CN102167682A - (Meth)acrylic ethidene urethyl ester monomer and preparation method thereof - Google Patents
(Meth)acrylic ethidene urethyl ester monomer and preparation method thereof Download PDFInfo
- Publication number
- CN102167682A CN102167682A CN 201110037793 CN201110037793A CN102167682A CN 102167682 A CN102167682 A CN 102167682A CN 201110037793 CN201110037793 CN 201110037793 CN 201110037793 A CN201110037793 A CN 201110037793A CN 102167682 A CN102167682 A CN 102167682A
- Authority
- CN
- China
- Prior art keywords
- monomer
- urea
- ethylidene
- methyl
- preparation
- 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.)
- Pending
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a (meth)acrylic ethidene urethyl ester monomer and a preparation method thereof. The monomer is characterized in that the monomer is a functional polymerizable acrylate monomer; and after the monomer is copolymerized with other common acrylate monomers, a synthetized polyacrylate macromolecular side chain has active ethidene urea functional groups. Because of the active side group, the prepared polyacrylate resin has the following functions: (1) formaldehyde gas molecules can be absorbed irreversibly; (2) the wetting property and adhesive force of the resin with various substrates can be greatly increased; and (3) active functional groups can be provided for the post-crosslinking of resin, etc. The invention provides a universal and effective synthesis and preparation method for the special functional acrylate monomer.
Description
Technical field
The present invention relates to the acrylate monomer technical field, relate to a kind of (methyl) vinylformic acid ethylidene-urea alkyl ester monomer and preparation method thereof more specifically.
Background technology
Be subjected to natural timber to fell quantitative limitation, have to generally use in the plate fitment of making by sheet people, because of using Precondensed UreaFormaldehyde Resin, melamine resin, Dyhard RU 100 resin, resol etc. with the cheap binder resin of formaldehyde in a large number as raw material, remaining inevitably a small amount of formaldehyde, and in the furniture use, along with the aging decomposition of these resins, also can constantly slowly discharge harmful, deleterious formaldehyde gas for a long time.Live for a long time at this inhabitation air ambient that contains poisonous formaldehyde molecule, multiple diseases such as meeting leukemogenesis, asthma, baby's teratogenesis cause serious injury to human body, and the too high acute formaldehyde poisoning incident that causes of content of formaldehyde gas also happens occasionally.This problem does not obtain fine solution in the world so far, is more outstanding in this problem of countries and regions underdeveloped.
The inner, external wall emulsion paint that uses in the house fitting-up, the overwhelming majority is to be matrix (comprising pure third resin, styrene-acrylic resin, organosilicon acrylic resin etc.) modulation, composite forming with the Emulsion acrylic resin at present.Although that high-grade inner, external wall emulsion paint has reached is nontoxic, flavor and environment protection requirement only, what can provide only limits to the beautifying and decorating function.LG-DOW company a kind of new function inner, external wall emulsion paint that just took the lead in before 10 years being devoted to develop with formaldehyde molecule function in the irreversible absorption air, the formaldehyde gas molecule that such emulsion paint constantly produces in can quick irreversible absorption home air, self-purging home air environment, effectively reduce the injury of formaldehyde to human body, at present, this function emulsion paint short run begins to come into the market, and is subjected to people's attention day by day.And the core technology of this new function emulsion paint just is will synthesize earlier the special acrylate monomer with irreversible function of absorbing formaldehyde, and then goes out to have the acrylic ester emulsion resin matrix of said function with general acrylate monomer copolymerization.This class features acrylate monomer just that the present invention relates to is used and synthesis preparation method.
Summary of the invention
Purpose of the present invention is exactly a kind of irreversible absorption formaldehyde gas molecule that provides for the deficiency that solves prior art, (methyl) vinylformic acid ethylidene-urea alkyl ester monomer that increases substantially with the wetting property and the bonding force of multiple base material.
Another object of the present invention provides the synthetic and preparation method of a kind of general, effective (methyl) vinylformic acid ethylidene-urea alkyl ester monomer.
The present invention adopts following technical solution to realize above-mentioned purpose: a kind of (methyl) vinylformic acid ethylidene-urea alkyl ester monomer, it is characterized in that, it is to contain ethylidene-urea functional group (methyl) acrylate monomer in the molecule structure, and its chemical structure of general formula is:
Wherein: R=H;-CH
3
Or:
n
2=1,2,3 ... 50.
A kind of (methyl) vinylformic acid ethylidene-urea alkyl fat synthesis preparation method is characterized in that it comprises the steps:
Step 1, (methyl) acrylic acid hydroxy alkyl ester chlorination:
Step 2, (methyl) vinylformic acid chloro alkyl ester and ethylidene-urea condensation reaction:
Step 3, include the irreversible absorption formaldehyde reaction of ethylidene-urea side group polyacrylate dispersion resin:
By ethylidene-urea active group and the irreversible addition reaction of formaldehyde, reach the effect that absorbs effectively and eliminate formaldehyde.
The beneficial effect that the present invention adopts above-mentioned technical solution to reach is:
The present invention is the functional polymerizable propylene of a class ester monomer, after other general acrylate monomer copolymerization, can make to have active ethylidene-urea functional group on institute's synthetic polyacrylic ester macromolecule side chain, this active lateral group can make the polyacrylate resin of preparation have: (1) irreversible absorption formaldehyde gas molecule; (2) wetting property and the bonding force with multiple base material increases substantially; (3) the back crosslinking curing for resin provides multiple functions such as active functional group group.
Embodiment
The present invention's a kind of (methyl) vinylformic acid ethylidene-urea alkyl ester monomer is (methyl) acrylate monomer that contains the ethylidene-urea functional group in the molecule structure, i.e. (methyl) vinylformic acid ethylidene-urea alkyl fat organic compound, and chemical structure of general formula is:
Wherein: R=H;-CH
3
Or:
n
2=1,2,3 ... 50.
A kind of (methyl) vinylformic acid ethylidene-urea alkyl fat synthesis preparation method, it comprises the steps:
Step 1, (methyl) acrylic acid hydroxy alkyl ester chlorination:
Step 2, (methyl) vinylformic acid chloro alkyl ester and ethylidene-urea condensation reaction:
Step 3, include the irreversible absorption formaldehyde reaction of ethylidene-urea side group polyacrylate dispersion resin:
By ethylidene-urea active group and the irreversible addition reaction of formaldehyde, reach the effect that absorbs effectively and eliminate formaldehyde.
Its specific implementation process is as follows:
Embodiment 1
Under stirring in 65 gram hydroxyethyl methylacrylates (0.5mol) the adding 500ml reaction three-necked bottles, be warming up to 70 ℃, slowly drip 60g (0.5mol) thionyl chloride, dropwise the SO that reaction produces in 30 minutes
2Import in the absorption gas cylinder that the 10%NaoH aqueous solution is housed by rubber hose with HCL gas and to be absorbed, be incubated 70～75 ℃ of reactions and reduced to room temperature in 6 hours, add the 150ml deionized water, agitator treating reaction product 20 minutes, again reaction product is poured into standing demix in the separating funnel, the SO of remnants in hydroxyethyl methylacrylate of this reaction and the system
2Be applied in the water layer with HCL gas and remaining thionyl chloride, and synthetic product methacrylic acid chloro ethyl ester is not applied to water and and aqueous phase separation, reach the purpose that product separates purification, operate through separatory, obtain liquid methacrylic acid chloro ethyl ester 71 grams, productive rate is about 96%.
The methacrylic acid chloro ethyl ester product 60 that the last step was obtained restrains (about 0.4mol), ethylidene-urea (powder crystal) 34.5 grams (about 0.4mol), sodium hydroxide 16 grams (0.4mol), dehydrated alcohol 100ml, add in another 500ml reaction three-necked bottle, be heated with stirring to 50 ℃, insulation reaction 10 hours, finish with ph test paper test system PH≤8.5 reactions, fall the system solids with filter paper filtering, basic is the Nacl powder, obtains light yellow ethanolic soln, 50 ℃ of following vacuum removal alcohol solvents, obtain faint yellow methacrylic acid ethyl carbamide ethyl ester (target product) liquid 66 grams, yield is about 97%, and institute's synthetic product detects product purity 〉=98% through nucleus magnetic resonance H spectrum.
Embodiment 2
65 gram Propylene glycol monoacrylates (0.5mol) are added in the 500ml reaction three-necked bottle, be warming up to 70 ℃ under stirring, slowly drip 60 gram (0.5mol) thionyl chlorides, dropwise the SO that reaction produces in 30 minutes
2Import in the aspirator bottle that the 10%NaoH aqueous solution is housed by rubber hose with Hcl gas and to be absorbed, be incubated 70～75 ℃ of reactions 6 hours, reduce to room temperature, add the 150ml deionized water, agitator treating reaction product 20 minutes, again reaction product is poured into standing demix in the separating funnel, residual thionyl chloride in unreacted Propylene glycol monoacrylate and the system, SO
2Be dissolved in the water layer with Hcl gas, and synthetic product vinylformic acid chloro propyl ester is not applied to water and with the water layering, thereby reach the purpose that product separates purifications, through separatory, the vinylformic acid chloro propyl ester 70 that obtains the light yellow liquid shape restrains, productive rate is about 95%.With front synthetic vinylformic acid chloro propyl ester 60 grams (0.4mol), ethylidene-urea 34.5 grams (0.4mol), sodium hydroxide 16 grams (0.4mol), dehydrated alcohol 100ml, add in another 500ml reaction three-necked bottle, be heated to 50 ℃, insulated and stirred reaction 10 hours, record system PH≤8.5 with the PH test paper, reaction is finished.Fall solids in the system (being the Nacl crystal powder substantially) with filter paper filtering, obtain faint yellow vinylformic acid ethyl carbamide propyl ester (target product) liquid 65 grams, yield is about 96%, and institute's synthetic product detects through proton nmr spectra, product purity 〉=98%.
Embodiment 3
With 131 gram methacrylic acid tetraethylene-glycol esters (0.5mol), add in the 500ml reaction three-necked bottle, be warming up to 70 ℃ under stirring, slowly drip 60 gram (0.5mol) thionyl chlorides, dropwise the SO that reaction produces in 30 minutes
2Import in the aspirator bottle that the 10%NaoH aqueous solution is housed by rubber hose with Hcl gas and to be absorbed, be incubated 70～80 ℃ of reactions 10 hours, reduce to 60 ℃, in vacuum tightness greater than 720mmHg under the high condition, vacuum extract system extremely in residual thionyl chloride, SO
2, about 2 hours of Hcl gas, till system PH 〉=5, successively 43 gram (0.5mol) ethyl carbamides, 20 gram NaOH (0.5mol) 150ml dehydrated alcohols are added in the three neck reaction flasks then, be heated to 80 ℃, insulated and stirred reaction 12 hours is measured system PH≤8.5 with the PH test paper, and reaction is finished.Fall solids in the system (being the Nacl crystal powder substantially) with filter paper filtering and obtain faint yellow ethanolic soln.50 ℃ of following vacuum removal ethanolic solns obtain faint yellow methacrylic acid ethylidene-urea tetraethylene-glycol ester (target product) 165 grams, and yield is about 95%, and institute's synthetic product detects through proton nmr spectra, product purity 〉=96%.
Embodiment 4
With 103 gram (0.5mol) vinylformic acid two three ethanol esters that contract, add in the 500ml reaction three-necked bottle, stir down and be warming up to 70 ℃, slowly drip 60 gram (0.5ml) thionyl chlorides, dropwise the SO of reaction generation in 30 minutes
2Imported in the aspirator bottle that the 10%NaOH aqueous solution is housed by rubber hose with Hcl gas and to be absorbed, be incubated 75～80 ℃ of reactions 10 hours, reduce to 60 ℃, greater than 720mmHg under the high condition, vacuum extracts the interior residual thionyl chloride of system, SO in vacuum tightness
2With Hcl gas, took out about 2 hours, survey till system PH 〉=5.Then successively with 43 gram (0.5mol) ethylidene-ureas, 20 gram NaOH (0.5mol), the 150ml dehydrated alcohol adds in the three neck reaction flasks, be heated to 80 ℃, insulated and stirred reaction 12 hours, till PH test paper test system PH≤8.5, reaction finishes, and falls solids in the system (being the Nacl crystal powder substantially) with filter paper filtering and obtains faint yellow ethanolic soln.50 ℃ of following vacuum removal alcohol solvents obtain faint yellow vinylformic acid ethylidene-urea Triethylene glycol (target product) 130 grams, and yield is about 95%.Institute's synthetic product detects through proton nmr spectra, product purity 〉=96%.
Above-described only is preferred implementation of the present invention, should be pointed out that for the person of ordinary skill of the art, under the prerequisite that does not break away from the invention design, can also make some distortion and improvement, and these all belong to protection scope of the present invention.
Claims (2)
1. (methyl) vinylformic acid ethylidene-urea alkyl ester monomer is characterized in that, it is to contain ethylidene-urea functional group (methyl) acrylate monomer in the molecule structure, and its chemical structure of general formula is:
Wherein: R=H;-CH
3
2. (methyl) vinylformic acid ethylidene-urea alkyl fat synthesis preparation method is characterized in that it comprises the steps:
A, (methyl) acrylic acid hydroxy alkyl ester chlorination:
B, (methyl) vinylformic acid chloro alkyl ester and ethylidene-urea condensation reaction:
C, include the irreversible absorption formaldehyde reaction of ethylidene-urea side group polyacrylate dispersion resin:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110037793 CN102167682A (en) | 2011-02-14 | 2011-02-14 | (Meth)acrylic ethidene urethyl ester monomer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110037793 CN102167682A (en) | 2011-02-14 | 2011-02-14 | (Meth)acrylic ethidene urethyl ester monomer and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102167682A true CN102167682A (en) | 2011-08-31 |
Family
ID=44489025
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110037793 Pending CN102167682A (en) | 2011-02-14 | 2011-02-14 | (Meth)acrylic ethidene urethyl ester monomer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102167682A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103613545A (en) * | 2013-11-27 | 2014-03-05 | 沧州康壮化工股份有限公司 | Method for preparing ethylidene-urea ethyl acrylate |
| CN104046146A (en) * | 2014-06-12 | 2014-09-17 | 三棵树涂料股份有限公司 | Building coating capable of removing methyl aldehyde and preparation method of building coating |
| CN104045759A (en) * | 2014-06-12 | 2014-09-17 | 三棵树涂料股份有限公司 | Styrene-acrylic emulsion for interior wall paint capable of removing formaldehyde and preparation method of styrene-acrylic emulsion |
| CN105504146A (en) * | 2016-01-06 | 2016-04-20 | 上海保立佳新材料有限公司 | Formaldehyde adsorption emulsion and preparation method thereof |
| CN111205414A (en) * | 2020-03-16 | 2020-05-29 | 福建华夏蓝新材料科技有限公司 | High-adhesion odor-free water-based acrylate emulsion and preparation method thereof |
| CN111234087A (en) * | 2020-02-20 | 2020-06-05 | 四川亭江新材料股份有限公司 | Acrylic acid retanning agent with formaldehyde capturing function and preparation method thereof |
| US10975017B2 (en) | 2016-12-15 | 2021-04-13 | Nouryon Chemicals International B.V. | Process for manufacturing ethylene amines |
| US10995058B2 (en) | 2016-12-15 | 2021-05-04 | Nouryon Chemicals International B.V. | Process for manufacturing hydroxyethyl ethylene amines |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1065075A (en) * | 1990-11-27 | 1992-10-07 | 罗姆和哈斯公司 | Low-formaldehyde, self-crosslinking polymer latex composition |
| CN1127750A (en) * | 1994-11-18 | 1996-07-31 | 埃勒夫阿托化学有限公司 | Process for the preparation of alkylimidazolidone (meth)acrylateds |
| US6008371A (en) * | 1995-12-16 | 1999-12-28 | Roehm Gmbh | Process for the preparation of (meth)acrylic acid esters |
-
2011
- 2011-02-14 CN CN 201110037793 patent/CN102167682A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1065075A (en) * | 1990-11-27 | 1992-10-07 | 罗姆和哈斯公司 | Low-formaldehyde, self-crosslinking polymer latex composition |
| CN1127750A (en) * | 1994-11-18 | 1996-07-31 | 埃勒夫阿托化学有限公司 | Process for the preparation of alkylimidazolidone (meth)acrylateds |
| US6008371A (en) * | 1995-12-16 | 1999-12-28 | Roehm Gmbh | Process for the preparation of (meth)acrylic acid esters |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103613545A (en) * | 2013-11-27 | 2014-03-05 | 沧州康壮化工股份有限公司 | Method for preparing ethylidene-urea ethyl acrylate |
| CN103613545B (en) * | 2013-11-27 | 2015-09-02 | 沧州康壮化工股份有限公司 | The preparation method of vinylformic acid ethylidene-urea ethyl ester |
| CN104046146A (en) * | 2014-06-12 | 2014-09-17 | 三棵树涂料股份有限公司 | Building coating capable of removing methyl aldehyde and preparation method of building coating |
| CN104045759A (en) * | 2014-06-12 | 2014-09-17 | 三棵树涂料股份有限公司 | Styrene-acrylic emulsion for interior wall paint capable of removing formaldehyde and preparation method of styrene-acrylic emulsion |
| CN105504146A (en) * | 2016-01-06 | 2016-04-20 | 上海保立佳新材料有限公司 | Formaldehyde adsorption emulsion and preparation method thereof |
| US10975017B2 (en) | 2016-12-15 | 2021-04-13 | Nouryon Chemicals International B.V. | Process for manufacturing ethylene amines |
| US10995058B2 (en) | 2016-12-15 | 2021-05-04 | Nouryon Chemicals International B.V. | Process for manufacturing hydroxyethyl ethylene amines |
| CN111234087A (en) * | 2020-02-20 | 2020-06-05 | 四川亭江新材料股份有限公司 | Acrylic acid retanning agent with formaldehyde capturing function and preparation method thereof |
| CN111205414A (en) * | 2020-03-16 | 2020-05-29 | 福建华夏蓝新材料科技有限公司 | High-adhesion odor-free water-based acrylate emulsion and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102167682A (en) | (Meth)acrylic ethidene urethyl ester monomer and preparation method thereof | |
| CN104087056B (en) | Organosilicon-modified hydrophilic activator and application thereof | |
| CN103205224B (en) | Acrylate emulsion laminating adhesive, and preparation method and application thereof | |
| CN106732774B (en) | A kind of vitamin B12Functionalization graphene composite material and preparation method and application | |
| CN106334548B (en) | A kind of CDs/TiO2The preparation method of composite material, a kind of preparation method and applications of modified EVA film | |
| CN104449205A (en) | Antibacterial and scrubbing-resistant waterborne coating for glass door and preparation method of waterborne coating | |
| CN103043919A (en) | Method for preparing waterproof and antifogging surface modified glass | |
| CN106632073B (en) | The synthetic method of ionic liquid constant temperature catalyzing 3,4- dihydropyrimidine-2-keto class compound | |
| CN105949843A (en) | Yellowing-resistant ultraviolet-curable paint | |
| CN102504087A (en) | Preparation method for silicic acrylic ester soap-free emulsion stabilized by protective colloid | |
| CN103740261B (en) | A kind of high color inhibition overlay film UV white and bright finish coat and preparation method thereof | |
| CN102442972B (en) | Industrial preparation method for pramipexole and its dihydrochloride monohydrate | |
| CN102040561A (en) | Method for synthesizing benzotriazole ultraviolet absorber | |
| CN109053934A (en) | A kind of rare earth modified photoinitiator and preparation method | |
| CN103664736B (en) | A kind of ester derivative containing acrylamido indoles and its preparation method and application | |
| CN103484060A (en) | Novel inorganic ultraviolet absorbent and preparation method thereof | |
| CN102408500A (en) | Novel siliceous macro-molecule photoinitiator and its preparation method | |
| CN102977682A (en) | Novel anti-formaldehyde night light printing ink | |
| CN102161654A (en) | Serial maleic acid diethylene urea alkyl esters and preparation method thereof | |
| CN103664809B (en) | A kind of preparation method of paclobutrazol | |
| CN108485452B (en) | Water-based paint suitable for wooden products and preparation method thereof | |
| CN102295851A (en) | Alcohol-soluble inorganic zinc silicate anti-corrosive coating curing agent without chloride ions | |
| CN104371043A (en) | Thioxanthone acetylfluorene photoinitiator and preparation method thereof | |
| CN105315194B (en) | A kind of synthetic method of 2- bromine carbazole and its intermediate | |
| CN103360996A (en) | Multi-purpose aqueous adhesive and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20110831 |