CN102179170A - Formaldehyde-removing alkyd resin and preparation method thereof - Google Patents
Formaldehyde-removing alkyd resin and preparation method thereof Download PDFInfo
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- CN102179170A CN102179170A CN2011100626204A CN201110062620A CN102179170A CN 102179170 A CN102179170 A CN 102179170A CN 2011100626204 A CN2011100626204 A CN 2011100626204A CN 201110062620 A CN201110062620 A CN 201110062620A CN 102179170 A CN102179170 A CN 102179170A
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Abstract
The invention provides a formaldehyde-removing alkyd resin and a preparation method thereof. The preparation method comprises the following steps: adding mixed solution of water and ethanol into a mixture of titanate and alkyd resin solution for reaction; and collecting the formaldehyde-removing alkyd resin from a reaction product. In the invention, nano titanium is introduced into an oily medium to prepare the formaldehyde-removing alkyd resin, the nano effect of the nano titanium serving as a photocatalyst is fully utilized, the obtained alkyd resin is uniform and transparent, the performances of the alkyd resin are not affected, and formaldehyde-removing capacity is high.
Description
Technical field
The present invention relates to a kind of alkyd resins and preparation method thereof with function of removing formaldehyde.
Background technology
The height volatility and the penetrating odor of formaldehyde are not only painful, and internal authority mechanism has also progressively found its harm.International cancer research institution (International Agency for Research on Cancer) is divided into human carcinogen with formaldehyde; U.S. environment protection mechanism (US Environmental Protection Agency) is divided into the possibility carcinogen with formaldehyde.At formaldehyde harm, a lot of patents have proposed to prepare the method for formaldehyde scavenger.What have utilizes activated adoption to pass through physics or chemisorbed to remove formaldehyde, active carbon (CN1405560,2003) for example, Tea Polyphenols, citric acid (CN101549198,2009), perhaps alkali, pulverized limestone (CN101379176,2007; CN101612517,2009); Thereby perhaps utilize active reactive group and formolite reaction decomposing formaldehyde.For example use amino acids (CN101007203,2007), imine compound (CN101530624,2009), hydrazide kind compound (CN1785436,2006; CN101890211,2010); Utilize the method (CN1230917A, 1999) of photocatalyst catalysis in addition.But the problem of photocatalyst maximum is to obtain real nanometer particle at present, perhaps causes reunion when adding nano photo-catalytic in the medium, makes the nano effect of photocatalyst can not get performance, and therefore the product function of removing formaldehyde that obtains can not get performance.
Summary of the invention
The purpose of this invention is to provide a kind of formaldehyde alkyd resins and preparation method thereof that removes, to overcome the above-mentioned defective that prior art exists.
The preparation method who removes the formaldehyde alkyd resins provided by the invention comprises the steps:
With the mixed liquor of water and ethanol, add the mixture of titanate esters and alkyd resin solution, preferably adopt the mode that drips to add, in 0.5～1 hour, add, 45～65 ℃ of reactions 1～3 hour, remove the formaldehyde alkyd resins in the collecting reaction product of back then.
Described collection method comprises being heated to 100～120 ℃, removes the step of unnecessary water, ethanol and other accessory substances.
Parts by weight are:
Preferably, parts by weight are:
Described titanate esters be selected from isopropyl ester or the tetrabutyl titanate a kind of with;
Described alkyd resin solution is the toluene solution of alkyd resins, the xylene solution of alkyd resins, the ethyl acetate solution of alkyd resins or the butyl acetate solution of alkyd resins, the weight percent content of alkyd resins is 50～80%, preferably 55～78%;
Described alkyd resins is the product of polyalcohol and polyacid, can adopt the preparation of following method: with polyalcohol and acid 200～250 ℃ of esterifications to acid number less than 7mgKOH/g, promptly obtain alkyd resins;
Alkyd resins and organic solvent mixed dissolutions such as toluene, dimethylbenzene, ethyl acetate or butyl acetate with obtaining can obtain alkyd resin solution;
Equivalent proportion is: polyacid: polyalcohol=1: 1～1.1;
Described polyalcohol is an ethylene glycol, 1,3 butanediols, neopentyl glycol, diethylene glycol, glycerine, 2-ethyl-2-methylol-1, ammediol, tetramethylol methane or 2,2-dihydroxymethyl-1, in the ammediol more than one, preferably glycerine, 2-ethyl-2-methylol-1, ammediol, pentaerythrite or 2,2-dihydroxymethyl-1, more than one in the ammediol;
Described polyacid is more than one in rosin, benzoic acid, right-p t butylbenzoic acid, 2 ethyl hexanoic acid, laurate, sad, capric acid, coco-nut oil fatty acid, soy(a)-bean oil fatty acid, oleic acid, linoleic acid, leukotrienes, castor oil acid, dehydrated castor oleic acid, talloleic acid, adipic acid, fumaric acid, maleic anhydride, phthalate anhydride, M-phthalic acid, decanedioic acid, trimellitic acid, trimellitic anhydride or the pyromellitic dianhydride.
The present invention introduces oil medium with the nanometer titanium, prepare thus except that the formaldehyde alkyd resins, the present invention has made full use of the nano effect as the nanometer titanium of photocatalyst, and the alkyd resins that obtains is even, transparent, every performance is all unaffected, has stronger removing formaldehyde function.
The specific embodiment
Detection method and result:
One. reagent and instrument:
1. the preparation of formaldehyde indicator: weigh 0.25g4-amino-3-hydrazine-5-sulfydryl 1,2,4-triazole (AHMT) is dissolved in the 0.5mol/L hydrochloric acid of 10ml, and is diluted with water to 50ml, obtains the formaldehyde indicator.
2. formalin: 50ppm;
3. potassium hydroxide aqueous solution: 5mol/L;
4. transparency glass plate, pH test paper, dropper, filter paper.
Two. formaldehyde colour developing principle:
Formaldehyde and 4-amino-3-hydrazine-5-sulfydryl 1,2,4-triazole (AHMT) is condensed into the aubergine compound under alkali condition, and its color and luster depth is directly proportional with content of formaldehyde.
Three. detect:
Paint film model preparation: the sample blade coating on glass plate, was dried 7 days;
Filter paper is immersed in the 50ppm formalin, takes out, remove supernatant liquid, paste and be put on the dried paint wait 1hr;
On above-mentioned filter paper, drip potassium hydroxide aqueous solution;
Getting one of formaldehyde indicator with dropper, splash on the filter paper, is alkalescence with the test of pH test paper, observes change color.Filter paper aubergine color is shallow more, shows that content of formaldehyde is low more, illustrates that resin aldehydes removal effect is good more.
Do blank test and contrast test as stated above simultaneously.
Blank test is a sample material with general alkyd resins.
Embodiment 1
With the 58.6kg soy(a)-bean oil fatty acid, the 19.8kg pentaerythrite, the 21.6kg phthalate anhydride adds reactor together, stirs, and is warming up to 200 ℃, carries out esterification, and the control temperature is not higher than 250 ℃ in the course of reaction.Every 30 minutes sampling detecting acid numbers, be 7mgKOH/g in reacting after 2 hours, stop reaction, obtain the 96.8kg alkyd resins until acid number; Add the 80kg xylene soluble then and become solution, obtain the alkyd resins xylene solution of 176.8kg, the filtration, purification cooling is stand-by.
In 100 parts of above-mentioned alkyd resin solutions, add 1 part of isopropyl titanate, stir, be warming up to 65 ℃, be added dropwise to the mixture of 1 part of deionized water and 5 parts of absolute ethyl alcohols, stir, in 1 hour, dropwise, kept again 3 hours at 65 ℃, stir, the nanometer titanium that obtain this moment is evenly coated by alkyd resins.Afterwards, the alkyd resin solution of clad nano titanium is heated to 110 ℃, steam by azeotropic and remove unnecessary water, absolute ethyl alcohol and other accessory substances, thereby obtain removing the formaldehyde alkyd resins.
Adopt above-mentioned detection method, detect, the result of blank test is as follows:
The color of filter paper presents aubergine on the blank test paint film model, and color shows as: tone 193～209, saturation degree 160～225, brightness 121～160; More obviously, color shows as: tone 199～203, saturation degree 170～190, brightness 110～205.Press the rgb color pattern: red 200～240, green 34～189, blue 171～241; More obviously, rgb color pattern: red 217～231, green 64～160, blue 200～231.
With embodiment 1 obtain to remove the formaldehyde alkyd resins be detected object, the result is as follows:
The color of removing filter paper on the formaldehyde resin paint film model presents very shallow aubergine, and color shows as: tone 193～209, saturation degree 160～225, brightness 231～239; More obviously, color shows as: tone 199～203, saturation degree are 170～190, brightness 235～239.Press the rgb color pattern: red 252～255, green 238～253, blue 253～255; More obviously, rgb color pattern: red 254～255, green 245～253, blue 254～255.Also may be light yellow, colourity is: tone 35～42, saturation degree 203～207, brightness 210～253; Press the rgb color pattern: red 252～254, green 248～253, blue 219～241.
Embodiment 2
With the 60.25kg linolenic acid, 16.87kg glycerine adds reactor together, stirs to feed CO
2Be warming up to 120 ℃ with 40 minutes, stop to stir, add 0.17kg yellow lead, continue to stir, in 1.5～2.0 hours, be warming up to 220 ℃, add the 10.0kg phthalate anhydride, added 7～10.0kg phthalate anhydride in later per 10 minutes, kept 1 hour at 220 ℃ after adding whole phthalate anhydrides, be warming up to 240 ℃ and kept 3 hours, the control temperature is not higher than 250 ℃ in the course of reaction.Every 30 minutes sampling detecting acid numbers, be 7mgKOH/g in reacting after 3 hours, stop reaction, obtain the 109.62kg alkyd resins until acid number; Add the 30kg xylene soluble then and become solution, obtain the alkyd resins xylene solution of 139.62kg, the filtration, purification cooling is stand-by.
In 100 parts of above-mentioned alkyd resin solutions, add 10 parts of tetraethyl titanates, stir, be warming up to 60 ℃, be added dropwise to the mixture of 15 parts of deionized waters and 10 parts of absolute ethyl alcohols, stir, in 1 hour, dropwise, kept again 3 hours at 65 ℃, stir, the nanometer titanium that obtain this moment is evenly coated by alkyd resins.Afterwards, the alkyd resin solution of clad nano titanium is heated to 110 ℃, steam by azeotropic and remove unnecessary water, absolute ethyl alcohol and other accessory substances, thereby obtain removing the formaldehyde alkyd resins.
Adopt above-mentioned detection method, detect, the result of blank test is as follows:
The color of filter paper presents aubergine on the blank test paint film model, and color shows as: tone 193～209, saturation degree 160～225, brightness 121～160; More obviously, color shows as: tone 199～203, saturation degree 170～190, brightness 110～205.Press the rgb color pattern: red 200～240, green 34～189, blue 171～241; More obviously, rgb color pattern: red 217～231, green 64～160, blue 200～231.
With embodiment 2 obtain to remove the formaldehyde alkyd resins be detected object, the result is as follows:
The color of removing filter paper on the formaldehyde resin paint film model presents very shallow aubergine, and color shows as: tone 193～209, saturation degree 160～225, brightness 231～239; More obviously, color shows as: tone 199～203, saturation degree are 170～190, brightness 235～239.Press the rgb color pattern: red 252～255, green 238～253, blue 253～255; More obviously, rgb color pattern: red 254～255, green 245～253, blue 254～255.Also may be light yellow, color shows as: tone 35～42, saturation degree 203～207, brightness 210～253; Press the rgb color pattern: red 252～254, green 248～253, blue 219～241.
Claims (8)
1. remove the preparation method of formaldehyde alkyd resins, it is characterized in that, comprise the steps: mixed liquor, add the mixture reaction of titanate esters and alkyd resin solution, remove the formaldehyde alkyd resins in the collecting reaction product then water and ethanol.
2. method according to claim 1 is characterized in that, adopts the mode that drips to add the mixture of titanate esters and alkyd resin solution the mixed liquor of water and ethanol, adds in 0.5～1 hour, 45～65 ℃ of reactions 1～3 hour.
3. method according to claim 1 is characterized in that, the parts by weight of each component are:
4. method according to claim 1 is characterized in that, the parts by weight of each component are:
5. according to each described method of claim 1～4, it is characterized in that, described titanate esters be selected from isopropyl ester or the tetrabutyl titanate a kind of with;
Described alkyd resins is the product of polyalcohol and acid;
Described polyalcohol is an ethylene glycol, 1,3 butanediols, neopentyl glycol, diethylene glycol, glycerine, 2-ethyl-2-methylol-1, ammediol, tetramethylol methane or 2,2-dihydroxymethyl-1, in the ammediol more than one, preferably glycerine, 2-ethyl-2-methylol-1, ammediol, pentaerythrite or 2,2-dihydroxymethyl-1, more than one in the ammediol;
Described polyacid is more than one in rosin, benzoic acid, right-p t butylbenzoic acid, 2 ethyl hexanoic acid, laurate, sad, capric acid, coco-nut oil fatty acid, soy(a)-bean oil fatty acid, oleic acid, linoleic acid, leukotrienes, castor oil acid, dehydrated castor oleic acid, talloleic acid, adipic acid, fumaric acid, maleic anhydride, phthalate anhydride, M-phthalic acid, decanedioic acid, trimellitic acid, trimellitic anhydride or the pyromellitic dianhydride.
6. method according to claim 5, it is characterized in that, described alkyd resin solution is the toluene solution of alkyd resins, the xylene solution of alkyd resins, the ethyl acetate solution of alkyd resins or the butyl acetate solution of alkyd resins, and the weight percent content of alkyd resins is 50～80%.
7. method according to claim 5 is characterized in that, equivalent proportion is: polyacid: polyalcohol=1: 1～1.1.
8. remove the formaldehyde alkyd resins according to each 5 described method preparation of claim 1～7.
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Cited By (7)
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| CN103214662A (en) * | 2013-05-03 | 2013-07-24 | 嘉宝莉化工集团股份有限公司 | Modified alkyd resin as well as preparation method of alkyd resin and double-component matte white finish |
| CN103333553A (en) * | 2013-07-12 | 2013-10-02 | 三棵树涂料股份有限公司 | Antibacterial and aldehyde-removing titanium dioxide pulp for oily carpentry paint, and preparation method of dioxide pulp |
| CN103509457A (en) * | 2013-09-23 | 2014-01-15 | 三棵树涂料股份有限公司 | Matt polyurethane wood floor paint with formaldehyde removing function and preparation method thereof |
| CN105542139A (en) * | 2016-01-26 | 2016-05-04 | 成都杰晟蜀邦新材料科技有限公司 | Novel alkyd resin containing titanium and preparation method of alkyd resin |
| CN103232801B (en) * | 2013-04-11 | 2016-09-07 | 三棵树涂料股份有限公司 | Employing removes polyurethane carpentry paint of urea formaldehyde and preparation method thereof |
| CN109082220A (en) * | 2018-06-22 | 2018-12-25 | 安徽菱湖漆股份有限公司 | A kind of bicomponent environment-friendly type tobacco machine corrosion-resistanting decoration finishing coat and preparation method thereof |
| CN112724377A (en) * | 2020-12-28 | 2021-04-30 | 江苏苏青水处理工程集团有限公司 | Preparation method of process liquid formaldehyde-removing resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103333553A (en) * | 2013-07-12 | 2013-10-02 | 三棵树涂料股份有限公司 | Antibacterial and aldehyde-removing titanium dioxide pulp for oily carpentry paint, and preparation method of dioxide pulp |
| CN103509457A (en) * | 2013-09-23 | 2014-01-15 | 三棵树涂料股份有限公司 | Matt polyurethane wood floor paint with formaldehyde removing function and preparation method thereof |
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| CN105542139A (en) * | 2016-01-26 | 2016-05-04 | 成都杰晟蜀邦新材料科技有限公司 | Novel alkyd resin containing titanium and preparation method of alkyd resin |
| CN109082220A (en) * | 2018-06-22 | 2018-12-25 | 安徽菱湖漆股份有限公司 | A kind of bicomponent environment-friendly type tobacco machine corrosion-resistanting decoration finishing coat and preparation method thereof |
| CN112724377A (en) * | 2020-12-28 | 2021-04-30 | 江苏苏青水处理工程集团有限公司 | Preparation method of process liquid formaldehyde-removing resin |
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