CN112225879A - A kind of modified amine curing agent and preparation method thereof - Google Patents
A kind of modified amine curing agent and preparation method thereof Download PDFInfo
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- CN112225879A CN112225879A CN202011115748.8A CN202011115748A CN112225879A CN 112225879 A CN112225879 A CN 112225879A CN 202011115748 A CN202011115748 A CN 202011115748A CN 112225879 A CN112225879 A CN 112225879A
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- 150000001412 amines Chemical class 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 47
- 239000003822 epoxy resin Substances 0.000 claims abstract description 13
- 229920000768 polyamine Polymers 0.000 claims abstract description 13
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 13
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 claims description 6
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- QNYBOILAKBSWFG-UHFFFAOYSA-N 2-(phenylmethoxymethyl)oxirane Chemical compound C1OC1COCC1=CC=CC=C1 QNYBOILAKBSWFG-UHFFFAOYSA-N 0.000 claims description 3
- KFUSXMDYOPXKKT-UHFFFAOYSA-N 2-[(2-methylphenoxy)methyl]oxirane Chemical compound CC1=CC=CC=C1OCC1OC1 KFUSXMDYOPXKKT-UHFFFAOYSA-N 0.000 claims description 3
- JGRXEBOFWPLEAV-UHFFFAOYSA-N 2-ethylbutyl prop-2-enoate Chemical compound CCC(CC)COC(=O)C=C JGRXEBOFWPLEAV-UHFFFAOYSA-N 0.000 claims description 3
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 3
- ZVYGIPWYVVJFRW-UHFFFAOYSA-N 3-methylbutyl prop-2-enoate Chemical compound CC(C)CCOC(=O)C=C ZVYGIPWYVVJFRW-UHFFFAOYSA-N 0.000 claims description 3
- CUXGDKOCSSIRKK-UHFFFAOYSA-N 7-methyloctyl prop-2-enoate Chemical compound CC(C)CCCCCCOC(=O)C=C CUXGDKOCSSIRKK-UHFFFAOYSA-N 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical group CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 claims description 2
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 claims description 2
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 2
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 claims description 2
- OZCWUNHGNVXCCO-UHFFFAOYSA-N oxiran-2-ylmethyl hydrogen carbonate Chemical group OC(=O)OCC1CO1 OZCWUNHGNVXCCO-UHFFFAOYSA-N 0.000 claims description 2
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 claims description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 2
- -1 acrylic ester Chemical class 0.000 claims 2
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 125000001424 substituent group Chemical group 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 26
- 238000010276 construction Methods 0.000 abstract description 16
- 239000011248 coating agent Substances 0.000 abstract description 13
- 239000000126 substance Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 4
- 239000004593 Epoxy Substances 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- 230000001588 bifunctional effect Effects 0.000 abstract description 3
- 238000007790 scraping Methods 0.000 abstract description 3
- 238000005507 spraying Methods 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000005096 rolling process Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000012360 testing method Methods 0.000 description 10
- 239000003973 paint Substances 0.000 description 8
- 239000012855 volatile organic compound Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000005028 tinplate Substances 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- ZYUVGYBAPZYKSA-UHFFFAOYSA-N 5-(3-hydroxybutan-2-yl)-4-methylbenzene-1,3-diol Chemical compound CC(O)C(C)C1=CC(O)=CC(O)=C1C ZYUVGYBAPZYKSA-UHFFFAOYSA-N 0.000 description 1
- XEUCQOBUZPQUMQ-UHFFFAOYSA-N Glycolone Chemical compound COC1=C(CC=C(C)C)C(=O)NC2=C1C=CC=C2OC XEUCQOBUZPQUMQ-UHFFFAOYSA-N 0.000 description 1
- XZAHJRZBUWYCBM-UHFFFAOYSA-N [1-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1(CN)CCCCC1 XZAHJRZBUWYCBM-UHFFFAOYSA-N 0.000 description 1
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- NHADDZMCASKINP-HTRCEHHLSA-N decarboxydihydrocitrinin Natural products C1=C(O)C(C)=C2[C@H](C)[C@@H](C)OCC2=C1O NHADDZMCASKINP-HTRCEHHLSA-N 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
Abstract
本发明公开了一种改性胺类固化剂及其制备方法,所述改性胺类固化剂含有以下分子结构:
或中的一种或两种,其中P1为双官环氧树脂或者单环氧化合物,P2为含有烷基取代基的丙烯酸酯类单体,为多元胺。本发明制备得到的改性胺类固化剂,粘度低,将其用于涂料中后,可降低施工难度,使涂料施工方式多样,可喷涂、刮涂、滚涂;所制备的改性胺类固化剂不含任何溶剂,可挥发性有机物含量为零,对环境和施工人员等无害,且固化剂经环氧改性提高了固化剂与环氧树脂的相容性,烷基取代基所产生的位阻及屏蔽效应,可增加涂层的疏水性,且保护涂层中弱化学键,提高涂层对各类腐蚀性介质的耐性。The invention discloses a modified amine curing agent and a preparation method thereof. The modified amine curing agent contains the following molecular structure:
or One or both of them, wherein P 1 is a bifunctional epoxy resin or a mono-epoxy compound, and P 2 is an acrylate-based monomer containing an alkyl substituent, For polyamines. The modified amine curing agent prepared by the invention has low viscosity, and after it is used in coatings, the construction difficulty can be reduced, and the coating construction methods can be various, such as spraying, scraping and rolling; the prepared modified amines The curing agent does not contain any solvent, has zero volatile organic content, and is harmless to the environment and construction personnel. The epoxy modification of the curing agent improves the compatibility between the curing agent and epoxy resin. The resulting steric hindrance and shielding effect can increase the hydrophobicity of the coating, protect the weak chemical bonds in the coating, and improve the resistance of the coating to various corrosive media.Description
技术领域technical field
本发明属于环保涂料技术领域,具体涉及一种改性胺类固化剂及其制备方法。The invention belongs to the technical field of environmental protection coatings, and particularly relates to a modified amine curing agent and a preparation method thereof.
背景技术Background technique
目前中国市场上的涂料领域,仍是油性涂料占据主要市场。油性涂料使用过程中为了能达到可施工粘度,通常需要加入大量的有机溶剂,使得涂料中含有大量的VOC(可挥发性有机物),在涂料固化过程中对施工人员的身体以及环境造成不利影响。在施工完的一段时间内,施工区域会存在异味。近几年全球各国接连颁布法律法规限制油性涂料的使用,环保涂料的研究越来越得以重视。当前已开发应用的环保涂料依然存在着各种各样的问题,有的施工条件苛刻,有的成本过高。市场上的环保涂料中水性涂料以其施工便捷,节能环保被广泛接受。然而水性涂料对涂装设备的腐蚀性大,耐化学性能远低于油性涂料,难以满足人们苛刻的需求。另外,水性涂料在温度低的环境下存储或使用时性能会变差,且涂料中有水的存在时容易滋生细菌。At present, in the field of coatings in the Chinese market, oil-based coatings still occupy the main market. In order to achieve the constructable viscosity during the use of oil-based coatings, it is usually necessary to add a large amount of organic solvent, so that the coating contains a large amount of VOC (volatile organic compounds), which will cause adverse effects on the body of the construction personnel and the environment during the curing process of the coating. For a period of time after construction, there will be peculiar smell in the construction area. In recent years, countries around the world have successively promulgated laws and regulations to restrict the use of oil-based coatings, and more and more attention has been paid to the research on environmentally friendly coatings. There are still various problems in the currently developed and applied environmental protection coatings, some of which have harsh construction conditions and some that are too expensive. The water-based coatings in the environmentally friendly coatings on the market are widely accepted for their convenient construction, energy saving and environmental protection. However, water-based coatings are highly corrosive to coating equipment, and their chemical resistance is much lower than that of oil-based coatings, making it difficult to meet people's harsh needs. In addition, the performance of water-based paints will deteriorate when stored or used in a low temperature environment, and bacteria can easily breed in the presence of water in the paint.
涂料中所使用的固化剂对于涂料施工条件、涂料性质具有重要影响,目前市场上普遍使用的胺类固化剂,添加了许多溶剂以提高其性能,但同时导致其可挥发性有机物(VOC)含量高,对环境造成一定的影响;固化剂中含有水,使所得涂料容易滋生细菌;固化剂挥发性强、极性高、耐化学性能较差,难以达到人们的要求;且固化剂粘度高,造成施工难度大、施工时间短等问题。因此,亟需开发一种不含溶剂、粘度低且耐化学性能强的胺类固化剂。The curing agent used in the coating has an important impact on the coating construction conditions and coating properties. The amine curing agent commonly used in the market currently has many solvents added to improve its performance, but at the same time it leads to its volatile organic compound (VOC) content. high, which has a certain impact on the environment; the curing agent contains water, which makes the resulting coating easy to breed bacteria; the curing agent has strong volatility, high polarity, and poor chemical resistance, which is difficult to meet people's requirements; and the curing agent has high viscosity, It causes problems such as difficult construction and short construction time. Therefore, there is an urgent need to develop an amine curing agent with no solvent, low viscosity and strong chemical resistance.
发明内容SUMMARY OF THE INVENTION
为解决上述现有技术存在的问题,本发明提供一种改性胺类固化剂及其制备方法,通过对胺类固化剂进行改性,解决了未改性胺类固化剂施工时间短,挥发性强,高极性等缺点。同时所制备的固化剂粘度低,固化剂不含可挥发性有机物(VOC)、不含水,环保、储存稳定、易施工;其分子结构中含有烷基取代基,结构疏水性较强,空间位阻较大,屏蔽效应可为固化剂中的弱键提供保护,从而增加涂层的耐化学性。In order to solve the problems existing in the above-mentioned prior art, the present invention provides a modified amine curing agent and a preparation method thereof. Disadvantages such as strong sex and high polarity. At the same time, the prepared curing agent has low viscosity, no volatile organic compounds (VOC), no water, environmental protection, stable storage and easy construction; its molecular structure contains alkyl substituents, the structure is hydrophobic, and the steric position The greater the resistance, the shielding effect provides protection for weak bonds in the curing agent, thereby increasing the chemical resistance of the coating.
本发明技术方案之一:一种改性胺类固化剂,含有以下分子结构:
中的一种或两种,其中P1为双官环氧树脂或者单环氧化合物,P2为含有烷基取代基的丙烯酸酯类单体,为多元胺。One of the technical solutions of the present invention: a modified amine curing agent, containing the following molecular structure: One or both of them, wherein P 1 is a bifunctional epoxy resin or a mono-epoxy compound, and P 2 is an acrylate-based monomer containing an alkyl substituent, For polyamines.进一步地,所述P1为双酚A型环氧树脂E-51、双酚A型环氧树脂E-54、三木SM-828、聚乙二醇二缩水甘油醚、聚丙二醇二缩水甘油醚、叔碳酸缩水甘油酯、丁基缩水甘油醚、长链烷烃缩水甘油醚、苄基缩水甘油醚、苯基缩水甘油醚、和邻甲苯基缩水甘油醚中的一种或多种。Further, the P 1 is bisphenol A type epoxy resin E-51, bisphenol A type epoxy resin E-54, Miki SM-828, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether , one or more of tertiary glycidyl carbonate, butyl glycidyl ether, long chain alkane glycidyl ether, benzyl glycidyl ether, phenyl glycidyl ether, and o-tolyl glycidyl ether.
进一步地,所述双官环氧树脂的粘度低于200mpa.s。Further, the viscosity of the bifunctional epoxy resin is lower than 200mpa.s.
进一步地,所述P2为丙烯酸异丙酯、丙烯酸异丁酯、丙烯酸异戊酯、丙烯酸异壬酯、丙烯酸异辛酯、丙烯酸异癸酯和丙烯酸-2-乙基丁酯中的一种或多种。Further, described P 2 is a kind of in isopropyl acrylate, isobutyl acrylate, isoamyl acrylate, isononyl acrylate, isooctyl acrylate, isodecyl acrylate and 2-ethylbutyl acrylate or more.
进一步地,所述多元胺为二乙烯三胺、三乙烯四胺、四乙烯五胺、五乙烯六胺、多乙烯多胺、间苯二甲胺、异佛尔酮二胺和1,3-环己二甲胺中的一种或多种。Further, the polyamines are diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyethylenepolyamine, m-xylylenediamine, isophoronediamine and 1,3- One or more of cyclohexanedimethylamine.
本发明的技术方案之二:上述改性胺类固化剂的制备方法,包括以下步骤:The second technical solution of the present invention: the preparation method of the above-mentioned modified amine curing agent, comprising the following steps:
45-70℃条件下,向多元胺中加入P1,保温反应1-1.5h,之后将温度升至75-90℃,反应1.5-3h;温度降至55-60℃,加入P2,保温反应1-1.5h,之后将温度升至90-130℃,反应3-5h。Under the condition of 45-70°C, add P 1 to the polyamine, keep the reaction for 1-1.5h, then raise the temperature to 75-90°C and react for 1.5-3h; drop the temperature to 55-60°C, add P 2 , keep the temperature The reaction was carried out for 1-1.5 h, and then the temperature was raised to 90-130° C. and the reaction was carried out for 3-5 h.
进一步地,P1、P2与多元胺的摩尔比为1:(0.8-2):(1-3)。Further, the molar ratio of P 1 , P 2 and polyamine is 1:(0.8-2):(1-3).
进一步地,P1以滴加的方式加入多元胺中。Further, P 1 was added to the polyamine in a dropwise manner.
本发明制备过程中,P1的环氧基团与多元胺的胺氢发生开环反应,P2丙烯酸酯类单体双键与多元胺的胺氢发生加成反应,形成本发明中的改性胺类固化剂。In the preparation process of the present invention, the epoxy group of P 1 undergoes a ring-opening reaction with the amine hydrogen of the polyamine, and the double bond of the P 2 acrylate monomer undergoes an addition reaction with the amine hydrogen of the polyamine to form the modified amine hydrogen of the present invention. amine curing agent.
本发明的有益效果:Beneficial effects of the present invention:
1.本发明通过环氧树脂或者单环氧化合物,丙烯酸酯类单体与胺类固化剂反应制备得到改性对胺类固化剂,解决了未改性胺类固化剂施工时间短,挥发性强,高极性等缺点,同时本发明制备工艺简单,所制备的改性胺类固化剂不含任何溶剂(包括水),VOC(可挥发性有机物)含量为零,对环境和施工人员等无害;1. The present invention prepares the modified para-amine curing agent through the reaction of epoxy resin or monoepoxy compound, acrylate monomer and amine curing agent, which solves the problem that the unmodified amine curing agent has a short construction time and is volatile. Strong, high polarity and other shortcomings, at the same time, the preparation process of the present invention is simple, the prepared modified amine curing agent does not contain any solvent (including water), and the VOC (volatile organic compound) content is zero, which is harmful to the environment and construction personnel. harmless;
2.本发明所制备的改性胺类固化剂粘度低,固含量高,将其用于涂料中后,可降低施工难度,使涂料施工方式多样,可喷涂、刮涂、滚涂;2. The modified amine curing agent prepared by the present invention has low viscosity and high solid content. After it is used in coatings, construction difficulty can be reduced, and the coating construction methods can be varied, such as spraying, scraping and rolling;
3.本发明所制备的改性胺类固化剂含有多取代结构,其位阻屏蔽效应对水及各类腐蚀性溶液具有超强的耐性。3. The modified amine curing agent prepared by the present invention contains a multi-substituted structure, and its steric hindrance shielding effect has super resistance to water and various corrosive solutions.
附图说明Description of drawings
为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例中所需要使用的附图作简单地介绍。In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the accompanying drawings required in the embodiments will be briefly introduced below.
图1为实施例5制备得到的漆膜未浸泡样及经过耐水耐化学性检测后的样品实物图,其中图(a)为未浸泡样,图(b)为在10wt%H2SO4中浸泡1300h后的试样,图(c)为在10wt%HCl中浸泡1300h后的试样,图(d)为在10wt%NaOH中浸泡1300h后的试样,图(e)为在10wt%NaCl中浸泡1300h后的试样,图(f)为在120#汽油中浸泡1300h后的试样,图(g)为在H2O中浸泡1300h后的试样。Figure 1 is the actual picture of the unsoaked sample of the paint film prepared in Example 5 and the sample after the water and chemical resistance test, in which Figure (a) is the unsoaked sample, and Figure (b) is in 10wt% H 2 SO 4 . The sample after soaking for 1300h, picture (c) is the sample after soaking in 10wt% HCl for 1300h, picture (d) is the sample after soaking in 10wt% NaOH for 1300h, picture (e) is the sample after soaking in 10wt% NaCl Figure (f) is the sample after immersion in 120# gasoline for 1300h, Figure (g) is the sample after immersion in H 2 O for 1300h.
具体实施方式Detailed ways
现详细说明本发明的多种示例性实施方式,该详细说明不应认为是对本发明的限制,而应理解为是对本发明的某些方面、特性和实施方案的更详细的描述。Various exemplary embodiments of the present invention will now be described in detail, which detailed description should not be construed as a limitation of the invention, but rather as a more detailed description of certain aspects, features, and embodiments of the invention.
应理解本发明中所述的术语仅仅是为描述特别的实施方式,并非用于限制本发明。It should be understood that the terms described in the present invention are only used to describe particular embodiments, and are not used to limit the present invention.
另外,对于本发明中的数值范围,应理解为还具体公开了该范围的上限和下限之间的每个中间值。在任何陈述值或陈述范围内的中间值以及任何其他陈述值或在所述范围内的中间值之间的每个较小的范围也包括在本发明内。这些较小范围的上限和下限可独立地包括或排除在范围内。Additionally, for numerical ranges in the present disclosure, it should be understood that each intervening value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated value or intervening value in that stated range is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
除非另有说明,否则本文使用的所有技术和科学术语具有本发明所述领域的常规技术人员通常理解的相同含义。虽然本发明仅描述了优选的方法和材料,但是在本发明的实施或测试中也可以使用与本文所述相似或等同的任何方法和材料。本说明书中提到的所有文献通过引用并入,用以公开和描述与所述文献相关的方法和/或材料。在与任何并入的文献冲突时,以本说明书的内容为准。Unless otherwise defined, 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 relates. Although only the preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials in connection with which the documents are referred. In the event of conflict with any incorporated document, the contents of this specification shall control.
在不背离本发明的范围或精神的情况下,可对本发明说明书的具体实施方式做多种改进和变化,这对本领域技术人员而言是显而易见的。由本发明的说明书得到的其他实施方式对技术人员而言是显而易见得的。本发明说明书和实施例仅是示例性的。It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present invention without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from the description of the present invention. The description and examples of the present invention are exemplary only.
实施例1Example 1
改性胺类固化剂的合成,步骤如下:The synthesis of modified amine curing agent, the steps are as follows:
(1)取14.2g 1,3-环己二甲胺加入三颈烧瓶中;(1) get 14.2g 1,3-cyclohexanedimethylamine and add in the three-necked flask;
(2)取34.32g粘度为30-70mpa.s的聚丙二醇二缩水甘油醚在70℃的温度下缓慢滴加入三颈烧瓶中,边滴加边搅拌,使其混合均匀,5min滴加完成,之后保持70℃反应1h,升温至85℃反应2h;(2) Take 34.32g of polypropylene glycol diglycidyl ether with a viscosity of 30-70mpa.s and slowly add it dropwise to the three-necked flask at a temperature of 70°C, stir while adding dropwise to make it evenly mixed, and complete the dropwise addition in 5 min. After that, the reaction was kept at 70 °C for 1 h, and the temperature was raised to 85 °C for 2 h;
(3)将温度降至60℃;(3) Lower the temperature to 60°C;
(4)取17.82g丙烯酸异壬酯加入三颈烧瓶中保温反应1h;(4) get 17.82g of isononyl acrylate and add in the three-necked flask to keep warm for 1h;
(5)将温度升至125℃反应4h,取出即可得改性胺类固化剂。(5) Raise the temperature to 125°C and react for 4 hours, then take out to obtain the modified amine curing agent.
实施例2Example 2
改性胺类固化剂的合成,步骤如下:The synthesis of modified amine curing agent, the steps are as follows:
(1)取13.6g间苯二甲胺加入三颈烧瓶中;(1) get 13.6g m-xylylenediamine and add in the three-necked flask;
(2)取22.8g叔碳酸缩水甘油酯在55℃的温度下缓慢滴加入三颈烧瓶中,边滴加边搅拌,使其混合均匀,5min滴加完成,之后保持55℃反应1.5h,升温至80℃反应3h;(2) Take 22.8g of glycidyl tertiary carbonate and slowly add it dropwise to the three-necked flask at a temperature of 55°C, stir while adding dropwise to make it evenly mixed, and complete the dropwise addition in 5min, then keep the reaction at 55°C for 1.5h, and heat up. Reaction at 80°C for 3h;
(3)将温度降至60℃;(3) Lower the temperature to 60°C;
(4)取29.7g丙烯酸异辛酯加入三颈烧瓶中保温反应1.5h;(4) get 29.7g of isooctyl acrylate and add it to the three-necked flask for thermal insulation reaction for 1.5h;
(5)将温度升至120℃反应3h,取出即可得改性胺类固化剂。(5) Raise the temperature to 120°C and react for 3 hours, then take out the modified amine curing agent.
实施例3Example 3
改性胺类固化剂的合成,步骤如下:The synthesis of modified amine curing agent, the steps are as follows:
(1)取20.6g二乙烯三胺加入三颈烧瓶中;(1) get 20.6g diethylenetriamine and add in the three-necked flask;
(2)取13.12g邻甲苯基缩水甘油醚在45℃的温度下缓慢滴加入三颈烧瓶中,边滴加边搅拌,使其混合均匀,10min滴加完成,之后保持45℃反应1.5h,升温至75℃反应1.5h;(2) 13.12g of o-tolyl glycidyl ether was slowly added dropwise to the three-necked flask at a temperature of 45°C, and stirred while adding dropwise to make it evenly mixed, and the dropwise addition was completed in 10min, and then kept at 45°C for 1.5h reaction, The temperature was raised to 75°C for 1.5h;
(3)将温度降至60℃;(3) Lower the temperature to 60°C;
(4)取24.96g丙烯酸-2-乙基丁酯加入三颈烧瓶中保温反应1h;(4) get 24.96g acrylic acid-2-ethyl butyl ester and add in the three-necked flask to heat insulation reaction 1h;
(5)将温度升至100℃反应4h,取出即可得改性胺类固化剂。(5) The temperature was raised to 100°C for 4 hours, and the modified amine curing agent was obtained by taking it out.
实施例4Example 4
改性胺类固化剂的合成,包括以下步骤:The synthesis of modified amine curing agent includes the following steps:
(1)取27.2g三乙烯四胺加入三颈烧瓶中;(1) get 27.2g triethylenetetramine and add in the three-necked flask;
(2)取30.3g苄基缩水甘油醚在50℃的温度下缓慢滴加入三颈烧瓶中,边滴加边搅拌,使其混合均匀,10min滴加完成,之后保持50℃反应1h,升温至80℃反应2h;(2) Take 30.3g of benzyl glycidyl ether and slowly drop it into the three-necked flask at a temperature of 50°C, stir while adding dropwise to make it evenly mixed, complete the dropwise addition in 10min, then keep the reaction at 50°C for 1h, and heat up to 80℃reaction for 2h;
(3)将温度降至60℃;(3) Lower the temperature to 60°C;
(4)取44.67g丙烯酸异戊酯加入三颈烧瓶中保温反应1h;(4) get 44.67g isoamyl acrylate and add in the three-necked flask to keep warm for 1h;
(5)将温度升至110℃反应5h,取出即可得改性胺类固化剂。(5) Raise the temperature to 110°C and react for 5 hours, then take out the modified amine curing agent.
实施例5Example 5
改性胺类固化剂的合成,步骤如下:The synthesis of modified amine curing agent, the steps are as follows:
(1)取34.04g异佛尔酮二胺加入三颈烧瓶中;(1) get 34.04g isophorone diamine and add in the three-necked flask;
(2)取10.1g聚乙二醇二缩水甘油醚和1.64g双酚A型环氧树脂E-51混合,混合物粘度低于200mpa.s,在60℃的温度下缓慢将混合物滴加入三颈烧瓶中,边滴加边搅拌,使其混合均匀,8min滴加完成,之后保持60℃反应1h,升温至80℃反应2h;(2) Mix 10.1g polyethylene glycol diglycidyl ether and 1.64g bisphenol A epoxy resin E-51, the viscosity of the mixture is lower than 200mpa.s, and slowly add the mixture dropwise to the three necks at a temperature of 60°C In the flask, add dropwise while stirring to make it evenly mixed, and the dropwise addition is completed in 8 minutes, then keep the temperature at 60 °C for 1 hour, and then raise the temperature to 80 °C for 2 hours;
(3)将温度降至60℃;(3) Lower the temperature to 60°C;
(4)取20.45g丙烯酸异辛酯加入三颈烧瓶中保温反应1h;(4) get 20.45g of isooctyl acrylate and add it to the three-necked flask for 1h of insulation reaction;
(5)将温度升至110℃反应4h,取出即可得改性胺类固化剂。(5) The temperature was raised to 110°C for 4 hours, and the modified amine curing agent was obtained by taking it out.
效果验证例1:Effect verification example 1:
分别对实施例1-5制备得到的固化剂进行粘度及固含量检测,检测标准见表1,检测结果见表2。The viscosity and solid content of the curing agents prepared in Examples 1-5 were respectively detected, the detection standards were shown in Table 1, and the detection results were shown in Table 2.
表1Table 1
表2Table 2
效果验证例2:Effect verification example 2:
分别将实施例1-5制备得到的固化剂与消泡剂BYK-A530,润湿剂TEGO Wet KL245,流平剂BYK333以质量比为99.4:0.2:0.2:0.2混合作为A组分;以双酚A型环氧树脂E-51,含量为95-100wt%,与环氧活性稀释剂AGE,含量为5-0wt%混合为B组分,其中双酚A型环氧树脂E-51与环氧活性稀释剂AGE的总量为100wt%;并将A组分与B组分以活泼氢与环氧基团1:(1-1.1)的摩尔比配制成清漆,通过线棒将其涂敷在马口铁板上,室温固化。待漆膜完全固化后对其性能进行检测,检测项目检测标准见表3,检测结果见表4。The curing agent prepared in Examples 1-5 was mixed with defoamer BYK-A530, wetting agent TEGO Wet KL245, and leveling agent BYK333 in a mass ratio of 99.4:0.2:0.2:0.2 as component A; Phenol A type epoxy resin E-51, the content is 95-100wt%, mixed with epoxy reactive diluent AGE, the content is 5-0wt% to be the B component, wherein the bisphenol A type epoxy resin E-51 and the ring The total amount of the oxygen-active diluent AGE is 100wt%; and the A component and the B component are formulated into a varnish with a molar ratio of active hydrogen to epoxy group 1:(1-1.1), which is coated by a wire rod On tinplate, cure at room temperature. After the paint film is completely cured, its performance is tested. The test standards of the test items are shown in Table 3, and the test results are shown in Table 4.
表3table 3
表4Table 4
图1为采用实施例5中的改性固化剂制备的漆膜的未浸泡试样及耐水耐化学性检测后的样品实物图。FIG. 1 is an unsoaked sample of a paint film prepared by using the modified curing agent in Example 5 and a physical diagram of the sample after water and chemical resistance testing.
由表2、表4及图1可以得出,采用本发明的技术方案制备得到的改性胺类固化剂粘度低,固含量高,将其制成漆膜后,所得漆膜硬度高,耐水性及耐腐蚀性强。It can be drawn from Table 2, Table 4 and Figure 1 that the modified amine curing agent prepared by the technical solution of the present invention has low viscosity and high solid content. After it is made into a paint film, the obtained paint film has high hardness and water resistance. Strong resistance and corrosion resistance.
对实施例1-5制备得到的改性胺类固化剂按照上述方法制成的清漆采用喷涂及刮涂方式涂覆在马口铁板上,室温固化,待漆膜完全固化后对其性能进行检测,得到其同样具有硬度高,耐水性及耐腐蚀性强等特点,说明将本发明制备得到的改性胺类固化剂用于涂料中后,可降低施工难度,使涂料施工方式多样,可喷涂、刮涂、滚涂。The modified amine curing agent prepared in Examples 1-5 was coated on the tinplate by spraying and scraping on the varnish prepared by the above method, and cured at room temperature. After the paint film was completely cured, its performance was detected, It is obtained that it also has the characteristics of high hardness, strong water resistance and corrosion resistance. Scratch, Roller.
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明披露的技术范围内,根据本发明的技术方案及其发明构思加以等同替换或改变,都应涵盖在本发明的保护范围之内。The above is only a preferred embodiment of the present invention, but the protection scope of the present invention is not limited to this. The equivalent replacement or change of the inventive concept thereof shall be included within the protection scope of the present invention.
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