CN1173942C - Large monomer containing methacrylate structure, its preparing method and use - Google Patents
Large monomer containing methacrylate structure, its preparing method and use Download PDFInfo
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- CN1173942C CN1173942C CNB021343926A CN02134392A CN1173942C CN 1173942 C CN1173942 C CN 1173942C CN B021343926 A CNB021343926 A CN B021343926A CN 02134392 A CN02134392 A CN 02134392A CN 1173942 C CN1173942 C CN 1173942C
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Abstract
The present invention relates to a large monomer with a methyl propiolate structure, and the molecule is also provided with structures of 3-(o-tolyloxy)-1, 2-propanediol, glycol acetal, succinic acid monoester and sodium sulfonate. The preparation method of the large monomer has three steps that monoester is prepared by maleic anhydride and diethylene glycol, a polymer is prepared by the monoester, toluene diisocyanate (mixed) and methacrylic-2-hydroxyl acetate, and the large monomer is generated by the reaction of the polymer and sodium sulfite. The present invention has the advantages of wide raw material source, good performance and low cost and can be used as a surface activity monomer for preparing paint or adhesive, the present invention has moderate preparing method and reaction condition, and reactant can be used without separation.
Description
The present invention relates to a kind of big monomer that contains metacrylic acid ester structure, be meant the big monomer that can be used as surface active monomer especially, the invention still further relates to this big monomeric preparation method.
Containing on one side hydrophilic-structure (polar structure), the other side, to contain oleophylic structure (nonpolar structure) be the common trait of surface active monomer.For surface active monomer (tensio-active agent that has carbon-carbon double bond), existing at present a large amount of reports, as people such as Zhang Mao's root with feedstock production such as MALEIC ANHYDRIDE, lauryl alcohol, polyoxyethylene glycol, glycidyl allyl ether, methyl propenoic acid glycidyl ether, sodium bisulfites surface active monomer (SCI, 1998,9:1518～1521; 1999,12:1969～1973).And for example human vinylcarbinol, epoxy chloropropane, S-WAT such as Tang Guang grain prepared tensio-active agent (polymer journal, 2000,3:267～270).But above-mentioned surface active monomer of enumerating and preparation method thereof in the production of reality, all exist in various degree raw material sources relatively difficulty, price is than problems such as height.
The objective of the invention is to the problem at the prior art existence, a kind of big monomer that contains metacrylic acid ester structure is provided, it can be used as surface active monomer, and its raw material sources are extensive, performance good, cost is lower.The present invention simultaneously also provides this big monomeric preparation method, and this method has reaction conditions gentleness, reactant and need not to separate and advantage such as can use.
The big monomer of the present invention also contains carbamate, condensed ethandiol, succinate monoester, sodium sulfonate structure except that containing metacrylic acid ester structure, its molecular structural formula is as follows:
The present invention is big, and monomeric preparation method comprises the steps:
(1) be the feedstock production monoesters with the MALEIC ANHYDRIDE (MA) of 1.00～1.06 molar part and the glycol ether (DEG) of 1.00 molar part, 70 ± 2 ℃ of reaction conditionss, the reaction times is 6～7h hour (representing with h, down together);
(2) with the tolylene diisocyanate (TDI) of step (1) gained monoesters and 1.00～1.05 molar part and the methacrylic acid of 1.00～1.05 molar part-2-hydroxy methacrylate (HEMA) prepared in reaction polymer: at first in reactor, add the TDI of formula ratio and the stannous octoate of 0.6～1.0%TDI massfraction, in 45 ± 2 ℃ step (1) reactant is added dropwise in 1.0～1.2h in the reactor and reacts with TDI, constant temperature 0.8～1.0h, be warming up to 65 ± 2 ℃ of reaction 1.0～1.2h then, be cooled to 45 ± 2 ℃ again, dropping contains the formula ratio HEMA of 0.5～1.0% massfraction Resorcinol, 1.0 drip off in～the 1.2h, 45 ± 2 ℃ of isothermal reaction 0.8～1.0h, be warming up to 65～70 ℃, react 1.2～2.0h again;
(3) pour in 60 ± 2 ℃ of reactants and contain 1.00～1.06 molar part Na step (2)
2SO
3, concentration is no more than in the aqueous solution of 15% massfraction, reaction 3～5h makes big monomer of the present invention.
The chemical equation of the inventive method can be expressed as:
The prepared product of aforesaid method is faint yellow paste, and after measured, its non-volatile content is that 35～40%, 4% pH value of water solution is 6.FT-IR analysis is as follows: 3310cm
-1(secondary amide, υ
N-H); 2860～2960cm
-1(CH
2-,-CH
3, υ
C-H); 1719cm
-1(ester, υ
C=O); 1540cm
-1(secondary amide, δ
N-H); 1454cm
-1(δ
CH2); 1413cm
-1(carboxylate salt, υ
COO-); 1387cm
-1(δ
S CH3); 1289cm
-1(secondary amide, υ
C-N); 1229cm
-1(υ
C-O); 1186cm
-1, 1049cm
-1(sulfonate, υ
S=O); 873cm
-1, 817cm
-1(1,2,4-trisubstituted benzene, γ
C=H); υ
C=CBe subjected to the shielding effect at further feature peak, at 1640cm
-1Place's vibration is not obvious, but the experiment of the water tolerance of emulsion glued membrane can exist activity double key in the interpret sample really.Therefore, obtained big monomer required for the present invention by the inventive method.
Product of the present invention has the good emulsifying ability to polymerization single polymerization monomer commonly used, can be used as the surface active monomer of preparation coating or tackiness agent.
The present invention has following advantage or effect:
1, raw material sources are extensive, obtain easily;
2, the price of raw material is lower, so cost is lower;
3, product of the present invention is functional as surface active monomer, and the emulsion polymer that is prepared by the present invention has better water tolerance than the emulsion of doing the emulsifying agent preparation with SDBS;
4, the inventive method reaction conditions gentleness, reactant need not to separate and can use.
Below in conjunction with concrete embodiment the present invention is further detailed:
Embodiment 1:
(1) in the three-necked bottle that electric mixer, thermometer and reflux condensing tube are housed, adds the MA of 1.03mol (101.0g) and the DEG of 1.00mol (106.1g), under agitation in 70 ℃ of oil bath reaction 7h.
(2) device is as described in (1), add 1.00mol (174.2g) TDI in three-necked bottle, the stannous octoate of 0.6%TDI massfraction under agitation is added dropwise in the bottle in step (1) reactant 1h in 45 ℃ and reacts with TDI, drip back constant temperature 1h, be warming up to 65 ℃ of reaction 1h then, be cooled to 45 ℃ again, stir and drip 1.00mol (130.2g) HEMA that contains 1% massfraction Resorcinol down, drip off in the 1h, 45 ℃ of isothermal reaction 1h are warming up to 65 ℃, react 1.5h again.
(3) device is as described in (1), under high degree of agitation, in 60 ℃ step (2) reactant poured into and to contain 1.03mol (129.8g) Na
2SO
3, concentration is no more than in the aqueous solution of 15% massfraction, reaction 5h, and reaction is finished, and obtains required big monomer.
Embodiment 2:
(1) in the three-necked bottle that electric mixer, thermometer and reflux condensing tube are housed, adds the MA of 1.00mol (98.1g) and the DEG of 1.00mol (106.1g), under agitation in 70 ℃ of oil bath reaction 6h.
(2) device is as described in (1), add 1.00mol (174.2g) TDI in three-necked bottle, the stannous octoate of 0.7%TDI massfraction under agitation is added dropwise in the bottle in step (1) reactant 1h in 45 ℃ and reacts with TDI, drip back constant temperature 0.8h, be warming up to 65 ℃ of reaction 1h then, be cooled to 45 ℃ again, stir and drip 1.00mol (130.2g) HEMA that contains 0.5% massfraction Resorcinol down, 1.2h in drip off, 45 ℃ of isothermal reaction 1h are warming up to 65 ℃, react 1.2h again.
(3) device is as described in (1), under high degree of agitation, in 60 ℃ step (2) reactant poured into and to contain 1.00mol (126.0g) Na
2SO
3, concentration is no more than in the aqueous solution of 15% massfraction, reaction 3h, and reaction is finished, and obtains required big monomer.
Embodiment 3:
(1) in the three-necked bottle that electric mixer, thermometer and reflux condensing tube are housed, adds the MA of 1.06mol (103.9g) and the DEG of 1.00mol (106.1g), under agitation in 70 ℃ of oil bath reaction 7h.
(2) device is as described in (1), add 1.03mol (179.4g) TDI in three-necked bottle, the stannous octoate of 1.0%TDI massfraction under agitation is added dropwise in the bottle in step (1) reactant 1.2h in 45 ℃ and reacts with TDI, drip back constant temperature 1h, be warming up to 65 ℃ of reaction 1.2h then, be cooled to 45 ℃ again, stir and drip 1.05mol (136.7g) HEMA that contains 1.0% massfraction Resorcinol down, drip off in the 1h, 45 ℃ of isothermal reaction 0.8h are warming up to 70 ℃, react 2.0h again.
(3) device is as described in (1), under high degree of agitation, in 60 ℃ step (2) reactant poured into and to contain 1.06mol (133.6g) Na
2SO
3, concentration is no more than in the aqueous solution of 15% massfraction, reaction 4h, and reaction is finished, and obtains required big monomer.
Embodiment 4
In order to illustrate that the present invention has the good emulsifying ability to polymerization single polymerization monomer commonly used.With Sodium dodecylbenzene sulfonate (SDBS) is contrast, adopts monomer vinyl-acetic ester (VAc) commonly used, methyl methacrylate (MMA), vinylbenzene (St) and butyl acrylate (BA) to compare experiment (result such as table 1).The comparative approach of emulsifying property is: the 10g monomer mixes back stirring 5min with the water phase surfactant mixture that 10ml contains 2.0% massfraction, pours in the 25ml graduated cylinder, leaves standstill 1h, observes the water yield of separating out.As can be seen from Table 1, performance of the present invention is apparently higher than control group.
Table 1 the present invention and SDBS leave standstill condensate rate (ml), 21 ℃ after using monomer emulsification always
VAc MMA St BA
The present invention 2.6 2.0 5.8 6.5
SDBS 6.0 3.5 6.7 6?0
Emulsion polymer by the present invention's preparation has better water tolerance than the emulsion of doing the emulsifying agent preparation with SDBS.When monomer is MMA/BA=3: 4 mixtures (massfraction), when the emulsifying agent consumption is monomer 3% (massfraction), obtained emulsion is filmed on slide glass, after the drying, wave carrier piece is immersed in the water, glued membrane is downward, is that the glued membrane of emulsifying agent came off naturally at 3～4 days with SDBS, and the obtained glued membrane of the present invention then comes off after 8～9 days.
Claims (3)
1, a kind of big monomer that contains metacrylic acid ester structure is characterized in that its molecular structural formula is as follows:
2, big according to claim 1 monomeric preparation method is characterized in that comprising the steps:
(1) be the feedstock production monoesters with the MALEIC ANHYDRIDE of 1.00～1.06 molar part and the glycol ether of 1.00 molar part, reaction conditions is 70 ± 2 ℃, and the reaction times is 6～7h;
(2) with the tolylene diisocyanate of step (1) gained monoesters and 1.00～1.05 molar part and the methacrylic acid of 1.00～1.05 molar part-2-hydroxy methacrylate prepared in reaction polymer: at first in reactor, add the tolylene diisocyanate of formula ratio and the stannous octoate of 0.6～1.0% tolylene diisocyanate massfraction, in 45 ± 2 ℃ step (1) reactant is added dropwise in 1.0～1.2h in the reactor and reacts with tolylene diisocyanate, constant temperature 0.8～1.0h, be warming up to 65 ± 2 ℃ of reaction 1.0～1.2h then, be cooled to 45 ± 2 ℃ again, dropping contains the formula ratio methacrylic acid-2-hydroxy methacrylate of 0.5～1.0% massfraction Resorcinol, 1.0 drip off in～the 1.2h, 45 ± 2 ℃ of isothermal reaction 0.8～1.0h, be warming up to 65～70 ℃, react 1.2～2.0h again;
(3) pour in 60 ± 2 ℃ of reactants and contain 1.00～1.06 molar part Na step (2)
2SO
3, concentration is no more than in the aqueous solution of 15% massfraction, reaction 3～5h makes big monomer of the present invention.
3, big monomer as claimed in claim 1 is characterized in that it can be used as the surface active monomer of preparation coating or tackiness agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021343926A CN1173942C (en) | 2002-07-18 | 2002-07-18 | Large monomer containing methacrylate structure, its preparing method and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021343926A CN1173942C (en) | 2002-07-18 | 2002-07-18 | Large monomer containing methacrylate structure, its preparing method and use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1392139A CN1392139A (en) | 2003-01-22 |
| CN1173942C true CN1173942C (en) | 2004-11-03 |
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ID=4747725
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021343926A Expired - Fee Related CN1173942C (en) | 2002-07-18 | 2002-07-18 | Large monomer containing methacrylate structure, its preparing method and use |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101429260B (en) * | 2008-08-22 | 2010-12-01 | 中国科学院上海应用物理研究所 | Polymethacrylate, preparation method and application thereof |
| EP2813249A1 (en) * | 2013-06-14 | 2014-12-17 | Biowintech | Implantable material grafted with a cell antiproliferative and/or antibacterial film synthetized from a bifunctional molecule |
| CN104559610A (en) * | 2013-12-20 | 2015-04-29 | 东莞市长安东阳光铝业研发有限公司 | Organic hydrophilic coating for air conditioner aluminum foil and preparation method of organic hydrophilic coating |
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2002
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| CN1392139A (en) | 2003-01-22 |
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