CN112011036B - 一种水性亚麻油酸改性醇酸树脂及其制备方法 - Google Patents
一种水性亚麻油酸改性醇酸树脂及其制备方法 Download PDFInfo
- Publication number
- CN112011036B CN112011036B CN202010886365.4A CN202010886365A CN112011036B CN 112011036 B CN112011036 B CN 112011036B CN 202010886365 A CN202010886365 A CN 202010886365A CN 112011036 B CN112011036 B CN 112011036B
- Authority
- CN
- China
- Prior art keywords
- mass
- alkyd resin
- linoleic acid
- waterborne
- pentaerythritol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920000180 alkyd Polymers 0.000 title claims abstract description 45
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 title claims abstract description 10
- 235000020778 linoleic acid Nutrition 0.000 title claims abstract description 10
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title abstract description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 56
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 23
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 23
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 15
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 claims abstract description 12
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims abstract description 12
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims abstract description 12
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims abstract description 11
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003085 diluting agent Substances 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical group CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000005886 esterification reaction Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 4
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical group C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 abstract description 11
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 239000003973 paint Substances 0.000 description 11
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 9
- 239000012975 dibutyltin dilaurate Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000013065 commercial product Substances 0.000 description 5
- 229910052797 bismuth Inorganic materials 0.000 description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 description 3
- 239000008158 vegetable oil Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000007519 polyprotic acids Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 2
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- ZBBLRPRYYSJUCZ-GRHBHMESSA-L (z)-but-2-enedioate;dibutyltin(2+) Chemical compound [O-]C(=O)\C=C/C([O-])=O.CCCC[Sn+2]CCCC ZBBLRPRYYSJUCZ-GRHBHMESSA-L 0.000 description 1
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- CANRESZKMUPMAE-UHFFFAOYSA-L Zinc lactate Chemical compound [Zn+2].CC(O)C([O-])=O.CC(O)C([O-])=O CANRESZKMUPMAE-UHFFFAOYSA-L 0.000 description 1
- JJLKTTCRRLHVGL-UHFFFAOYSA-L [acetyloxy(dibutyl)stannyl] acetate Chemical compound CC([O-])=O.CC([O-])=O.CCCC[Sn+2]CCCC JJLKTTCRRLHVGL-UHFFFAOYSA-L 0.000 description 1
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- NSPSPMKCKIPQBH-UHFFFAOYSA-K bismuth;7,7-dimethyloctanoate Chemical compound [Bi+3].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O NSPSPMKCKIPQBH-UHFFFAOYSA-K 0.000 description 1
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical compound CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- -1 chloromethylmonobutyltin Chemical compound 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000031877 prophase Effects 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- VNTDZUDTQCZFKN-UHFFFAOYSA-L zinc 2,2-dimethyloctanoate Chemical compound [Zn++].CCCCCCC(C)(C)C([O-])=O.CCCCCCC(C)(C)C([O-])=O VNTDZUDTQCZFKN-UHFFFAOYSA-L 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 235000013904 zinc acetate Nutrition 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 229940050168 zinc lactate Drugs 0.000 description 1
- 239000011576 zinc lactate Substances 0.000 description 1
- 235000000193 zinc lactate Nutrition 0.000 description 1
- ADJMNWKZSCQHPS-UHFFFAOYSA-L zinc;6-methylheptanoate Chemical compound [Zn+2].CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O ADJMNWKZSCQHPS-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/46—Polyesters chemically modified by esterification
- C08G63/48—Polyesters chemically modified by esterification by unsaturated higher fatty oils or their acids; by resin acids
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
本发明提供了一种水性亚麻油酸改性醇酸树脂及其制备方法。本发明的改性水性醇酸树脂,由以下原料制备而成:亚麻油酸、三羟甲基丙烷、邻苯二甲酸酐、季戊四醇、苯甲酸、甲苯,偏苯三酸酐、催化剂、抗氧剂和稀释剂,其中质量比,季戊四醇:甲苯:苯甲酸=1:1:2。本发明的有益效果为:本发明的水性亚麻油酸改性醇酸树脂解决了醇酸树脂存在的柔性大、硬度低等缺陷,同时兼顾了环保安全的技术问题。大大延长了使用寿命。
Description
技术领域
本发明涉及一种水性亚麻油酸改性醇酸树脂及其制备方法。
背景技术
水性醇酸树脂是一种经缩合酯化而成的聚合物,其合成原料是多官能醇、多元酸和植物油或脂肪酸,其以聚酯为主链,侧链为不饱和脂肪酸、残留羧基和小部分羟基,侧链的分子量较低。侧链不饱和脂肪酸中的双键与氧交联、水和溶剂挥发即可使醇酸树脂固化,形成最后的涂膜。水性醇酸树脂漆具有高光泽、高丰满度、附着力强、易施工等优点,但是由于水性醇酸树脂是由植物油或者植物油脂肪酸、多元醇、多元酸、缩合而成,漆中含有的铵盐基、羟基均为亲水基团,因而其具有一定的水溶性,导致最终的漆膜耐水性较差。在接触水的12小时内,漆膜便会出现起泡甚至漆膜脱落等现象,严重影响了漆膜的正常使用。
发明内容
本发明提供了一种水性亚麻油酸改性醇酸树脂及其制备方法。本发明的改性水性醇酸树脂,由以下原料制备而成:亚麻油酸、三羟甲基丙烷、邻苯二甲酸酐、季戊四醇、苯甲酸、甲苯,偏苯三酸酐、催化剂、抗氧剂和稀释剂,其中质量比,季戊四醇:甲苯:苯甲酸=1:1:2。本发明的有益效果为:本发明的改性水性醇酸树脂解决了醇酸树脂存在的柔性大、硬度低等缺陷,同时兼顾了环保安全的技术问题。大大延长了使用寿命。具体的方案如下:
一种制备水性亚麻油酸改性醇酸树脂的方法,其特征在于,所述方法包括以下步骤:
(1)取15~25质量%亚麻油酸、15~20质量%三羟甲基丙烷、邻苯二甲酸酐15~25质量%、2~5质量%季戊四醇、苯甲酸4~10质量%、甲苯2~5质量%、0.05~0.1质量%催化剂和抗氧剂0.05~0.1质量%,加入反应容器,其中质量比,季戊四醇:甲苯:苯甲酸=1:1:2,加热使上述原料溶解;
(2)当温度达到160~180℃时,停止加热,开始保温,进行酯化反应;
(3)以10℃/h的速度升温至210~220℃后,保温2.5小时;然后抽真空再测中控;
(4)测定酸值到达17~20mg KOH/g后,降温至160~180℃,向反应容器中加入5~10质量%偏苯三酸酐,在160~180℃持续保温2-3h;
(5)当酸值达到50-55mg KOH/g,停止保温,进行降温并加入稀释剂。
进一步的,其特征在于,步骤(1)中,当温度达到120℃时,向反应容器中通入氮气。
进一步的,其特征在于,所述抗氧剂为亚磷酸三苯酯。
进一步的,其特征在于,所述稀释剂为乙二醇丁醚。
进一步的,一种水性亚麻油酸改性醇酸树脂,采用所述的制备方法制备得到。
当苯甲酸加入量小于4%时,不会产生改性效果;但是当大于4%时,有可能造成树脂浑浊、储存期间树脂分层、制漆后漆液稳定性差、漆面显影性不良、雾影等漆病。
针对上述情况,加入季戊四醇和甲苯,并且季戊四醇:甲苯:苯甲酸的比例满足1:1:2时,则可抑制苯甲酸加入后所带来的上述副作用。
根据本发明的具体实施方式的改性水性醇酸树脂,所述抗氧剂可选用有机有磷酸类催化剂、次亚磷酸类催化剂。
催化剂可选用有机锡类催化剂、有机铋类催化剂、有机锌类催化剂。
有机锡类催化剂包括二月桂酸二丁基锡、二月桂酸二辛基锡、单丁基氧化锡、氯代单丁基锡酸、二丁基醋酸锡、马来酸二丁基锡、辛酸亚锡等。
有机铋类催化剂包括异辛酸铋、月桂芁酸铋、新癸酸铋等。
有机锌类催化剂包括异辛酸锌、新癸酸锌、环烷酸锌、碳酸锌、乙酸锌、乳酸锌等。
根据本发明的具体实施方式的改性水性醇酸树脂,所述稀释剂为醇醚类稀释剂,优选为乙二醇丁醚。
使用乙二醇丁醚做为稀释剂,在制漆过程中无需再次加入其他溶剂来协助水溶,从而有效的降低体系的VOC含量,保证了漆的绿色环保,而且能够提高漆的稳定性。
本发明的有益效果为:
1)本发明的改性醇酸树脂具有优越的耐水性能,耐水性能可达200小时以上,且耐盐雾能力显著优于市售产品,大大延长了使用寿命;同时,本发明的改性醇酸树脂的表干时间短于市售产品。
2)发明人发现,当原料中的季戊四醇:甲苯:苯甲酸的比例满足1:1:2时,耐水和耐冲击性能得到极大提升,机理尚不明确,推测由于季戊四醇和甲苯的加入,一致了苯甲酸的副作用;
3)本发明的制备方法简便、易于操作,可获得耐水性能优良、耐盐雾性能提高、且表干时间短的改性醇酸树脂。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚,下面将对本发明的技术方案进行详细的描述。显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动的前提下所得到的所有其它实施方式,都属于本发明所保护的范围。
实施例1
以制备1kg本发明的改性水性醇酸树脂为例,其包括以下原料:
亚麻油酸18质量%、三羟甲基丙烷17质量%、苯酐21质量%、季戊四醇2质量%、苯甲酸4质量%、甲苯2质量%,抗氧剂0.05质量%、偏苯三酸酐5质量%、二月桂酸二丁基锡0.05质量%,余量为乙二醇丁醚。
本发明的制备方法如下:
(1)按照上述重量,将亚麻油酸、三羟甲基丙烷、苯酐、季戊四醇、苯甲酸、二月桂酸二丁基锡、抗氧剂加入装有回流冷凝管、搅拌器、分水器、加热套、温度计、通氮气保护的四口烧瓶中,固定四口瓶,加热,温度到达120℃时,开启搅拌器,通入氮气保护,继续升温,溶解原料;
(2)温度达到160℃时,停止加热,开始保温,进行酯化反应;
(3)以10℃/h的速度升温至210℃后,保温2.5h;然后抽真空再测中控;
(4)测定酸值到达17mg KOH/g后,降温至160℃;
(5)向四口瓶中加入偏苯三酸酐,在160℃持续保温3h;
(6)当酸值达到55mg KOH/g,停止保温,进行降温并同时加入乙二醇丁醚;
(7)温度降至60℃后,灌装出料。
实施例2
以制备1kg本发明的改性水性醇酸树脂为例,其包括以下原料:
亚麻油酸20质量%、三羟甲基丙烷17质量%、苯酐20.5质量%、季戊四醇3.5质量%、苯甲酸7质量%、甲苯3.5质量%,偏苯三酸酐6质量%、二月桂酸二丁基锡0.1质量%、抗氧剂0.05质量%,余量为乙二醇丁醚。
本发明的制备方法如下:
(1)按照上述重量,将亚麻油酸、三羟甲基丙烷、环己二醇、季戊四醇、对苯二甲酸、二月桂酸二丁基锡、抗氧剂加入装有回流冷凝管、搅拌器、分水器、加热套、温度计、通氮气保护的四口烧瓶中,固定四口瓶,加热,温度到达120℃时,开启搅拌器,通入氮气保护,继续升温,溶解原料;
(2)温度达到170℃时,停止加热,开始保温,进行酯化反应;
(3)以10℃/h的速度升温至220℃后,保温2.5h;然后抽真空再测中控;
(4)测定酸值到达18mg KOH/g后,降温至170℃;
(5)向四口瓶中加入偏苯三酸酐,在170℃持续保温2h;
(6)当酸值达到55mg KOH/g,停止保温,进行降温并同时加入乙二醇丁醚进行稀释;
(7)温度降至60℃后,灌装出料。
实施例3
以制备1kg本发明的改性水性醇酸树脂为例,其包括以下原料:
亚麻油酸19质量%、三羟甲基丙烷18质量%、苯酐21.5质量%、季戊四醇5质量%、苯甲酸10质量%、甲苯5质量%、偏苯三酸酐7质量%、二月桂酸二丁基锡0.05质量%、抗氧剂0.05质量%,余量为乙二醇丁醚。
本发明的制备方法如下:
(1)按照上述重量,将亚麻油酸、三羟甲基丙烷、苯酐、季戊四醇、苯甲酸、二月桂酸二丁基锡、抗氧剂加入装有回流冷凝管、搅拌器、分水器、加热套、温度计、通氮气保护的四口烧瓶中,固定四口瓶,加热,温度到达120℃时,开启搅拌器,通入氮气保护,继续升温,溶解原料;
(2)温度达到180℃时,停止加热,开始保温,进行酯化反应;
(3)以10℃/h的速度升温至210℃后,保温;然后抽真空再测中控;
(4)测定酸值到达20mg KOH/g后,降温至180℃;
(5)向四口瓶中加入偏苯三酸酐,在180℃持续保温3h;
(6)当酸值达到55mg KOH/g,停止保温,进行降温并同时加入乙二醇丁醚进行稀释;
(7)温度降至60℃后,灌装出料。
对比例1
以制备1kg本发明的改性水性醇酸树脂为例,其包括以下原料:
亚麻油酸19质量%、三羟甲基丙烷18质量%、苯酐21.5质量%、季戊四醇4质量%、苯甲酸10质量%、甲苯4质量%、偏苯三酸酐7质量%、二月桂酸二丁基锡0.05质量%、抗氧剂0.05质量%,余量为乙二醇丁醚。
其他制备工艺参数与实施例3相同。
对比例2
以制备1kg本发明的改性水性醇酸树脂为例,其包括以下原料:
亚麻油酸19质量%、三羟甲基丙烷18质量%、苯酐21.5质量%、季戊四醇5质量%、苯甲酸8质量%、甲苯5质量%、偏苯三酸酐7质量%、二月桂酸二丁基锡0.05质量%、抗氧剂0.05质量%,余量为乙二醇丁醚。
其他制备工艺参数与实施例3相同。
测试与数据
分别将实施例1~3和对比例1~2的样品、市售未改性醇酸树脂与催干剂、中和剂、去离子水加入到搅拌罐内,同时以400-600r/min速率搅拌,直至混合均匀;然后再加入去离子水,再依次加入分散剂、钛白粉、碳黑、硫酸钡及分散剂,同时以600-800r/min速率继续搅拌,调整转速至800-1000r/min搅拌30min,得到混合液;将混合液进行研磨1小时,刮板常规配方细度≤10μ用200目滤布过滤得前期浆;将前期浆加入搅拌缸内以900-1000r/min速率搅拌,然后加入消泡剂、流平剂、增稠剂,继续搅拌20min后调整黏度至85-90ku(25±1℃)得到可涂刷成品。比较各成品之间的性能,结果见表1:
表1本发明样品与市售样品的性能对比
表1
由表1可知,本发明的改性水性醇酸树脂涂覆后,耐水性能可达48小时以上,而市售产品耐水性不超过24小时;同时,本发明的改性水性醇酸树脂自干7d再划叉,72h后无异常,而市售产品划叉处有少量生锈,板面少量起泡,本发明的改性水性醇酸显著优于市售产品;本发明的改性水性醇酸树脂表干时间约2.5h,而市售产品的表干时间为4h,因此,本改性水性醇酸树的表干时间较市售产品明显缩短。并且由表1可见,当原料中的季戊四醇:甲苯:苯甲酸的比例满足1:1:2时,耐水以及热存储稳定性得到极大提升,而当不满足当原料中的季戊四醇:甲苯:苯甲酸的比例满足1:1:2时,表干时间,耐水性和热存储稳定性明显变差。
以上所述仅为本发明的优选实施例,不能解释为以此限定本发明的范围,凡在本发明的权利要求书要求保护的范围内所做出的等同的变形和改变的实施方式均在本发明所要求保护的范围内。
Claims (3)
1.一种制备水性亚麻油酸改性醇酸树脂的方法,其特征在于,所述方法包括以下步骤:
(1)取15~25质量%亚麻油酸、15~20质量%三羟甲基丙烷、邻苯二甲酸酐15~25质量%、2~5质量%季戊四醇、4~10质量%苯甲酸、2~5质量%甲苯、0.05~0.1质量%催化剂和0.05~0.1质量%抗氧剂,所述抗氧剂为亚磷酸三苯酯;加入反应容器,其中质量比,季戊四醇:甲苯:苯甲酸=1:1:2,加热使上述原料溶解;
(2)当温度达到160~180℃时,停止加热,开始保温,进行酯化反应;
(3)以10℃/h的速度升温至210~220℃后,保温2.5小时;然后抽真空再测中控;
(4)测定酸值到达17~20mg KOH/g后,降温至160~180℃,向反应容器中加入5~10质量%偏苯三酸酐,在160~180℃持续保温2-3h;
(5)当酸值达到50-55mg KOH/g,停止保温,进行降温并加入稀释剂,所述稀释剂为乙二醇丁醚。
2.根据权利要求1所述的改性醇酸树脂的制备方法,其特征在于,步骤(1)中,当温度达到120℃时,向反应容器中通入氮气。
3.一种水性亚麻油酸改性醇酸树脂,其特征在于,采用权利要求1-2任一项所述的制备方法制备得到。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010886365.4A CN112011036B (zh) | 2020-08-28 | 2020-08-28 | 一种水性亚麻油酸改性醇酸树脂及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010886365.4A CN112011036B (zh) | 2020-08-28 | 2020-08-28 | 一种水性亚麻油酸改性醇酸树脂及其制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN112011036A CN112011036A (zh) | 2020-12-01 |
CN112011036B true CN112011036B (zh) | 2022-09-27 |
Family
ID=73502362
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010886365.4A Active CN112011036B (zh) | 2020-08-28 | 2020-08-28 | 一种水性亚麻油酸改性醇酸树脂及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN112011036B (zh) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103319699A (zh) * | 2013-06-25 | 2013-09-25 | 桂林理工大学 | 一种采用废弃食用油制备的气干型醇酸树脂及应用 |
CN106854277A (zh) * | 2016-12-07 | 2017-06-16 | 陕西宝塔山油漆股份有限公司 | 一种超快干醇酸树脂及其制备方法 |
CN107337786A (zh) * | 2017-07-11 | 2017-11-10 | 长木(宁波)新材料科技有限公司 | 一种水性醇酸树脂及其制备方法 |
CN109642108A (zh) * | 2016-09-07 | 2019-04-16 | 阿科玛股份有限公司 | 醇酸聚合物组合物及由其形成的产品制剂 |
-
2020
- 2020-08-28 CN CN202010886365.4A patent/CN112011036B/zh active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103319699A (zh) * | 2013-06-25 | 2013-09-25 | 桂林理工大学 | 一种采用废弃食用油制备的气干型醇酸树脂及应用 |
CN109642108A (zh) * | 2016-09-07 | 2019-04-16 | 阿科玛股份有限公司 | 醇酸聚合物组合物及由其形成的产品制剂 |
CN106854277A (zh) * | 2016-12-07 | 2017-06-16 | 陕西宝塔山油漆股份有限公司 | 一种超快干醇酸树脂及其制备方法 |
CN107337786A (zh) * | 2017-07-11 | 2017-11-10 | 长木(宁波)新材料科技有限公司 | 一种水性醇酸树脂及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
CN112011036A (zh) | 2020-12-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR100732076B1 (ko) | 폴리에스테르 수지의 제조 방법 | |
CN107082860B (zh) | 一种自乳化型水性聚氨酯固化剂及其制备方法 | |
CN114133541B (zh) | 一种高耐水解聚酯多元醇及其制备方法和在水性聚氨酯树脂中的应用 | |
WO2015058682A1 (zh) | 一种水溶性饱和聚酯树脂 | |
EP3095826A1 (en) | Cobalt-based catalytic dryer for polymer coatings | |
WO2021048879A1 (en) | Polyester based wood coating composition | |
EP3090005B1 (en) | Modified water-borne alkyd resin | |
CN112011036B (zh) | 一种水性亚麻油酸改性醇酸树脂及其制备方法 | |
EP2949687B1 (en) | Water feed methods to control mw distribution and byproducts of the carbamylation of urea | |
MXPA04009503A (es) | Agentes de recubrimiento acuosos para recubrimiento de latas. | |
CN106008965B (zh) | 用于制备交联聚氨酯的环境温度可固化的不含异氰酸酯的组合物 | |
CN109608849A (zh) | 改性水性醇酸树脂及其制备方法 | |
US4229331A (en) | Process for producing water-emulsifiable air-drying binders, the binders, and emulsions made therefrom | |
CA1153839A (en) | Aqueous polyester dispersions | |
CN111499848B (zh) | 一种零voc水性聚酯分散体用聚酯聚合物、分散体及涂料组合物 | |
CN112654658B (zh) | 一种水性聚酯共聚物及其制备方法与应用 | |
US4978741A (en) | Method for preparing essentially haze-free isophthalic acid- and polymethylolalkanoic acid-containing resins | |
CN113773744A (zh) | 一种水性醇酸防腐涂料及其制备方法 | |
CN112062923B (zh) | 一种指甲油用水性聚氨酯-脲分散体及其制备方法 | |
EP0668305B1 (en) | Environmentally friendly autoxidisable alkyd coating composition | |
US3900336A (en) | Novel autoxidisable liquids | |
JPS646222B2 (zh) | ||
CN111499847B (zh) | 零voc水性聚酯分散体用聚酯聚合物、分散体及涂料组合物 | |
CN113396043A (zh) | 用于涂料的降低雾度的组合物 | |
AU2016252895B2 (en) | Water-dispersible polyester resin having improved water resistance and chemical resistance, water-dispersion emulsion containing same, and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A waterborne linoleic acid modified alkyd resin and its preparation method Effective date of registration: 20231208 Granted publication date: 20220927 Pledgee: Bank of Nanjing Co.,Ltd. Taizhou Branch Pledgor: TAIXING SHENGJIA RESIN CO.,LTD. Registration number: Y2023980069641 |
|
PE01 | Entry into force of the registration of the contract for pledge of patent right |