of 23.5 ℃, a rotating speed of 0.6-3.0rpm and a torque of 30-65%.
In another aspect, the present invention also provides a method for preparing a polyamideimide resin, wherein the method comprises: diamine is contacted with trimellitic anhydride under the condition of water separation in the presence of an organic solvent to generate amidation reaction; wherein the diamine comprises at least one of 2, 2-bis [4- (4-aminophenoxy) benzene ] propane, 2-bis [4- (3-aminophenoxy) benzene ] propane, 4 '-bis (3-aminophenoxy) diphenyl sulfone, 4' -bis (4-aminophenoxy) biphenyl, 1, 3-bis (4-aminophenoxy) benzene, and diaminodiphenyl ether.
Wherein, the 2, 2-bis [4- (4-aminophenoxy) benzene ] propane is shown as the following formula (9):
wherein, the 2, 2-bis [4- (3-aminophenoxy) benzene ] propane is shown as the formula (10):
wherein, the 4, 4' -bis (3-aminophenoxy) diphenyl sulfone is shown as the formula (11):
wherein, 4, 4' -bis (4-aminophenoxy) biphenyl is shown as the formula (12):
wherein, the 1, 3-bis (4-aminophenoxy) benzene is shown as the formula (13):
wherein the diaminodiphenyl ether is represented by the formula (14):
among them, the organic solvent that can be used for the preparation of the polyamideimide resin of the present invention includes at least one of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, sulfolane, dioxane, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, m-cresol, toluene, xylene, and benzene.
Wherein the molar ratio of the trimellitic anhydride to the diamine can be 1: (0.95-1.05), preferably 1: (0.98-1.02). The organic solvent may be used in an amount of 0.8 to 2L, preferably 1 to 1.5L, relative to 1 mole of trimellitic anhydride.
Wherein, the material after amidation reaction can be purified by removing the organic solvent by fractional distillation under reduced pressure, and the solid content of the purified polyamideimide resin can be 10 to 40 wt%, preferably 17 to 30 wt%.
Wherein the conditions of the reduced pressure fractionation may include: the temperature is 50-150 ℃; the pressure is 50-100 kPa.
In another aspect, the present invention also provides a resin adhesive, wherein the resin adhesive comprises an epoxy resin, a nitrile rubber and the above polyamideimide resin; wherein, the content of the nitrile rubber is 30-100 parts by weight relative to 100 parts by weight of the epoxy resin; the content of the polyamide-imide resin is 3-25 parts by weight.
Wherein, as a preferred embodiment of the present invention, the content of the nitrile rubber is 40 to 80 parts by weight relative to 100 parts by weight of the epoxy resin; the content of the polyamide-imide resin is 5-20 parts by weight. In this preferred embodiment, the resin adhesive of the present invention has a higher reinforcing ratio and better thermal stability.
The number average molecular weight of the epoxy resin can be varied in a large range, such as 500-5000, preferably 500-4000, and the epoxy equivalent can be varied in a large range, such as 300-500 g/equivalent, preferably 310-475 g/equivalent.
Wherein the number average molecular weight of the nitrile rubber can be changed in a large range, such as 1000-5000, preferably 1500-4000, and the acrylonitrile content can be changed in a large range, such as 25-50 wt%, preferably 25-42 wt%.
Among these, as a preferable embodiment of the present invention, the resin adhesive further contains styrene-butadiene rubber. In the preferred embodiment, the styrene-butadiene rubber can further enhance the reinforcing ratio and thermal stability of the resin adhesive.
Wherein the content of the styrene-butadiene rubber may vary within a wide range, for example, may be 10 to 30 parts by weight, preferably 10 to 20 parts by weight, with respect to 100 parts by weight of the epoxy resin.
Wherein, the weight average molecular weight of the styrene-butadiene rubber can be changed in a large range, such as 100000-200000, preferably 120000-150000; the styrene content can vary within wide limits and can be, for example, from 22 to 35% by weight, preferably from 22 to 27% by weight.
In order to further enhance the comprehensive performance of the resin adhesive, the resin adhesive preferably further contains a plasticizer, a curing agent, a filler and carbon black.
Wherein the plasticizer comprises at least one of dimethyl sulfur, dioctyl phthalate, dibutyl phthalate and triphenyl phosphate; the curing agent comprises at least one of dicyandiamide, diaminodiphenylmethane, dimethylimidazole and ethylenediamine; the filler comprises at least one of calcium carbonate, talcum powder, nano titanium dioxide, mica powder, zinc oxide, cuprous oxide, magnesium hydroxide and aluminum hydroxide.
Wherein, the plasticizer may be contained in an amount of 3 to 15 parts by weight, preferably 5 to 10 parts by weight, the curing agent may be contained in an amount of 2 to 10 parts by weight, preferably 2 to 6 parts by weight, the filler may be contained in an amount of 20 to 100 parts by weight, preferably 30 to 80 parts by weight, and the carbon black may be contained in an amount of 5 to 25 parts by weight, preferably 5 to 20 parts by weight, with respect to 100 parts by weight of the epoxy resin.
The particle size of the filler may vary within wide limits, for example from 1 to 50 μm, preferably from 1 to 20 μm. Among them, it is particularly preferable that the filler is calcium carbonate having a particle size of 1 to 5 μm.
In a further aspect, the present invention also provides the use of a polyamideimide resin as described above and/or a resin adhesive as described above for the preparation of an automotive reinforcing patch. Among them, the use of the polyamideimide resin as described above and/or the resin adhesive as described above for the reinforcement (or reinforcement) of automobiles falls within the scope of the present invention.
The present invention will be described in further detail below with reference to examples.
Example 1
0.02mol of 2, 2-bis [4- (4-aminophenoxy) benzene ] propane and 55mL of toluene are added into a three-necked flask connected with a condenser and a thermometer, stirred at room temperature until the mixture is completely dissolved, then 0.02mol of trimellitic anhydride is added, the mixture is continuously stirred until the mixture is homogeneous, and water is distilled by heating in a water bath. After the water is completely separated, continuously heating and reacting for 3h, and then distilling under reduced pressure to remove the solvent to obtain the polyamide-imide resin.
100 parts by weight of an epoxy resin (bisphenol A epoxy resin of south Asia epoxy resin Co., Ltd., number average molecular weight of 650, epoxy equivalent of 212 g/eq), 80 parts by weight of a nitrile rubber (nitrile rubber of Jilin petrochemical Co., number average molecular weight of 1600, acrylonitrile content of 30), 10 parts by weight of the above-obtained polyamideimide resin, 60 parts by weight of calcium carbonate (average particle diameter of 3.5 to 10 μm), 10 parts by weight of dimethyl sulfide, 10 parts by weight of dicyandiamide, and 20 parts by weight of carbon black were stirred and mixed at 110 ℃ and a rotation speed of 150 rpm for 1 hour, and then the mixture was naturally cooled to room temperature and pressed into a sheet having a thickness of 2 mm.
Example 2
A polyamideimide resin was obtained in the same manner as in example 1.
100 parts by weight of an epoxy resin (bisphenol A epoxy resin of south Asia epoxy resin Co., Ltd., number average molecular weight 650, epoxy equivalent 212 g/eq), 80 parts by weight of a nitrile rubber (nitrile rubber of Jilin petrochemical Co., number average molecular weight 2700, acrylonitrile content 39), 20 parts by weight of the above-obtained polyamideimide resin, 60 parts by weight of calcium carbonate (average particle diameter 3.5 to 10 μm), 10 parts by weight of dimethyl sulfide, 10 parts by weight of dicyandiamide, and 20 parts by weight of carbon black were stirred and mixed at 110 ℃ and 150 rpm for 1.5 hours, and then the mixture was naturally cooled to room temperature and pressed into a sheet of 2mm thickness.
Example 3
A polyamideimide resin was obtained in the same manner as in example 1.
100 parts by weight of an epoxy resin (bisphenol A epoxy resin of south Asia epoxy resin Co., Ltd., number average molecular weight 3000, epoxy equivalent 307 g/equivalent), 40 parts by weight of a nitrile rubber (nitrile rubber of Jilin petrochemical Co., number average molecular weight 1600, acrylonitrile content 30), 40 parts by weight of a styrene butadiene rubber (styrene butadiene rubber 1502, styrene content 23 wt%), 5 parts by weight of the above-obtained polyamideimide resin, 60 parts by weight of calcium carbonate (average particle diameter 3.5-10 μm), 10 parts by weight of dimethyl sulfide, 10 parts by weight of dicyandiamide, and 20 parts by weight of carbon black were stirred and mixed at 110 ℃ and a rotation speed of 150 rpm for 3 hours, and then the mixture was naturally cooled to room temperature and pressed into a sheet having a thickness of 2 mm.
Example 4
A polyamideimide resin was obtained in the same manner as in example 1.
100 parts by weight of an epoxy resin (bisphenol A epoxy resin of south Asia epoxy resin Co., Ltd., number average molecular weight 3000, epoxy equivalent 307 g/equivalent), 40 parts by weight of a nitrile rubber (nitrile rubber of Jilin petrochemical Co., number average molecular weight 1600, acrylonitrile content 30), 40 parts by weight of a styrene butadiene rubber (styrene butadiene rubber 1502, styrene content 23 wt%), 1 part by weight of the above-obtained polyamideimide resin, 60 parts by weight of calcium carbonate (average particle diameter 3.5 to 10 μm), 10 parts by weight of dimethyl sulfide, 10 parts by weight of dicyandiamide, and 20 parts by weight of carbon black were stirred and mixed at 110 ℃ and a rotation speed of 150 rpm for 3 hours, and then the mixture was naturally cooled to room temperature and pressed into a sheet having a thickness of 2 mm.
Example 5
A polyamideimide resin was obtained in the same manner as in example 1.
100 parts by weight of an epoxy resin (bisphenol A epoxy resin of south Asia epoxy resin Co., Ltd., number average molecular weight 3000, epoxy equivalent 307 g/equivalent), 40 parts by weight of a nitrile rubber (nitrile rubber of Jilin petrochemical Co., number average molecular weight 1600, acrylonitrile content 30), 40 parts by weight of a styrene butadiene rubber (styrene butadiene rubber 1502, styrene content 23 wt%), 50 parts by weight of the above-obtained polyamideimide resin, 60 parts by weight of calcium carbonate (average particle diameter 3.5 to 10 μm), 10 parts by weight of dimethyl sulfide, 10 parts by weight of dicyandiamide, and 20 parts by weight of carbon black were stirred and mixed at 110 ℃ and a rotation speed of 150 rpm for 3 hours, and then the mixture was naturally cooled to room temperature and pressed into a sheet having a thickness of 2 mm.
Example 6
A polyamideimide resin and a reinforcing sheet were prepared according to the method of example 3; except that 2, 2-bis [4- (4-aminophenoxy) benzene ] propane was replaced with an equimolar amount of 2, 2-bis [4- (3-aminophenoxy) benzene ] propane.
Example 7
A polyamideimide resin and a reinforcing sheet were prepared according to the method of example 3; except that 2, 2-bis [4- (4-aminophenoxy) benzene ] propane was replaced with equimolar amounts of 4, 4' -bis (3-aminophenoxy) diphenyl sulfone.
Example 8
A polyamideimide resin and a reinforcing sheet were prepared according to the method of example 3; except that 2, 2-bis [4- (4-aminophenoxy) benzene ] propane was replaced with equimolar amounts of 4, 4' -bis (4-aminophenoxy) biphenyl.
Example 9
A polyamideimide resin and a reinforcing sheet were prepared according to the method of example 3; except that 2, 2-bis [4- (4-aminophenoxy) benzene ] propane was replaced with equimolar 1, 3-bis (4-aminophenoxy) benzene.
Example 10
A polyamideimide resin and a reinforcing sheet were prepared according to the method of example 3; except that 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane was replaced with equimolar diaminodiphenyl ether.
Comparative example 1
A polyamideimide resin and a reinforcing sheet were prepared according to the method of example 3; except that 2, 2-bis [4- (4-aminophenoxy) benzene ] propane was replaced with equimolar 2, 2-bis [4- (4-aminophenoxy) benzene ] hexafluoropropane.
Comparative example 2
123.2g (0.3mol) of 2, 2-bis- [4- (4-aminophenoxy) phenyl ] propane as the diamine, 115.3g (0.6mol) of trimellitic anhydride and 716g of NMP (N-methyl-2-pyrrolidone) as the solvent were charged into a 1 liter separable flask equipped with a reflux condenser, a thermometer and a stirrer, in which a vertical 25mL water receiver was connected to the reflux condenser, and stirred at 80 ℃ for 30 minutes. 143g of toluene were then added as aromatic hydrocarbon capable of forming an azeotrope with water and the mixture was heated to around 160 ℃ and refluxed for 2 hours. After 10.8mL of water was received in the water receiver and no further evaporation of water was observed, the distillate stored in the water receiver was removed and the temperature was raised to about 190 ℃ to remove toluene. Then, the solution was cooled to room temperature, and 75.1g (0.3mol) of 4, 4-diphenylmethane diisocyanate was added to conduct the reaction at 190 ℃ for 2 hours. This reaction produced an NMP solution of polyamideimide resin. Then, NMP was removed by decompression and ballasting to obtain a polyamide-imide resin.
100 parts by weight of an epoxy resin (bisphenol A epoxy resin of south Asia epoxy resin Co., Ltd., number average molecular weight 3000, epoxy equivalent 307 g/equivalent), 40 parts by weight of a nitrile rubber (nitrile rubber of Jilin petrochemical Co., number average molecular weight 1600, acrylonitrile content 30), 40 parts by weight of a styrene butadiene rubber (styrene butadiene rubber 1502, styrene content 23 wt%), 5 parts by weight of the above-obtained polyamideimide resin, 60 parts by weight of calcium carbonate (average particle diameter 3.5-10 μm), 10 parts by weight of dimethyl sulfide, 10 parts by weight of dicyandiamide, and 20 parts by weight of carbon black were stirred and mixed at 110 ℃ and a rotation speed of 150 rpm for 3 hours, and then the mixture was naturally cooled to room temperature and pressed into a sheet having a thickness of 2 mm.
Comparative example 3
100 parts by weight of epoxy resin (bisphenol A epoxy resin of south Asia epoxy resin Co., Ltd., number average molecular weight of 650, epoxy equivalent of 212 g/equivalent), 80 parts by weight of nitrile rubber (nitrile rubber of Jilin petrochemical Co., number average molecular weight of 1600, acrylonitrile content of 30), 60 parts by weight of calcium carbonate (average particle diameter of 3.5-10 μm), 10 parts by weight of dimethyl sulfide, 10 parts by weight of dicyandiamide and 20 parts by weight of carbon black are stirred and mixed for 1 hour at 110 ℃ and 150 r/min, then the mixture is naturally cooled to room temperature and pressed into a sheet with the thickness of 2mm
Test example 1
The polyamideimide resin obtained in example 1 was subjected to infrared spectroscopic examination, and the infrared spectroscopic examination result showed 915cm-1Located at 1184cm of an epoxy ring stretching vibration peak-1At 1398cm, is a C-O bond stretching vibration peak of fat-1Is located at 1630cm of imide ring C-N stretching vibration peak-1The position is a benzene ring C ═ C bond stretching vibration peak, 1725cm-1And 1779cm-1In each case being an imine ringSymmetric stretching vibration peak of C ═ O bond and asymmetric stretching vibration peak of C ═ O bond, 2930cm-1Is represented by CH3、CH2CH stretching vibration peak of 2966cm-1The peak is the C-O stretching vibration peak of the epoxy ring.
According to the infrared spectrum data, the structural unit of the polyamideimide resin of example 1 includes a structural unit M and a structural unit R, and the structural unit M and the structural unit R are alternately connected, wherein the structural unit M is represented by formula (1), and the structural unit R is represented by formula (2).
The polyamideimide resins obtained in examples 1 and 6 to 10 and comparative examples 1 and 2 were measured using a Brookfield rotational viscometer LVDV-II + Pro at a test temperature of 23.5 deg.C, a rotation speed of 0.6 to 3.0rpm, and a torque of 30 to 65% to obtain viscosity values at various concentrations, and the intrinsic viscosity was calculated, and the results are shown in Table 1.
TABLE 1
Test example 2
The sheets of examples 1 to 10 and comparative examples 1 to 3 were respectively applied to a glass cloth (200 g/m)2) Cutting into strips with length and width of 150 × 25mm + -3 mm, spreading on 150 × 25 × 0.8mm steel plates, rolling for 5 times, and heating in oven.
Applying a pressure to the sample at a rate of 5mm/min, measuring a maximum load value at a displacement of 2.5mm, using a steel plate as an original sample, and calculating a reinforcement ratio which is the load value of the sample to which the reinforcing sheet is attached/the load value of the original sample × 100%; the room-temperature reinforcement ratio was obtained, and the results are shown in Table 1.
The sheets of examples 1 to 10 and comparative examples 1 to 3 were respectively applied to a glass cloth (200 g/m)2) Cutting into strips with length and width of 150 × 25mm + -3 mm, spreading on 150 × 25 × 0.8mm steel plates, rolling for 5 times, and heating in oven. And (3) baking the cured sample at 220 ℃ for 8h, then cooling to 80 ℃ at the speed of 5 ℃/min, and then preserving heat for 200 h.
The sample was pressed at a rate of 5mm/min, the maximum load value at a displacement of 2.5mm was measured, and the reinforcement ratio was calculated as load value of the sample to which the reinforcement sheet was attached/load value of the original sample × 100% using a steel plate as an original sample, and the reinforcement ratio after high-temperature baking was obtained, and the results are shown in table 2.
TABLE 2
As can be seen from the results in table 2, the reinforcing magnification of the adhesive resin for reinforcing automobiles is greatly increased, and the adhesive resin for reinforcing automobiles of the present invention has good thermal stability. And, preferably, the content of the nitrile rubber is 40-80 parts by weight with respect to 100 parts by weight of the epoxy resin; under the condition that the content of the polyamide-imide resin is 5-20 parts by weight, the resin adhesive has higher reinforcing multiplying power and better thermal stability.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (7)
1. A resin adhesive is characterized by comprising epoxy resin, nitrile rubber and polyamide-imide resin; wherein, the content of the nitrile rubber is 40-80 parts by weight relative to 100 parts by weight of the epoxy resin; the content of the polyamide-imide resin is 5-20 parts by weight;
the inherent viscosity number of the polyamide-imide resin is 0.6-2 dL/g; the structural unit of the polyamide-imide resin comprises a structural unit M and a structural unit R, wherein the structural unit M and the structural unit R are alternately connected, the structural unit M is shown as a formula (1),
Wherein R is selected from at least one of formula (2) to formula (7);
2. The resin adhesive according to claim 1, wherein the epoxy resin has a number average molecular weight of 500-5000 and an epoxy equivalent weight of 300-550 g/eq; the number average molecular weight of the nitrile rubber is 1000-5000, and the content of acrylonitrile is 25-50 wt%.
3. The resin adhesive according to claim 1, wherein the resin adhesive further comprises styrene-butadiene rubber in an amount of 10 to 50 parts by weight per 100 parts by weight of the epoxy resin.
4. The resin adhesive according to claim 3, wherein the weight-average molecular weight of the styrene-butadiene rubber is 100000-200000, and the styrene content is 22-35 wt%.
5. The resin adhesive according to any one of claims 1 to 4, further comprising a plasticizer, a curing agent, a filler and carbon black; the plasticizer comprises at least one of dimethyl sulfur, dioctyl phthalate, dibutyl phthalate and triphenyl phosphate; the curing agent comprises at least one of dicyandiamide, diaminodiphenylmethane, dimethylimidazole and ethylenediamine; the filler comprises at least one of calcium carbonate, talcum powder, nano titanium dioxide, mica powder, zinc oxide, cuprous oxide, magnesium hydroxide and aluminum hydroxide; the content of the plasticizer is 3-15 parts by weight, the content of the curing agent is 2-10 parts by weight, the content of the filler is 20-100 parts by weight, and the content of the carbon black is 5-25 parts by weight, relative to 100 parts by weight of the epoxy resin.
6. The resin adhesive according to claim 5, wherein the filler has a particle size of 1 to 50 μm.
7. Use of the resin adhesive of any one of claims 1 to 6 in the preparation of an automotive reinforcing patch.
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| CN114605910B (en) * | 2020-12-22 | 2022-12-06 | 苏州太湖电工新材料股份有限公司 | Semi-inorganic silicon steel sheet paint |
| CN112646484B (en) * | 2020-12-22 | 2022-05-06 | 苏州太湖电工新材料股份有限公司 | Polyamide-imide varnish and preparation method thereof |
| CN113637422A (en) * | 2021-08-18 | 2021-11-12 | 昆山兆科电子材料有限公司 | Efficient heat-conducting double-sided adhesive tape and preparation process thereof |
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| CN101130679A (en) * | 2006-08-25 | 2008-02-27 | 比亚迪股份有限公司 | Adhesion agent and method of manufacturing the same |
| CN102260480A (en) * | 2011-07-13 | 2011-11-30 | 东华大学 | High-temperature-resistant modified epoxy resin adhesive and preparation method thereof |
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