CN113045863A - Large-diameter core rod and preparation method thereof - Google Patents
Large-diameter core rod and preparation method thereof Download PDFInfo
- Publication number
- CN113045863A CN113045863A CN202110435185.9A CN202110435185A CN113045863A CN 113045863 A CN113045863 A CN 113045863A CN 202110435185 A CN202110435185 A CN 202110435185A CN 113045863 A CN113045863 A CN 113045863A
- Authority
- CN
- China
- Prior art keywords
- parts
- epoxy resin
- core rod
- glass fiber
- diameter core
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000003365 glass fiber Substances 0.000 claims abstract description 102
- 239000003822 epoxy resin Substances 0.000 claims abstract description 73
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 73
- 239000003999 initiator Substances 0.000 claims abstract description 31
- LYGVROAKFTYZBL-UHFFFAOYSA-N 2-ethenyl-1,3-benzodioxole Chemical compound C1=CC=C2OC(C=C)OC2=C1 LYGVROAKFTYZBL-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 239000012745 toughening agent Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000003292 glue Substances 0.000 claims description 44
- 238000002791 soaking Methods 0.000 claims description 42
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 20
- 229920005672 polyolefin resin Polymers 0.000 claims description 16
- 125000001931 aliphatic group Chemical group 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 14
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 14
- 239000002518 antifoaming agent Substances 0.000 claims description 14
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 14
- 238000005520 cutting process Methods 0.000 claims description 14
- -1 unsaturated fatty acid methyl ester Chemical group 0.000 claims description 14
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 14
- 238000007598 dipping method Methods 0.000 claims description 12
- 238000005470 impregnation Methods 0.000 claims description 12
- 239000003607 modifier Substances 0.000 claims description 12
- 238000004806 packaging method and process Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 150000007524 organic acids Chemical class 0.000 claims description 6
- 150000002978 peroxides Chemical class 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000007142 ring opening reaction Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 30
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 16
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 16
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 9
- 229910000423 chromium oxide Inorganic materials 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 8
- 235000019253 formic acid Nutrition 0.000 description 8
- 239000002131 composite material Substances 0.000 description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 7
- 229920002554 vinyl polymer Polymers 0.000 description 7
- 238000005452 bending Methods 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000012212 insulator Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000032683 aging Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011151 fibre-reinforced plastic Substances 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/156—Heterocyclic compounds having oxygen in the ring having two oxygen atoms in the ring
- C08K5/1565—Five-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention belongs to the technical field of material chemical industry, and discloses a large-diameter core rod and a preparation method thereof, wherein the large-diameter core rod is prepared from the following raw materials, by mass, 75-82 parts of glass fibers, 20 parts of epoxy resin, 5-12 parts of an anhydride curing agent, 1-3 parts of a toughening agent, 5-10 parts of vinyl benzodioxole and 0.5-2 parts of an initiator, wherein the glass fibers are pretreated by using an impregnating compound. The invention has the beneficial effects that: the vinyl benzodioxole has good compatibility with the epoxy resin and can be fully mixed with the epoxy resin, and in the heating and curing process of the epoxy resin, under the action of an initiator, the vinyl benzodioxole can perform a ring-opening reaction, so that the volume of the epoxy resin is increased, the shrinkage generated in the curing process of the epoxy resin can be compensated, the epoxy resin is prevented from generating a gap between the epoxy resin and the glass fiber due to the curing shrinkage, and the bonding strength of the epoxy resin and the glass fiber is enhanced.
Description
Technical Field
The invention belongs to the technical field of material chemical industry, and particularly relates to a large-diameter core rod and a preparation method thereof.
Background
The post insulator is an indispensable insulation fitting for a transformer substation and a power conversion alternating current station, and has important influence on the construction and operation of electric power engineering. The post insulator mainly comprises three parts, namely a silicon rubber shed sheath, a glass fiber reinforced plastic core rod and an end hardware fitting, wherein the core rod is generally made of glass fiber reinforced epoxy resin composite material. Different from a common small-diameter core rod, the material and the process of the composite large-diameter core body of the strut have obvious difference, and mainly have the following differences: firstly, a microscopic interface exists in the large-diameter core body, and if the process is not reasonable, the core body has interface defects to cause insulation degradation, so that the operation fault of the post insulator is caused; secondly, the thermal expansion coefficient mismatching of the glass fiber and the epoxy resin matrix can cause local stress concentration of an interface and finally can cause microcracks of the interface, and the microcracks provide a path for oxygen to enter the composite material, so that the oxidative degradation rate of the resin matrix in the composite material is accelerated; thirdly, in the damp-heat aging process, the resin matrix in the core rod material is not matched with the glass fiber in a swelling way, so that the internal stress is generated between the glass fiber and the resin matrix, and further the debonding of the glass fiber/resin interface is caused.
The Chinese patent with application publication number CN104952565A discloses a method for manufacturing a large-diameter multi-core combined core rod, which comprises the following steps: firstly, selecting a single-core rod according to the design requirement of a large-diameter multi-core combined core rod to be manufactured, and then preprocessing the selected single-core rod; secondly, preparing glue solution; thirdly, putting the pretreated core rod into a mold of an injection molding machine for preheating, then preheating the glue solution, injecting the preheated glue solution into the preheated mold, and preserving heat to obtain a molded product; and fourthly, post-curing the formed product to obtain the large-diameter multi-core combined core rod. The multi-core combined core rod manufactured by the method is formed by bundling and combining a plurality of single-core rods and then injecting and molding glue solution, the section diameter of the manufactured core rod is more than 170mm, the core rod belongs to the large-diameter category, the performance of the core rod is excellent, and the related technical requirements of the core rod for the composite insulator are met.
According to the large-diameter core rod prepared by the method, the bonding interface between the single-core rod and the glue solution is large, the situation that the thermal expansion rate and the swelling rate of the single-core rod and the solidified glue solution are not matched easily occurs under the high-temperature and high-humidity condition, so that cracks are generated on the interface, oxygen and water vapor easily invade the interior of the core rod, the ageing of the core rod is accelerated, and the practical service life of the large-diameter core rod is short.
Disclosure of Invention
The invention aims to provide a large-diameter core rod which has the effects of strong toughness, long service life and good electrical property.
The technical purpose of the invention is realized by the following technical scheme: the glass fiber is prepared from the following raw materials, by mass, 75-82 parts of glass fiber, 20 parts of epoxy resin, 5-12 parts of an anhydride curing agent, 1-3 parts of a toughening agent, 1-3 parts of vinyl benzodioxole and 0.5-2 parts of an initiator, wherein the glass fiber is pretreated by using an impregnating compound.
The invention is further provided with: the epoxy resin is an aliphatic epoxidized olefin resin.
The invention is further provided with: the initiator comprises benzoyl peroxide and N, N-dimethylaniline.
The invention is further provided with: the initiator also includes a nano transition metal oxide.
The invention is further provided with: the toughening agent is a sea-island toughening modifier.
The invention is further provided with: the impregnating compound is prepared by reacting a component A and a component B, wherein the component A comprises organic acid and peroxide, and the component B is unsaturated fatty acid methyl ester.
The invention is further provided with: the raw materials further comprise 1-2 parts by mass of a defoaming agent.
The invention is further provided with: the radius of the large-diameter core rod is 150-280 mm.
A preparation method of a large-diameter core rod comprises the following steps:
s1, epoxy resin glue solution preparation: stirring and mixing 20 parts of epoxy resin, 5-12 parts of curing agent, 1-3 parts of toughening agent, 0.5-2 parts of initiator, 5-10 parts of vinyl benzodioxole and 1-2 parts of defoaming agent uniformly at 40-60 ℃, putting the stirred epoxy resin glue solution into a vacuum-pressure impregnation furnace, and vacuumizing for 30min to remove bubbles in the glue solution;
s2, pretreatment of glass fibers: adding organic acid and peroxide into the soaking tank, soaking the glass fiber in the soaking tank for 10-30 min, then adding unsaturated fatty acid methyl ester into the soaking tank, uniformly mixing, reacting for 20-30 min, taking out the pretreated glass fiber, and drying in the air;
s3, pultrusion: arranging the pretreated glass fibers through a threading plate, immersing the glass fibers into an epoxy resin dipping tank, and putting the glass fibers dipped with glue under the traction of a drafting machine into a mold for curing and forming, wherein the traction speed of the drafting machine is 0.5-1 m/h, and the curing temperature is 110-170 ℃;
s4, cutting: and cutting and packaging the cured and molded large-diameter core rod according to requirements to obtain the finished large-diameter core rod.
The invention has the beneficial effects that:
1. the vinyl benzodioxole has good compatibility with the epoxy resin and can be fully mixed with the epoxy resin, and in the heating and curing process of the epoxy resin, under the action of an initiator, the vinyl benzodioxole can perform a ring-opening reaction, so that the volume of the epoxy resin is increased, the shrinkage generated in the curing process of the epoxy resin can be compensated, the epoxy resin is prevented from generating a gap between the epoxy resin and the glass fiber due to the curing shrinkage, and the bonding strength of the epoxy resin and the glass fiber is enhanced.
2. The vinylbenzodioxole can introduce phenyl into the epoxy resin, and the benzene ring structure can endow the epoxy resin with excellent heat resistance and improve the thermal performance of the large-diameter core rod.
3. The method comprises the following steps of pretreating glass fibers by using an impregnating compound, firstly adding organic acid and peroxide in the process of impregnating the glass fibers, etching the surfaces of the glass fibers to form pores on the surfaces of the glass fibers, then adding unsaturated fatty acid methyl ester into the impregnating compound, reacting the unsaturated fatty acid methyl ester with the organic acid and the peroxide to generate epoxy fatty acid methyl ester, introducing active groups on the surfaces of the glass fibers, and facilitating the enhancement of the interface bonding force between the glass fibers and epoxy resin; and the epoxidized fatty acid methyl ester has a similar structure and good compatibility with the aliphatic epoxidized olefin resin, and cannot damage the characteristics of toughness, electrical property and the like when added into the aliphatic epoxidized olefin resin.
4. The vinylbenzodioxole can generate ring-opening polymerization reaction to compensate the shrinkage generated in the curing process of the epoxy resin, and further expand the volume of the epoxy resin to be embedded into pores on the surface of the glass fiber, so that the adhesion between the epoxy resin and the glass fiber is enhanced; after the surface of the glass fiber is pretreated, the glass fiber contains a large number of unsaturated double bonds, and the glass fiber can react with vinyl in the aliphatic epoxidized olefin resin, so that molecular chains on the surface of the glass fiber and epoxy resin molecular chains are entangled with each other, firm interface combination is formed in the large-diameter core rod, and debonding and cracks of a glass fiber/resin interface can be effectively avoided.
5. The epoxy resin is linear macromolecule epoxy olefin resin, has a polybutadiene rubber structure and an epoxy resin structure, has good impact toughness and bonding performance, contains hydroxyl in resin molecules, is easy to combine with glass fiber, has good bonding performance to the glass fiber, is suitable for preparing a large-diameter core rod due to the characteristics of good compatibility and strong bonding performance with the glass fiber, and has high toughness, difficult fracture, good weather resistance and good electrical performance.
6. The benzoyl peroxide and the N, N-dimethylaniline are compounded to generate an oxidation-reduction reaction, free radicals generated in the oxidation-reduction reaction process can initiate a polymerization reaction, the reaction of epoxy resin and a curing agent is promoted, the curing efficiency of the epoxy resin is improved, and a large amount of phenyl is contained in a benzoyl peroxide and N, N-dimethylaniline system, so that a benzene ring can be introduced into the epoxy resin, and the heat resistance of the epoxy resin is improved.
7. The nanometer transition metal oxide can catalyze vinyl polymerization reaction to promote the polymerization of epoxy resin vinyl and vinyl on the glass fiber, enhance the interface bonding force of the glass fiber and the epoxy resin, and prolong the service life of the large-diameter core rod; and the nanometer transition metal oxide can increase the toughness of the epoxy resin, so that the tensile strength and the impact strength of the large-diameter core rod are improved.
Detailed Description
The technical solutions in the examples will be clearly and completely described below. It is to be understood that the described embodiments are merely a few embodiments of the invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without any inventive step, are within the scope of the present invention.
Example 1
Stirring and mixing 20 parts of aliphatic epoxidized olefin resin, 5 parts of anhydride curing agent, 3 parts of sea-island toughening modifier, 0.5 part of initiator, 10 parts of vinyl benzodioxole and 2 parts of defoaming agent uniformly at 40-60 ℃, wherein the initiator is prepared from benzoyl peroxide, N-dimethylaniline and nano chromium oxide, and putting the stirred epoxy resin glue solution into a vacuum-pressure impregnation furnace for vacuumizing for 30min to remove bubbles in the glue solution;
adding formic acid and hydrogen peroxide into the soaking tank, soaking the glass fiber in the soaking tank for 10-30 min, then adding unsaturated fatty acid methyl ester into the soaking tank, uniformly mixing, reacting for 20-30 min, taking out the pretreated glass fiber, and drying in the air;
arranging the pretreated glass fibers through a threading plate, immersing the glass fibers into an epoxy resin dipping tank, and putting the glass fibers dipped with glue under the traction of a drafting machine into a mold for curing and forming, wherein the traction speed of the drafting machine is 0.5-1 m/h, and the curing temperature is 110-170 ℃;
and cutting and packaging the cured and molded large-diameter core rod according to requirements to obtain a finished large-diameter core rod, wherein the diameter of the prepared large-diameter core rod is 150 mm.
Example 2
Stirring and mixing 20 parts of aliphatic epoxidized olefin resin, 12 parts of anhydride curing agent, 1 part of sea-island toughening modifier, 2 parts of initiator, 5 parts of vinyl benzodioxole and 1 part of defoaming agent uniformly at 40-60 ℃, wherein the initiator is prepared from benzoyl peroxide, N-dimethylaniline and nano chromium oxide, and putting the stirred epoxy resin glue solution into a vacuum-pressure impregnation furnace for vacuumizing for 30min to remove bubbles in the glue solution;
adding formic acid and hydrogen peroxide into the soaking tank, soaking the glass fiber in the soaking tank for 10-30 min, then adding unsaturated fatty acid methyl ester into the soaking tank, uniformly mixing, reacting for 20-30 min, taking out the pretreated glass fiber, and drying in the air;
arranging the pretreated glass fibers through a threading plate, immersing the glass fibers into an epoxy resin dipping tank, and putting the glass fibers dipped with glue under the traction of a drafting machine into a mold for curing and forming, wherein the traction speed of the drafting machine is 0.5-1 m/h, and the curing temperature is 110-170 ℃;
and cutting and packaging the cured and molded large-diameter core rod according to requirements to obtain a finished large-diameter core rod, wherein the diameter of the prepared large-diameter core rod is 280 mm.
Example 3
20 parts of aliphatic epoxidized olefin resin, 8.5 parts of anhydride curing agent, 2 parts of sea-island toughening modifier, 1.25 parts of initiator, 7.5 parts of vinyl benzodioxole and 1 part of defoaming agent are stirred and mixed uniformly at 40-60 ℃, the initiator is prepared from benzoyl peroxide, N-dimethylaniline and nano chromium oxide, and the stirred epoxy resin glue solution is put into a vacuum-pressure impregnation furnace for vacuumizing for 30min to remove bubbles in the glue solution;
adding formic acid and hydrogen peroxide into the soaking tank, soaking the glass fiber in the soaking tank for 10-30 min, then adding unsaturated fatty acid methyl ester into the soaking tank, uniformly mixing, reacting for 20-30 min, taking out the pretreated glass fiber, and drying in the air;
arranging the pretreated glass fibers through a threading plate, immersing the glass fibers into an epoxy resin dipping tank, and putting the glass fibers dipped with glue under the traction of a drafting machine into a mold for curing and forming, wherein the traction speed of the drafting machine is 0.5-1 m/h, and the curing temperature is 110-170 ℃;
and cutting and packaging the cured and molded large-diameter core rod according to requirements to obtain a finished large-diameter core rod, wherein the diameter of the prepared large-diameter core rod is 280 mm.
Example 3
20 parts of aliphatic epoxidized olefin resin, 8.5 parts of anhydride curing agent, 2 parts of sea-island toughening modifier, 1.25 parts of initiator, 7.5 parts of vinyl benzodioxole and 1 part of defoaming agent are stirred and mixed uniformly at 40-60 ℃, the initiator is prepared from benzoyl peroxide, N-dimethylaniline and nano chromium oxide, and the stirred epoxy resin glue solution is put into a vacuum-pressure impregnation furnace for vacuumizing for 30min to remove bubbles in the glue solution;
adding formic acid and hydrogen peroxide into the soaking tank, soaking the glass fiber in the soaking tank for 10-30 min, then adding unsaturated fatty acid methyl ester into the soaking tank, uniformly mixing, reacting for 20-30 min, taking out the pretreated glass fiber, and drying in the air;
arranging the pretreated glass fibers through a threading plate, immersing the glass fibers into an epoxy resin dipping tank, and putting the glass fibers dipped with glue under the traction of a drafting machine into a mold for curing and forming, wherein the traction speed of the drafting machine is 0.5-1 m/h, and the curing temperature is 110-170 ℃;
and cutting and packaging the cured and molded large-diameter core rod according to requirements to obtain a finished large-diameter core rod, wherein the diameter of the prepared large-diameter core rod is 280 mm.
Example 4
In comparison with example 3, in example 4, vinylbenzodioxole was not added, and other conditions were substantially the same as in example 3.
20 parts of aliphatic epoxidized olefin resin, 8.5 parts of anhydride curing agent, 2 parts of sea-island toughening modifier, 1.25 parts of initiator and 1 part of defoaming agent are stirred and mixed uniformly at 40-60 ℃, the initiator is prepared from benzoyl peroxide, N-dimethylaniline and nano chromium oxide, and the stirred epoxy resin glue solution is put into a vacuum-pressure impregnation furnace for vacuumizing for 30min to remove bubbles in the glue solution;
adding formic acid and hydrogen peroxide into the soaking tank, soaking the glass fiber in the soaking tank for 10-30 min, then adding unsaturated fatty acid methyl ester into the soaking tank, uniformly mixing, reacting for 20-30 min, taking out the pretreated glass fiber, and drying in the air;
arranging the pretreated glass fibers through a threading plate, immersing the glass fibers into an epoxy resin dipping tank, and putting the glass fibers dipped with glue under the traction of a drafting machine into a mold for curing and forming, wherein the traction speed of the drafting machine is 0.5-1 m/h, and the curing temperature is 110-170 ℃;
and cutting and packaging the cured and molded large-diameter core rod according to requirements to obtain a finished large-diameter core rod, wherein the diameter of the prepared large-diameter core rod is 280 mm.
Example 5
In comparison with example 3, in example 4, vinylbenzodioxole was not added, and other conditions were substantially the same as in example 3.
20 parts of aliphatic epoxidized olefin resin, 8.5 parts of anhydride curing agent, 2 parts of sea-island toughening modifier, 1.25 parts of initiator, 5 parts of vinyl benzodioxole and 1 part of defoaming agent are stirred and mixed uniformly at 40-60 ℃, the initiator is prepared from benzoyl peroxide, N-dimethylaniline and nano chromium oxide, and the stirred epoxy resin glue solution is put into a vacuum-pressure impregnation furnace for vacuumizing for 30min to remove bubbles in the glue solution;
adding formic acid and hydrogen peroxide into the soaking tank, soaking the glass fiber in the soaking tank for 10-30 min, then adding unsaturated fatty acid methyl ester into the soaking tank, uniformly mixing, reacting for 20-30 min, taking out the pretreated glass fiber, and drying in the air;
arranging the pretreated glass fibers through a threading plate, immersing the glass fibers into an epoxy resin dipping tank, and putting the glass fibers dipped with glue under the traction of a drafting machine into a mold for curing and forming, wherein the traction speed of the drafting machine is 0.5-1 m/h, and the curing temperature is 110-170 ℃;
and cutting and packaging the cured and molded large-diameter core rod according to requirements to obtain a finished large-diameter core rod, wherein the diameter of the prepared large-diameter core rod is 280 mm.
Example 6
In comparison with example 3, in example 4, vinylbenzodioxole was not added, and other conditions were substantially the same as in example 3.
Stirring and mixing 20 parts of aliphatic epoxidized olefin resin, 8.5 parts of anhydride curing agent, 2 parts of sea-island toughening modifier, 1.25 parts of initiator, 10 parts of vinyl benzodioxole and 1 part of defoaming agent uniformly at 40-60 ℃, wherein the initiator is prepared from benzoyl peroxide, N-dimethylaniline and nano chromium oxide, and putting the stirred epoxy resin glue solution into a vacuum-pressure impregnation furnace for vacuumizing for 30min to remove bubbles in the glue solution;
adding formic acid and hydrogen peroxide into the soaking tank, soaking the glass fiber in the soaking tank for 10-30 min, then adding unsaturated fatty acid methyl ester into the soaking tank, uniformly mixing, reacting for 20-30 min, taking out the pretreated glass fiber, and drying in the air;
arranging the pretreated glass fibers through a threading plate, immersing the glass fibers into an epoxy resin dipping tank, and putting the glass fibers dipped with glue under the traction of a drafting machine into a mold for curing and forming, wherein the traction speed of the drafting machine is 0.5-1 m/h, and the curing temperature is 110-170 ℃;
and cutting and packaging the cured and molded large-diameter core rod according to requirements to obtain a finished large-diameter core rod, wherein the diameter of the prepared large-diameter core rod is 280 mm.
Example 7
20 parts of aliphatic epoxidized olefin resin, 8.5 parts of anhydride curing agent, 2 parts of sea-island toughening modifier, 1.25 parts of initiator, 7.5 parts of vinyl benzodioxole and 1 part of defoaming agent are stirred and mixed uniformly at 40-60 ℃, the initiator is prepared from benzoyl peroxide and N, N-dimethylaniline, and the stirred epoxy resin glue solution is put into a vacuum-pressure impregnation furnace for vacuumizing for 30min to remove bubbles in the glue solution;
adding formic acid and hydrogen peroxide into the soaking tank, soaking the glass fiber in the soaking tank for 10-30 min, then adding unsaturated fatty acid methyl ester into the soaking tank, uniformly mixing, reacting for 20-30 min, taking out the pretreated glass fiber, and drying in the air;
arranging the pretreated glass fibers through a threading plate, immersing the glass fibers into an epoxy resin dipping tank, and putting the glass fibers dipped with glue under the traction of a drafting machine into a mold for curing and forming, wherein the traction speed of the drafting machine is 0.5-1 m/h, and the curing temperature is 110-170 ℃;
and cutting and packaging the cured and molded large-diameter core rod according to requirements to obtain a finished large-diameter core rod, wherein the diameter of the prepared large-diameter core rod is 280 mm.
Example 8
20 parts of aliphatic epoxidized olefin resin, 8.5 parts of anhydride curing agent, 2 parts of sea-island toughening modifier, 1.25 parts of initiator, 7.5 parts of vinyl benzodioxole and 1 part of defoaming agent are stirred and mixed uniformly at 40-60 ℃, the initiator is prepared from benzoyl peroxide, N-dimethylaniline and nano chromium oxide, and the stirred epoxy resin glue solution is put into a vacuum-pressure impregnation furnace for vacuumizing for 30min to remove bubbles in the glue solution;
adding epoxy fatty acid methyl ester into the soaking tank, placing the glass fiber into the soaking tank for reaction for 20-30 min, taking out the pretreated glass fiber, and drying in the air;
arranging the pretreated glass fibers through a threading plate, immersing the glass fibers into an epoxy resin dipping tank, and putting the glass fibers dipped with glue under the traction of a drafting machine into a mold for curing and forming, wherein the traction speed of the drafting machine is 0.5-1 m/h, and the curing temperature is 110-170 ℃;
and cutting and packaging the cured and molded large-diameter core rod according to requirements to obtain a finished large-diameter core rod, wherein the diameter of the prepared large-diameter core rod is 280 mm.
Comparative example
20 parts of aliphatic epoxidized olefin resin, 8.5 parts of anhydride curing agent, 2 parts of sea-island toughening modifier, 1.25 parts of initiator and 1 part of defoaming agent are stirred and mixed uniformly at 40-60 ℃, the initiator is prepared from benzoyl peroxide and N, N-dimethylaniline, and the stirred epoxy resin glue solution is put into a vacuum-pressure impregnation furnace for vacuumizing for 30min to remove bubbles in the glue solution;
arranging glass fibers through a threading plate, immersing the glass fibers into an epoxy resin dipping tank, and putting the glass fibers dipped with glue into a mold for curing and forming under the traction of a drafting machine, wherein the traction speed of the drafting machine is 0.5-1 m/h, and the curing temperature is 110-170 ℃;
and cutting and packaging the cured and molded large-diameter core rod according to requirements to obtain a finished large-diameter core rod, wherein the diameter of the prepared large-diameter core rod is 280 mm.
Procedure of the test
The large-diameter core rods prepared in examples 1 to 8 and comparative example were sampled to examine the bending strength, interlaminar shear properties, and glass transition temperature of the large-diameter core rods.
Bending strength: according to GB/T1449-. And (3) adopting an unconstrained support to break the composite material sample which is newly cast and molded at a constant loading rate by three-point bending, wherein the test speed is 10 mm/min.
Interlaminar shear performance: the test was carried out on a universal testing machine of WDW-30 type according to GB 3357-1982 method for testing interlaminar shear strength of unidirectional fiber reinforced plastics. And continuously loading the prepared composite material sample on a universal testing machine by a three-point short beam method until the sample is damaged, recording the maximum load value, and calculating the interlaminar shear strength of the fiber.
Glass transition temperature: the glass transition temperature of a material is characterized by the temperature at which the loss factor peak in the DMA test is located. The detection apparatus is a dynamic thermomechanical analyzer, model DMA-242, produced by Netzsch, Germany. The test mode is a double cantilever beam vibration mode, the frequency is 16.7Hz, the temperature interval is from room temperature to 220 ℃, and the heating rate is 5 ℃/min.
The test results are shown in the following table:
as can be seen from the above table, in examples 4-6, the bending strength and glass transition temperature of the large-diameter core are gradually increased with the increase of vinylbenzodioxol, which indicates that vinylbenzodioxol can enhance the interfacial bonding force between the epoxy resin and the glass fiber and improve the heat resistance of the large-diameter core; the interlaminar shear strength in example 6 is slightly lower than that in example 5, indicating that too much vinylbenzodioxole dilutes the epoxy resin, resulting in a decrease in the viscosity of the epoxy resin and affecting the interfacial bonding strength of the large diameter core.
In example 7, no nano chromium oxide is added, and the bending strength and the interlayer shear force of the large-diameter core are reduced, which indicates that the nano transition metal oxide can catalyze vinyl polymerization reaction to promote the polymerization of epoxy resin vinyl and vinyl on the glass fiber, and enhance the interface bonding force between the glass fiber and the epoxy resin.
In example 8, the glass fiber is directly pretreated by epoxy fatty acid methyl ester, and the bending strength and the interlayer shearing force of the large-diameter core rod are greatly reduced, which indicates that the surface of the glass fiber cannot be etched by directly pretreating the glass fiber by epoxy fatty acid methyl ester, and the bonding force between the epoxy resin and the surface of the glass fiber is reduced.
In the comparative example, the large-diameter core rod is prepared by the conventional method, and the bending strength, the interlaminar shear force and the glass transition temperature of the obtained product are lower, which shows that the large-diameter core rod produced by the method of the invention can achieve excellent performance.
Claims (9)
1. A large diameter core rod, characterized by: the glass fiber is prepared from the following raw materials, by mass, 75-82 parts of glass fiber, 20 parts of epoxy resin, 5-12 parts of an anhydride curing agent, 1-3 parts of a toughening agent, 5-10 parts of vinyl benzodioxole and 0.5-2 parts of an initiator, wherein the glass fiber is pretreated by using an impregnating compound.
2. A large diameter mandrel as claimed in claim 1 wherein: the epoxy resin is an aliphatic epoxidized olefin resin.
3. A large diameter mandrel as claimed in claim 1 wherein: the initiator comprises benzoyl peroxide and N, N-dimethylaniline.
4. A large diameter mandrel as claimed in claim 1 wherein: the initiator also includes a nano transition metal oxide.
5. A large-diameter mandrel according to claim 4, wherein: the toughening agent is a sea-island toughening modifier.
6. A large diameter mandrel as claimed in claim 1 wherein: the impregnating compound is prepared by reacting a component A and a component B, wherein the component A comprises organic acid and peroxide, and the component B is unsaturated fatty acid methyl ester.
7. A large diameter mandrel as claimed in claim 1 wherein: the raw materials further comprise 1-2 parts by mass of a defoaming agent.
8. A large diameter mandrel as claimed in claim 1 wherein: the diameter of the large-diameter core rod is 150-280 mm.
9. The method for producing a large-diameter core rod according to any one of claims 1 to 8, characterized in that: the method comprises the following steps:
s1, epoxy resin glue solution preparation: stirring and mixing 20 parts of epoxy resin, 5-12 parts of curing agent, 1-3 parts of toughening agent, 0.5-2 parts of initiator, 5-10 parts of vinyl benzodioxole and 1-2 parts of defoaming agent uniformly at 40-60 ℃, putting the stirred epoxy resin glue solution into a vacuum-pressure impregnation furnace, and vacuumizing for 30min to remove bubbles in the glue solution;
s2, pretreatment of glass fibers: adding organic acid and peroxide into the soaking tank, soaking the glass fiber in the soaking tank for 10-30 min, then adding unsaturated fatty acid methyl ester into the soaking tank, uniformly mixing, reacting for 20-30 min, taking out the pretreated glass fiber, and drying in the air;
s3, pultrusion: arranging the pretreated glass fibers through a threading plate, immersing the glass fibers into an epoxy resin dipping tank, and putting the glass fibers dipped with glue under the traction of a drafting machine into a mold for curing and forming, wherein the traction speed of the drafting machine is 0.5-1 m/h, and the curing temperature is 110-170 ℃;
s4, cutting: and cutting and packaging the cured and molded large-diameter core rod according to requirements to obtain the finished large-diameter core rod.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110435185.9A CN113045863A (en) | 2021-04-22 | 2021-04-22 | Large-diameter core rod and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110435185.9A CN113045863A (en) | 2021-04-22 | 2021-04-22 | Large-diameter core rod and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113045863A true CN113045863A (en) | 2021-06-29 |
Family
ID=76520136
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110435185.9A Pending CN113045863A (en) | 2021-04-22 | 2021-04-22 | Large-diameter core rod and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113045863A (en) |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3852439A (en) * | 1970-09-11 | 1974-12-03 | Ciba Geigy Ag | Compositions with a base of phosphoric esters combined with a stabiliser |
| JPH08286375A (en) * | 1995-04-12 | 1996-11-01 | Shin Etsu Chem Co Ltd | Polymer compound and chemically amplified positive resist composition |
| JPH09169832A (en) * | 1995-12-19 | 1997-06-30 | Asahi Chem Ind Co Ltd | Aqueous resin dispersion composition |
| CN1530216A (en) * | 2003-03-14 | 2004-09-22 | 云 白 | Fibreglass reinforced epoxy resin insulator core rod producing technology and apparatus |
| CN1550889A (en) * | 2002-11-20 | 2004-12-01 | 希普雷公司 | Multilayer Photoresist System |
| JP2005226014A (en) * | 2004-02-13 | 2005-08-25 | Showa Highpolymer Co Ltd | Resin composition for pultrusion, fiber-reinforced resin composition, method for molding the same and molded article |
| CN101741042A (en) * | 2010-01-07 | 2010-06-16 | 西安唯实输配电技术有限公司 | Preparation method of composite insulated cross-arm used for outdoor anti-ultraviolet overhead lines of electric power |
| CN101798441A (en) * | 2010-03-12 | 2010-08-11 | 西安银河复合绝缘子有限公司 | Vacuum pressure high-temperature impregnating resin suitable for high voltage equipment insulators |
| US20120273736A1 (en) * | 2009-12-23 | 2012-11-01 | Merck Patent Gmbh | Compositions comprising polymeric binders |
| CN105097148A (en) * | 2015-07-31 | 2015-11-25 | 江苏神马电力股份有限公司 | Composite insulator, core rod of composite insulator and preparation method of core rod |
| CN105711033A (en) * | 2016-03-18 | 2016-06-29 | 西安高强绝缘电气有限责任公司 | Manufacturing method of lager-diameter single-core injection pultrusion rod |
| CN106158170A (en) * | 2016-06-20 | 2016-11-23 | 北京玻钢院复合材料有限公司 | The preparation method of core rod of insulator |
| CN106750111A (en) * | 2016-12-27 | 2017-05-31 | 安徽潜源教学设备有限公司 | A kind of polyurethane plastic runway of glass fiber reinforcement and preparation method thereof |
| CN109423010A (en) * | 2017-08-21 | 2019-03-05 | 味之素株式会社 | Resin combination |
| CN112592560A (en) * | 2020-11-25 | 2021-04-02 | 中国电力科学研究院有限公司 | Modified resin for preparing insulator core rod, insulator core rod and insulator |
-
2021
- 2021-04-22 CN CN202110435185.9A patent/CN113045863A/en active Pending
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3852439A (en) * | 1970-09-11 | 1974-12-03 | Ciba Geigy Ag | Compositions with a base of phosphoric esters combined with a stabiliser |
| JPH08286375A (en) * | 1995-04-12 | 1996-11-01 | Shin Etsu Chem Co Ltd | Polymer compound and chemically amplified positive resist composition |
| JPH09169832A (en) * | 1995-12-19 | 1997-06-30 | Asahi Chem Ind Co Ltd | Aqueous resin dispersion composition |
| CN1550889A (en) * | 2002-11-20 | 2004-12-01 | 希普雷公司 | Multilayer Photoresist System |
| CN1530216A (en) * | 2003-03-14 | 2004-09-22 | 云 白 | Fibreglass reinforced epoxy resin insulator core rod producing technology and apparatus |
| JP2005226014A (en) * | 2004-02-13 | 2005-08-25 | Showa Highpolymer Co Ltd | Resin composition for pultrusion, fiber-reinforced resin composition, method for molding the same and molded article |
| US20120273736A1 (en) * | 2009-12-23 | 2012-11-01 | Merck Patent Gmbh | Compositions comprising polymeric binders |
| CN101741042A (en) * | 2010-01-07 | 2010-06-16 | 西安唯实输配电技术有限公司 | Preparation method of composite insulated cross-arm used for outdoor anti-ultraviolet overhead lines of electric power |
| CN101798441A (en) * | 2010-03-12 | 2010-08-11 | 西安银河复合绝缘子有限公司 | Vacuum pressure high-temperature impregnating resin suitable for high voltage equipment insulators |
| CN105097148A (en) * | 2015-07-31 | 2015-11-25 | 江苏神马电力股份有限公司 | Composite insulator, core rod of composite insulator and preparation method of core rod |
| CN105711033A (en) * | 2016-03-18 | 2016-06-29 | 西安高强绝缘电气有限责任公司 | Manufacturing method of lager-diameter single-core injection pultrusion rod |
| CN106158170A (en) * | 2016-06-20 | 2016-11-23 | 北京玻钢院复合材料有限公司 | The preparation method of core rod of insulator |
| CN106750111A (en) * | 2016-12-27 | 2017-05-31 | 安徽潜源教学设备有限公司 | A kind of polyurethane plastic runway of glass fiber reinforcement and preparation method thereof |
| CN109423010A (en) * | 2017-08-21 | 2019-03-05 | 味之素株式会社 | Resin combination |
| CN112592560A (en) * | 2020-11-25 | 2021-04-02 | 中国电力科学研究院有限公司 | Modified resin for preparing insulator core rod, insulator core rod and insulator |
Non-Patent Citations (2)
| Title |
|---|
| CÉLINE BONNEAUD: "Diversity of Synthetic Approaches to Functionalized Perfluoropolyalkylether Polymers" * |
| 杨静军: "苯乙烯共聚物改性低介电环氧树脂的研究" * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN117487324B (en) | Basalt fiber reinforced corrosion-resistant composite rib and preparation method thereof | |
| CN105671937A (en) | Modification method of ramie fibers using as environment-friendly composite material reinforcement | |
| CN102585106B (en) | A kind of unsaturated polyester resin for molding and preparation method thereof | |
| CN112194900A (en) | Silicon rubber mold for integral molding of composite skirt and preparation method thereof | |
| CN113292819A (en) | Epoxy resin composition capable of being rapidly cured at medium and low temperature, epoxy resin-based composite material and preparation method thereof | |
| CN108962423B (en) | Carbon fiber composite core for cable and manufacturing method thereof | |
| CN110105717B (en) | Carbon fiber composite core wire and preparation method thereof | |
| CN113045863A (en) | Large-diameter core rod and preparation method thereof | |
| CN104419157A (en) | Novel cable bracket hoop and preparation method thereof | |
| CN110305450A (en) | Fiber-reinforced resin-based composite core for overhead lines and preparation method thereof | |
| CN114999726B (en) | A high-toughness aluminum-based carbon fiber composite rod and preparation method thereof | |
| CN113004655A (en) | Preparation method of glass fiber reinforced thermosetting resin prepreg | |
| CN117659613A (en) | Epoxy resin system composition and application thereof | |
| CN112029375B (en) | Inorganic-organic hybrid polymer anticorrosive paint and preparation method thereof | |
| CN115109386A (en) | Basalt fiber reinforced epoxy resin-based core rod for composite insulating cross arm and preparation method thereof | |
| CN116278060A (en) | Epoxy vinyl glass fiber reinforced plastic wedge-shaped strip, preparation method and preparation system thereof | |
| CN115322717A (en) | Fiber-reinforced resin-based adhesive capable of being used for underwater construction and repairing underwater vehicle shell, and preparation method and construction method thereof | |
| CN114672137B (en) | A modified epoxy resin and preparation method thereof | |
| CN114350114A (en) | Fluorine-doped graphene oxide modified epoxy resin and preparation method of carbon fiber composite material thereof | |
| CN119008145B (en) | A lightweight, high-performance composite foam insulation core material, preparation process and application thereof | |
| CN113035472A (en) | Preparation method of toughened rod-shaped porcelain insulator | |
| CN113637290A (en) | Epoxy resin-based composite material with high glass transition temperature and capable of being rapidly molded for wind power pultrusion girder and preparation method of epoxy resin-based composite material | |
| Huang et al. | Optimization of Mechanical Properties of Insulation Materials for Dry-Type Transformers | |
| CN114350131B (en) | SMC material for pick-up hopper | |
| CN106592242B (en) | Modified epoxy resin large tow universal carbon fiber sizing agent, preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210629 |