CN111748115B - Epoxy glass cloth prepreg for superconducting magnet coil framework and production method thereof - Google Patents
Epoxy glass cloth prepreg for superconducting magnet coil framework and production method thereof Download PDFInfo
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- CN111748115B CN111748115B CN202010410148.8A CN202010410148A CN111748115B CN 111748115 B CN111748115 B CN 111748115B CN 202010410148 A CN202010410148 A CN 202010410148A CN 111748115 B CN111748115 B CN 111748115B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
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- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- C08K7/00—Use of ingredients characterised by shape
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Abstract
The invention relates to a production method of an epoxy glass cloth prepreg for a superconducting magnet coil framework, which comprises the steps of glue mixing, glue forming testing, impregnation, drying, appearance inspection, characteristic testing, coiling/cutting and packaging; the adhesive in the test glue comprises the following components in parts by weight: 100-125 parts of mixed resin, 3-3.4 parts of dicyandiamide, 0.1-0.12 part of dimethyl imidazole, 34-40 parts of dimethyl formamide and 3-33 parts of rubber complexing agent. The invention can solve the problems of insufficient thermal stability of the traditional prepreg and colloidal particles, pinholes, fish eyes and the like of the prepreg caused by the stress change on the surface of the glass cloth in the production process.
Description
Technical Field
The invention relates to a prepreg and a production method thereof, in particular to an epoxy glass cloth prepreg for a superconducting magnet coil framework and a production method thereof.
Background
The prepreg is one of main materials in the production of multilayer boards, and mainly comprises resin and reinforcing materials, the reinforcing materials are further divided into several types such as glass fiber cloth, paper base, composite materials and the like, and most prepregs (bonding sheets) used for manufacturing the multilayer printed boards adopt the glass fiber cloth as the reinforcing materials.
In the existing prepreg in the market at present, glass fiber cloth, epoxy resin and some chemicals are respectively subjected to IQC (in-line quality test), the epoxy resin and the chemicals which are qualified in test are mixed in a certain proportion to form a mixture, then the mixture is combined with glue, then impregnation is carried out, baking is carried out after the impregnation is finished, the glue content, the glue flow, the volatile matter, impurities, bent wefts and the like are required to be subjected to process quality control test after the baking is finished, and the glue is coiled after the inspection is finished; because the requirement of the superconducting magnet on the semi-cured sheet is high, the selection of chemicals is very important, the type of the chemicals determines the performance of the semi-cured sheet, in addition, the using amount of the chemicals is also very important, the using effect of the semi-cured sheet is influenced if the use is not mastered properly, and finally, the normal work of the superconducting magnet is adversely affected.
The traditional prepreg for the superconducting magnet coil framework is insufficient in thermal stability, and the service life of the prepreg can be shortened when the superconducting magnet works for a long time; in the production process of the traditional prepreg for the superconducting magnet coil framework, the defects of uneven gel content, colloidal particles, pinholes, fish eyes and the like are easy to occur due to the change of the surface stress of the glass cloth.
In order to avoid the occurrence of colloidal particles, the glass cloth with thread ends or broken yarns in the production process is not used as much as possible; in addition, the formula and the treatment process of the adhesive are improper during impregnation, so that the ionic concentration of the adhesive is different, colloidal particles are formed at positions with high ionic concentration on the glass cloth, the adhesive is uniform, the formula and the content of the adhesive are proper, and an adhesive layer on the glass cloth cannot be too thick; pinholes appear on the prepreg mainly because the glass cloth is too thin, for example, the nominal thickness of 1080 glass cloth is 0.053mm, the pinhole defect is easy to appear, and the nominal thickness of 7628 glass cloth is 0.173mm, the pinhole defect is not easy to appear; the fisheye defect is mainly the quality problem of the glass cloth, the surface tension of the glass cloth is changed due to stains, and finally, fisheyes are formed, and in the impregnation process, the speed of the glass cloth impregnated with the adhesive liquid flowing from the center to a higher surface tension area is as follows:
V＝(h/u)×(dθ/dx)
wherein h is the thickness of the adhesive and u is the viscosity of the adhesive.
The flow out of the center was:
Q＝(h2/2u)×(dθ/dx)
from the above, it is known that the fisheye defect can be avoided by reducing the surface tension by thinning the coating and increasing the viscosity of the adhesive, but the adhesive is not preferred to be too viscous.
Therefore, a method for producing a prepreg for a superconducting magnet coil former is urgently needed to solve the problem.
Disclosure of Invention
The invention aims to provide an epoxy glass cloth prepreg for a superconducting magnet coil framework and a production method thereof, and the prepreg produced by the method can solve the problems that the traditional prepreg is not enough in thermal stability and the prepreg is in colloidal particles, pinholes, fish eyes and the like caused by the stress change of the surface of glass cloth in the production process.
In order to achieve the purpose, the invention provides the following technical scheme: a production method of epoxy glass cloth prepreg for a superconducting magnet coil skeleton comprises the following steps:
step one, glue mixing;
step two, testing to form gel;
step three, impregnation;
step four, drying;
step five, checking the appearance;
step six, testing characteristics;
step seven, coiling/cutting;
step eight, packaging;
the adhesive in the second step comprises the following components in parts by weight:
in the third step, when impregnation is carried out, a vacuum auxiliary gluing method is utilized;
the vacuum-assisted sizing method is realized by the following steps: the vacuum auxiliary gluing system is provided with a discharge hole on the left side and a feed hole on the right side, an impregnation mechanism and a baking device are sequentially arranged inside the vacuum auxiliary gluing system from right to left, a glue flattening mechanism is arranged between the impregnation mechanism and the baking device, and a plurality of glass cloth conveying rollers are arranged inside the impregnation mechanism;
the interior of the vacuum auxiliary gluing system is a vacuum environment;
the impregnation mechanism is communicated with the outside and is not positioned in a vacuum system;
the glue leveling mechanism comprises a frame, guide posts are respectively arranged at four corners of the top of the frame, the guide posts are vertically arranged downwards, an oil cylinder is arranged at the center of the top of the frame, the oil cylinder is vertically arranged downwards, the maximum stroke of the oil cylinder is equal to the maximum length of the guide posts, a glue leveling component is arranged below the oil cylinder and the guide posts, the glue leveling component comprises an upper glue leveling roller component and a lower glue leveling roller component, guide post connecting seats are arranged at the four corners of the top of the upper glue leveling roller component corresponding to the guide posts, oil cylinder connecting seats are arranged at the center of the top of the upper glue leveling roller component corresponding to the oil cylinder, piston rod ends of the guide posts are connected to the guide post connecting seats, piston rod ends of the oil cylinder are connected to the oil cylinder connecting seats, the lower glue leveling roller component is connected to the frame, and the upper glue leveling roller component comprises an upper roller mounting frame, a row of upper glue leveling rollers are horizontally arranged on the upper roller mounting frame, the lower glue leveling roller assembly comprises a lower roller mounting frame, a row of lower glue leveling rollers are horizontally arranged on the lower roller mounting frame, and the upper glue leveling rollers and the lower glue leveling rollers are in one-to-one correspondence up and down;
the preparation method of the mixed resin comprises the following steps:
weighing bismaleimide resin and brominated epoxy resin, and taking a certain amount of methyl phenylacetate;
secondly, mixing bismaleimide resin and brominated epoxy resin to obtain a resin mixture;
thirdly, putting the resin mixture and methyl phenylacetate into a container, heating to 110-180 ℃, reacting for 10-150 min, and cooling to room temperature;
fourthly, grinding the cooled mixed resin into powder;
the preparation method of the rubber compounding agent comprises the following steps:
firstly, mixing trimethyl methanol, ethylimine, water glass and nitrile rubber;
secondly, adding hydrochloric acid into water glass, reacting and generating precipitate, and then drying.
Preferably, the control parameters of the prepreg are as follows:
baking temperature: 170-200 DEG C
Impregnation speed: 10 to 20m/min
Resin content: 35 to 50 percent
Testing the gelling time: 80-100 s
Fluidity: 21 +/-3%
Volatile components: less than or equal to 0.7 percent.
Preferably, the feeding sequence of the test gelling in the step two is as follows: dimethylformamide, dicyandiamide, dimethyl imidazole, mixed resin and a rubber complexing agent; the process of testing the gelling is as follows: the preparation method comprises the steps of stirring, mixing and dissolving dimethyl formamide, dicyandiamide and dimethyl imidazole in a mixing kettle, adding mixed resin, stirring uniformly, adding a rubber complexing agent, and stirring for 2.5-3 hours.
Preferably, 7628 glass cloth is dipped into the adhesive in the impregnation in the third step.
Preferably, the mixed resin comprises the following raw materials in parts by weight:
40-50 parts of brominated epoxy resin
40-50 parts of bismaleimide resin
65-87 parts of methyl phenylacetate.
Preferably, the adhesive comprises the following components in parts by weight:
control parameters of the prepreg:
baking temperature: 170 ℃;
impregnation speed: 16 m/min;
resin content: 41 percent;
testing the gelling time: 100 s;
fluidity: 21 percent;
volatile components: 0.3 percent;
the mixed resin comprises the following raw materials in parts by weight:
brominated epoxy resin 50
Bismaleimide resin 50
Phenylacetic acid methyl ester 80
The rubber compounding agent comprises the following components in parts by weight:
the mass ratio of the water glass to the nitrile rubber is 1: 10;
the mass ratio of the water glass to the trimethyl methanol is 100: 2;
the mass ratio of the water glass to the ethylimine is 100: 2;
when the glass cloth is impregnated, a vacuum auxiliary gluing method is adopted.
Preferably, the adhesive comprises the following components in parts by weight:
control parameters of the prepreg:
baking temperature: 180 ℃;
impregnation speed: 18 m/min;
resin content: 46 percent;
testing the gelling time: 97 s;
fluidity: 23 percent;
volatile components: 0.35 percent;
the mixed resin comprises the following raw materials in parts by weight:
brominated epoxy resin 43
Bismaleimide resin 45
Phenylacetic acid methyl ester 77
The rubber compounding agent comprises the following components in parts by weight:
the mass ratio of the water glass to the nitrile rubber is 1: 5;
the mass ratio of the water glass to the trimethyl methanol is 99: 1;
the mass ratio of the water glass to the ethylimine is 100: 1;
when the glass cloth is impregnated, a vacuum auxiliary gluing method is adopted.
Preferably, the adhesive comprises the following components in parts by weight:
control parameters of the prepreg:
baking temperature: 200 ℃;
impregnation speed: 20 m/min;
resin content: 50 percent;
testing the gelling time: 95 s;
fluidity: 24 percent;
volatile components: 0.37 percent;
the mixed resin comprises the following raw materials in parts by weight:
brominated epoxy resin 50
Bismaleimide resin 45
Phenylacetic acid methyl ester 85
The rubber compounding agent comprises the following components in parts by weight:
the mass ratio of the water glass to the nitrile rubber is 1: 10;
the mass ratio of the water glass to the trimethyl methanol is 50: 1;
the mass ratio of the water glass to the ethylimine is 100: 3;
when the glass cloth is impregnated, a vacuum auxiliary gluing method is adopted.
Compared with the prior art, the epoxy glass cloth prepreg for the superconducting magnet coil framework and the production method thereof provided by the invention have the following beneficial effects:
1. according to the epoxy glass cloth prepreg for the superconducting magnet coil framework and the production method thereof, brominated epoxy resin and bismaleimide resin are mixed according to a certain proportion to prepare mixed resin, so that the thermal stability of the prepreg is effectively enhanced;
2. according to the epoxy glass cloth prepreg for the superconducting magnet coil framework and the production method thereof, the nitrile rubber, the water glass and the trimethyl methanol are adopted to synthesize the rubber complexing agent according to a certain proportion, so that the bonding force of the adhesive is enhanced, the quality of the prepreg is improved, and the thermal stability of the prepreg is enhanced;
3. according to the epoxy glass cloth prepreg for the superconducting magnet coil framework and the production method thereof, the glass cloth is in a vacuum state after impregnation, the glass cloth just coming out from an impregnation area is subjected to glue spreading by the glue spreading mechanism to enable the surface of the glass cloth to be coated with glue more uniformly, the defects of colloidal particles, pinholes, fish eyes and the like are effectively reduced, the glass cloth enters the baking device immediately after the glue spreading mechanism, the condition that glue solution on the glass cloth is not uniform due to stress change is reduced, and the quality of the prepreg is improved.
In summary, the following steps: according to the epoxy glass cloth prepreg for the superconducting magnet coil framework and the production method thereof, the produced prepreg has better thermal stability; the probability of the appearance of defects such as colloidal particles, pinholes, fish eyes and the like is obviously reduced.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention without limiting the invention in which:
FIG. 1 is a schematic view of a vacuum-assisted gluing system according to the present invention;
FIG. 2 is a front view of the glue spreading mechanism of FIG. 1;
FIG. 3 is a side view of FIG. 2;
FIG. 4 is a top view of the leveling roll assembly of FIG. 2;
FIG. 5 is a top view of the lower glue roller assembly of FIG. 2;
in the figure: 1. a vacuum-assisted gluing system; 2. a discharge port; 3. a feed inlet; 4. an impregnation mechanism; 5. a baking device; 6. a glue leveling mechanism; 601. a frame; 601.1, a guide post; 601.2, an oil cylinder; 602. a glue leveling component; 602.1, feeding a glue roller assembly; 602.11, guide post connecting seat; 602.12, oil cylinder connecting seat; 602.13, an upper roller mounting bracket; 602.14, leveling the rubber roller; 602.2, flattening the rubber roller assembly; 602.21, lower roll mounting bracket; 602.22, lower flat rubber roller; 7. and a glass cloth conveying roller.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a technical scheme that: the production method of the epoxy glass cloth prepreg for the superconducting magnet coil framework is realized by the following steps:
step one, glue mixing;
step two, testing to form gel;
step three, impregnation;
step four, drying;
step five, checking the appearance;
step six, testing characteristics;
step seven, coiling/cutting;
step eight, packaging;
the adhesive in the second step comprises the following components in parts by weight:
the feeding sequence in the second step is as follows: dimethylformamide, dicyandiamide, dimethyl imidazole, mixed resin and a rubber complexing agent; the process of testing the gelling is as follows: firstly, stirring, mixing and dissolving dimethyl formamide, dicyandiamide and dimethyl imidazole in a mixing kettle, then adding mixed resin, stirring uniformly, adding a rubber complexing agent, and then stirring for 2.5-3 hours;
step three, 7628 glass cloth is soaked in the adhesive;
during impregnation, a vacuum auxiliary gluing method is utilized, namely the glass cloth is in a vacuum state after impregnation, the glass cloth just coming out of an impregnation area passes through a glue flattening mechanism to enable the glue on the surface of the glass cloth to be more uniform, and the glass cloth immediately enters a baking device after the glue flattening mechanism; the vacuum auxiliary gluing method can also effectively overcome the defects of uneven glue content and residual stress of the prepreg caused by uneven tension of the glass fiber cloth, so that the quality of the prepreg is better.
As shown in fig. 1 to 5, the vacuum-assisted sizing method is realized by: impregnating and drying in a vacuum auxiliary gluing system 1, wherein a discharge port 2 is arranged on the left side of the vacuum auxiliary gluing system 1, a feed port 3 is arranged on the right side of the vacuum auxiliary gluing system 1, an impregnating mechanism 4 and a baking device 5 are sequentially arranged in the vacuum auxiliary gluing system 1 from right to left, a glue flattening mechanism 6 is arranged between the impregnating mechanism 4 and the baking device 5, and a plurality of glass cloth conveying rollers 7 are arranged in the impregnating mechanism 4;
the interior of the vacuum auxiliary gluing system 1 is a vacuum environment;
the impregnation mechanism 4 is communicated with the outside and is not positioned in a vacuum system;
the glue spreading mechanism 6 comprises a frame 601, four corners of the top of the frame 601 are respectively provided with a guide post 601.1, the guide posts 601.1 are vertically arranged downwards, the top center of the frame 601 is provided with an oil cylinder 601.2, the oil cylinder 601.2 is vertically arranged downwards, the maximum stroke of the oil cylinder 601.2 is equal to the maximum length of the guide post 601.1, a glue spreading component 602 is arranged below the oil cylinder 601.2 and the guide post 601.1, the glue spreading component 602 comprises an upper glue spreading roller component 602.1 and a lower glue spreading roller component 602.2, guide post connecting seats 602.11 are arranged at four corners of the top of the upper glue spreading roller component 602.1 corresponding to the guide post 601.1, an oil cylinder connecting seat 602.12 is arranged at the center of the top of the upper glue spreading roller component 602.1 corresponding to the oil cylinder 601.2, a piston rod end of the guide post 601.1 is connected to the guide post connecting seat 602.11, a piston rod end of the oil cylinder 601.2 is connected to the oil cylinder connecting seat 602.12, the lower glue leveling roller assembly 602.2 is connected to the frame 601, the upper glue leveling roller assembly 602.1 comprises an upper roller mounting frame 602.13, a row of upper glue leveling rollers 602.14 is horizontally mounted on the upper roller mounting frame 602.13, the lower glue leveling roller assembly 602.2 comprises a lower roller mounting frame 602.21, a row of lower glue leveling rollers 602.22 is horizontally mounted on the lower roller mounting frame 602.21, and the upper glue leveling rollers 602.14 correspond to the lower glue leveling rollers 602.22 in a one-to-one up and down manner;
the working principle of the glue leveling mechanism 6 is as follows:
the oil cylinder 601.2 and the guide column 601.1 on the glue spreading mechanism 6 accurately control the upper glue spreading roller assembly 602.1 to move along the longitudinal direction, so that the distance between the upper glue spreading roller assembly 602.1 and the fixed lower glue spreading roller assembly 602.2 can be accurately controlled, the distance can be determined according to the specific thickness of the prepreg, of course, the longitudinal movement of the upper glue spreading roller assembly 602.1 is completed before the impregnated glass cloth enters the glue spreading mechanism 6, when the impregnated glass cloth is positioned between two rows of glue spreading rollers, the distance between the upper glue spreading roller assembly 602.1 and the lower glue spreading roller assembly 602.2 cannot be adjusted, the glue spreading mechanism 6 not only can accurately control the thickness of the prepreg, but also can effectively eliminate the defects of bubbles, uneven glue solution and the like generated on the surface of the impregnated glass cloth;
control parameters of the prepreg:
| baking temperature | Impregnation speed | Resin content | Testing the gel forming time | Degree of fluidity | Volatile matter |
| 170～200℃ | 10～20m/min | 35～50％ | 80～100s | 21±3％ | ≤0.7％ |
The main defects possibly appearing in the appearance checked in the step five are respectively as follows: colloidal particles, pinholes, fish eyes, etc.;
the preparation method of the mixed resin comprises the following steps:
weighing bismaleimide resin and brominated epoxy resin, and taking a certain amount of methyl phenylacetate;
secondly, mixing bismaleimide resin and brominated epoxy resin to obtain a resin mixture;
thirdly, putting the resin mixture and methyl phenylacetate into a container, heating to 110-180 ℃, reacting for 10-150 min, and cooling to room temperature;
and fourthly, grinding the cooled mixed resin into powder.
The mixed resin comprises the following raw materials in parts by weight:
40-50 parts of brominated epoxy resin
40-50 parts of bismaleimide resin
65-87 parts of methyl phenylacetate
The preparation method of the rubber compounding agent comprises the following steps:
firstly, mixing trimethyl methanol, ethylimine, water glass and nitrile rubber;
secondly, adding hydrochloric acid into water glass, reacting to generate precipitate, and drying;
the mass ratio of the water glass to the nitrile rubber is 1: 10;
the mass ratio of the water glass to the trimethyl methanol is 100: 1;
the mass ratio of the water glass to the ethylimine is 100: 1;
example 1
1. The adhesive formula comprises:
2. control parameters of the prepreg:
| baking temperature | Impregnation speed | Resin content | Testing the gel forming time | Degree of fluidity | Volatile matter |
| 170℃ | 16m/min | 41％ | 100s | 21％ | 0.3％ |
The preparation method of the mixed resin comprises the following steps:
weighing bismaleimide resin and brominated epoxy resin, and taking a certain amount of methyl phenylacetate;
secondly, mixing bismaleimide resin and brominated epoxy resin to obtain a resin mixture;
thirdly, putting the resin mixture and methyl phenylacetate into a container, heating to 110-180 ℃, reacting for 10-150 min, and cooling to room temperature;
and fourthly, grinding the cooled mixed resin into powder.
The mixed resin comprises the following raw materials in parts by weight:
brominated epoxy resin 50
Bismaleimide resin 50
Phenylacetic acid methyl ester 80
The preparation method of the rubber compounding agent comprises the following steps:
firstly, mixing trimethyl methanol, ethylimine, water glass and nitrile rubber;
secondly, adding hydrochloric acid into water glass, reacting to generate precipitate, and drying;
the mass ratio of the water glass to the nitrile rubber is 1: 10;
the mass ratio of the water glass to the trimethyl methanol is 100: 2;
the mass ratio of the water glass to the ethylimine is 100: 2;
when the glass cloth is impregnated, a vacuum auxiliary gluing method is adopted;
example 2
1. The adhesive formula comprises:
2. control parameters of the prepreg:
| baking temperature | Impregnation speed | Resin content | Testing the gel forming time | Degree of fluidity | Volatile matter |
| 180℃ | 18m/min | 46％ | 97s | 23％ | 0.35％ |
The preparation method of the mixed resin comprises the following steps:
weighing bismaleimide resin and brominated epoxy resin, and taking a certain amount of methyl phenylacetate;
secondly, mixing bismaleimide resin and brominated epoxy resin to obtain a resin mixture;
thirdly, putting the resin mixture and methyl phenylacetate into a container, heating to 110-180 ℃, reacting for 10-150 min, and cooling to room temperature;
and fourthly, grinding the cooled mixed resin into powder.
The mixed resin comprises the following raw materials in parts by weight:
brominated epoxy resin 43
Bismaleimide resin 45
Phenylacetic acid methyl ester 77
The preparation method of the rubber compounding agent comprises the following steps:
firstly, mixing trimethyl methanol, ethylimine, water glass and nitrile rubber;
secondly, adding hydrochloric acid into water glass, reacting to generate precipitate, and drying;
the mass ratio of the water glass to the nitrile rubber is 1: 5;
the mass ratio of the water glass to the trimethyl methanol is 99: 1;
the mass ratio of the water glass to the ethylimine is 100: 1;
when the glass cloth is impregnated, a vacuum auxiliary gluing method is adopted;
example 3
1. The adhesive formula comprises:
2. control parameters of the prepreg:
| baking temperature | Impregnation speed | Resin content | Testing the gel forming time | Degree of fluidity | Volatile matter |
| 200℃ | 20m/min | 50％ | 95s | 24％ | 0.37％ |
The preparation method of the mixed resin comprises the following steps:
weighing bismaleimide resin and brominated epoxy resin, and taking a certain amount of methyl phenylacetate;
secondly, mixing bismaleimide resin and brominated epoxy resin to obtain a resin mixture;
thirdly, putting the resin mixture and methyl phenylacetate into a container, heating to 110-180 ℃, reacting for 10-150 min, and cooling to room temperature;
and fourthly, grinding the cooled mixed resin into powder.
The mixed resin comprises the following raw materials in parts by weight:
brominated epoxy resin 50
Bismaleimide resin 45
Phenylacetic acid methyl ester 85
The preparation method of the rubber compounding agent comprises the following steps:
firstly, mixing trimethyl methanol, ethylimine, water glass and nitrile rubber;
secondly, adding hydrochloric acid into water glass, reacting to generate precipitate, and drying;
the mass ratio of the water glass to the nitrile rubber is 1: 10;
the mass ratio of the water glass to the trimethyl methanol is 50: 1;
the mass ratio of the water glass to the ethylimine is 100: 3;
when the glass cloth is impregnated, a vacuum auxiliary gluing method is adopted;
comparative example 1
With reference to example 1 above, using an existing adhesive formulation, this conventional adhesive formulation is as follows:
control parameters of the prepreg:
| baking temperature | Impregnation speed | Resin content | Testing the gel forming time | Degree of fluidity | Volatile matter |
| 170℃ | 16m/min | 41％ | 100s | 21％ | 0.3％ |
When the glass cloth is impregnated, the glass cloth is glued in a conventional mode, namely the glass cloth is in a standard atmospheric pressure environment immediately after being glued, and the subsequent drying is also carried out in the standard atmospheric pressure environment;
comparative example 2
With reference to example 2 above, using an existing adhesive formulation, this conventional adhesive formulation is as follows:
control parameters of the prepreg:
| baking temperature | Impregnation speed | Resin content | Testing the gel forming time | Degree of fluidity | Volatile matter |
| 180℃ | 18m/min | 46％ | 97s | 23％ | 0.35％ |
When the glass cloth is impregnated, the glass cloth is glued in a conventional mode, namely the glass cloth is in a standard atmospheric pressure environment immediately after being glued, and the subsequent drying is also carried out in the standard atmospheric pressure environment;
comparative example 3
With reference to example 3 above, using an existing adhesive formulation, this conventional adhesive formulation is as follows:
control parameters of the prepreg:
| baking temperature | Impregnation speed | Resin content | Testing the gel forming time | Degree of fluidity | Volatile matter |
| 200℃ | 20m/min | 50％ | 95s | 24％ | 0.37％ |
When the glass cloth is impregnated, the glass cloth is glued in a conventional mode, namely the glass cloth is in a standard atmospheric pressure environment immediately after being glued, and the subsequent drying is also carried out in the standard atmospheric pressure environment;
the adhesive viscosity, maximum temperature and surface gel content of the prepregs (7628) prepared in examples 1-3 and comparative examples 1-3 were compared as follows (note: the glass cloth used in all items was perfect):
from the above table, it can be seen that, under the condition that the control parameters of the prepregs are the same, the viscosity, the maximum bearing temperature and the surface gel content of the adhesive are compared with those of the comparative examples 1 to 3 in the embodiments 1 to 3, and finally, the conclusion is that the schemes of the embodiments 1 to 3 are superior to those of the comparative examples 1 to 3.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. A production method of epoxy glass cloth prepreg for a superconducting magnet coil skeleton comprises the following steps:
step one, glue mixing;
step two, testing to form gel;
step three, impregnation;
step four, drying;
step five, checking the appearance;
step six, testing characteristics;
step seven, coiling/cutting;
step eight, packaging;
the method is characterized in that:
the adhesive in the second step comprises the following components in parts by weight:
in the third step, when impregnation is carried out, a vacuum auxiliary gluing method is utilized;
the vacuum-assisted sizing method is realized by the following steps: the vacuum auxiliary gluing system (1) is characterized in that a discharge hole (2) is formed in the left side of the vacuum auxiliary gluing system (1), a feed hole (3) is formed in the right side of the vacuum auxiliary gluing system (1), an impregnation mechanism (4) and a baking device (5) are sequentially arranged inside the vacuum auxiliary gluing system (1) from right to left, a glue flattening mechanism (6) is arranged between the impregnation mechanism (4) and the baking device (5), and a plurality of glass cloth conveying rollers (7) are arranged inside the impregnation mechanism (4);
the interior of the vacuum auxiliary gluing system (1) is in a vacuum environment;
the impregnation mechanism (4) is communicated with the outside and is not positioned in a vacuum system;
the glue leveling mechanism (6) comprises a frame (601), guide posts (601.1) are respectively arranged at four corners of the top of the frame (601), the guide posts (601.1) are vertically arranged downwards, an oil cylinder (601.2) is arranged at the center of the top of the frame (601), the oil cylinder (601.2) is vertically arranged downwards, the maximum stroke of the oil cylinder (601.2) is equal to the maximum length of the guide posts (601.1), a glue leveling component (602) is arranged below the oil cylinder (601.2) and the guide posts (601.1), the glue leveling component (602) comprises an upper glue leveling roller component (602.1) and a lower glue leveling roller component (602.2), guide post connecting seats (602.11) are arranged at the four corners of the top of the upper glue leveling roller component (602.1) corresponding to the guide posts (601.1), and oil cylinder connecting seats (602.12) are arranged at the center of the top of the upper glue leveling roller component (602.1) corresponding to the oil cylinder (601.2), the piston rod end of the guide column (601.1) is connected to a guide column connecting seat (602.11), the piston rod end of the oil cylinder (601.2) is connected to an oil cylinder connecting seat (602.12), the lower glue flattening roller assembly (602.2) is connected to the frame (601), the upper glue flattening roller assembly (602.1) comprises an upper roller mounting frame (602.13), a row of upper glue flattening rollers (602.14) are horizontally mounted on the upper roller mounting frame (602.13), the lower glue flattening roller assembly (602.2) comprises a lower roller mounting frame (602.21), a row of lower glue flattening rollers (602.22) are horizontally mounted on the lower roller mounting frame (602.21), and the upper glue flattening rollers (602.14) correspond to the lower glue flattening rollers (602.22) one by one;
the preparation method of the mixed resin comprises the following steps:
weighing bismaleimide resin and brominated epoxy resin, and taking a certain amount of methyl phenylacetate;
secondly, mixing bismaleimide resin and brominated epoxy resin to obtain a resin mixture;
thirdly, putting the resin mixture and methyl phenylacetate into a container, heating to 110-180 ℃, reacting for 10-150 min, and cooling to room temperature;
fourthly, grinding the cooled mixed resin into powder;
the preparation method of the rubber compounding agent comprises the following steps:
firstly, mixing trimethyl methanol, ethylimine, water glass and nitrile rubber;
secondly, adding hydrochloric acid into water glass, reacting and generating precipitate, and then drying.
2. The method for producing the epoxy glass cloth prepreg for the superconducting magnet coil former according to claim 1, wherein the epoxy glass cloth prepreg comprises: the control parameters of the prepreg are as follows:
baking temperature: 170-200 DEG C
Impregnation speed: 10 to 20m/min
Resin content: 35 to 50 percent
Testing the gelling time: 80-100 s
Fluidity: 21 +/-3%
Volatile components: less than or equal to 0.7 percent.
3. The method for producing the epoxy glass cloth prepreg for the superconducting magnet coil former according to claim 1, wherein the epoxy glass cloth prepreg comprises: the feeding sequence of the test gelling in the second step is as follows: dimethylformamide, dicyandiamide, dimethyl imidazole, mixed resin and a rubber complexing agent; the process of testing the gelling is as follows: the preparation method comprises the steps of stirring, mixing and dissolving dimethyl formamide, dicyandiamide and dimethyl imidazole in a mixing kettle, adding mixed resin, stirring uniformly, adding a rubber complexing agent, and stirring for 2.5-3 hours.
4. The method for producing the epoxy glass cloth prepreg for the superconducting magnet coil former according to claim 1, wherein the epoxy glass cloth prepreg comprises: in the third step, 7628 of glass cloth is dipped into the adhesive.
5. The method for producing the epoxy glass cloth prepreg for the superconducting magnet coil former according to claim 1, wherein the epoxy glass cloth prepreg comprises: the mixed resin comprises the following raw materials in parts by weight:
40-50 parts of brominated epoxy resin
40-50 parts of bismaleimide resin
65-87 parts of methyl phenylacetate.
6. The method for producing the epoxy glass cloth prepreg for the superconducting magnet coil former according to claim 1, wherein the epoxy glass cloth prepreg comprises:
the adhesive comprises the following components in parts by weight:
control parameters of the prepreg:
baking temperature: 170 ℃;
impregnation speed: 16 m/min;
resin content: 41 percent;
testing the gelling time: 100 s;
fluidity: 21 percent;
volatile components: 0.3 percent;
the mixed resin comprises the following raw materials in parts by weight:
brominated epoxy resin 50
Bismaleimide resin 50
Phenylacetic acid methyl ester 80
The rubber compounding agent comprises the following components in parts by weight:
the mass ratio of the water glass to the nitrile rubber is 1: 10;
the mass ratio of the water glass to the trimethyl methanol is 100: 2;
the mass ratio of the water glass to the ethylimine is 100: 2;
when the glass cloth is impregnated, a vacuum auxiliary gluing method is adopted.
7. The method for producing the epoxy glass cloth prepreg for the superconducting magnet coil former according to claim 1, wherein the epoxy glass cloth prepreg comprises:
the adhesive comprises the following components in parts by weight:
control parameters of the prepreg:
baking temperature: 180 ℃;
impregnation speed: 18 m/min;
resin content: 46 percent;
testing the gelling time: 97 s;
fluidity: 23 percent;
volatile components: 0.35 percent;
the mixed resin comprises the following raw materials in parts by weight:
brominated epoxy resin 43
Bismaleimide resin 45
Phenylacetic acid methyl ester 77
The rubber compounding agent comprises the following components in parts by weight:
the mass ratio of the water glass to the nitrile rubber is 1: 5;
the mass ratio of the water glass to the trimethyl methanol is 99: 1;
the mass ratio of the water glass to the ethylimine is 100: 1;
when the glass cloth is impregnated, a vacuum auxiliary gluing method is adopted.
8. The method for producing the epoxy glass cloth prepreg for the superconducting magnet coil former according to claim 1, wherein the epoxy glass cloth prepreg comprises:
the adhesive comprises the following components in parts by weight:
control parameters of the prepreg:
baking temperature: 200 ℃;
impregnation speed: 20 m/min;
resin content: 50 percent;
testing the gelling time: 95 s;
fluidity: 24 percent;
volatile components: 0.37 percent;
the mixed resin comprises the following raw materials in parts by weight:
brominated epoxy resin 50
Bismaleimide resin 45
Phenylacetic acid methyl ester 85
The rubber compounding agent comprises the following components in parts by weight:
the mass ratio of the water glass to the nitrile rubber is 1: 10;
the mass ratio of the water glass to the trimethyl methanol is 50: 1;
the mass ratio of the water glass to the ethylimine is 100: 3;
when the glass cloth is impregnated, a vacuum auxiliary gluing method is adopted.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102514304A (en) * | 2011-11-14 | 2012-06-27 | 上海南亚覆铜箔板有限公司 | Common Tg lead-free copper clad laminate and preparation method thereof |
| CN104263306A (en) * | 2014-09-26 | 2015-01-07 | 四川东材科技集团股份有限公司 | Preparation method of polyphenyl ether adhesive and copper-clad plate thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102514304A (en) * | 2011-11-14 | 2012-06-27 | 上海南亚覆铜箔板有限公司 | Common Tg lead-free copper clad laminate and preparation method thereof |
| CN104263306A (en) * | 2014-09-26 | 2015-01-07 | 四川东材科技集团股份有限公司 | Preparation method of polyphenyl ether adhesive and copper-clad plate thereof |
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