CN110387114B - Light-cured resin for reconstruction of filling station buried oil tank lining and prepreg - Google Patents

Light-cured resin for reconstruction of filling station buried oil tank lining and prepreg Download PDF

Info

Publication number
CN110387114B
CN110387114B CN201810365821.3A CN201810365821A CN110387114B CN 110387114 B CN110387114 B CN 110387114B CN 201810365821 A CN201810365821 A CN 201810365821A CN 110387114 B CN110387114 B CN 110387114B
Authority
CN
China
Prior art keywords
thermal initiator
light
resin composition
unsaturated polyester
curable resin
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.)
Active
Application number
CN201810365821.3A
Other languages
Chinese (zh)
Other versions
CN110387114A (en
Inventor
钱建华
刘华
黄锐
刘世强
施迎玫
严俊鹏
沙垣
吕晓平
雷浩
刘坐镇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huachang Polymer Co Ltd East China University Of Science & Technology
Original Assignee
Huachang Polymer Co Ltd East China University Of Science & Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Huachang Polymer Co Ltd East China University Of Science & Technology filed Critical Huachang Polymer Co Ltd East China University Of Science & Technology
Priority to CN201810365821.3A priority Critical patent/CN110387114B/en
Publication of CN110387114A publication Critical patent/CN110387114A/en
Application granted granted Critical
Publication of CN110387114B publication Critical patent/CN110387114B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/06—Unsaturated polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/222—Magnesia, i.e. magnesium oxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/2224—Magnesium hydroxide
    • 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)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Reinforced Plastic Materials (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

The invention provides a light-cured resin for reforming an inner liner of a buried oil tank of a gas station and a prepreg, and particularly discloses an ultraviolet light-cured resin composition and a light-cured prepreg containing the resin composition.

Description

Light-cured resin for reconstruction of filling station buried oil tank lining and prepreg
Technical Field
The invention belongs to the technical field of modification of inner liners of buried oil tanks of gas stations, and relates to a light-cured resin and a prepreg for modifying a buried single-layer oil tank of a gas station into a glass fiber reinforced plastic double-layer inner liner.
Background
At present, in China, about 10 thousands of seats and 40 thousands of oil storage tanks exist in a gas station, most of the gas stations adopt single-layer steel horizontal buried oil tanks, and most of the oil tanks are used for more than 10 years. The steel oil tank is buried underground all the year round, and is easy to corrode to cause leakage, so that soil and underground water are polluted. The double-layer oil tank can effectively solve the problem of leakage of the underground oil storage tank and protect the safety of underground water. The buried oil tank lining is reformed by directly coating prime resin on the inner surface of the original buried steel tank, manufacturing a glass fiber reinforced plastic double-layer lining, forming a through gap in the double-layer lining by adopting 3D glass fiber fabric, and installing a leakage detection system for leakage detection. The double-layer lining transformation does not need on-site excavation, the transformation cost is low, and the period is short.
When the existing buried oil tank lining is reconstructed, the glass fiber reinforced plastic double-layer lining is made of light-cured unsaturated polyester resin and glass fiber chopped strand mats serving as main raw materials by a hand pasting process, and then is cured by irradiation of an ultraviolet lamp. Because the buried oil tank belongs to a closed limited space, styrene in the photocuring unsaturated polyester resin is volatile during the lining transformation construction, and irritant odor organic compounds (VOCs) are formed, so that the environment is polluted, the health is harmed, the breathing of constructors is influenced in the limited space, and even suffocation and explosion can occur. In addition, because the linear light transmission and ultraviolet light penetration capacity are limited, for glass fiber reinforced plastics with larger thickness, one-time irradiation often causes incomplete curing, and layer-by-layer curing is needed, so that the construction progress is influenced; meanwhile, the degree of curing of the shadow and the backlight part is low, the curing uniformity is poor, and the quality of a final product is influenced.
Therefore, the development of a novel construction-convenient, safe and environment-friendly buried oil tank lining modification technology is urgently needed in the field.
Disclosure of Invention
The invention aims to provide ultraviolet curing resin which is used for modifying an inner liner of a buried oil tank of a gas station and can be molded at one time and prepreg thereof.
In a first aspect of the present invention, there is provided a uv curable resin composition comprising:
unsaturated polyester resin, free radical photoinitiator, cationic photoinitiator, thermal initiator and thickening agent.
In another preferred embodiment, the uv curable resin composition includes:
unsaturated polyester resin: 80-120 parts by weight;
free radical photoinitiator: 0.2 to 1.0 weight part;
cationic photoinitiator: 0.1-1.0 weight parts;
thermal initiator: 0.1-1.0 weight parts; and
thickening agent: 1-4 parts by weight.
In another preferred embodiment, the content of the unsaturated polyester resin is 100 parts by weight.
In another preferred embodiment, the unsaturated polyester resin is a p-benzene type unsaturated polyester resin.
In another preferred embodiment, the radical photoinitiator is acylphosphine oxide, including 2,4, 6-trimethylbenzoyldiphenylphosphine oxide (TPO), 2,4, 6-trimethylbenzoylethoxyphenylphosphine oxide (TEPO), bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide (BAPO)1) Bis (2, 6-dimethoxybenzoyl) - (4, 4' -dimethyloctyl-2) phosphine oxide (BAPO)2) One or more of; preferably, the radical photoinitiator is the polyacylphosphine oxide compound.
In another preferred embodiment, the weight ratio of the free radical photoinitiator to the unsaturated polyester resin is (0.2-1.0): 100.
in another preferred embodiment, the cationic photoinitiator is an onium salt type cationic photoinitiator, including one or more of 4, 4-dimethyl-diphenyliodonium hexafluorophosphate, triphenylsulfonium salt, and diphenyl- (4-phenylthio) phenylsulfonium hexafluorophosphate.
In another preferred embodiment, the weight ratio of the cationic photoinitiator to the unsaturated polyester resin is (0.1-1.0): 100.
in another preferred embodiment, the thermal initiator is an organic peroxide.
In another preferred embodiment, the thermal initiator comprises a first thermal initiator component, and a second thermal initiator component; wherein the first thermal initiator component is benzoyl peroxide and the second thermal initiator component is cumene hydroperoxide. Preferably, the thermal initiator further comprises a third thermal initiator component which is tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexanoate, 4-tert-butylcyclohexyl peroxydicarbonate, or 2, 5-bis (2-ethylhexanoylperoxide) -2, 5-dimethylhexane. More preferably, the weight ratio of the first thermal initiator component, the second thermal initiator component and the third thermal initiator component in the thermal initiator is (1.0-3.0): 1.0.
In another preferred embodiment, the organic peroxide is prepared by compounding benzoyl peroxide, cumene hydroperoxide and tert-butyl peroxybenzoate in a weight ratio of (1.0-3.0): 1.0.
In another preferred embodiment, the weight ratio of the thermal initiator to the unsaturated polyester resin is (0.1-1.0): 100.
in another preferred embodiment, the thickener is magnesium oxide or magnesium hydroxide.
In a second aspect of the present invention, there is provided a method of preparing a photo-cured prepreg, the method comprising the steps of:
(1) preparing the ultraviolet curing resin composition of the first aspect of the invention;
(2) impregnating glass fibers with the resin composition obtained in step (1) to obtain an impregnated article.
In another preferred example, the method further comprises the steps of:
(3) preparing the impregnated obtained in the step (2) into a sheet.
In another preferred embodiment, the weight ratio of the resin composition to the glass fibers in the impregnate is about (30-50): (100-50); preferably, the ratio is (30-50) to (70-50).
In another preferred example, the step (1) includes:
under the condition of keeping out of the sun, adding the unsaturated polyester resin, the free radical photoinitiator, the cationic photoinitiator, the thermal initiator and the thickening agent into a stirring device in sequence for stirring, and vacuumizing to remove air bubbles after stirring is finished to obtain the resin paste.
In another preferred example, the step (2) includes:
impregnating glass fibers with the resin paste of step (1) to obtain the impregnation.
In another preferred example, the step (3) includes:
the impregnation is prepared into a sheet using an SMC sheet unit, and the surface of the sheet is covered with a light-shielding film.
In another preferred example, the method further comprises the step (4):
and (3) curing the sheet obtained in the step (3) in a drying room at 35-45 ℃ (preferably 40 ℃) for 24-72h (preferably 48h), thereby obtaining the light-cured prepreg.
In another preferred embodiment, the glass fibers are selected from the group consisting of: one or more of glass chopped strands, glass chopped mats, and glass cloth.
In another preferred example, the thickness of the light-cured prepreg is 0.5-5 mm; preferably 1.5-2.5 mm.
In a third aspect of the invention, there is provided use of the light-cured prepreg of the second aspect of the invention in the modification of a filling station buried tank liner.
It is to be understood that within the scope of the present invention, the above-described features of the present invention and those specifically described below (e.g., in the examples) may be combined with each other to form new or preferred embodiments. Not to be reiterated herein, but to the extent of space.
Detailed Description
The ultraviolet curing resin composition and the light curing prepreg containing the resin composition are obtained through extensive and intensive research by the inventor, and experimental results show that the light curing prepreg is moderate in hardness, convenient to lay and paste, simple to operate, high in light curing speed, capable of being formed at one time, and capable of saving the construction period.
Before the present invention is described, it is to be understood that this invention is not limited to the particular methodology and experimental conditions described, as such methodologies and conditions may vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting, since the scope of the present invention will be limited only by the appended claims.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. As used herein, the term "about" when used in reference to a specifically recited value means that the value may vary by no more than 1% from the recited value. For example, as used herein, the expression "about 100" includes 99 and 101 and all values in between (e.g., 99.1, 99.2, 99.3, 100, 100.8, 100.9, etc.).
Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, the preferred methods and materials are now exemplified.
In a preferred embodiment of the invention, the invention provides a light-cured resin for improving a double-layer lining of a buried oil tank of a gas station and a method for preparing a prepreg, which ensure that the construction environment of the buried oil tank is safe and environment-friendly, and thicker glass fiber reinforced plastics can be cured and molded at one time.
The invention provides a formula of an ultraviolet curing resin composition, wherein the formula comprises the following raw materials in parts by weight:
unsaturated polyester resin: 100
Free radical photoinitiator: 0.2-1.0
Cationic photoinitiator: 0.1-1.0
Thermal initiator: 0.1-1.0
Thickening agent: 1-4
The unsaturated polyester resin is a p-benzene unsaturated polyester resin, which is prepared by polycondensation reaction of terephthalic acid, dihydric alcohol and maleic anhydride as main raw materials, and is diluted by adding styrene to form viscous liquid resin.
The free radical photoinitiator comprises 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide (TPO), 2,4, 6-trimethylbenzoyl ethoxy phenyl phosphine oxide (TEPO), bis (2,4, 6-trimethylbenzoyl) phenyl phosphine oxide (BAPO)1) Bis (2, 6-dimethoxybenzoyl) - (4, 4' -dimethyloctyl-2) phosphine oxide (BAPO)2) 0.2-1.0% of the weight of the resin;
the cationic initiator is an onium salt cationic photoinitiator and comprises one or more of 4, 4-dimethyl-diphenyliodonium hexafluorophosphate, triphenylsulfonium salt and diphenyl- (4-phenylthio) phenylsulfonium hexafluorophosphate, and the cationic initiator accounts for 0.1-1.0% of the weight of the resin;
the thermal initiator is organic peroxide and comprises one or more of dibenzoyl peroxide, cumene hydroperoxide, tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexanoate, tert-butyl peroxy-3, 5, 5-trimethylhexanoate, 4-tert-butylcyclohexyl peroxydicarbonate, 2, 5-bis (2-ethylhexanoylperoxide) -2, 5-dimethylhexane and tert-butylperoxy carbonate-2-ethylhexyl ester, and the proportion of the thermal initiator is 0.1-1% of the resin;
the thickening agent is magnesium oxide or magnesium hydroxide.
Another preferred embodiment of the present invention provides a method of preparing a light-cured prepreg:
adding unsaturated polyester resin, a free radical photoinitiator, a cationic photoinitiator, a thermal initiator and a thickening agent into a stirring device with high-speed shearing in sequence, stirring at a high speed for 30 minutes, standing, vacuumizing to remove bubbles for 20 minutes, and keeping out of the sun when preparing and stirring to obtain the ultraviolet curing resin composition.
Secondly, placing the dispersed ultraviolet curing resin composition into a feeding tank of an SMC sheet machine set, impregnating glass fiber yarns, controlling the resin content in the light curing prepreg to be about 30-50%, and covering the upper part and the lower part with shading polyester films.
Removing air bubbles through a rolling process, rolling, curing in a drying room at 40 ℃ for 48 hours, packaging the photocuring prepreg by adopting a black film, and storing in a shady and cool place away from light.
A further preferred embodiment of the present invention provides the use of a light-cured prepreg in the modification of a filling station buried tank liner:
the inner surface of the original buried steel oil tank is subjected to sand blasting for rust removal, and is coated with primer resin, the photo-cured prepreg is directly paved and adhered on the inner surface of the steel oil tank, the paving and adhering layer number is determined according to the thickness of the inner layer glass fiber reinforced plastic and the outer layer glass fiber reinforced plastic calculated and designed through structural strength, and the outer layer glass fiber reinforced plastic, the middle gap layer and the inner layer glass fiber reinforced plastic are sequentially manufactured. The middle gap layer is made of 3D glass fiber fabric, and a through gap is formed between the glass fiber reinforced plastic double-layer linings. Tearing off the top layer film of the applied prepreg, and irradiating the prepreg by using an ultraviolet light source with the power of 2-5kw to finish curing.
Compared with the prior art, the invention has the main advantages that:
1. the resin is added with a compound of three initiators, namely a free radical photoinitiator, a cationic photoinitiator and a thermal initiator, wherein the cationic photoinitiator makes up the limitation of the free radical photoinitiator on the light transmission depth and can continue to react after the ultraviolet light stops irradiating, and the thermal initiator can further improve the curing degree and ensure the strength of the glass fiber reinforced plastic double-layer lining. The compound photoinitiator solves the problems of limited ultraviolet light penetration capability and incomplete one-time curing of thick composite material products. The compound initiator system is suitable for completely curing glass fiber reinforced plastics with larger thickness at one time, improves the construction speed and the mechanical property, and is suitable for the modification engineering of the inner lining of the underground oil storage tank of a gas station.
2. The operation is carried out in the sealed limited space of the buried oil tank, the light-cured prepreg is adopted to replace the traditional hand lay-up process to manufacture the glass fiber reinforced plastic, the volatilization of styrene in the construction process is reduced, the construction environment is improved, the injury to personnel is reduced, the possible safety risks of suffocation, explosion and the like are reduced, and the safety and environmental protection in the construction process are realized.
3. The photo-curing prepreg is adopted, so that the paving and the sticking are convenient, the operation is simple, and the labor is saved; compared with a hand pasting process, the construction speed of the light-cured prepreg is high, the curing time is greatly shortened, and the construction period is shortened.
4. The photocuring prepreg is custom-made and produced by an automatic production line, the thickness and the resin content of the photocuring prepreg are consistent, the product quality is ensured to be stable, and the influence of human factors on the construction quality in the construction process is reduced.
The present invention will be described in further detail with reference to the following examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Experimental procedures without specifying the detailed conditions in the following examples are generally carried out under the conventional conditions or under the conditions recommended by the manufacturers. Unless otherwise indicated, percentages and parts are by weight. The test materials and reagents used in the following examples are commercially available without specific reference.
Example 1
The light-cured resin for the light-cured prepreg for reforming the inner liner of the buried oil tank of the gas station provided by the embodiment comprises the following formula components: 10kg of p-benzene type unsaturated polyester resin, 0.03kg of 2,4, 6-trimethylbenzoyldiphenylphosphine oxide (TPO), 0.05kg of diphenyliodonium hexafluorophosphate, 0.02kg of benzoyl peroxide, 0.02kg of cumene hydroperoxide, 0.01kg of tert-butyl peroxybenzoate and 0.2kg of magnesium oxide.
Sequentially adding the raw materials into a stirring device with high-speed shearing, stirring at a high speed for 30 minutes, standing, vacuumizing to remove bubbles for 20 minutes, and keeping away from light during preparation and stirring. And (3) putting the dispersed resin paste into a charging tank of an SMC sheet machine set, impregnating glass fibers, controlling the resin content in the photo-cured prepreg to be about 40%, controlling the thickness of the prepreg to be 1.5mm, and covering black polyester films or polyethylene films up and down. Removing air bubbles through a rolling process, rolling, curing in a drying room at 40 ℃ for 48 hours, packaging the photocuring prepreg by adopting a black film, and storing the photocuring prepreg in a shady and cool place in a dark place.
The inner surface of the original buried steel oil tank is subjected to sand blasting for rust removal, and is coated with priming resin. According to the layout from top to bottom, a layer of light-cured prepreg is uniformly laid on a base layer with a punched bottom, a roller is used for uniformly rolling and compacting the base layer, air bubbles are removed completely, then a surface film is torn off, a second layer of prepreg is immediately pasted according to the width of 1/2 with the width of the base layer, the roller is used for uniformly rolling and compacting the base layer, air bubbles are removed completely, and the steps are continued until a complete tank is completed. And 3 layers of light-cured prepreg sheets are paved, so that the thicknesses of the inner layer glass fiber reinforced plastic and the outer layer glass fiber reinforced plastic are both 4.5mm, the middle gap layer is made of 3D glass fiber fabrics, and a through gap is formed between the double layers of linings. Irradiating the light-cured prepreg for 20min by using a 3kw power ultraviolet lamp, then heating to 100 ℃ by using a baking lamp, curing for 30min, and testing the Barkel hardness to be 48.
Compared with the conventional hand lay-up construction method, the method can realize one-time curing of the light-cured prepreg by 4 gas stations with the length of 30m3The oil tank is taken as an example, the construction period is about 12 days, the time is saved by 40 percent compared with the conventional construction method, the styrene volatilization is reduced, the harm to the body of a constructor is reduced, and the pollution to the environment is reduced.
Example 2
10kg of p-benzene type unsaturated polyester resin, 0.06kg of 2,4, 6-trimethylbenzoylethoxyphenylphosphine oxide (TEPO), 0.08kg of 4, 4-dimethyl-diphenyliodonium hexafluorophosphate, 0.03kg of benzoyl peroxide, 0.03kg of cumene hydroperoxide, 0.01kg of tert-butyl peroxy-2-ethylhexanoate and 0.3kg of magnesium oxide.
By adopting the preparation method in the embodiment 1, the light-cured prepreg is prepared by the formula, and the obtained light-cured prepreg is moderate in hardness. Irradiating the light-cured prepreg for 20min by using a 3kw power ultraviolet lamp, then heating to 80 ℃ by using a baking lamp, curing for 30min, and testing the Barkel hardness to be 42.
The embodiment can realize one-time curing of the light-cured prepreg, the construction period is about 12 days, and the time is saved by 40% compared with the conventional construction method.
Example 3
10kg of p-benzene type unsaturated polyester resin, bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide (BAPO)1)0.09kg, 0.02kg of triphenylsulfonium salt, 0.01kg of benzoyl peroxide, 0.01kg of cumene hydroperoxide, 0.01kg of tert-amyl peroxy-2-ethylhexanoate and 0.2kg of magnesium oxide.
By adopting the preparation method in the embodiment 1, the light-cured prepreg is prepared by the formula, and the obtained light-cured prepreg is moderate in hardness. Irradiating the light-cured prepreg for 20min by using a 3kw power ultraviolet lamp, then heating to 100 ℃ by using a baking lamp, curing for 30min, and testing the Barkel hardness to be 40.
The embodiment can realize one-time curing of the light-cured prepreg, the construction period is about 12 days, and about 40% of time is saved by the conventional construction method.
Example 4
10kg of p-benzene type unsaturated polyester resin, 0.05kg of 2,4, 6-trimethylbenzoylethoxyphenylphosphine oxide (TEPO), 0.06kg of diphenyliodonium hexafluorophosphate, 0.02kg of benzoyl peroxide, 0.02kg of cumene hydroperoxide, 0.01kg of (4-tert-butylcyclohexyl) peroxydicarbonate and 0.1kg of magnesium oxide.
By adopting the preparation method in the embodiment 1, the light-cured prepreg is prepared by the formula, and the obtained light-cured prepreg is moderate in hardness. Irradiating the light-cured prepreg for 20min by using a 3kw power ultraviolet lamp, then heating to 90 ℃ by using a baking lamp, curing for 30min, and testing the Barkel hardness to be 45.
The embodiment can realize one-time curing of the light-cured prepreg, the construction period is about 12 days, and the time is saved by 40% compared with the conventional construction method.
Example 5
10kg of p-benzene type unsaturated polyester resin, and bis (2, 6-dimethoxybenzoyl) - (4, 4' -dimethyloctyl-2) phosphine oxide (BAPO)2)0.1kg, 0.03kg of diphenyl- (4-phenylthio) phenylsulfonium hexafluorophosphate, 0.02kg of benzoyl peroxide, 0.02kg of cumene hydroperoxide, 0.01kg of 2, 5-bis (2-ethylhexanoylperoxide) -2, 5-dimethylhexane, and 0.4 kg of magnesium hydroxide.
By adopting the preparation method in the embodiment 1, the light-cured prepreg is prepared by the formula, and the obtained light-cured prepreg is moderate in hardness. Irradiating the light-cured prepreg for 20min by using a 3kw power ultraviolet lamp, then heating to 80 ℃ by using a baking lamp, curing for 30min, and testing the Barkel hardness to be 42.
The embodiment can realize one-time curing of the light-cured prepreg, the construction period is about 12 days, and the time is saved by 40% compared with the conventional construction method.
Example 6
10kg of p-benzene type unsaturated polyester resin, 0.02kg of 2,4, 6-trimethylbenzoyldiphenylphosphine oxide (TPO), 0.1kg of diphenyl- (4-phenylthio) phenylsulfonium hexafluorophosphate, 0.02kg of benzoyl peroxide, 0.02kg of cumene hydroperoxide, 0.01kg of tert-butyl peroxy carbonic acid-2-ethylhexyl ester and 0.3kg of magnesium oxide.
By adopting the preparation method in the embodiment 1, the light-cured prepreg is prepared by the formula, and the obtained light-cured prepreg is moderate in hardness. Irradiating the light-cured prepreg with a 3kw ultraviolet lamp for 20min, heating to 80 ℃ with a baking lamp, curing for 30min, and testing the Barkel hardness to 46.
The embodiment can realize one-time curing of the light-cured prepreg, the construction period is about 12 days, and the time is saved by 40% compared with the conventional construction method.
Comparative example 1
The light-cured resin for the light-cured prepreg for modifying the inner liner of the buried oil tank of the gas station comprises the following formula components: 100kg of p-benzene type unsaturated polyester resin, 0.3kg of 2,4, 6-trimethylbenzoyldiphenylphosphine oxide (TPO), 0.5kg of diphenyliodonium hexafluorophosphate and 2kg of magnesium oxide.
The resin of comparative example 1 was charged with only the free radical photoinitiator and the cationic photoinitiator. The resin formula of the comparative example 1 is adopted to prepare the light-cured prepreg, the light-cured prepreg is irradiated for 20min by using a 3kw power ultraviolet lamp, then the temperature is heated to 80 ℃ by using a baking lamp, the curing time is 30min, the tested Barr hardness is 20, the curing speed is slow, and the construction period is prolonged to more than 20 days.
Comparative example 2
The light-cured resin for the light-cured prepreg for reforming the inner liner of the buried oil tank of the gas station provided by the embodiment comprises the following formula components: 100kg of p-benzene type unsaturated polyester resin, 0.3kg of 2,4, 6-trimethylbenzoyldiphenylphosphine oxide (TPO), 0.6kg of tert-butyl peroxybenzoate and 2kg of magnesium oxide.
The resin of comparative example 2 was charged with only the free radical photoinitiator and the thermal initiator. The resin formula of comparative example 2 is adopted to prepare the light-cured prepreg, the light-cured prepreg is irradiated for 20min by using a 3kw power ultraviolet lamp, then the temperature is heated to 80 ℃ by using a baking lamp, the curing time is 30min, the Bakel hardness on the surface of the glass fiber reinforced plastic is tested to be 40, but the inner layer of the glass fiber reinforced plastic is sticky, the strength is only about 10, and the curing cannot be completed.
Comparative example 3
The formula of the light-cured resin for the light-cured prepreg for reforming the inner liner of the buried oil tank of the gas station is basically the same as that of the example 1, and the formula comprises the following components: 10kg of p-benzene type unsaturated polyester resin, 0.03kg of 2,4, 6-trimethylbenzoyldiphenylphosphine oxide (TPO), 0.05kg of diphenyliodonium hexafluorophosphate, 0.05kg of benzoyl peroxide and 0.2kg of magnesium oxide.
By adopting the preparation method in the embodiment 1, the light-cured prepreg prepared by the formula is hard and has poor bonding property in use. Irradiating the light-cured prepreg for 20min by using a 3kw power ultraviolet lamp, then heating to 100 ℃ by using a baking lamp, curing for 30min, and testing the Barkel hardness to be 24. The curing speed is slow, and the construction requirements cannot be met.
All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes and modifications of the present invention can be made by those skilled in the art after reading the above teachings of the present invention, and these equivalents also fall within the scope of the present invention as defined by the appended claims.

Claims (10)

1. An ultraviolet-curable resin composition, comprising:
unsaturated polyester resin: 80-120 parts by weight;
free radical photoinitiator: 0.2 to 1.0 part by weight;
cationic photoinitiator: 0.1 to 1.0 part by weight;
thermal initiator: 0.1 to 1.0 part by weight; and
thickening agent: 1-4 parts by weight;
wherein the thermal initiator comprises a first thermal initiator component, a second thermal initiator component, and a third thermal initiator component; wherein the first thermal initiator component is benzoyl peroxide, the second thermal initiator component is cumene hydroperoxide, and the third thermal initiator component is tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexanoate, 4-tert-butylcyclohexyl peroxydicarbonate, 2, 5-bis (2-ethylhexanoylperoxide) -2, 5-dimethylhexane, or 2-ethylhexyl tert-butylperoxycarbonate.
2. The ultraviolet-curable resin composition according to claim 1, wherein the thermal initiator comprises the first thermal initiator component, the second thermal initiator component and the third thermal initiator component in a weight ratio of 1.0 to 3.0: 1.0.
3. The UV curable resin composition according to claim 1, wherein the unsaturated polyester resin is a p-benzene type unsaturated polyester resin.
4. The UV-curable resin composition according to claim 1, wherein the radical photoinitiator is acylphosphine oxide comprising 2,4, 6-trimethylbenzoyldiphenylphosphine oxide (TPO), 2,4, 6-trimethylbenzoylethoxyphenylphosphine oxide (TEPO), bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide (BAPO)1) Bis (2, 6-dimethoxybenzoyl) - (4, 4' -dimethyloctyl-2) phosphine oxide (BAPO)2) One or more of (a).
5. The UV curable resin composition according to claim 4, wherein the weight ratio of the radical photoinitiator to the unsaturated polyester resin is 0.2 to 1.0: 100.
6. the uv curable resin composition according to claim 1, wherein the cationic photoinitiator is an onium salt type cationic photoinitiator comprising one or more of 4, 4-dimethyl-diphenyliodonium hexafluorophosphate, triphenylsulfonium salt, diphenyl- (4-phenylthio) phenylsulfonium hexafluorophosphate.
7. The ultraviolet-curable resin composition according to claim 6, wherein the weight ratio of the cationic photoinitiator to the unsaturated polyester resin is from 0.1 to 1.0: 100.
8. the ultraviolet-curable resin composition according to claim 1, wherein the weight ratio of the thermal initiator to the unsaturated polyester resin is from 0.1 to 1.0: 100.
9. a method of making a light-cured prepreg, the method comprising the steps of:
(1) preparing the ultraviolet light curable resin composition of claim 1;
(2) impregnating glass fibers with the resin composition obtained in the step (1) to obtain an impregnated material;
(3) preparing the impregnated obtained in the step (2) into a sheet.
10. Use of a light-cured prepreg prepared by the method of claim 9 in the modification of a filling station buried tank liner.
CN201810365821.3A 2018-04-23 2018-04-23 Light-cured resin for reconstruction of filling station buried oil tank lining and prepreg Active CN110387114B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810365821.3A CN110387114B (en) 2018-04-23 2018-04-23 Light-cured resin for reconstruction of filling station buried oil tank lining and prepreg

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810365821.3A CN110387114B (en) 2018-04-23 2018-04-23 Light-cured resin for reconstruction of filling station buried oil tank lining and prepreg

Publications (2)

Publication Number Publication Date
CN110387114A CN110387114A (en) 2019-10-29
CN110387114B true CN110387114B (en) 2021-11-02

Family

ID=68284362

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810365821.3A Active CN110387114B (en) 2018-04-23 2018-04-23 Light-cured resin for reconstruction of filling station buried oil tank lining and prepreg

Country Status (1)

Country Link
CN (1) CN110387114B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113024741B (en) * 2021-03-16 2023-07-04 扬州工业职业技术学院 High-low temperature resistant resin composition for preparing oil tank
CN114410192A (en) * 2021-12-23 2022-04-29 江苏新澄瑞材料科技有限公司 UV thermal expansion coating liquid composition and lithium battery thermal runaway protection paster

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20090072518A (en) * 2007-12-28 2009-07-02 (주)디피아이 홀딩스 Preparing method of unsaturated polyester resins containing phosphate and uv-curing flame retarding paint
CN104312192A (en) * 2014-10-27 2015-01-28 武汉理工大学 Composite material prepreg for restoring ultraviolet light curing structure and preparation method thereof
CN105199643A (en) * 2015-10-26 2015-12-30 黑龙江省科学院石油化学研究院 Cationic UV and heat dual deeply-curing adhesive and preparation method thereof
CN105602203A (en) * 2016-02-01 2016-05-25 四川远鸣科技有限公司 Visible-light-curing vinyl ester resin composite prepreg, and preparation method and application method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20090072518A (en) * 2007-12-28 2009-07-02 (주)디피아이 홀딩스 Preparing method of unsaturated polyester resins containing phosphate and uv-curing flame retarding paint
CN104312192A (en) * 2014-10-27 2015-01-28 武汉理工大学 Composite material prepreg for restoring ultraviolet light curing structure and preparation method thereof
CN105199643A (en) * 2015-10-26 2015-12-30 黑龙江省科学院石油化学研究院 Cationic UV and heat dual deeply-curing adhesive and preparation method thereof
CN105602203A (en) * 2016-02-01 2016-05-25 四川远鸣科技有限公司 Visible-light-curing vinyl ester resin composite prepreg, and preparation method and application method thereof

Also Published As

Publication number Publication date
CN110387114A (en) 2019-10-29

Similar Documents

Publication Publication Date Title
CN110387114B (en) Light-cured resin for reconstruction of filling station buried oil tank lining and prepreg
EP2513206B1 (en) Repair of composite materials
CA2905866C (en) Liquid (meth)acrylic syrup for impregnating a fibrous substrate, method of impregnating a fibrous substrate, composite material obtained following polymerisation of the pre-impregnated substrate
CN108357101A (en) A kind of environment-friendly type powder 3D printer
CN101953651B (en) Bathroom chassis and manufacturing method thereof
CN105602203A (en) Visible-light-curing vinyl ester resin composite prepreg, and preparation method and application method thereof
CN101497730A (en) Fluoride bearing release agent and release paper with release coating formed thereby
EP0025359B1 (en) Preimpregnated materials and methods of making and using them
CN109306150A (en) A kind of preparation method of room temperature curing epoxy composite material
AU2003302612A1 (en) Reinforced polymer composition
CN107778782A (en) A kind of epoxy vinyl ester resin prepreg and preparation method thereof of rapid curing, high-performance and low-cost
CN106366996A (en) Heat and moisture resisting organosilicone-modified ultraviolet-curable resin composition, composite comprising same and composite patch repair method
CN110484165B (en) High-temperature-resistant and low-temperature-resistant environment-friendly chloroprene rubber adhesive and preparation method thereof
CN105694239A (en) Waste PCB (printed circuit board) nonmetal powder/EPDM rubber composite material and preparation method thereof
CN107964228A (en) A kind of preparation process of transparent SMC moulding materials
CN114410192A (en) UV thermal expansion coating liquid composition and lithium battery thermal runaway protection paster
CN106433453A (en) Ultraviolet-moisture dual-curing solvent-free anti-pollution flashover coating
CN103802410B (en) Give up fibre/bamboo fiber of PET strengthens unsaturated polyester composite and preparation method thereof
ATE144644T1 (en) METHOD FOR PRODUCING FLEXIBLE FIBER-BASED PROTECTIVE, AUXILIARY AND INSULATING MATERIALS FOR ELECTRICAL PURPOSES USING IMPREGNATING COMPOUNDS CURED BY ENERGY RADIATION
CN117656620A (en) Fiber-containing mica organosilicon composition suitable for large offshore wind turbine generator
CN116731621A (en) UV (ultraviolet) light-cured epoxy prepreg and production process thereof
CN108192515A (en) It is a kind of rubber water-proofing coiled and preparation method thereof
JPH11263857A (en) Photocurable, waterproofing prepreg sheet and preparation process, preparation device and waterproofing coating process of prepreg sheet
CN115534283A (en) Winding thermoplastic pipe and manufacturing method thereof
EP1044777A1 (en) Molding method for corrosion-resistant FRP

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
GR01 Patent grant
GR01 Patent grant