CN1749289A - Propenoic acid beta-hydroxy ethyl ester modified vinyl epoxy resin - Google Patents
Propenoic acid beta-hydroxy ethyl ester modified vinyl epoxy resin Download PDFInfo
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- CN1749289A CN1749289A CN 200510030132 CN200510030132A CN1749289A CN 1749289 A CN1749289 A CN 1749289A CN 200510030132 CN200510030132 CN 200510030132 CN 200510030132 A CN200510030132 A CN 200510030132A CN 1749289 A CN1749289 A CN 1749289A
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Abstract
The present invention relates to beta-hydroxy ethyl acrylate modified vinyl epoxy resin, and features that the resin consists of vinyl epoxy resin slurry and beta-hydroxy ethyl acrylate in the weight ratio of 0.1-10 and contains also free radical initiator in the amount of 1-10 % of their total weight. The resin after initiation of the polymer forms thermosetting polymer. Owing to the beta-hydroxy ethyl acrylate, the polymer has obviously improved anticorrosion property, especially anticorrosion property against high concentration inorganic acid. In addition, the polymer has raised adhesion strength to melamine. The polymer may be used in various anticorrosive table tops for chemical experiment, anticorrosive pipes and anticorrosive device to be used in extreme condition.
Description
Technical field
The present invention relates to a kind of vinyl epoxy resin of modification, particularly a kind of by propenoic acid beta-hydroxy ethyl ester modified vinyl epoxy resin.
Background technology
The history that vinyl epoxy resin (often being called vinyl ester resin) came out and has about 40 years so far from sixties Mo.At first release the Epocrgl brand by U.S.'s shell chemistry (Shell Chemical), released the Derakane brand in 1966 by U.S. Dow chemistry subsequently, what follow release closely is the Hetron brand of Ashland chemistry, and the Ripoxy brand of Japanese showa highpolymer Co., Ltd., other foreign brand name or manufacturer have AOC, Interplastics etc.Because vinyl epoxy resin has good solidity to corrosion, ideal physical strength, water white transparency and construction technology comparatively easily, in the last thirty years, be widely used in industries such as oil, chemical industry, papermaking, metallurgy, thermoelectricity, medicine, food, traffic, environmental protection, building as corrosion-resisting resin of new generation.
The research and development of China's vinyl epoxy resin start from the late nineteen seventies in last century.In two times more than ten years after this, owing to be subjected to influence of various factors such as technology, starting material, year output is paced up and down in about thousands of tons of all the time.Along with the economic fast development of China, the production application amount of domestic vinyl ester resin presented the impetus that increases rapidly in recent years.Because its good performance, and product price progressively reduces, and now more and more understood by people and accepts.The vinyl epoxy resin of commercialization is many at present makes through addition with unsaturated monoprotic acid and epoxy compounds, and end group has unsaturated double-bond.It has kept the basic segment of Resins, epoxy, and the good process performance of unsaturated polyester resin is arranged again, after it solidifies under optimum conditions, shows some special premium properties.In theory, different epoxy compoundss and different unsaturated monoprotic acid reaction, different according to its synthesis technique and method can make structure, physics, vinyl epoxy resin that chemical property is different, are applied to different occasions.The type of vinyl epoxy resin is various on the domestic and international market at present, and representative company and production code member see Table 1.
Table 1 is vinyl ester resin trade mark table look-up both at home and abroad
| Company | DOW Chemical | The Ya Shilan chemistry | Clear and polymkeric substance | DSM N. V. | Last latitude enterprise | Shanghai rich morning | Reichhold |
| Country | The U.S. | The U.S. | Japan | Holland | TaiWan, China | Shanghai | Norway |
| Trade(brand)name | Derakane | Hetron | Ripoxy | Atlac | Swancor | Fuchem | Norpol Dion |
| The standard type bisphenol-A epoxy | 411 | 922 | 806 | 430 | 901 | 854，879， | 9100 |
| Vinyl ester | 880 | ||||||
| The flame retardant type epoxy vinyl ester | 510 | 992 | 550 | 750 | 905 | 892 | 9300 |
| The phenolic aldehyde epoxy vinyl ester | 470 | 980 | 630 | 590 | 907 | 890 | 9400 |
| High crosslink density type epoxy vinyl ester | - | 970 | 600 | - | 977 | 898 | 9700 |
| The flexible epoxy vinyl ester | 8084 | - | - | - | 980 | 810 | - |
| PU modified version epoxy vinyl ester | - | - | - | 580 | - | 820 | 9800 |
Except that above-mentioned kind, the domestic market also has other two big classes at present: a class is the acrylic type vinyl epoxy resin that more producer adopts, or on this resin basis, use urethane-modified processing, the type resin temperature resistant grade descends 10～20 ℃ than corresponding methacrylic acid type vinyl ester resin, the unit elongation of resin rises, but owing to lack the provide protection of methyl, cause the corrosion resistance nature of resin, descend as alkaline resistance properties to ester bond; Another kind of resin is a modified product with Chinese characteristics, it is a fumaric acid modified bisphenol A epoxy Vinylite, but say from the strict sense, it does not belong to vinyl ester resin, a but transition kind in vinyl ester resin and the dihydroxyphenyl propane unsaturated polyester resin, such vinyl ester resin has the big characteristics of cross-linking density height, fragility and contraction, because the ester bond content in the resin is higher by 40～50% than standard type Vinylite, so its alkali resistance is relatively poor relatively.
Though above-mentioned vinyl epoxy resin has remarkable advantages than other macromolecular material on physics, chemical property, under some extreme condition, its performance, particularly chemical rotproofness aspect is still inadequate.Such as, all kinds of vinyl epoxy resins of selling on the domestic market at anti-strong acid, as obviously not enough on anti-98% vitriol oil or the 65% concentrated nitric acid ability, have influenced its popularization, application in high-end product to a great extent at present.
Summary of the invention:
One of purpose of the present invention is to provide a kind of erosion resistance preferably that has, particularly at the corrosive propenoic acid beta-hydroxy ethyl ester modified vinyl epoxy resin of high-concentration inorganic acid resistant.
For achieving the above object, technical conceive of the present invention is:
The present invention is on the basis of original vinyl epoxy resin, adds an amount of propenoic acid beta-hydroxy ethyl ester, finishes resin polymerization in the free radical initiator system, generates the propenoic acid beta-hydroxy ethyl ester modified vinyl resinous polymer.Concrete reaction is as follows:
The vinyl epoxy resin propenoic acid beta-hydroxy ethyl ester
R=forms the used all kinds of alkyl of vinyl epoxy resin
R′＝H，CH
3
n＝0.1～10
According to above-mentioned reaction mechanism, the present invention has adopted following technical scheme:
A kind of propenoic acid beta-hydroxy ethyl ester modified vinyl epoxy resin, it is characterized in that, consisting of of this resin: vinyl epoxy resin slurries and propenoic acid beta-hydroxy ethyl ester, both weight ratios are 0.1～10: 1, and the 1-10% that presses both weight in addition again adds radical initiator.
Above-mentioned vinyl epoxy resin slurries are commercially available standard type bisphenol-A epoxy vinyl ester or phenolic aldehyde epoxy vinyl ester or flame retardant type epoxy vinyl ester or high crosslink density type epoxy vinyl ester or PU modified version epoxy vinyl esters, wherein contain 30% vinylbenzene.
Above-mentioned radical initiator is: dibenzoyl peroxide, or Diisopropyl azodicarboxylate, or tert-butyl peroxide, or dicumyl peroxide, or t-butylperoxyl benzoate.
Propenoic acid beta-hydroxy ethyl ester modified vinyl epoxy resin using method of the present invention is: will evenly coat the substrate surface that needs covering according to the slurry that aforementioned proportion mixes, toasted 40 minutes down at 85 ℃, temperature programming to 125 is ℃ (1 ℃/minute then, need 40 minutes), and under 125 ℃, kept 30 minutes.Naturally cool to room temperature, wear out under the room temperature and can use after 3 days.
Propenoic acid beta-hydroxy ethyl ester modified vinyl epoxy resin of the present invention formed polymkeric substance after free radical causes is a thermosetting polymer, because propenoic acid beta-hydroxy ethyl ester participates in copolymerization, can obviously improve the erosion resistance of polymkeric substance, particularly in high-concentration inorganic acid resistant, do well.Can effectively increase simultaneously the cohesive strength of polymkeric substance and trimeric cyanamide (general composition board top layer all scribbles the trimeric cyanamide material), can be used for the relevant all kinds of anticorrosion table top of chemical experiment, all kinds of insides of pipes that need corrosion resistant, and other need under extreme conditions realize the device of corrosion resistant.
Specific implementation method:
Raw material is prepared: add the p methoxy phenol (stopper) of 1% weight ratio in the propenoic acid beta-hydroxy ethyl ester monomer, 90～92 ℃/12 mmhg cuts are collected in underpressure distillation, place refrigerator or refrigerator to preserve.Pure acrylic acid beta-hydroxy ethyl ester monomer is a colourless transparent liquid, and density is 1.011, and molecular weight is 116.
Embodiment one: propenoic acid beta-hydroxy ethyl ester modified standard type bisphenol-A epoxy vinyl ester polymer (part by weight of vinyl epoxy resin and propenoic acid beta-hydroxy ethyl ester is 5: 1)
With standard type bisphenol-A epoxy vinyl ester slurries (resin content 70%, styrene content 30%) 10 grams at room temperature mix with propenoic acid beta-hydroxy ethyl ester 2 grams, add dibenzoyl peroxide (BPO) 0.60 gram (5% weight ratio) again, be stirred well to the dibenzoyl peroxide powder and disappear, standby.
The slurries that mix are evenly coated the composite surface that the surface is covered with trimeric cyanamide, place composition board that constant temperature toasted 40 minutes in 85 ℃ baking oven, temperature programming to 125 ℃ (1 ℃/minute, totally 40 minutes) then, and kept 30 minutes down at 125 ℃.Composition board is taken out in baking oven, naturally cool to room temperature, and at room temperature aging after 3 days.
Composition board top layer polymkeric substance is water white transparency, smooth smooth.
The corrosion resistance nature test:
◆ 98% vitriol oil, following 1 minute post polymerization thing surface of room temperature is incarnadine, still is incarnadine after 3 hours, and water flushing back incarnadine disappears, and does not have the obviously corrosion marking.
◆ 50 ℃ of 98% vitriol oil, the post polymerization thing surface of dripping takes on a red color at once, still is red after 3 hours, is incarnadine after the water flushing, and the slight corrosion marking is arranged.
◆ 65% concentrated nitric acid, following 1 minute post polymerization thing surface of room temperature is incarnadine, still is incarnadine after 3 hours, and water flushing back incarnadine disappears, and does not have the obviously corrosion marking.
◆ 50 ℃ of 65% concentrated nitric acid, the post polymerization thing surface of dripping takes on a red color at once, still is red after 3 hours, is incarnadine after the water flushing, and the corrosion marking is arranged.
◆ to various concentration hydrogen sodium hydroxide solution, potassium hydroxide solution, other mineral acid except that 98% sulfuric acid, 65% nitric acid, organic solvents such as acetone, ethyl acetate, ethanol, ether, tetrahydrofuran (THF), and organic acid such as acetic acid, benzoic acid solution, p-nitrobenzoic acid solution, propanedioic acid solution does not all have any colour-change or corrosion.
Mechanical strength test (, after the slide surface polymerization, take off, detect and get) with proportioning of the same race and preparation method:
◆ tensile strength Mpa 78
◆ flexural strength Mpa 105
◆ elongation at break % 4.9
Embodiment two: the preparation of propenoic acid beta-hydroxy ethyl ester modified standard type bisphenol-A epoxy vinyl ester polymer (ratio of vinyl epoxy resin and propenoic acid beta-hydroxy ethyl ester is 4: 1)
With standard type bisphenol-A epoxy vinyl ester slurries (resin content 70%, styrene content 30%) 10 grams at room temperature mix with propenoic acid beta-hydroxy ethyl ester 2.5 grams, add dibenzoyl peroxide (BPO) 0.63 gram (5% weight ratio) again, be stirred well to the dibenzoyl peroxide powder and disappear, standby.
The slurries that mix are evenly coated the composite surface that the surface is covered with trimeric cyanamide, place composition board that constant temperature toasted 40 minutes in 85 ℃ baking oven, temperature programming to 125 ℃ (1 ℃/minute, totally 40 minutes) then, and kept 30 minutes down at 125 ℃.Composition board is taken out in baking oven, naturally cool to room temperature, and at room temperature aging after 3 days.
Composition board top layer polymkeric substance is water white transparency, smooth smooth.
The corrosion resistance nature test:
◆ 98% vitriol oil, following 1 minute post polymerization thing surface of room temperature is incarnadine, still is incarnadine after 3 hours, and water flushing back incarnadine disappears, and does not have the obviously corrosion marking.
◆ 50 ℃ of 98% vitriol oil, the post polymerization thing surface of dripping takes on a red color at once, still is red after 3 hours, is incarnadine after the water flushing, and the slight corrosion marking is arranged.
◆ 65% concentrated nitric acid, following 1 minute post polymerization thing surface of room temperature is incarnadine, still is incarnadine after 3 hours, and water flushing back incarnadine disappears, and does not have the obviously corrosion marking.
◆ 50 ℃ of 65% concentrated nitric acid, the post polymerization thing surface of dripping takes on a red color at once, still is red after 3 hours, is incarnadine after the water flushing, and the corrosion marking is arranged.
◆ to various concentration hydrogen sodium hydroxide solution, potassium hydroxide solution, other mineral acid except that 98% sulfuric acid, 65% nitric acid, organic solvents such as acetone, ethyl acetate, ethanol, ether, tetrahydrofuran (THF), and organic acid such as acetic acid, benzoic acid solution, p-nitrobenzoic acid solution, propanedioic acid solution does not all have any colour-change or corrosion.
Mechanical strength test:
◆ tensile strength Mpa 77
◆ flexural strength Mpa 105
◆ elongation at break % 5.0
Embodiment three: the preparation of propenoic acid beta-hydroxy ethyl ester modified standard type bisphenol-A epoxy vinyl ester polymer (ratio of vinyl epoxy resin and propenoic acid beta-hydroxy ethyl ester is 3: 1)
With standard type bisphenol-A epoxy vinyl ester slurries (resin content 70%, styrene content 30%) 10 grams at room temperature mix with propenoic acid beta-hydroxy ethyl ester 3.3 grams, add dibenzoyl peroxide (BPO) 0.67 gram (5% weight ratio) again, be stirred well to the dibenzoyl peroxide powder and disappear, standby.
The slurries that mix are evenly coated the composite surface that the surface is covered with trimeric cyanamide, place composition board that constant temperature toasted 40 minutes in the baking oven of 85oC, temperature programming to 125 ℃ (1 ℃/minute, totally 40 minutes) then, and kept 30 minutes down at 125 ℃.Composition board is taken out in baking oven, naturally cool to room temperature, and at room temperature aging after 3 days.
Composition board top layer polymkeric substance is water white transparency, smooth smooth.
The corrosion resistance nature test:
◆ 98% vitriol oil, following 1 minute post polymerization thing surface of room temperature is incarnadine, still is incarnadine after 3 hours, is blush after the water flushing, does not have the obviously corrosion marking.
◆ 50 ℃ of 98% vitriol oil, the post polymerization thing surface of dripping takes on a red color at once, still is red after 3 hours, is incarnadine after the water flushing, and the corrosion marking is arranged.
◆ 65% concentrated nitric acid, following 1 minute post polymerization thing surface of room temperature is incarnadine, still is incarnadine after 3 hours, is blush after the water flushing, does not have the obviously corrosion marking.
◆ 50 ℃ of 65% concentrated nitric acid, the post polymerization thing surface of dripping takes on a red color at once, still is red after 3 hours, is incarnadine after the water flushing, and the corrosion marking is arranged.
◆ to various concentration hydrogen sodium hydroxide solution, potassium hydroxide solution, other mineral acid except that 98% sulfuric acid, 65% nitric acid, organic solvents such as acetone, ethyl acetate, ethanol, ether, tetrahydrofuran (THF), and organic acid such as acetic acid, benzoic acid solution, p-nitrobenzoic acid solution, propanedioic acid solution does not all have any colour-change or corrosion.
Mechanical strength test:
◆ tensile strength Mpa 76
◆ flexural strength Mpa 103
◆ elongation at break % 5.3
Embodiment four: the preparation of propenoic acid beta-hydroxy ethyl ester modified standard type bisphenol-A epoxy vinyl ester polymer (ratio of vinyl epoxy resin and propenoic acid beta-hydroxy ethyl ester is 2: 1)
With standard type bisphenol-A epoxy vinyl ester slurries (resin content 70%, styrene content 30%) 10 grams at room temperature mix with propenoic acid beta-hydroxy ethyl ester 5.0 grams, add dibenzoyl peroxide (BPO) 0.75 gram (5% weight ratio) again, be stirred well to the dibenzoyl peroxide powder and disappear, standby.
The slurries that mix are evenly coated the composite surface that the surface is covered with trimeric cyanamide, place composition board that constant temperature toasted 40 minutes in 85 ℃ baking oven, temperature programming to 125 ℃ (1 ℃/minute, totally 40 minutes) then, and kept 30 minutes down at 125 ℃.Composition board is taken out in baking oven, naturally cool to room temperature, and at room temperature aging after 3 days.
Composition board top layer polymkeric substance is water white transparency, smooth smooth, but soft.
The corrosion resistance nature test:
◆ 98% vitriol oil, the room temperature post polymerization thing surface pinkiness at once of dripping is red after 3 hours, is incarnadine after the water flushing, and the corrosion marking is arranged.
◆ 50 ℃ of 98% vitriol oil, the post polymerization thing surface of dripping takes on a red color at once, is scarlet after 1 minute, still is scarlet after 3 hours, takes on a red color after the water flushing, and the obvious corrosion marking is arranged.
◆ 65% concentrated nitric acid, following 1 minute post polymerization thing surface of room temperature takes on a red color, and still is scarlet after 3 hours, takes on a red color after the water flushing, and the corrosion marking is arranged.
◆ 50 ℃ of 65% concentrated nitric acid, the post polymerization thing surface of dripping takes on a red color at once, is scarlet after 1 minute, still is red after 3 hours, is incarnadine after the water flushing, and the obvious corrosion marking is arranged.
◆ acetone does not make the polymkeric substance variable color, but the obvious corrosion marking is arranged.
◆ to various concentration hydrogen sodium hydroxide solution, potassium hydroxide solution, other mineral acid except that 98% sulfuric acid, 65% nitric acid, organic solvents such as ethyl acetate, ethanol, ether, tetrahydrofuran (THF), and organic acid such as acetic acid, benzoic acid solution, p-nitrobenzoic acid solution, propanedioic acid solution does not all have any colour-change or corrosion.
Mechanical strength test: polymkeric substance is soft, and it is anticorrosion not to be suitable for composite surface.
Embodiment five: the preparation of propenoic acid beta-hydroxy ethyl ester modified standard type bisphenol-A epoxy vinyl ester polymer (ratio of vinyl epoxy resin and propenoic acid beta-hydroxy ethyl ester is 6: 1)
With standard type bisphenol-A epoxy vinyl ester slurries (resin content 70%, styrene content 30%) 10 grams at room temperature mix with propenoic acid beta-hydroxy ethyl ester 1.7 grams, add dibenzoyl peroxide (BPO) 0.59 gram (5% weight ratio) again, be stirred well to the dibenzoyl peroxide powder and disappear, standby.
The slurries that mix are evenly coated the composite surface that the surface is covered with trimeric cyanamide, place composition board that constant temperature toasted 40 minutes in 85 ℃ baking oven, temperature programming to 125 ℃ (1 ℃/minute, totally 40 minutes) then, and kept 30 minutes down at 125 ℃.Composition board is taken out in baking oven, naturally cool to room temperature, and at room temperature aging after 3 days.
Composition board top layer polymkeric substance is water white transparency, smooth smooth.
The corrosion resistance nature test:
◆ 98% vitriol oil, following 1 minute post polymerization thing surface of room temperature is incarnadine, still is incarnadine after 3 hours, and water flushing back incarnadine disappears, and does not have the obviously corrosion marking.
◆ 50 ℃ of 98% vitriol oil, the post polymerization thing surface of dripping takes on a red color at once, still is red after 3 hours, is incarnadine after the water flushing, and the slight corrosion marking is arranged.
◆ 65% concentrated nitric acid, following 1 minute post polymerization thing surface of room temperature is incarnadine, still is incarnadine after 3 hours, and water flushing back incarnadine disappears, and does not have the obviously corrosion marking.
◆ 50 ℃ of 65% concentrated nitric acid, the post polymerization thing surface of dripping takes on a red color at once, still is red after 3 hours, is incarnadine after the water flushing, and the corrosion marking is arranged.
◆ to various concentration hydrogen sodium hydroxide solution, potassium hydroxide solution, other mineral acid except that 98% sulfuric acid, 65% nitric acid, organic solvents such as acetone, ethyl acetate, ethanol, ether, tetrahydrofuran (THF), and organic acid such as acetic acid, benzoic acid solution, p-nitrobenzoic acid solution, propanedioic acid solution does not all have any colour-change or corrosion.
Mechanical strength test:
◆ tensile strength Mpa 78
◆ flexural strength Mpa 107
◆ elongation at break % 4.9
Embodiment six: the preparation of propenoic acid beta-hydroxy ethyl ester modified standard type bisphenol-A epoxy vinyl ester polymer (ratio of vinyl epoxy resin and propenoic acid beta-hydroxy ethyl ester is 8: 1)
With standard type bisphenol-A epoxy vinyl ester slurries (resin content 70%, styrene content 30%) 10 grams at room temperature mix with propenoic acid beta-hydroxy ethyl ester 1.3 grams, add dibenzoyl peroxide (BPO) 0.57 gram (5% weight ratio) again, be stirred well to the dibenzoyl peroxide powder and disappear, standby.
The slurries that mix are evenly coated the composite surface that the surface is covered with trimeric cyanamide, place composition board that constant temperature toasted 40 minutes in 85 ℃ baking oven, temperature programming to 125 ℃ (1 ℃/minute, totally 40 minutes) then, and kept 30 minutes down at 125 ℃.Composition board is taken out in baking oven, naturally cool to room temperature, and at room temperature aging after 3 days.
Composition board top layer polymkeric substance is water white transparency, smooth smooth.
The corrosion resistance nature test:
◆ 98% vitriol oil, following 1 minute post polymerization thing surface of room temperature is incarnadine, still is incarnadine after 3 hours, and water flushing back incarnadine disappears, and does not have the corrosion marking.
◆ 50 ℃ of 98% vitriol oil, the post polymerization thing surface of dripping takes on a red color at once, still is red after 3 hours, is incarnadine after the water flushing, and the obvious corrosion marking is arranged.
◆ 65% concentrated nitric acid, following 1 minute post polymerization thing surface of room temperature is incarnadine, still is incarnadine after 3 hours, and water flushing back incarnadine disappears, and does not have the corrosion marking.
◆ 50 ℃ of 65% concentrated nitric acid, the post polymerization thing surface of dripping takes on a red color at once, still is red after 3 hours, is incarnadine after the water flushing, and the obvious corrosion marking is arranged.
◆ to various concentration hydrogen sodium hydroxide solution, potassium hydroxide solution, other mineral acid except that 98% sulfuric acid, 65% nitric acid, organic solvents such as acetone, ethyl acetate, ethanol, ether, tetrahydrofuran (THF), and organic acid such as acetic acid, benzoic acid solution, p-nitrobenzoic acid solution, propanedioic acid solution does not all have any colour-change or corrosion.
Mechanical strength test:
◆ tensile strength Mpa 80
◆ flexural strength Mpa 109
◆ elongation at break % 4.7
Embodiment seven: the preparation of propenoic acid beta-hydroxy ethyl ester modified standard type bisphenol-A epoxy vinyl ester polymer (ratio of vinyl epoxy resin and propenoic acid beta-hydroxy ethyl ester is 5: 1) (feather weight)
With standard type bisphenol-A epoxy vinyl ester slurries (resin content 70%, styrene content 30%) 1 kilogram at room temperature mixes for 0.2 kilogram with propenoic acid beta-hydroxy ethyl ester, add 0.06 kilogram of dibenzoyl peroxide (BPO) (5% weight ratio) again, be stirred well to the dibenzoyl peroxide powder and disappear, standby.
The slurries that mix are evenly coated the composite surface that the surface is covered with trimeric cyanamide, place composition board that constant temperature toasted 40 minutes in 85 ℃ baking oven, temperature programming to 125 ℃ (1 ℃/minute, totally 40 minutes) then, and kept 30 minutes down at 125 ℃.Composition board is taken out in baking oven, naturally cool to room temperature, and at room temperature aging after 3 days.
Composition board top layer polymkeric substance is water white transparency, smooth smooth.
The corrosion resistance nature test:
◆ 98% vitriol oil, following 1 minute post polymerization thing surface of room temperature is incarnadine, still is incarnadine after 3 hours, and water flushing back incarnadine disappears, and does not have the obviously corrosion marking.
◆ 50 ℃ of 98% vitriol oil, the post polymerization thing surface of dripping takes on a red color at once, still is red after 3 hours, is incarnadine after the water flushing, and the slight corrosion marking is arranged.
◆ 65% concentrated nitric acid, following 1 minute post polymerization thing surface of room temperature is incarnadine, still is incarnadine after 3 hours, and water flushing back incarnadine disappears, and does not have the obviously corrosion marking.
◆ 50 ℃ of 65% concentrated nitric acid, the post polymerization thing surface of dripping takes on a red color at once, still is red after 3 hours, is incarnadine after the water flushing, and the corrosion marking is arranged.
◆ to various concentration hydrogen sodium hydroxide solution, potassium hydroxide solution, other mineral acid except that 98% sulfuric acid, 65% nitric acid, organic solvents such as acetone, ethyl acetate, ethanol, ether, tetrahydrofuran (THF), and organic acid such as acetic acid, benzoic acid solution, p-nitrobenzoic acid solution, propanedioic acid solution does not all have any colour-change or corrosion.
Mechanical strength test (, after the slide surface polymerization, take off, detect and get) with proportioning of the same race and preparation method:
◆ tensile strength Mpa 77
◆ flexural strength Mpa 105
◆ elongation at break % 5.0
Embodiment eight: the preparation of propenoic acid beta-hydroxy ethyl ester modified standard type bisphenol-A epoxy vinyl ester polymer (ratio of vinyl epoxy resin and propenoic acid beta-hydroxy ethyl ester is 5: 1) (100 feather weight)
With standard type bisphenol-A epoxy vinyl ester slurries (resin content 70%, styrene content 30%) double centner and propenoic acid beta-hydroxy ethyl ester at room temperature mix for 20 kilograms, add 6 kilograms of dibenzoyl peroxide (BPO) (5% weight ratio) again, be stirred well to the dibenzoyl peroxide powder and disappear, standby.
The slurries that mix are evenly coated composite surface (1.5 meters wide 2.0 meters long composition boards that the surface is covered with trimeric cyanamide, be coated with 30 altogether, divide 6 batches and place operation in the large-scale baking oven), placing composition board, constant temperature toasted 40 minutes in 85 ℃ large-scale baking oven, temperature programming to 125 is ℃ (1 ℃/minute then, totally 40 minutes), and under 125 ℃, kept 30 minutes.Composition board is taken out in baking oven, naturally cool to room temperature, and at room temperature aging after 3 days.
Composition board top layer polymkeric substance is water white transparency, smooth smooth.
The corrosion resistance nature test:
◆ 98% vitriol oil, following 1 minute post polymerization thing surface of room temperature is incarnadine, still is incarnadine after 3 hours, and water flushing back incarnadine disappears, and does not have the obviously corrosion marking.
◆ 50 ℃ of 98% vitriol oil, the post polymerization thing surface of dripping takes on a red color at once, still is red after 3 hours, is incarnadine after the water flushing, and the slight corrosion marking is arranged.
◆ 65% concentrated nitric acid, following 1 minute post polymerization thing surface of room temperature is incarnadine, still is incarnadine after 3 hours, and water flushing back incarnadine disappears, and does not have the obviously corrosion marking.
◆ 50 ℃ of 65% concentrated nitric acid, the post polymerization thing surface of dripping takes on a red color at once, still is red after 3 hours, is incarnadine after the water flushing, and the corrosion marking is arranged.
◆ to various concentration hydrogen sodium hydroxide solution, potassium hydroxide solution, other mineral acid except that 98% sulfuric acid, 65% nitric acid, organic solvents such as acetone, ethyl acetate, ethanol, ether, tetrahydrofuran (THF), and organic acid such as acetic acid, benzoic acid solution, p-nitrobenzoic acid solution, propanedioic acid solution does not all have any colour-change or corrosion.
Mechanical strength test (, after the slide surface polymerization, take off, detect and get) with proportioning of the same race and preparation method:
◆ tensile strength Mpa 77
◆ flexural strength Mpa 106
◆ elongation at break % 4.9
Embodiment nine: the preparation of propenoic acid beta-hydroxy ethyl ester modified phenolic aldehyde epoxy vinyl ester polymer (ratio of vinyl epoxy resin and propenoic acid beta-hydroxy ethyl ester is 5: 1) (feather weight)
With standard type bisphenol-A epoxy vinyl ester slurries (resin content 70%, styrene content 30%) 1 kilogram at room temperature mixes for 0.2 kilogram with propenoic acid beta-hydroxy ethyl ester, add 0.06 kilogram of dibenzoyl peroxide (BPO) (5% weight ratio) again, be stirred well to the dibenzoyl peroxide powder and disappear, standby.
The slurries that mix are evenly coated the composite surface that the surface is covered with trimeric cyanamide, place composition board that constant temperature toasted 40 minutes in 85 ℃ baking oven, temperature programming to 125 ℃ (1 ℃/minute, totally 40 minutes) then, and kept 30 minutes down at 125 ℃.Composition board is taken out in baking oven, naturally cool to room temperature, and at room temperature aging after 3 days.
Composition board top layer polymkeric substance is water white transparency, smooth smooth.
The corrosion resistance nature test:
◆ 98% vitriol oil, following 2 minutes post polymerization thing surfaces of room temperature are incarnadine, still are incarnadine after 3 hours, and water flushing back incarnadine disappears, and does not have the obviously corrosion marking.
◆ 50 ℃ of 98% vitriol oil, the post polymerization thing surface of dripping takes on a red color at once, still is red after 3 hours, is incarnadine after the water flushing, and the slight corrosion marking is arranged.
◆ 65% concentrated nitric acid, following 5 minutes post polymerization thing surfaces of room temperature are incarnadine, still are incarnadine after 3 hours, and water flushing back incarnadine disappears, and does not have the obviously corrosion marking.
◆ 50 ℃ of 65% concentrated nitric acid, the post polymerization thing surface of dripping takes on a red color at once, still is red after 3 hours, is incarnadine after the water flushing, and the corrosion marking is arranged.
◆ to various concentration hydrogen sodium hydroxide solution, potassium hydroxide solution, other mineral acid except that 98% sulfuric acid, 65% nitric acid, organic solvents such as acetone, ethyl acetate, ethanol, ether, tetrahydrofuran (THF), and organic acid such as acetic acid, benzoic acid solution, p-nitrobenzoic acid solution, propanedioic acid solution does not all have any colour-change or corrosion.
Mechanical strength test (, after the slide surface polymerization, take off, detect and get) with proportioning of the same race and preparation method:
◆ tensile strength Mpa 81
◆ flexural strength Mpa 135
◆ elongation at break % 4.7
Embodiment ten: the preparation of propenoic acid beta-hydroxy ethyl ester modified standard type bisphenol-A epoxy vinyl ester polymer (ratio of vinyl epoxy resin and propenoic acid beta-hydroxy ethyl ester is 5: 1) (feather weight, Diisopropyl azodicarboxylate causes)
With standard type bisphenol-A epoxy vinyl ester slurries (resin content 70%, styrene content 30%) 1 kilogram at room temperature mixes for 0.2 kilogram with propenoic acid beta-hydroxy ethyl ester, add 0.06 kilogram of Diisopropyl azodicarboxylate (AIBN) (5% weight ratio) again, be stirred well to the dibenzoyl peroxide powder and disappear, standby.
The slurries that mix are evenly coated the composite surface that the surface is covered with trimeric cyanamide, place composition board that constant temperature toasted 40 minutes in 85 ℃ baking oven, temperature programming to 125 ℃ (1 ℃/minute, totally 40 minutes) then, and kept 30 minutes down at 125 ℃.Composition board is taken out in baking oven, naturally cool to room temperature, and at room temperature aging after 3 days.
Composition board top layer polymkeric substance is water white transparency, smooth smooth.
The corrosion resistance nature test:
◆ 98% vitriol oil, following 1 minute post polymerization thing surface of room temperature is incarnadine, still is incarnadine after 3 hours, and water flushing back incarnadine disappears, and does not have the obviously corrosion marking.
◆ 50 ℃ of 98% vitriol oil, the post polymerization thing surface of dripping takes on a red color at once, still is red after 3 hours, is incarnadine after the water flushing, and the slight corrosion marking is arranged.
◆ 65% concentrated nitric acid, following 1 minute post polymerization thing surface of room temperature is incarnadine, still is incarnadine after 3 hours, and water flushing back incarnadine disappears, and does not have the obviously corrosion marking.
◆ 50 ℃ of 65% concentrated nitric acid, the post polymerization thing surface of dripping takes on a red color at once, still is red after 3 hours, is incarnadine after the water flushing, and the corrosion marking is arranged.
◆ to various concentration hydrogen sodium hydroxide solution, potassium hydroxide solution, other mineral acid except that 98% sulfuric acid, 65% nitric acid, organic solvents such as acetone, ethyl acetate, ethanol, ether, tetrahydrofuran (THF), and organic acid such as acetic acid, benzoic acid solution, p-nitrobenzoic acid solution, propanedioic acid solution does not all have any colour-change or corrosion.
Mechanical strength test (, after the slide surface polymerization, take off, detect and get) with proportioning of the same race and preparation method:
◆ tensile strength Mpa 78
◆ flexural strength Mpa 105
Elongation at break % 4.9.
Claims (3)
1. propenoic acid beta-hydroxy ethyl ester modified vinyl epoxy resin, it is characterized in that, consisting of of this resin: vinyl epoxy resin slurries and propenoic acid beta-hydroxy ethyl ester, both weight ratios are 0.1～10: 1, and the 1-10% that presses both weight in addition again adds radical initiator.
2. propenoic acid beta-hydroxy ethyl ester modified vinyl epoxy resin according to claim 1, it is characterized in that, described vinyl epoxy resin slurries are commercially available standard type bisphenol-A epoxy vinyl ester or phenolic aldehyde epoxy vinyl ester or flame retardant type epoxy vinyl ester or high crosslink density type epoxy vinyl ester or PU modified version epoxy vinyl esters, wherein contain 30% vinylbenzene.
3. propenoic acid beta-hydroxy ethyl ester modified vinyl epoxy resin according to claim 1 is characterized in that described radical initiator is: dibenzoyl peroxide, or Diisopropyl azodicarboxylate, or tert-butyl peroxide, or dicumyl peroxide, or t-butylperoxyl benzoate.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103013054A (en) * | 2011-09-27 | 2013-04-03 | 上海机电工程研究所 | Anti-burning type epoxy vinyl ester resin and preparation method thereof |
| CN104017402A (en) * | 2014-05-23 | 2014-09-03 | 浙江鸿浩科技有限公司 | Flame retardation type exterior coating capable of automatically cleaning |
| CN104817933A (en) * | 2015-04-28 | 2015-08-05 | 上海大学 | Self-cleaning super-hydrophobic corrosion-resisting coating |
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| KR100195757B1 (en) * | 1996-12-10 | 1999-06-15 | 한영재 | Organic-inorganic composite metal surface coating composition |
| JP2000192255A (en) * | 1998-12-22 | 2000-07-11 | Kawasaki Steel Corp | Surface treating agent for galvanized steel sheet and surface treated galvanized steel sheet |
| JP4444432B2 (en) * | 2000-03-01 | 2010-03-31 | 関西ペイント株式会社 | Epoxy resin emulsion and aqueous coating composition containing the same |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103013054A (en) * | 2011-09-27 | 2013-04-03 | 上海机电工程研究所 | Anti-burning type epoxy vinyl ester resin and preparation method thereof |
| CN104017402A (en) * | 2014-05-23 | 2014-09-03 | 浙江鸿浩科技有限公司 | Flame retardation type exterior coating capable of automatically cleaning |
| CN104817933A (en) * | 2015-04-28 | 2015-08-05 | 上海大学 | Self-cleaning super-hydrophobic corrosion-resisting coating |
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