CN1463753A - Novel methylene oxide scavenging agent - Google Patents
Novel methylene oxide scavenging agent Download PDFInfo
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- CN1463753A CN1463753A CN 02113857 CN02113857A CN1463753A CN 1463753 A CN1463753 A CN 1463753A CN 02113857 CN02113857 CN 02113857 CN 02113857 A CN02113857 A CN 02113857A CN 1463753 A CN1463753 A CN 1463753A
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Abstract
The novel formaldehyde eliminating agent consists of formaldehyde trapping solution mixture with one selected from lauric acid, oleic acid, azone and menthol as efficient penetrant; hydrazide; at least one selected from metal halide, nitrate, sulfite, etc.; and mixture of polyol, methylol urea, ferrous sulfate, and vitamin C or EDTA. The formaldehyde eliminating agent can trap free formaldehyde released by building material and can penetrate into inside of building material to eliminate un-released formaldehyde.
Description
The present invention relates to be used for removing a kind of compositions of formaldehyde, particularly remove the used building materials that contain chemical substance such as formaldehyde of newly-built dwelling house, as the compositions of artificial board with formaldehyde in the Lauxite.
Domestic and international many data show, when people contact a certain amount of formaldehyde, can occur stimulate eyes and skin, dyspnea, eczema, headache, feel sick even symptom such as stupor, free formaldehyde seriously influences the healthy of people and causes environmental pollution, so people require artificial board more and more lower with the burst size of methanal of Lauxite.Reduce the burst size of methanal of artificial board with Lauxite, effective method is to reduce the formaldehyde of Lauxite and the mol ratio of carbamide, but mol ratio is crossed the low decline that usually causes the physical and mechanical property of artificial board, this method is of little use, and people just place hope on artificial board is added the burst size of methanal that formaldehyde scavenger carries out post processing or the adding formaldehyde scavenger reduces artificial board in Lauxite.The formaldehyde removing of having reported (seizure) agent kind report is more, as the patent that adds formaldehyde catching agent in the Lauxite EP94797 is arranged, EP13372, DE2917159, US4397756, DE3733630 and US5268502, US5194674 etc., be the formaldehyde catching agent with the mixture of malonic acid esters and polyhydric alcohol or product of transesterification reaction etc., thereby the reduction curing reaction of urea formaldehyde resin speed that the adding of these agent for capturing has influences the decline of the physical and mechanical property of artificial board, the cost that has is higher.Artificial board adding formaldehyde catching agent is sprayed post processing reduction burst size of methanal JP114879 is arranged, patents such as JP10315423 are caught formaldehyde with the chemical reaction of hydrazides class material and formaldehyde, the seizure effect of free formaldehyde is better, but the free formaldehyde trapping effect that artificial board inside is not discharged temporarily is relatively poor.
The object of the present invention is to provide a kind of novel formaldehyde scavenger, this scavenger by high-efficient penetrant, can form with hydrazides class material and other auxiliary agent of formaldehyde generation chemical reaction, it can not only catch the used building materials that contain chemical substances such as formaldehyde of newly-built dwelling house, as artificial board with the free formaldehyde that discharges in the Lauxite, and porous is to material internals such as chemical building materials such as artificial board, timber, thoroughly remove the formaldehyde that does not discharge temporarily in this class material, reach the purpose of for a long time, forever removing formaldehyde.
The object of the present invention is achieved like this: formaldehyde scavenger is made of A, B, C, D, five kinds of compositions of E.Wherein A is the mixture that in lauryl alcohol, oleic acid, azone, Mentholum, the refreshing ketone any one used or used two kinds and two or more materials separately, and it plays efficient osmosis in product.B is that carboxylic acid or dicarboxylic acids (or ester) react the hydrazides class material that forms with ammonia or hydrazine hydrate.Hydrazides class thing refers to contain in the molecule monobasic hydrazide-based compound of 1 hydrazide group; Contain the polyhydrazide based compound that contains 3 above hydrazide groups in two hydrazide-based compound of 2 hydrazide groups and the molecule in the molecule.
The monobasic hydrazide-based compound specifically refers to following formula (1) formula works.
R-CO-NHNH
2(1) formula
(in the formula, R represents hydrogen atom, alkyl or has substituent aryl.) the straight chain shape alkyl of C1～C12 such as alkyl fingernail base, ethyl, n-pro-pyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base.Aryl refers to phenyl, biphenylyl, naphthyl etc.Wherein phenyl is best.And the substituent group of aryl can be hydrogen base, fluorine, chlorine, bromine, etc. halogen atom; Straight chain shape or the branched-chain alkyl of C1～C4 such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group.
(1) hydrazide compound of formula specifically refers to dodecyl acid (lauric acid) hydrazides, oxybenzoic acid (salicylic acid) hydrazides, formylhydrazine, acethydrazide, propionyl hydrazine, right-hydroxy benzenes (first) amide hydrazides, the sour hydrazides of naphthalene (first), 3-hydroxyl-sour hydrazides of 2-naphthalene (first) etc.
(2) formula works below dihydrazide compound specifically refers to.
H
2NHN-X-NHH
2(2) formula
(in the formula, X represents CO-base or CO-A-CO-base, and A represents alkylene or propinyl.) alkylene of A representative, the straight chain shape alkylene of C1～C12 such as concrete fingernail support, ethylene, trimethylene, fourth support, pentamethylene, hexamethylene, support in heptan, octamethylene, support in the ninth of the ten Heavenly Stems, decamethylene, hendecane support.Also the available hydrogen base replaces alkylene.Propinyl can be used penylene, biphenylene, naphthylene, anthracene support, luxuriant and rich with fragrance support etc.Wherein, penylene, naphthylene are relatively good.The substituent group of propinyl can be with the same substituent group of above-mentioned aryl.
(2) dihydrazide compound of formula specifically refers to symmetrical diaminourea, oxalic acid two hydrazides, malonic acid two hydrazides, succinic acid hydrazide ii, adipic dihydrazide, Azelaic Acid two hydrazides, sebacic dihydrazide, dodecyl-2 acid dihydrazide, Malaysia acid dihydrazide, fumaric acid two hydrazides, diethylene glycol acid dihydrazide, winestone acid dihydrazide, Fructus Mali pumilae acid dihydrazide, isophthalic acid two hydrazides, terephthaldehyde's acid dihydrazide, big horse acid dihydrazide, 2,6-naphthoic acid two hydrazides etc.The various 2 chloric acid dihydrazide compounds, 2 that publish on also available special justice-2-4607 patent, 4-two diazanyls-6-methylamino-sym-triazine (triazine) etc.Wherein dihydrazide compound is pretty good, and they can also can two or morely be used with separately with a kind of, and it can react with formaldehyde generation quantitative chemical.
C is the mixture that among polyhydric alcohol, methylolurea, ferrous sulfate, vitamin C or the EDTA any one used or used two kinds and two or more materials separately.
D be metal halogenide, nitrate, sulfate, sulphite, and hydroxide in any one use or use the mixture of two kinds and two or more materials separately.Metal halide available metal chloride, metal bromide.Metal chloride refers to alkaline-earth metal chlorides such as calcium chloride, magnesium chloride, magnesium chloride potassium, barium chloride, strontium chloride; Zinc chloride, antimony chloride, aluminum chloride, cerium chloride, titanium chloride, manganese chloride lithium chloride, tungsten chloride etc.Metal bromide refers to alkaline-earth metal bromides such as calcium bromide, magnesium bromide, strontium bromide, barium bromide; Zinc bromide, aluminium bromide, nickelous bromide, lithium bromide, tungsten bromide etc.Metal nitrate can be used aluminum nitrate, lime nitrate, magnesium nitrate, Chile saltpeter.Metal sulfate can be used sodium sulfate, magnesium sulfate, Antimonous sulfate, potassium sulfate, titanium sulfate, manganese sulfate, calcium sulfate.Metal sulphite can be used sodium sulfite, potassium sulfite, calcium sulfite, magnesium sulfite, aluminium sulfite, zinc sulfite, sodium sulfite, Potassium acid sulfite.Metal hydroxides available hydrogen sodium oxide, potassium hydroxide, Strontium hydrate..Wherein metal halide is relatively good, and the alkaline-earth metal chloride is better, and especially calcium chloride is best.
When C and D material use separately aldehydes is not removed ability, the ability of removing in other words is relatively poor, if but use with together with B and A composition, can further improve B and A composition removing ability to aldehyde.
E is water or organic solvent.The straight chain shape of polyalcohols things such as ester ring type alcohols thing, ethylene glycol such as the straight chain shape of C1～C8 that organic solvent can be familiar with everybody or a catenate aliphatic saturated alcohols class thing, cyclopentanol, Hexalin, C1～C8 or a chain or ring-type fat aromatic hydrocarbons thing, moieties are straight chain shape or the branched-chain alkyl of C1～C8.As nitrile thing, dimethyl formamide, dimethyl sulfoxine isopolarity solvent, the phosphoric acid ester thing of ring-type ethers thing, ketone thing, esters thing, acetonitriles etc. such as dialkyl ether thing, diaryl ethers thing, oxolane, diox, they can be two or more mixed solvents.
A material consumption of the present invention is 0.0001%～15% of a formaldehyde scavenger total amount, wherein selects 0.01%～5% for use for best.B material consumption is 0.1%～50% of a formaldehyde scavenger total amount, wherein selects 1%～20% for use for best.C material consumption is 0%～50% of a formaldehyde scavenger total amount, wherein selects 0%～10% for use for best.D material consumption is 0%～50% of a formaldehyde scavenger total amount, wherein selects 1%～20% for use for best.E material consumption is 0%～95% of a formaldehyde scavenger total amount, wherein selects 5%～92% for use for best.
Merely the formaldehyde removing agent solution that is made of B, C, D component is removed respond wellly for being discharged into the artificial board surface or spreading to free formaldehyde in the room air, has quick removing formaldehyde and forms the characteristics of stable compound; Yet it is general to catch effect for the free or unsettled methanal complex that artificial board inside is not discharged into the surface, therefore also needs to add the A high-efficient penetrant active component of formaldehyde scavenger is penetrated into the inside of artificial board very soon, catches formaldehyde fast.Well-known lauryl alcohol, oleic acid, azone, Mentholum, refreshing ketone are used widely in medicine, cosmetics, pesticide, printing and dyeing etc. as high-efficient penetrant, select for use one or more mixture to join can to remove the artificial board surface the above formaldehyde removing agent solution apace and artificial board inside is not discharged into surperficial free formaldehyde from lauryl alcohol, oleic acid, azone, Mentholum, refreshing ketone.
Preparation method of the present invention is comparatively simple, A, B, C, D, five kinds of components of E in accordance with regulations the content mix homogeneously then can.
Embodiments of the invention are as follows:
The formaldehyde removing effect is measured by the exsiccator method among the Chinese Industrial Standards (CIS) GB 18580-2001 " formaldehyde discharges and limits the quantity of in indoor decorating material-wood-based plate and the goods thereof ".
Embodiment one:
Get 91 kilograms of distilled water, add 6 kilograms of adipic dihydrazide, 2 kilograms in calcium chloride, 0.001 kilogram of azone, 0.999 kilogram of vitamin C is made the formaldehyde scavenger compositions after fully stirring, and is used for removing wood-based plate formaldehyde, and the formaldehyde removing effect reaches standard-required after measured.
Embodiment two:
Get 80 kilograms of distilled water, add 5 kilograms of oxalic acid two hydrazides, 10 kilograms in magnesium chloride, 5 kilograms of azones are made the formaldehyde scavenger compositions after fully stirring, and are used for removing wood-based plate formaldehyde, and the formaldehyde removing effect reaches standard-required after measured.
Embodiment three:
Get 80 kilograms of malonyl hydrazines, 10 kilograms of sodium sulfitees, 1 kilogram of azone, 9 kilograms of vitamin Cs are made the formaldehyde scavenger compositions after fully stirring, and are used for removing wood-based plate formaldehyde, and the formaldehyde removing effect reaches standard-required after measured.
Embodiment four:
Get 89 kilograms of distilled water, add 5 kilograms of adipic dihydrazide, 4 kilograms of barium bromides, 1.5 kilograms of azones, 0.5 kilogram of oleic acid is made the formaldehyde scavenger compositions after fully stirring, and is used for removing wood-based plate formaldehyde, and the formaldehyde removing effect reaches standard-required after measured.
Embodiment five:
Get 91 kilograms of distilled water, add 4 kilograms of hexanoyl hydrazines, 2 kilograms in magnesium chloride, 0.1 kilogram of azone, 2.9 kilograms of propylene glycol are made the formaldehyde scavenger compositions after fully stirring, and are used for removing wood-based plate formaldehyde, and the formaldehyde removing effect reaches standard-required after measured.
Claims (9)
1. formaldehyde scavenger, this scavenger is made of A, B, C, D, five kinds of compositions of E.Wherein A is a penetrating agent.B is that carboxylic acid or dicarboxylic acids (or ester) react the hydrazides class material that forms with ammonia or hydrazine hydrate.C is the mixture that among polyhydric alcohol, methylolurea, ferrous sulfate, vitamin C or the EDTA any one used or used two kinds and two or more materials separately.D be metal halogenide, nitrate, sulfate, sulphite, and hydroxide in any one use or use the mixture of two kinds and two or more materials separately.E is water or organic solvent.
2. the described formaldehyde scavenger of claim 1 is characterized in that, penetrating agent A is the mixture that in lauryl alcohol, oleic acid, azone, Mentholum, the refreshing ketone any one used or used two kinds and two or more materials separately.
3. formaldehyde scavenger according to claim 1 and 2 is characterized in that, A material consumption is 0.0001%～15% of a formaldehyde scavenger total amount, wherein selects 0.01%～5% for use for best.
4. formaldehyde scavenger according to claim 1 is characterized in that, hydrazides class thing refers to contain in the molecule monobasic hydrazide-based compound of 1 hydrazide group; Contain the polyhydrazide based compound that contains 3 above hydrazide groups in two hydrazide-based compound of 2 hydrazide groups and the molecule in the molecule.
The monobasic hydrazide-based compound specifically refers to following formula (1) formula works.
R-CO-NHNH
2(1) formula
(in the formula, R represents hydrogen atom, alkyl or has substituent aryl.) the straight chain shape alkyl of C1～C12 such as alkyl fingernail base, ethyl, n-pro-pyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base.Aryl refers to phenyl, biphenylyl, naphthyl etc.Wherein phenyl is best.And the substituent group of aryl can be hydrogen base, fluorine, chlorine, bromine, etc. halogen atom; Straight chain shape or the branched-chain alkyl of C1～C4 such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group.(1) hydrazide compound of formula specifically refers to dodecyl acid (lauric acid) hydrazides, oxybenzoic acid (salicylic acid) hydrazides, formylhydrazine, acethydrazide, propionyl hydrazine, right-hydroxy benzenes (first) amide hydrazides, the sour hydrazides of naphthalene (first), 3-hydroxyl-sour hydrazides of 2-naphthalene (first) etc.
(2) formula works below dihydrazide compound specifically refers to.
H
2NHN-X-NHNH
2(2) formula
(in the formula, X represents CO-base or CO-A-CO-base, and A represents alkylene or propinyl.) alkylene of A representative, the straight chain shape alkylene of C1～C12 such as concrete fingernail support, ethylene, trimethylene, fourth support, pentamethylene, hexamethylene, support in heptan, octamethylene, support in the ninth of the ten Heavenly Stems, decamethylene, hendecane support.Also the available hydrogen base replaces alkylene.Propinyl can be used penylene, biphenylene, naphthylene, anthracene support, luxuriant and rich with fragrance support etc.Wherein, penylene, naphthylene are relatively good.The substituent group of propinyl can be with the same substituent group of above-mentioned aryl.
(2) dihydrazide compound of formula specifically refers to symmetrical diaminourea, oxalic acid two hydrazides, malonic acid two hydrazides, succinic acid hydrazide ii, adipic dihydrazide, Azelaic Acid two hydrazides, sebacic dihydrazide, dodecyl-2 acid dihydrazide, Malaysia acid dihydrazide, fumaric acid two hydrazides, diethylene glycol acid dihydrazide, winestone acid dihydrazide, Fructus Mali pumilae acid dihydrazide, isophthalic acid two hydrazides, terephthaldehyde's acid dihydrazide, big horse acid dihydrazide, 2,6-naphthoic acid two hydrazides etc.The various 2 chloric acid dihydrazide compounds, 2 that publish on also available special justice-2-4607 patent, 4-two diazanyls-6-methylamino-sym-triazine (triazine) etc.They can also can two or morely be used with separately with a kind of.
5. according to claim 1 or 4 described formaldehyde scavengers, it is characterized in that B material consumption is 0.1%～50% of a formaldehyde scavenger total amount, wherein select 1%～20% for use for best.
6. formaldehyde scavenger according to claim 1 is characterized in that, C material consumption is 0%～50% of a formaldehyde scavenger total amount, wherein selects 0%～10% for use for best.
7. formaldehyde scavenger according to claim 1 is characterized in that, metal halide available metal chloride, metal bromide.Metal chloride refers to alkaline-earth metal chlorides such as calcium chloride, magnesium chloride, magnesium chloride potassium, barium chloride, strontium chloride; Zinc chloride, antimony chloride, aluminum chloride, cerium chloride, titanium chloride, manganese chloride lithium chloride, tungsten chloride etc.Metal bromide refers to alkaline-earth metal bromides such as calcium bromide, magnesium bromide, strontium bromide, barium bromide; Zinc bromide, aluminium bromide, nickelous bromide, lithium bromide, tungsten bromide etc.Metal nitrate can be used aluminum nitrate, lime nitrate, magnesium nitrate, Chile saltpeter.Metal sulfate can be used sodium sulfate, magnesium sulfate, Antimonous sulfate, potassium sulfate, titanium sulfate, manganese sulfate, calcium sulfate.Metal sulphite can be used sodium sulfite, potassium sulfite, calcium sulfite, magnesium sulfite, aluminium sulfite, zinc sulfite, sodium sulfite, Potassium acid sulfite.Metal hydroxides available hydrogen sodium oxide, potassium hydroxide, Strontium hydrate..Wherein metal halide is relatively good, and the alkaline-earth metal chloride is better, and especially calcium chloride is best.
8. according to claim 1 or 7 described formaldehyde scavengers, it is characterized in that D material consumption is 0%～50% of a formaldehyde scavenger total amount, wherein select 1%～20% for use for best.
9. formaldehyde scavenger according to claim 1 is characterized in that, E material consumption is 0%～95% of a formaldehyde scavenger total amount, wherein selects 5%～92% for use for best.
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| CN 02113857 CN1463753A (en) | 2002-06-11 | 2002-06-11 | Novel methylene oxide scavenging agent |
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| CN 02113857 CN1463753A (en) | 2002-06-11 | 2002-06-11 | Novel methylene oxide scavenging agent |
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| CN100398609C (en) * | 2006-04-18 | 2008-07-02 | 陕西科技大学 | Method of preparing aldehyde remover by utilizing leather heels |
| CN100420723C (en) * | 2006-03-30 | 2008-09-24 | 浙江林学院 | Free formaldehyde trapping agent and process for preparing same |
| CN101648109A (en) * | 2008-08-12 | 2010-02-17 | 王崇富 | Preparation method for decoration odor scavenging agent |
| CN101037576B (en) * | 2007-02-02 | 2010-08-25 | 永港伟方（北京）科技股份有限公司 | Formaldehyde elimination agent |
| CN101011623B (en) * | 2007-02-06 | 2010-10-13 | 江苏飞翔化工股份有限公司 | Formaldehyde removing agent composition |
| CN101007203B (en) * | 2006-01-23 | 2010-11-17 | 胡默言 | An amino acid type formol release agent and its preparation method |
| CN101992012A (en) * | 2009-08-12 | 2011-03-30 | 长沙普照生化科技有限公司 | Formaldehyde scavenger and preparation method thereof |
| CN101125212B (en) * | 2007-09-24 | 2011-06-15 | 北京林业大学 | Formaldehyde absorptive reagent and preparation process thereof |
| CN101502748B (en) * | 2009-02-12 | 2011-07-20 | 张文磊 | Deodouring agent for removing formaldehyde |
| CN101549248B (en) * | 2009-04-15 | 2011-08-03 | 孟璐 | Natural green formaldehyde high-efficiency scavenging agent |
| CN101585926B (en) * | 2009-04-20 | 2012-02-01 | 永港伟方（北京）科技股份有限公司 | Urea-formaldehyde resin additive, preparing method and application thereof |
| CN102500090A (en) * | 2011-10-28 | 2012-06-20 | 赵春付 | Long-acting formaldehyde scavenging agent |
| CN101890212B (en) * | 2009-05-20 | 2012-10-03 | 广州优克日用品有限公司 | Strong penetration type formaldehyde scavenger |
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| CN104437027A (en) * | 2014-11-26 | 2015-03-25 | 成都顺发消洗科技有限公司 | Household formaldehyde elimination agent |
| CN104475031A (en) * | 2014-11-26 | 2015-04-01 | 成都顺发消洗科技有限公司 | Preparation method of adsorption reaction type formaldehyde remover |
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| CN106390352A (en) * | 2016-08-31 | 2017-02-15 | 苏州华泰空气过滤器有限公司 | Formaldehyde removing agent and preparing method thereof |
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| CN111195410A (en) * | 2018-11-16 | 2020-05-26 | 深圳市尤佳环境科技有限公司 | Formaldehyde scavenger and preparation process thereof |
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| CN101007203B (en) * | 2006-01-23 | 2010-11-17 | 胡默言 | An amino acid type formol release agent and its preparation method |
| CN100420723C (en) * | 2006-03-30 | 2008-09-24 | 浙江林学院 | Free formaldehyde trapping agent and process for preparing same |
| CN100398609C (en) * | 2006-04-18 | 2008-07-02 | 陕西科技大学 | Method of preparing aldehyde remover by utilizing leather heels |
| CN101037576B (en) * | 2007-02-02 | 2010-08-25 | 永港伟方（北京）科技股份有限公司 | Formaldehyde elimination agent |
| CN101011623B (en) * | 2007-02-06 | 2010-10-13 | 江苏飞翔化工股份有限公司 | Formaldehyde removing agent composition |
| CN101125212B (en) * | 2007-09-24 | 2011-06-15 | 北京林业大学 | Formaldehyde absorptive reagent and preparation process thereof |
| CN101648109A (en) * | 2008-08-12 | 2010-02-17 | 王崇富 | Preparation method for decoration odor scavenging agent |
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| CN101549248B (en) * | 2009-04-15 | 2011-08-03 | 孟璐 | Natural green formaldehyde high-efficiency scavenging agent |
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