CN114249966A - UV (ultraviolet) light-cured epoxy prepreg and production process thereof - Google Patents
UV (ultraviolet) light-cured epoxy prepreg and production process thereof Download PDFInfo
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- CN114249966A CN114249966A CN202210189343.1A CN202210189343A CN114249966A CN 114249966 A CN114249966 A CN 114249966A CN 202210189343 A CN202210189343 A CN 202210189343A CN 114249966 A CN114249966 A CN 114249966A
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- 239000004593 Epoxy Substances 0.000 title claims abstract description 85
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 239000003822 epoxy resin Substances 0.000 claims description 126
- 229920000647 polyepoxide Polymers 0.000 claims description 126
- 239000000203 mixture Substances 0.000 claims description 85
- 239000003365 glass fiber Substances 0.000 claims description 56
- 239000004744 fabric Substances 0.000 claims description 29
- 239000002562 thickening agent Substances 0.000 claims description 29
- 239000003085 diluting agent Substances 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 25
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 22
- 238000001723 curing Methods 0.000 claims description 21
- 239000012952 cationic photoinitiator Substances 0.000 claims description 19
- 239000000835 fiber Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 238000001125 extrusion Methods 0.000 claims description 9
- 239000002759 woven fabric Substances 0.000 claims description 8
- DJUWPHRCMMMSCV-UHFFFAOYSA-N bis(7-oxabicyclo[4.1.0]heptan-4-ylmethyl) hexanedioate Chemical compound C1CC2OC2CC1COC(=O)CCCCC(=O)OCC1CC2OC2CC1 DJUWPHRCMMMSCV-UHFFFAOYSA-N 0.000 claims description 7
- 125000002091 cationic group Chemical group 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- 238000003848 UV Light-Curing Methods 0.000 claims description 6
- 125000003700 epoxy group Chemical group 0.000 claims description 6
- 230000008719 thickening Effects 0.000 claims description 6
- ORTMHVMCRHIAHL-UHFFFAOYSA-N 4-methyl-5-(7-oxabicyclo[4.1.0]heptan-4-yl)-7-oxabicyclo[4.1.0]heptane-4-carboxylic acid Chemical compound C1CC2OC2CC1C1C2OC2CCC1(C)C(O)=O ORTMHVMCRHIAHL-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 5
- 238000004806 packaging method and process Methods 0.000 claims description 5
- 238000005096 rolling process Methods 0.000 claims description 5
- 235000012424 soybean oil Nutrition 0.000 claims description 5
- 239000003549 soybean oil Substances 0.000 claims description 5
- 229920000768 polyamine Polymers 0.000 claims description 4
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 3
- 125000005520 diaryliodonium group Chemical group 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims description 3
- 125000005409 triarylsulfonium group Chemical group 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000012779 reinforcing material Substances 0.000 claims 1
- 230000008439 repair process Effects 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 description 34
- 239000011347 resin Substances 0.000 description 34
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 30
- 229910052742 iron Inorganic materials 0.000 description 15
- 239000003292 glue Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 11
- -1 hexafluoroantimonate Chemical compound 0.000 description 8
- 238000000016 photochemical curing Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 230000001678 irradiating effect Effects 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- FODCFYIWOJIZQL-UHFFFAOYSA-N 1-methylsulfanyl-3,5-bis(trifluoromethyl)benzene Chemical compound CSC1=CC(C(F)(F)F)=CC(C(F)(F)F)=C1 FODCFYIWOJIZQL-UHFFFAOYSA-N 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- LTYMSROWYAPPGB-UHFFFAOYSA-O diphenylsulfanium Chemical compound C=1C=CC=CC=1[SH+]C1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-O 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 201000003373 familial cold autoinflammatory syndrome 3 Diseases 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 238000011417 postcuring Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012949 free radical photoinitiator Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Images
Classifications
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/21—Paper; Textile fabrics
-
- 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
- C09J11/06—Non-macromolecular additives organic
-
- 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
- C09J11/08—Macromolecular additives
-
- 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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
-
- 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
- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/20—Presence of organic materials
- C09J2400/26—Presence of textile or fabric
- C09J2400/263—Presence of textile or fabric in the substrate
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention belongs to the technical field of epoxy prepreg, and particularly relates to a UV (ultraviolet) light-cured epoxy prepreg and a production process thereof. The prepreg can be completely cured after being irradiated by ultraviolet rays for 20min, has high mechanical strength and high peel strength after being cured, and is suitable for the fields of interior wall repair, pipeline repair and the like with high environmental protection requirements.
Description
Technical Field
The invention relates to the field of application of fiber-reinforced light-cured resin composite materials, in particular to a UV light-cured epoxy prepreg and a production process thereof.
Background
Along with the rapid development of the country, various infrastructures are increasingly perfected, and as time goes on, the infrastructures are blown by wind, rain and impact damage for a long time, so that the problems of corrosion, fracture, collapse and the like are caused.
At present, most of photocuring prepregs in the market adopt unsaturated polyester resin and vinyl resin as resin matrixes for presoaking, but the problems of VOC (volatile organic compounds) emission, low mechanical strength, poor corrosion resistance and the like do not meet the specific use requirements of certain scenes, and the prepregs are influenced by oxygen inhibition during curing, have no post-curing phenomenon, and are easy to cause incomplete surface curing and material performance reduction. The epoxy resin matrix has the advantages of high photocuring mechanical strength, excellent corrosion resistance, no oxygen influence, capability of continuously initiating polymerization crosslinking after illumination is stopped, post curing, curing thickness of more than 10mm and the like, and can meet the requirement that the traditional photocuring prepreg cannot meet under specific conditions.
Epoxy prepreg is generally manufactured by adopting a wet method and a dry method, the wet method is usually added with a large amount of solvent to ensure that the resin has low enough viscosity and can fully soak fibers in order to well meet the prepreg requirements at room temperature, the solvent is removed by drying to achieve a tearable film state, so that atmospheric pollution is caused, the dry method prepreg is subjected to two-step prepreg through hot melting, the production and manufacturing cost is high, and the production period is long. Therefore, the development of a wet-process prepreg light-cured epoxy prepreg which is free of solvent, low in initial viscosity and capable of self-thickening is a problem to be solved at present.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the UV light-cured epoxy prepreg and the production process thereof, so that the light-cured epoxy prepreg which has high strength, high corrosion resistance and no pollution and can be thickened automatically is obtained, and can be used in the fields of pipeline repair, storage tank lining repair, pile protection and the like.
One object of the present invention is to provide a UV light-cured epoxy prepreg, which includes 50 to 65% by weight of a fiber reinforcement material and 35 to 50% by weight of a thickenable UV light-cured epoxy resin composition, wherein the thickenable UV light-cured epoxy resin composition includes an epoxy resin composition and an epoxy thickener containing amino active hydrogen, and a molar ratio of epoxy groups in the epoxy resin composition to amino active hydrogen in the epoxy thickener is 100: 12-100: 40.
the fiber reinforced material is continuous glass fiber checkered cloth, continuous glass fiber felt, non-woven glass fiber felt andat least one of the glass fiber woven cloth and the mixed fabric. The preferred density of the cloth cover of the continuous glass fiber square lattice is 400-600 g/m2(ii) a The surface density of the continuous glass fiber felt is 100-400 g/m2(ii) a The surface density of the mixed fabric of the non-woven glass fiber felt and the glass fiber woven cloth is 400-800 g/m2The fiber length of the non-woven glass fiber felt is 15-50 mm, and the weight ratio of the non-woven glass fiber felt to the glass fiber woven fabric is 1-4: 6-9.
The epoxy resin composition consists of 58-70 wt% of epoxy resin, 29-40 wt% of cationic active diluent and 1-2 wt% of cationic photoinitiator.
The cationic photoinitiator is selected from cationic photoinitiators with high reactivity to ultraviolet wavelength of 250-400 nm, preferably diaryl iodonium salt and triaryl sulfonium salt. The cationic photoinitiator is selected from at least one of PAG101 (bis (4-tert-butylphenyl) iodonium hexafluorophosphate), 6976 (bis (4- (diphenylsulfonium) phenyl) sulfide-bis hexafluoroantimonate), UV6992 (diphenyl- (4-phenylthio) phenylsulfonium hexafluorophosphate), and PAG-002 (diphenyl- (4-phenylsulfide) phenylsulfonium hexafluoroantimonate).
The cation reactive diluent is at least one of 3, 4-epoxy cyclohexyl methyl-3, 4-epoxy cyclohexyl formic acid reactive diluent, bis ((3, 4-epoxy cyclohexyl) methyl) adipate reactive diluent and epoxy soybean oil acrylate reactive diluent.
The epoxy resin is bisphenol A epoxy resin or bisphenol F epoxy resin.
The initial viscosity of the epoxy resin composition is 3000-.
The epoxy thickener containing an amino active hydrogen is at least one of a monoamine or a polyamine containing one or more primary amino groups or secondary amino groups, and may be at least one of an aliphatic amine, an alicyclic amine, an aromatic amine, a polyether amine, and a polyamide, and is more preferably isophorone diamine, polyether amine D230, and the like.
The invention also aims to provide a production process of the UV light cured epoxy prepreg, which comprises the following steps:
a. weighing 58-70% of epoxy resin, 29-40% of cationic active diluent and 1-2% of cationic photoinitiator by weight percent, stirring and fully and uniformly mixing under the condition of keeping out of the sun, wherein the stirring speed is 300-800 rpm, obtaining the epoxy resin composition with the initial viscosity of 3000-;
b. mixing the epoxy resin composition and an epoxy thickener containing amino active hydrogen according to a proportion, and stirring at a high speed, wherein the molar ratio of the epoxy group in the epoxy resin composition to the amino active hydrogen in the epoxy thickener is 100: 12-100: 40, uniformly mixing under the condition of keeping out of the sun to obtain a thickened UV light curing epoxy resin composition;
c. uniformly coating the thickened UV light-cured epoxy resin composition on black upper and lower carrier films to form an epoxy resin film with the thickness of 0.15-0.3 mm;
d. compounding a fiber reinforced material with the epoxy resin film, extruding, infiltrating and exhausting, wherein the extrusion pressure is 0.1-0.2MPa, so that the UV light-cured epoxy resin composition fully infiltrates the fiber reinforced material, and then closing the light, rolling and packaging;
e. curing the UV light-cured epoxy prepreg which is wound and packaged, and curing for 10-40 hrs at 30-55 ℃ to complete the process.
The viscosity of the light-cured epoxy resin composition at 25 ℃ is 2000-50000 Pa.s after curing treatment.
The invention has the beneficial effects that: the invention takes the epoxy resin as a matrix, has low initial viscosity, is prepared into the UV light-cured epoxy prepreg through wet prepreg, has low manufacturing cost, and adopts the polyamine compound containing amino groups as the epoxy thickening agent to modify and thicken the epoxy resin system, so that the viscosity of the prepreg resin is increased to reach a tearable film state. Epoxy resin and cationic photoinitiator are adopted, so that the phenomena of incomplete curing and the like caused by oxygen inhibition of the free radical photoinitiator are avoided.
The photocuring epoxy prepreg disclosed by the invention is easy to separate a carrier film, epoxy resin is not sticky to transfer, and the photocuring epoxy prepreg is suitable for prepreg paving operation. The prepreg can be completely cured by irradiating the prepreg for 15-20min through ultraviolet rays with the wavelength of 250-400 nm. The curing thickness of the plate can reach more than 10mm, the mechanical property of the cured product is good, the tensile strength reaches more than 350MPa, the tensile modulus reaches more than 15Gpa, the bending strength reaches more than 400MPa, the bending modulus reaches more than 20Gpa, and the interlaminar shear strength is more than 50 MPa. Has the characteristics of rapid curing, high bonding strength, large peel strength, high mechanical strength and the like.
The prepreg is suitable for the fields of interior wall repair, pipeline repair and the like with high environmental protection requirements.
Drawings
Fig. 1 is a schematic structural diagram of a sheet iron funnel with a ball valve.
In the figure: 1. the funnel body, 2, ball valve, 3, iron sheet lid.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the present invention will be described in further detail with reference to embodiments, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, 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.
One object of the present invention is to provide a UV light-cured epoxy prepreg, which includes 50 to 65% by weight of a fiber reinforcement material and 35 to 50% by weight of a thickenable UV light-cured epoxy resin composition, wherein the thickenable UV light-cured epoxy resin composition includes an epoxy resin composition and an epoxy thickener containing amino active hydrogen, and a molar ratio of epoxy groups in the epoxy resin composition to amino active hydrogen in the epoxy thickener is 100: 12-100: 40.
the fiber reinforced material is at least one of continuous glass fiber check cloth, continuous glass fiber felt, non-woven glass fiber felt and glass fiber woven cloth mixed fabric. The preferred density of the cloth cover of the continuous glass fiber square lattice is 400-600 g/m2(ii) a The surface density of the continuous glass fiber felt is 100-400 g/m2(ii) a The surface density of the mixed fabric of the non-woven glass fiber felt and the glass fiber woven cloth is 400-800 g/m2The fiber length of the non-woven glass fiber felt is 15-50 mm, and the weight ratio of the non-woven glass fiber felt to the glass fiber woven fabric is 1-4: 6-9.
The epoxy resin composition consists of 58-70 wt% of epoxy resin, 29-40 wt% of cationic active diluent and 1-2 wt% of cationic photoinitiator.
The cationic photoinitiator is selected from cationic photoinitiators with high reactivity to ultraviolet wavelength of 250-400 nm, preferably diaryl iodonium salt and triaryl sulfonium salt. The cationic photoinitiator is selected from at least one of PAG101 (bis (4-tert-butylphenyl) iodonium hexafluorophosphate), 6976 (bis (4- (diphenylsulfonium) phenyl) sulfide-bis hexafluoroantimonate), UV6992 (diphenyl- (4-phenylthio) phenylsulfonium hexafluorophosphate), and PAG-002 (diphenyl- (4-phenylsulfide) phenylsulfonium hexafluoroantimonate).
The cation reactive diluent is at least one of 3, 4-epoxy cyclohexyl methyl-3, 4-epoxy cyclohexyl formic acid reactive diluent, bis ((3, 4-epoxy cyclohexyl) methyl) adipate reactive diluent and epoxy soybean oil acrylate reactive diluent.
The epoxy resin is bisphenol A epoxy resin or bisphenol F epoxy resin.
The initial viscosity of the epoxy resin composition is 3000-.
The epoxy thickener containing an amino active hydrogen is at least one of a monoamine or a polyamine containing one or more primary amino groups or secondary amino groups, and may be at least one of an aliphatic amine, an alicyclic amine, an aromatic amine, a polyether amine, and a polyamide, and is more preferably isophorone diamine, polyether amine D230, and the like.
The invention also aims to provide a production process of the UV light cured epoxy prepreg, which comprises the following steps:
a. weighing 58-70% of epoxy resin, 29-40% of cationic active diluent and 1-2% of cationic photoinitiator according to weight percentage, adding the weighed materials into a resin mixer, stirring the materials fully and uniformly, wherein the stirring speed is 300-800 rpm, carrying out light-resistant treatment on a resin reaction kettle, and storing the obtained product in a resin storage tank after complete reaction to obtain an epoxy resin composition with the initial viscosity of 3000-;
b. pumping the epoxy resin composition and the epoxy thickener containing amino active hydrogen into a series mixer in proportion through a resin feed pump and a thickener feed pump, and stirring at a high speed, wherein the molar ratio of the epoxy group in the epoxy resin composition to the amino active hydrogen in the epoxy thickener is 100: 12-100: 40, uniformly mixing to obtain a thickened UV (ultraviolet) light-cured epoxy resin composition, then draining the thickened UV light-cured epoxy resin composition into a resin sheet iron funnel through a glue guide groove subjected to shading treatment, and controlling the resin content in the glue groove through a funnel ball valve; an iron sheet cover with the same size as the glue groove is arranged below the funnel ball valve and covers the glue groove to achieve the light-shielding effect, and an ultraviolet-light-proof film is paved on the glue guide groove;
c. uniformly coating the thickened UV light-cured epoxy resin composition led out from the iron sheet funnel on a black bearing film by a resin glue groove scraper to form an epoxy resin film with the thickness of 0.15-0.3 mm;
d. compounding a fiber reinforced material with the epoxy resin film, extruding and soaking and exhausting through a compaction area, wherein the extrusion pressure is 0.1-0.2MPa, so that the fiber reinforced material is fully soaked by the UV light-cured epoxy resin composition, and then, closing the light, rolling and packaging;
e. curing the UV light-cured epoxy prepreg in a drying room at the temperature of 30-55 ℃ for 10-40 hrs to complete the process.
The viscosity of the light-cured epoxy resin composition at 25 ℃ is 2000-50000 Pa.s after curing treatment.
The UV light-cured epoxy prepreg is easy to separate a carrier film, epoxy resin is not sticky to transfer by hands, and the method is suitable for prepreg paving operation.
Example 1:
the UV light-cured epoxy prepreg of the present example comprises 60 wt% of continuous glass fiber scrim (areal density of 400 g/m)2) 40% by weight of a thickening UV light-curable epoxy resin composition.
The thickened UV light-cured epoxy resin composition comprises an epoxy resin composition and an epoxy thickener containing amino active hydrogen, wherein the weight ratio of the epoxy resin composition to the epoxy thickener is 100:5.4, the epoxy thickener is isophorone diamine; the epoxy resin composition comprises 70 parts of bisphenol A epoxy resin, 2 parts of cationic photoinitiator UV6992 diphenyl- (4-phenyl sulfur) phenyl sulfonium hexafluorophosphate and 30 parts of 3, 4-epoxy cyclohexyl methyl-3, 4-epoxy cyclohexyl formic acid reactive diluent.
The production process of the UV light curing epoxy prepreg comprises the following steps:
a. adding 70 parts of bisphenol A epoxy resin, 30 parts of 3, 4-epoxy cyclohexyl methyl-3, 4-epoxy cyclohexyl formic acid reactive diluent and 2 parts of UV6992 photoinitiator into a double-shaft resin mixer, stirring at room temperature at the stirring speed of 400rpm for 30min to obtain an epoxy resin composition, storing the epoxy resin composition in a resin storage tank, and testing the initial viscosity of the epoxy composition at 25 ℃ by adopting a Bohler fly DVS + rotational viscometer according to the standard GB/T22314-2008, wherein the initial viscosity is 5218 cps;
b. mixing the epoxy resin composition and isophorone diamine according to the weight ratio of 100:5.4 by a series mixer, and stirring at high speed at room temperature, wherein the stirring speed is 800rpm, and the stirring time is 5min, so as to obtain the UV (ultraviolet) photocuring epoxy resin composition capable of being thickened rapidly;
c. b, draining the uniformly mixed resin paste in the step b into a resin iron sheet funnel through a glue guiding groove subjected to shading treatment, and controlling the resin content in the glue groove through a funnel ball valve; the iron sheet funnel comprises a funnel body 1, a glue guide groove is formed in the funnel body 1, an ultraviolet ray-proof film is paved on the glue guide groove and used for guiding resin paste into the funnel body 1 from a mixer, and a ball valve 2 is installed below the funnel body 1 and used for controlling the flow of the resin paste; an iron sheet cover 3 sleeved below the funnel body 1 is arranged below the ball valve 2 to ensure that the resin paste is in a shading state after being drained to the next container. The structure is shown in fig. 1.
d. Uniformly coating the epoxy resin composition led out from the iron sheet funnel on the black upper bearing film and the black lower bearing film by using a scraper to form an epoxy resin film with the thickness of 0.25-0.30 mm;
e. the areal density is 400g/m2Placing the continuous glass fiber checkered cloth, laying the continuous glass fiber checkered cloth on the lower epoxy resin film, covering the upper epoxy resin film on the surface of the continuous glass fiber checkered cloth, extruding and exhausting, wherein the extrusion pressure is 0.2MPa, so that the epoxy resin paste fully infiltrates the glass fiber cloth to form a photocuring epoxy prepreg, and then rolling and packaging the prepreg by a roll of 50 m;
f. curing the wound and packaged light-cured epoxy prepreg in a drying room at 50 ℃ for 10hrs to thicken the epoxy resin, so as to obtain the epoxy prepreg with the easily-torn film.
Example 2:
the UV light-cured epoxy prepreg of the present example comprises 65 wt% of a continuous glass fiber mat (areal density of 200 g/m)2) 35 percent by weight of the thickening light-cured epoxy resin composition;
the thickened UV light-cured epoxy resin composition comprises an epoxy resin composition and an epoxy thickener containing amino active hydrogen, wherein the weight ratio of the epoxy resin composition to the epoxy thickener is 100:8, wherein the epoxy resin thickener is polyetheramine D230; the epoxy resin composition comprises 60 parts of bisphenol A epoxy resin, 40 parts of bis ((3, 4-epoxycyclohexyl) methyl) adipate reactive diluent and 2 parts of cationic photoinitiator PAG-002 diphenyl- (4-phenylthio) phenyl sulfonium hexafluoroantimonate.
The production process of the UV light curing epoxy prepreg comprises the following steps:
a. adding 60 parts of bisphenol A epoxy resin, 40 parts of bis ((3, 4-epoxycyclohexyl) methyl) adipate reactive diluent and 2 parts of PAG-002 photoinitiator into a double-shaft resin mixer, stirring at the room temperature of 400rpm for 40min to obtain a photocured epoxy resin composition, storing the photocured epoxy resin composition in a resin storage tank, and testing the initial viscosity of the epoxy resin composition at 25 ℃ by adopting a Bohler fly DVS + rotational viscometer according to the standard GB/T22314-2008, wherein the initial viscosity is 3218 cps;
b. mixing the light-cured epoxy resin composition and D230 according to the weight ratio of 100:8 by using a series mixer, stirring at a high speed of 800rpm for 5min at room temperature to obtain a UV light-cured epoxy resin composition capable of being thickened rapidly;
c. b, draining the uniformly mixed resin paste in the step b into a resin iron sheet funnel (shown in figure 1) through a glue guiding groove subjected to shading treatment, and controlling the resin content in the glue groove through a funnel ball valve;
d. uniformly coating the epoxy resin composition led out from the iron sheet funnel on the black upper bearing film and the black lower bearing film by using a scraper to form an epoxy resin film with the thickness of 0.17-0.25 mm;
e. the areal density is 200g/m2The continuous glass fiber felt is laid on the lower epoxy resin film in a discharging mode, then the upper epoxy resin film is covered on the surface of the continuous glass fiber felt, the glass fiber felt is fully soaked by the epoxy resin paste to form the light-cured epoxy prepreg through extrusion and exhaust, the extrusion pressure is 0.1MPa, and then the light-cured epoxy prepreg is rolled by a roll of 50m and packaged.
f. Curing the wound and packaged light-cured epoxy prepreg in a drying room at 45 ℃ for 15hrs to thicken the epoxy resin, so as to obtain the epoxy prepreg with the easily-torn film.
Example 3:
the UV light-cured epoxy prepreg of the embodiment comprises 50 wt% of a mixed fabric of a non-woven glass fiber felt and a glass fiber woven fabric (the areal density is 600 g/m)2) And 50% by weight of a thickening light-cured epoxy resin composition, wherein in the mixed fabric of the non-woven glass fiber felt and the glass fiber woven fabric, the mass ratio of the fiber fabric (namely the glass fiber woven fabric) to the fiber felt (namely the non-woven glass fiber felt) is 7: 3, the fiber length of the glass fiber felt is 15-50 mm.
The thickened UV light-cured epoxy resin composition comprises an epoxy resin composition and an epoxy thickener containing amino active hydrogen, wherein the weight ratio of the epoxy resin composition to the epoxy thickener is 100:8, wherein the epoxy resin thickener is polyetheramine D230; the epoxy resin composition comprises 70 parts of bisphenol A epoxy resin, 30 parts of bis ((3, 4-epoxycyclohexyl) methyl) adipate reactive diluent and 1.5 parts of cationic photoinitiator 6976 bis (4- (diphenyl sulfonium) phenyl) thioether-bis hexafluoroantimonate.
The production process of the UV light curing epoxy prepreg comprises the following steps:
a. adding 70 parts of bisphenol A epoxy resin, 30 parts of bis ((3, 4-epoxycyclohexyl) methyl) adipate reactive diluent and 1.5 parts of 6976 photoinitiator into a double-shaft resin mixer, stirring at room temperature at the stirring speed of 400rpm for 40min to obtain a photocured epoxy resin composition, storing the photocured epoxy resin composition in a resin storage tank, and testing the initial viscosity of the epoxy composition at 25 ℃ by using a Bohler fly DVS + rotational viscometer according to the standard GB/T22314-2008, wherein the initial viscosity is 5563 cps;
b. mixing the light-cured epoxy resin composition and D230 according to the weight ratio of 100:8 by using a series mixer, and stirring at high speed at room temperature, wherein the stirring speed is 800rpm, and the stirring time is 4min, so as to obtain the UV light-cured epoxy resin composition capable of being thickened rapidly;
c. b, draining the uniformly mixed resin paste in the step b into a resin iron sheet funnel (shown in figure 1) through a glue guiding groove subjected to shading treatment, and controlling the resin content in the glue groove through a funnel ball valve;
d. uniformly coating the epoxy resin composition led out from the iron sheet funnel on the black upper bearing film and the black lower bearing film by using a scraper to form an epoxy resin film with the thickness of 0.4-0.5 mm;
e. the surface density is 600g/m2Placing the non-woven glass fiber felt and glass fiber woven fabric mixed fabric on the lower epoxy resin film, covering the upper epoxy resin film on the surface of the non-woven glass fiber felt and glass fiber woven fabric mixed fabric, extruding and exhausting at the extrusion pressure of 0.2MPa to enable the epoxy resin paste to fully infiltrate the mixed fabric to form the light-cured epoxy prepreg, rolling by a roll of 50m, and packaging.
f. Curing the wound and packaged light-cured epoxy prepreg in a drying room at 45 ℃ for 15hrs to thicken the epoxy resin, so as to obtain the epoxy prepreg with the easily-torn film.
Example 4:
the UV light-cured epoxy prepreg of the present example comprises 55 wt% of continuous glass fiber scrim (areal density of 600 g/m)2) 45 percent by weight of the thickening light-cured epoxy resin composition;
the thickened UV light-cured epoxy resin composition comprises an epoxy resin composition and an epoxy thickener containing amino active hydrogen, wherein the weight ratio of the epoxy resin composition to the epoxy thickener is 100: and 8, wherein the epoxy resin thickener is polyetheramine D230, and the epoxy resin composition comprises 70 parts of bisphenol A epoxy resin, 30 parts of epoxidized soybean oil acrylate reactive diluent and 1.5 parts of cationic photoinitiator selected from PAG101 bis (4-tert-butylphenyl) iodonium hexafluorophosphate.
The production process of the UV light curing epoxy prepreg comprises the following steps:
a. adding 70 parts of bisphenol A epoxy resin, 30 parts of epoxidized soybean oil acrylate reactive diluent and 1.5 parts of PAG101 photoinitiator into a double-shaft resin mixer, stirring at room temperature with the stirring speed of 400rpm for 50min to obtain a photocured epoxy resin composition, storing the photocured epoxy resin composition in a resin storage tank, and testing the initial viscosity of the epoxy composition at 25 ℃ by adopting a Bohlei DVS + rotational viscometer according to the standard GB/T22314-2008, wherein the initial viscosity is 4189 cps;
b. mixing the light-cured epoxy resin composition and D230 according to the weight ratio of 100:8 by using a series mixer, and stirring at high speed at room temperature, wherein the stirring speed is 800rpm, and the stirring time is 5min, so as to obtain the UV light-cured epoxy resin composition capable of being thickened rapidly;
c. b, draining the uniformly mixed resin paste in the step b into a resin iron sheet funnel (shown in figure 1) in a shading state, and simultaneously controlling the resin content in the rubber groove through a funnel ball valve;
d. uniformly coating the epoxy resin composition led out from the iron sheet funnel on the black upper bearing film and the black lower bearing film by using a scraper to form an epoxy resin film with the thickness of 0.4-0.5 mm;
e. the surface density is 600g/m2The continuous glass fiber plaid is discharged and laid on the lower epoxy resin film, then the upper epoxy resin film is covered on the surface of the continuous glass fiber plaid, the epoxy resin paste is fully soaked in the glass cloth to form the light-cured epoxy prepreg through extrusion and exhaust, the extrusion pressure is 0.2MPa, and then the light-cured epoxy prepreg is rolled by a roll of 50m and packaged.
f. Curing the wound and packaged light-cured epoxy prepreg in a drying room at 45 ℃ for 15hrs to thicken the epoxy resin, so as to obtain the epoxy prepreg with the easily-torn film.
The UV light cured epoxy prepregs of examples 1-4 were cured and molded for mechanical property testing, and the curing and molding included the following procedures:
1. cutting the cured prepreg into pieces with the same size according to the requirement, wherein the size of each piece is 25 mm/25 mm; wherein the number of the cut sheets of the examples 1 to 4 is 6, 12, 4 and 4, respectively;
2. sequentially paving and pasting the prepregs with the same size according to the number of the cutting blocks, and exhausting and flattening by adopting a scraper when paving and pasting are carried out each time;
3. irradiating the prepreg of each embodiment by using a UV lamp to obtain a prepreg curing sheet; wherein, the irradiation conditions of example 1 were: irradiating with 500W 320nm UV lamp for 20 min; the irradiation conditions for example 2 were: a340 nm UV lamp at 500W was used for 20min, and the irradiation conditions in example 3 were as follows: a320 nm UV lamp at 500W was used for 20min, and the irradiation conditions in example 4 were as follows: irradiating for 15min by a 280nmUV lamp at 500W;
4. cutting into tensile and bending test strips according to the test standard requirements, and performing mechanical test.
The method and standard of the mechanical test are as follows: testing the mechanical property of a composite material product prepared from the photocured prepreg by adopting a determination method of an electronic universal tensile testing machine based on GB/T1446-; the bending property is tested based on the GB/T1449-; the interlaminar shear strength is tested based on the GB/T3355-2014 standard. The data obtained are shown in Table 1.
Tensile strength of the photo-cured epoxy prepreg bonding adherends of examples 1 to 4 was tested, comprising the following procedures:
1. preparing 2 aluminum alloy plates with the length of 100mm, the width of 25mm and the thickness of 2.5mm, and mechanically polishing the aluminum alloy plates by using No. 150 abrasive paper, wherein the polishing area is 12.5mm at the head end for later use;
2. cutting the cured prepreg of examples 1-4 into prepreg sheets of 25mm by 25mm, and performing air exhaust flattening by using a scraper during paving; the number of cuts is: 6 blocks, 12 blocks, 4 blocks and 4 blocks;
3. splicing the polished head ends of the 2 aluminum alloy plates, and bonding the prepreg sheets laid in the embodiments 1-4 at the spliced positions to obtain precured repairing sheets;
4. the above-described each patch was irradiated with a UV lamp to obtain a sample, wherein the irradiation conditions of example 1 were: irradiating with 500W 320nm UV lamp for 20 min; the irradiation conditions for example 2 were: a340 nm UV lamp at 500W was used for 20min, and the irradiation conditions in example 3 were as follows: a320 nm UV lamp at 500W was used for 20min, and the irradiation conditions in example 4 were as follows: irradiating for 15min by a 280nmUV lamp at 500 w;
5. the shear strength was tested according to GB/T3355-2014 standard and the data obtained are shown in Table 1.
TABLE 1 mechanical Properties and repair test data for prepreg curing
As is clear from the data in Table 1, the prepreg obtained by the present invention has high mechanical strength, prepreg interlaminar shear strength of more than 55MPa, high adhesive strength to an adherend, and prepreg adhesive adherend shear strength of more than 17 MPa.
The present invention has been described in detail with reference to the examples, but the present invention is only preferred examples of the present invention and should not be construed as limiting the scope of the present invention. All equivalent changes and modifications made within the scope of the present invention shall fall within the scope of the present invention.
Claims (10)
1. A UV light-cured epoxy prepreg characterized in that: the epoxy resin composition comprises 50-65 wt% of fiber reinforcing materials and 35-50 wt% of thickening UV light-cured epoxy resin composition, wherein the thickening UV light-cured epoxy resin composition comprises an epoxy resin composition and an epoxy thickener containing amino active hydrogen, and the molar ratio of epoxy groups in the epoxy resin composition to the amino active hydrogen in the epoxy thickener is 100: 12-100: 40.
2. the UV light cured epoxy prepreg of claim 1, characterized in that: the epoxy resin composition comprises 58-70% of epoxy resin, 29-40% of cationic reactive diluent and 1-2% of cationic photoinitiator by weight percentage.
3. The UV light cured epoxy prepreg of claim 2, characterized in that: the cationic photoinitiator is at least one of diaryl iodonium salt and triaryl sulfonium salt.
4. The UV light cured epoxy prepreg of claim 2, characterized in that: the cationic photoinitiator is selected from at least one of PAG101, 6976, UV6992 and PAG-002; the cationic active diluent is at least one of 3, 4-epoxy cyclohexyl methyl-3, 4-epoxy cyclohexyl formic acid active diluent, bis ((3, 4-epoxy cyclohexyl) methyl) adipate active diluent and epoxy soybean oil acrylate active diluent; the epoxy resin is bisphenol A epoxy resin or bisphenol F epoxy resin.
5. The UV light cured epoxy prepreg of claim 1, characterized in that: the amino active hydrogen-containing epoxy thickener is at least one of a monoamine or a polyamine containing a primary amino group or a secondary amino group.
6. The UV light cured epoxy prepreg of claim 1, characterized in that: the initial viscosity of the epoxy resin composition is 3000-.
7. The UV light cured epoxy prepreg of claim 1, characterized in that: the fiber reinforced material is at least one of continuous glass fiber check cloth, continuous glass fiber felt, non-woven glass fiber felt and glass fiber woven cloth mixed fabric.
8. The UV light cured epoxy prepreg of claim 7, characterized in that: the density of the continuous glass fiber square cloth cover is 400-600 g/m2(ii) a The surface density of the continuous glass fiber felt is 100-400 g/m2(ii) a The surface density of the mixed fabric of the non-woven glass fiber felt and the glass fiber woven cloth is 400-800 g/m2The fiber length of the non-woven glass fiber felt is 15-50 mm, and the weight ratio of the non-woven glass fiber felt to the glass fiber woven fabric is 1-4: 6-9.
9. A production process of a UV light-cured epoxy prepreg is characterized by comprising the following steps:
a. weighing 58-70 wt% of epoxy resin, 29-40 wt% of cationic active diluent and 1-2 wt% of cationic photoinitiator, stirring and mixing uniformly under the condition of keeping out of the sun to obtain an epoxy resin composition with initial viscosity of 3000-5600cps, and storing for later use;
b. mixing the epoxy resin composition and an epoxy thickener containing amino active hydrogen according to a proportion, and stirring at a high speed, wherein the molar ratio of the epoxy group in the epoxy resin composition to the amino active hydrogen in the epoxy thickener is 100: 12-100: 40, uniformly mixing under the condition of keeping out of the sun to obtain a thickened UV light curing epoxy resin composition;
c. uniformly coating the thickened UV light-cured epoxy resin composition on black upper and lower carrier films to form an epoxy resin film with the thickness of 0.15-0.3 mm;
d. compounding a fiber reinforced material with the epoxy resin film, extruding, infiltrating and exhausting, wherein the extrusion pressure is 0.1-0.2MPa, so that the UV light-cured epoxy resin composition fully infiltrates the fiber reinforced material, and then closing the light, rolling and packaging;
e. curing the UV light-cured epoxy prepreg which is wound and packaged, and curing for 10-40 hrs at 30-55 ℃ to complete the process.
10. The UV light cured epoxy prepreg of claim 9, characterized in that: the viscosity of the light-cured epoxy resin composition at 25 ℃ is 2000-50000 Pa.s after curing treatment.
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| CN202210738133.3A CN116731621A (en) | 2022-03-01 | 2022-06-28 | UV (ultraviolet) light-cured epoxy prepreg and production process thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1508951A (en) * | 1976-02-19 | 1978-04-26 | Ciba Geigy Ag | Epoxide resin based prepregs |
| JP2007270136A (en) * | 2006-03-09 | 2007-10-18 | Shin Dick Kako Kk | Sheet molding compound molding materials for heat compression molding, molding using the same, and method for producing the same |
| CN106987092A (en) * | 2016-01-20 | 2017-07-28 | 北京化工大学常州先进材料研究院 | Cation photocuring prepares the method and its resin combination of fiber-reinforced resin matrix compound material |
| CN112029234A (en) * | 2020-07-24 | 2020-12-04 | 艾达索高新材料芜湖有限公司 | Epoxy resin composition capable of being thickened rapidly and fiber-reinforced composite prepreg thereof |
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2022
- 2022-03-01 CN CN202210189343.1A patent/CN114249966A/en active Pending
- 2022-06-28 CN CN202210738133.3A patent/CN116731621A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1508951A (en) * | 1976-02-19 | 1978-04-26 | Ciba Geigy Ag | Epoxide resin based prepregs |
| JP2007270136A (en) * | 2006-03-09 | 2007-10-18 | Shin Dick Kako Kk | Sheet molding compound molding materials for heat compression molding, molding using the same, and method for producing the same |
| CN106987092A (en) * | 2016-01-20 | 2017-07-28 | 北京化工大学常州先进材料研究院 | Cation photocuring prepares the method and its resin combination of fiber-reinforced resin matrix compound material |
| CN112029234A (en) * | 2020-07-24 | 2020-12-04 | 艾达索高新材料芜湖有限公司 | Epoxy resin composition capable of being thickened rapidly and fiber-reinforced composite prepreg thereof |
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Application publication date: 20220329 |