CN1467262A - High temperature corrosion-resisting resin - Google Patents
High temperature corrosion-resisting resin Download PDFInfo
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- CN1467262A CN1467262A CNA021146659A CN02114665A CN1467262A CN 1467262 A CN1467262 A CN 1467262A CN A021146659 A CNA021146659 A CN A021146659A CN 02114665 A CN02114665 A CN 02114665A CN 1467262 A CN1467262 A CN 1467262A
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- high temperature
- temperature corrosion
- catalyzer
- resisting resin
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Abstract
An anticorrosion refractory resin used for the equipment and pipeline working at 120-180 deg.C is prepared from epoxy resin, unsaturated monocarboxylic acid, phenol, and cross-linking monomer through synthesizing at 85-115 deg.C under existance of catalyst which is the mixture of organic peroxide, alkali and organic amine.
Description
Technical field
The present invention relates to a kind of high temperature corrosion-resisting resin, particularly a kind of vinyl ester resin is used for anticorrosion under high-temperature corrosion environment of metal and non-metallic material, can substitute other class corrosion-resistant metal materials such as lass lining, graphite, fluoroplastics material.
Background technology
Vinyl ester resin all has manufacturer production both at home and abroad at present, but its use temperature is all not high, the Atlac590 of domestic W2-2, the Derakne470 of the U.S., Holland, and the life-time service temperature can reach 120 ℃.The Ripoxy of the Derakne-411 of domestic MFE-2, MFE-3, the U.S., Japan, the life-time service temperature has only 100 ℃.And vinyl ester resin organic solvent-resistant in the market and high dense acetic acid poor performance are lower than Resins, epoxy with the adhesive property of other materials.
The vinyl ester resin that U.S. Pat 4480077 is introduced, be by dihydroxyphenyl propane, bisphenol A epoxide resin, methacrylic acid, cis-butenedioic anhydride, under the katalysis of superoxide (as methylethyl ketone peroxide or tertbutyl peroxide etc.), carry out the synthetic product, heat-drawn wire has only 108 ℃.The vinyl ester resin that U.S. Pat 5614299 is introduced is by cis-butenedioic anhydride, phthalic anhydride, 2-methyl isophthalic acid, and 3 propylene glycol, 1,4 cyclohexanedimethanoester ester synthesize, though this product can be high temperature resistant more than 200 ℃, it is mainly used in the making substrate for printed circuit board.
Anticorrosion market is the main application fields of vinyl ester resin, and it has excellent acidproof, alkali corrosion resistance ability.When use temperature was lower than 100 ℃, used in the market vinyl ester resin can both satisfy, but was 120 ℃-180 ℃ scope in the life-time service temperature, and under the acid concentration condition with higher, example hydrochloric acid 32% when sulfuric acid 60% is above, just can't satisfy.
Summary of the invention
The object of the present invention is to provide a kind of high temperature corrosion-resisting resin, particularly a kind of high temperature corrosion-resisting resin that can be used for equipment, pipeline between 120 ℃～180 ℃ temperature.
High temperature corrosion-resisting resin of the present invention, its composition of raw materials consists of:
A.30％～50％
B.14.2％～18.5％
C.25％～40％
D.0.01％～0.05％
E.10％～15％
Wherein:
A. epoxy resin: can be selected from bisphenol A epoxide resin, novolac epoxy, polybutadiene epoxy resin, ester ring family epoxy etc., wherein bisphenol A epoxide resin, novolac epoxy are better.
B. unsaturated monocarboxylic acid: can be selected from methacrylic acid, vinylformic acid, butenoic acid etc.
C. crosslinkable monomers: can be selected from vinylbenzene, acrylate, methacrylic ester, chloro-styrene etc.
D. phenols: can be selected from Resorcinol, benzoquinones, p-ten.-butylcatechol, methyl hydroquinone etc.
E. catalyzer: be organo-peroxide, the mixture of alkali and organic amine.
This resin is by A, B, D, E are dropped into polymeric kettle, and under 100～125 ℃, polymerization isomery 1.5～2.5 hours adds C then, obtains at 80～100 ℃ times crosslinked 1.0～2.5 hours.
Organo-peroxide can be tertbutyl peroxide, benzoyl peroxide, methylethyl ketone peroxide etc. in the catalyzer of the present invention, and the organo-peroxide that the system vinyl ester resin catalyzer of being introduced among the similar US4480077 is commonly used all can; Alkali in the catalyzer is not limited, and alkaline matter gets final product, as NaOH, Na
2CO
3Or the like, the organic amine in the catalyzer can be trolamine, mphenylenediamine, benzyldimethylamine or the like; Catalyzer is formed proportioning and is formed and different according to the different material that adopts, and it is 85～90: 5～10 that the catalyzer that the present invention recommends is formed mass mixing ratio: 5～10; Preparation of catalysts can adopt simple blending, the powerful mode that stirs to prepare.
The catalyzer that the present invention is used not only can play katalysis, and have isomerization, and can decompose fully in resin is synthetic.The product that decomposes can participate in grafting, isomery and the addition reaction of resin fully, and can provide the resin formation high-temperature-resistant structure required partial monosomy, has therefore simplified preparation technology.Owing to once feed intake, series reaction such as open loop, grafting, isomery, decomposition, catalysis, addition, copolymerization are carried out in same device continuously, (for having now about half of production technique) with short production cycle, energy consumption and production cost are low, the earning rate height of resin the most important thing is to capture the difficult problem of recurrent in the production of resins " resin autohemagglutination ".
Cross-linking monomer of the present invention and consumption not only play a part to regulate the resin workability, and influence the corrosion resistance nature of resin, therefore can select the kind and the consumption of cross-linking monomer according to different needs.
High temperature corrosion-resisting resin of the present invention can be used instrument constructions such as spray gun, hairbrush, and saturable fiberglass products is made glass reinforced plastic lining and glass reinforced plastic equipment.
High temperature corrosion-resisting resin of the present invention can be widely used in petrochemical complex; chemical industry; metallurgical; electric power; light industry; pharmacy; electronics; aerospace; heating power; plumbing; municipal administration; the equipment of industries such as environment protection (comprising: reactor; tower; basin; storage tank; electrolyzer; shell and tube heat exchanger; plate-type heat exchanger; U type tubular heat exchanger; spiral-plate exchanger; fin-tube heat exchanger; tube exchanger); pipeline and pipeline accessory (comprising: pipeline; pipe fitting; pump; valve) protection against corrosion and high temperature corrosion-resisting sealing material and sealing article, and can be used to make glass fiber reinforced plastics product.It is anticorrosion that but life-time service carries out in equipment, the pipeline between 120 ℃～180 ℃ temperature, and result of use is good.
Embodiment
Embodiment 1:
A. bisphenol A epoxide resin (E-44) 45g
B. methacrylic acid 15g
C. vinylbenzene 32g
D. Resorcinol 0.02g
F. catalyzer
(mass ratio: benzoyl peroxide: NaOH: 12g benzyldimethylamine=85: 9.4: 5.6)
A, B, D, E are dropped into polymeric kettle, and under 110 ℃, polymerization isomery 2 hours adds C then, promptly gets product down in crosslinked 1.5 hours at 85 ℃.
Embodiment 2:
A. phenolic aldehyde epoxy (F-44) 50g
B. butenoic acid 18g
C. methacrylic ester 28g
D. methyl hydroquinone 0.03g
E. catalyzer (mass ratio: tertbutyl peroxide: KOH: 15g trolamine=87: 7: 6)
A, B, D, E are dropped into polymeric kettle, and under 115 ℃, polymerization isomery 1.5 hours adds C then, promptly gets product down in crosslinked 1.7 hours at 87 ℃.
Embodiment 3:
A. ester ring family epoxy (D-17) 42g
B. butenoic acid 20g
C. acrylate 40g
D. methyl hydroquinone 0.05g
E. catalyzer (mass ratio: methylethyl ketone peroxide: Na
2CO
3: 15g mphenylenediamine=86: 6: 8)
A, B, D, E are dropped into polymeric kettle, and under 105 ℃, polymerization isomery 2 hours adds C then, promptly gets product down in crosslinked 2 hours at 90 ℃.
To use the comparison of the key technical indexes with the similar products at home and abroad advanced person index of embodiments of the invention gained high temperature corrosion-resisting resin, see Table 1, shown in the table 2.1. mechanics index of physics
The contrast of table 1 mechanics index of physics
| Project | Domestic MFE-2 | Domestic W2-1 | U.S. DOW company | Holland | Japan | Embodiment 1 | Embodiment 2 | Embodiment 3 | ||
| ??Derakne470 | ??????Atlac-590 | ?????UE-5210 | ||||||||
| Casting matrix | Glass reinforced plastic | Casting matrix | Casting matrix | Glass reinforced plastic | Casting matrix | Glass reinforced plastic | Glass reinforced plastic | Glass reinforced plastic | Glass reinforced plastic | |
| Tensile strength MPa | ??35.2 | ??294 | ??85 | ??90 | ??111 | ??50～70 | ??80～ ??100 | ??282 | ??292 | ??291 |
| Bending strength MPa | ??69.0 | ??313.6 | ??131 | ??155 | ??208 | ??80～ ??120 | ??180～ ??200 | ??425 | ??428 | ??423 |
| Shock strength KJ/m 2 | ??18.5 | ??13 | ??2～4 | ??75～85 | ??120 | ??124 | ??131 | |||
| Thermal denaturation temperature ℃ | ??106 | ??120 | ??149～154 | ??140 | ??140 | ??150～ ??160 | ??150～ ??160 | ??220 | ??230 | ??250 |
2. resistance to chemical corrosion
The contrast of table 2 resistance to chemical corrosion
| Domestic MFE-2 Vinylite | External 470 Vinylites | Embodiment 1 | Embodiment 2 | Embodiment 3 | |||||||||||
| Concentration % | Temperature ℃ | Rate of weight loss % | Concentration % | Temperature ℃ | Rate of weight loss % | Concentration % | Temperature ℃ | Rate of weight loss % | Concentration % | Temperature ℃ | Rate of weight loss % | Concentration % | Temperature ℃ | Rate of weight loss % | |
| ????H 2SO 4 | ????5 ????30 | ????80 ????80 | Anti- | ????10 ????30 | ????80 ????80 | ????0.26 ????0.28 | ????20 ????60 ????60 | ????80 ????80 ????120 | ??-0.42 ??-0.43 ??-0.85 | ????50 ????70 | ????100 ????100 | ????-0.51 ????-0.66 | ????50 ????70 | ??100 ??100 | ????-0.45 ????-0.59 |
| ????HCl | ????5 ????30 | ????80 ????80 | Nai Shangnai | ????10 | ????80 | ????0.20 | ????20 ????30 | ????80 ????80 | ??-0.08 ??-0.10 | ????15 | ????100 | ????-0.76 | ????15 | ??100 | ????-0.31 |
| ????HNO 3 | ????5 | ????80 | Still anti- | ????10 | ????80 | ??-0.73 | ????5 | ????100 | ????-0.78 | ????5 | ??100 | ????-0.47 | |||
| Acetic acid | ????99 | ????110 | ??+2.89 | ????99 | ????100 | ????+2.64 | ????99 | ??100 | ????+1.43 | ||||||
| ????HCl0 | ????150 | ??-0.28 | ????150 | ????-0.25 | ??150 | ????-0.35 | |||||||||
| ????NaOH | ????5 | ????80 | Still anti- | ????10 | ????80 | ????0.30 | ????10 ????20 | ????80 ????80 | ??-0.12 ??-0.20 | ????5 ????15 | ????80 ????80 | ????-0.05 ????-0.07 | ????5 ????15 | ??80 ??80 | ????-0.25 ????-0.12 |
| Toluene | Still anti- | Reagent | Normal temperature | ??-0.36 | Reagent | ????80 | ????+2.37 | Reagent | ??80 | ????+1.24 | |||||
| Heatproof | ????≤100 | Qualified | ???????＜150 | Qualified | ?????????≤250 | Qualified | ???????≤270 | Qualified | ?????????≤270 | Qualified | |||||
Annotate: test method is GB3857-83 " a unsaturated polyester resin glass fiber reinforced plastics chemical resistance test method ",
Evaluation criteria derives from " corrosion data handbook "-" expression weightlessness, "+" expression weightening finish;
1. anti-corrosion weight rate-0.5%～+ 3.0%
2. still anti-corrosion weight rate+3.0%～+ 8.0% ,-0.5%～-3.0%
3. not anti-corrosion weight rate-3%,＞+8%
Claims (9)
1. high temperature corrosion-resisting resin, its composition of raw materials mass percent consists of:
A. Resins, epoxy 30%～50%
B. unsaturated monocarboxylic acid 14.2%～18.5%
C. crosslinkable monomers 25%～40%
D. phenols 0.01%～0.05%
E. catalyzer: 10%～15%
Wherein catalyzer is an organo-peroxide, the mixture of alkali and organic amine;
This resin is by A, B, D, E are dropped into polymeric kettle, and under 100～125 ℃, polymerization isomery 1.5～2.5 hours adds C then, obtains at 80～100 ℃ times crosslinked 1.0～2.5 hours.
2. according to the high temperature corrosion-resisting resin described in the claim 1, it is characterized in that Resins, epoxy is meant bisphenol A epoxide resin, phenolic aldehyde epoxy resin varnish, tetraphenyl oxyethane, ester ring family epoxy.
3. according to the high temperature corrosion-resisting resin described in the claim 1, it is characterized in that unsaturated monocarboxylic acid is meant methacrylic acid, vinylformic acid, butenoic acid.
4. according to the high temperature corrosion-resisting resin described in the claim 1, it is characterized in that crosslinkable monomers is meant vinylbenzene, acrylate, methacrylic ester, chloro-styrene.
5. according to the high temperature corrosion-resisting resin described in the claim 1, it is characterized in that phenols is meant Resorcinol, benzoquinones, p-ten.-butylcatechol, methyl hydroquinone.
6. according to the high temperature corrosion-resisting resin described in the claim 1, it is characterized in that the organo-peroxide of catalyzer, the mass mixing ratio of alkali and organic amine is 85～90: 5～10: 5～10.
7. according to the high temperature corrosion-resisting resin described in claim 1 or 6, it is characterized in that organo-peroxide is tertbutyl peroxide, benzoyl peroxide, methylethyl ketone peroxide in the catalyzer.
8. according to the high temperature corrosion-resisting resin described in claim 1 or 6, it is characterized in that the alkali in the catalyzer is NaOH, Na
2CO
3
9. according to the high temperature corrosion-resisting resin described in claim 1 or 6, it is characterized in that the organic amine in the catalyzer is trolamine, mphenylenediamine, benzyldimethylamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021146659A CN100334125C (en) | 2002-06-28 | 2002-06-28 | High temperature corrosion-resisting resin |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021146659A CN100334125C (en) | 2002-06-28 | 2002-06-28 | High temperature corrosion-resisting resin |
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| Publication Number | Publication Date |
|---|---|
| CN1467262A true CN1467262A (en) | 2004-01-14 |
| CN100334125C CN100334125C (en) | 2007-08-29 |
Family
ID=34142065
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021146659A Expired - Fee Related CN100334125C (en) | 2002-06-28 | 2002-06-28 | High temperature corrosion-resisting resin |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101982480A (en) * | 2010-10-19 | 2011-03-02 | 兰州瑞玛化机有限公司 | Solvent-containing high-temperature corrosion-resistant flame-resistant anti-fouling thermoplastic resin |
| CN1815365B (en) * | 2006-02-28 | 2011-04-20 | 上海昭和高分子有限公司 | Photocurable resin composition, and its preparing method and use |
| CN103709895A (en) * | 2013-12-05 | 2014-04-09 | 江苏金波新材料科技有限公司 | Anticorrosive paint used for pipes |
| CN103910855A (en) * | 2012-12-29 | 2014-07-09 | 常州华科聚合物股份有限公司 | Vinyl ester resin and preparation method thereof |
| CN103936942A (en) * | 2014-04-23 | 2014-07-23 | 苏州羽帆新材料科技有限公司 | High-temperature-resistant and acid-and-base-resistant plastic |
| CN104479498A (en) * | 2014-12-19 | 2015-04-01 | 苏州菲博特智能科技有限公司 | Monitoring equipment |
| CN104788648A (en) * | 2015-04-17 | 2015-07-22 | 大庆庆鲁朗润科技有限公司 | Modified solid epoxy resin with high glass transition temperature and high tenacity as well as preparation method thereof |
| CN105885011A (en) * | 2014-09-05 | 2016-08-24 | 薛俊峰 | High temperature oxidation resistant modified epoxy resin and preparation method thereof |
| CN106832795A (en) * | 2016-12-29 | 2017-06-13 | 浙江诺比高分子材料有限公司 | A kind of high-temperature resistant anti-corrosive vinylite |
| CN108164658A (en) * | 2018-01-23 | 2018-06-15 | 山东辉石新能源技术有限公司 | A kind of novel fire resistant corrosion-resisting resin |
| CN112068328A (en) * | 2020-09-09 | 2020-12-11 | 温州市皓朗眼镜有限公司 | Corrosion-resistant glasses frame and processing technology thereof |
| CN116355531A (en) * | 2023-02-27 | 2023-06-30 | 科兰建筑材料（马鞍山）有限公司 | Acid-resistant paint and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1029924C (en) * | 1992-07-06 | 1995-10-04 | 上海新华树脂厂 | isocyanate-modified vinyl ester resin |
| JPH06203627A (en) * | 1992-12-28 | 1994-07-22 | Dai Ichi Kogyo Seiyaku Co Ltd | Conductive composition |
| CN1178230A (en) * | 1996-07-30 | 1998-04-08 | 日本化药株式会社 | Epoxy resin liquid composition for semiconductor encapsulation |
| CN1117109C (en) * | 1999-12-30 | 2003-08-06 | 复旦大学 | Process for preparing compound aqueous dispersion system of epoxy resin and acrylic resin |
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2002
- 2002-06-28 CN CNB021146659A patent/CN100334125C/en not_active Expired - Fee Related
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| CN1815365B (en) * | 2006-02-28 | 2011-04-20 | 上海昭和高分子有限公司 | Photocurable resin composition, and its preparing method and use |
| CN101982480A (en) * | 2010-10-19 | 2011-03-02 | 兰州瑞玛化机有限公司 | Solvent-containing high-temperature corrosion-resistant flame-resistant anti-fouling thermoplastic resin |
| CN103910855A (en) * | 2012-12-29 | 2014-07-09 | 常州华科聚合物股份有限公司 | Vinyl ester resin and preparation method thereof |
| CN103910855B (en) * | 2012-12-29 | 2016-12-28 | 常州华科聚合物股份有限公司 | A kind of vinyl ester resin and preparation method thereof |
| CN103709895B (en) * | 2013-12-05 | 2016-08-17 | 江苏金波新材料科技有限公司 | A kind of anticorrosive paint for tubing |
| CN103709895A (en) * | 2013-12-05 | 2014-04-09 | 江苏金波新材料科技有限公司 | Anticorrosive paint used for pipes |
| CN103936942A (en) * | 2014-04-23 | 2014-07-23 | 苏州羽帆新材料科技有限公司 | High-temperature-resistant and acid-and-base-resistant plastic |
| CN105885011A (en) * | 2014-09-05 | 2016-08-24 | 薛俊峰 | High temperature oxidation resistant modified epoxy resin and preparation method thereof |
| CN104479498A (en) * | 2014-12-19 | 2015-04-01 | 苏州菲博特智能科技有限公司 | Monitoring equipment |
| CN104788648A (en) * | 2015-04-17 | 2015-07-22 | 大庆庆鲁朗润科技有限公司 | Modified solid epoxy resin with high glass transition temperature and high tenacity as well as preparation method thereof |
| CN106832795A (en) * | 2016-12-29 | 2017-06-13 | 浙江诺比高分子材料有限公司 | A kind of high-temperature resistant anti-corrosive vinylite |
| CN108164658A (en) * | 2018-01-23 | 2018-06-15 | 山东辉石新能源技术有限公司 | A kind of novel fire resistant corrosion-resisting resin |
| CN112068328A (en) * | 2020-09-09 | 2020-12-11 | 温州市皓朗眼镜有限公司 | Corrosion-resistant glasses frame and processing technology thereof |
| CN112068328B (en) * | 2020-09-09 | 2022-02-22 | 温州市皓朗眼镜有限公司 | Corrosion-resistant glasses frame and processing technology thereof |
| CN116355531A (en) * | 2023-02-27 | 2023-06-30 | 科兰建筑材料（马鞍山）有限公司 | Acid-resistant paint and preparation method and application thereof |
| CN116355531B (en) * | 2023-02-27 | 2024-03-26 | 科兰建筑材料（马鞍山）有限公司 | Acid-resistant paint and preparation method and application thereof |
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| CN100334125C (en) | 2007-08-29 |
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