CN101117381A - Method for synthesizing polyethylene glycol monomethyl ether methacrylate by nitrogen with water - Google Patents
Method for synthesizing polyethylene glycol monomethyl ether methacrylate by nitrogen with water Download PDFInfo
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- CN101117381A CN101117381A CNA2007100701552A CN200710070155A CN101117381A CN 101117381 A CN101117381 A CN 101117381A CN A2007100701552 A CNA2007100701552 A CN A2007100701552A CN 200710070155 A CN200710070155 A CN 200710070155A CN 101117381 A CN101117381 A CN 101117381A
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- CN
- China
- Prior art keywords
- glycol monomethyl
- polyethylene glycol
- water
- nitrogen
- monomethyl ether
- 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.)
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000002202 Polyethylene glycol Substances 0.000 title claims abstract description 28
- 229920001223 polyethylene glycol Polymers 0.000 title claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 19
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 13
- 238000005886 esterification reaction Methods 0.000 claims abstract description 13
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 11
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims description 26
- 150000002148 esters Chemical class 0.000 claims description 22
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 22
- 229920000151 polyglycol Polymers 0.000 claims description 14
- 239000010695 polyglycol Substances 0.000 claims description 14
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 8
- 230000032050 esterification Effects 0.000 claims description 7
- 239000003921 oil Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- -1 ester compounds Chemical class 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 abstract 4
- 239000003054 catalyst Substances 0.000 abstract 2
- 239000003112 inhibitor Substances 0.000 abstract 2
- 229950000688 phenothiazine Drugs 0.000 abstract 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 231100000331 toxic Toxicity 0.000 abstract 1
- 230000002588 toxic effect Effects 0.000 abstract 1
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical class COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 125000005395 methacrylic acid group Chemical class 0.000 description 2
- 230000001473 noxious effect Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A method for synthesizing polyethylene glycol monomethyl ether methacrylate with water in nitrogen belongs to the technical field of synthesis of ester compounds in organic chemistry, polyethylene glycol monomethyl ether and methacrylic acid are used as raw materials, p-toluenesulfonic acid or concentrated sulfuric acid is used as a catalyst, phenothiazine or hydroquinone is used as a polymerization inhibitor to carry out esterification reaction, and the polyethylene glycol monomethyl ether methacrylate is prepared in a nitrogen-introducing and water-carrying manner in the esterification reaction process; the molar ratio of the polyethylene glycol monomethyl ether to the methacrylic acid can be 1.0: 1.5-8.0. According to the invention, the polyethylene glycol monomethyl ether methacrylate is prepared by introducing nitrogen and carrying water, so that the cost can be effectively reduced; meanwhile, the method reasonably selects p-toluenesulfonic acid or concentrated sulfuric acid as a catalyst and phenothiazine or hydroquinone as a polymerization inhibitor to carry out esterification reaction, has mild reaction conditions, does not adopt toxic solvents as water-carrying agents, and is environment-friendly.
Description
Technical field
The present invention relates to a kind of method of synthesizing polyethylene glycol monomethyl ethermethacrylic acid esters by nitrogen with water, belong to technical field of synthesis of ester compounds in the organic chemistry.
Background technology
Polyethylene glycol monomethyl ethermethacrylic acid esters is the surface-active macromonomer of polycarboxylic acids dehydragent, and polycarboxylic acids dehydragent be continue with wooden calcium be the ordinary water-reducing agent of representative and with naphthalene be the high efficiency water reducing agent of representative after the third generation high-performance water reducing agent that grows up.This class water reducer volume is low, water-reducing rate greatly, do not emanate, bleeding not, the concrete slump property retention is good, and is good with cement, adulterant and other admixture consistency; Can effectively reduce the thermal cracking of early stage thermal insulation warming of concrete and mass concrete; Degree of freedom on the Molecular Structure Design is big, and the potentiality of the high performance of realization water reducer are bigger; Provide technical guarantee for promoting the use of industrial wastes such as flyash in great mixed amount, slag, slag.The synthetic method of polycarboxylic acids dehydragent mainly makes with polyethylene glycol monomethyl ethermethacrylic acid esters and other reactive monomer polymeric modes, but the synthetic method of polyethylene glycol monomethyl ethermethacrylic acid esters report is less, and mostly reported method is to adopt to add noxious solvent such as benzene in esterification reaction process also, toluene, hexanaphthenes etc. are as the band water solvent, proposing with poly glycol monomethyl ether (EO=25) and methacrylic acid as Japanese Patent JP2003327689 is reaction raw materials, with the hexanaphthene is the band water solvent, carry out esterification, thereby by the distillation mode hexanaphthene is removed again at last and made polyethylene glycol monomethyl ethermethacrylic acid esters, complex production process not only, cost is higher, and harmful to environment.
Summary of the invention
It is reasonable to the purpose of this invention is to provide a kind of technology, simple to operate, has the method for the synthesizing polyethylene glycol monomethyl ethermethacrylic acid esters by nitrogen with water of better use properties.
The expression formula of polyethylene glycol monomethyl ethermethacrylic acid esters is:
In the formula: n=5～45.
The present invention is the method for synthesizing polyethylene glycol monomethyl ethermethacrylic acid esters by nitrogen with water, with poly glycol monomethyl ether and methacrylic acid is raw material, it is characterized in that with the tosic acid or the vitriol oil be catalyzer, thiodiphenylamine or Resorcinol are that stopper carries out esterification, and the mode with logical nitrogen band water in the esterification reaction process makes polyethylene glycol monomethyl ethermethacrylic acid esters.
The polymerization degree of described poly glycol monomethyl ether can be 5～45.
The mol ratio of described poly glycol monomethyl ether and methacrylic acid can be 1.0: 1.5～and 8.0, can adjust accordingly according to the different polymerization degree of poly glycol monomethyl ether.
The add-on of described catalyzer can be 0.5～5.0% of poly glycol monomethyl ether and methacrylic acid gross weight.
The add-on of described stopper can be the 250ppm～2000ppm of poly glycol monomethyl ether and methacrylic acid gross weight.
The temperature of reaction of described esterification can be 100 ℃～140 ℃.
The time of described logical nitrogen band water can be 5.0～7.0 hours.
The present invention compared with prior art has following outstanding advantage and positively effect:
1, adopts the mode of logical nitrogen band water to make polyethylene glycol monomethyl ethermethacrylic acid esters, can effectively reduce cost.
2, rationally selecting the tosic acid or the vitriol oil for use is catalyzer, and thiodiphenylamine or Resorcinol are that stopper carries out esterification, and the reaction conditions gentleness does not adopt noxious solvent to make the band aqua, thereby environmentally friendly.
3, by synthetic polyethylene glycol monomethyl ethermethacrylic acid esters of the present invention, have characteristics such as degree of unsaturation height, esterification yield height, reactive behavior be good, be applicable to the synthetic field of high-performance polycarboxylic acids dehydragent.
Embodiment
Embodiment 1:
In reactor, add 1500 parts of poly glycol monomethyl ethers (polymerization degree n is 23), 258 parts of methacrylic acids, stir and add 50 parts of tosic acid down, 0.5 part thiodiphenylamine, connect condensing reflux and division box, feed nitrogen, be warming up to 100 ℃～140 ℃, reacted 6.5 hours, lower the temperature polyethylene glycol monomethyl ethermethacrylic acid esters.
Embodiment 2:
In reactor, add 1537 parts of poly glycol monomethyl ethers (polymerization degree n is 29), 238 parts of methacrylic acids, stir and add 17 parts of vitriol oils down, 1.7 part Resorcinol, connect condensing reflux and division box, feed nitrogen, be warming up to 100 ℃～140 ℃, reacted 6.0 hours, lower the temperature polyethylene glycol monomethyl ethermethacrylic acid esters.
Reaction equation in the foregoing description is:
Annotate: in the formula: n=5～45.
Claims (7)
1. the method for a synthesizing polyethylene glycol monomethyl ethermethacrylic acid esters by nitrogen with water, with poly glycol monomethyl ether and methacrylic acid is raw material, it is characterized in that with the tosic acid or the vitriol oil be catalyzer, thiodiphenylamine or Resorcinol are that stopper carries out esterification, and the mode with logical nitrogen band water in the esterification reaction process makes polyethylene glycol monomethyl ethermethacrylic acid esters.
2. by the method for the described synthesizing polyethylene glycol monomethyl ethermethacrylic acid esters by nitrogen with water of claim 1, the polymerization degree that it is characterized in that described poly glycol monomethyl ether is 5～45.
3. by the method for the described synthesizing polyethylene glycol monomethyl ethermethacrylic acid esters by nitrogen with water of claim 1, the mol ratio that it is characterized in that described poly glycol monomethyl ether and methacrylic acid is 1.0: 1.5～8.0.
4. by the method for the described synthesizing polyethylene glycol monomethyl ethermethacrylic acid esters by nitrogen with water of claim 1, the add-on that it is characterized in that described catalyzer is 0.5～5.0% of poly glycol monomethyl ether and a methacrylic acid gross weight.
5. by the method for the described synthesizing polyethylene glycol monomethyl ethermethacrylic acid esters by nitrogen with water of claim 1, the add-on that it is characterized in that described stopper is the 250ppm～2000ppm of poly glycol monomethyl ether and methacrylic acid gross weight.
6. by the method for the described synthesizing polyethylene glycol monomethyl ethermethacrylic acid esters by nitrogen with water of claim 1, the temperature of reaction that it is characterized in that described esterification is 100 ℃～140 ℃.
7. by the method for the described synthesizing polyethylene glycol monomethyl ethermethacrylic acid esters by nitrogen with water of claim 1, the time that it is characterized in that described logical nitrogen band water is 5.0～7.0 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100701552A CN101117381A (en) | 2007-07-24 | 2007-07-24 | Method for synthesizing polyethylene glycol monomethyl ether methacrylate by nitrogen with water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100701552A CN101117381A (en) | 2007-07-24 | 2007-07-24 | Method for synthesizing polyethylene glycol monomethyl ether methacrylate by nitrogen with water |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101117381A true CN101117381A (en) | 2008-02-06 |
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Family Applications (1)
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| CNA2007100701552A Pending CN101117381A (en) | 2007-07-24 | 2007-07-24 | Method for synthesizing polyethylene glycol monomethyl ether methacrylate by nitrogen with water |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102382289A (en) * | 2011-09-17 | 2012-03-21 | 深圳市五山建材实业有限公司 | Preparation method of active large monomers by dehydration and esterification |
| CN102746507A (en) * | 2011-04-27 | 2012-10-24 | 江苏尼高科技有限公司 | Esterification method in preparing polycarboxylate water reducer |
| CN105439852A (en) * | 2015-12-04 | 2016-03-30 | 湖北航天化学技术研究所 | Synthesis method for acrylic acid polyethylene glycol single-ended ester ether series compound |
| CN113372796A (en) * | 2021-06-21 | 2021-09-10 | 中铁上海工程局集团有限公司 | Ultraviolet-curing bisphenol F-type epoxy acrylate resin and preparation method thereof |
| US11254787B2 (en) | 2017-08-17 | 2022-02-22 | Sabic Global Technologies B.V. | Method of preparing fatty acid monoester of polyoxyethylene, ester made therewith, and uses thereof |
| CN116855157A (en) * | 2023-07-21 | 2023-10-10 | 深圳市普利凯新材料股份有限公司 | Coiled steel coating containing EEP and preparation method thereof |
-
2007
- 2007-07-24 CN CNA2007100701552A patent/CN101117381A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102746507A (en) * | 2011-04-27 | 2012-10-24 | 江苏尼高科技有限公司 | Esterification method in preparing polycarboxylate water reducer |
| CN102746507B (en) * | 2011-04-27 | 2015-04-01 | 江苏尼高科技有限公司 | Esterification method in preparing polycarboxylate water reducer |
| CN102382289A (en) * | 2011-09-17 | 2012-03-21 | 深圳市五山建材实业有限公司 | Preparation method of active large monomers by dehydration and esterification |
| CN105439852A (en) * | 2015-12-04 | 2016-03-30 | 湖北航天化学技术研究所 | Synthesis method for acrylic acid polyethylene glycol single-ended ester ether series compound |
| US11254787B2 (en) | 2017-08-17 | 2022-02-22 | Sabic Global Technologies B.V. | Method of preparing fatty acid monoester of polyoxyethylene, ester made therewith, and uses thereof |
| CN113372796A (en) * | 2021-06-21 | 2021-09-10 | 中铁上海工程局集团有限公司 | Ultraviolet-curing bisphenol F-type epoxy acrylate resin and preparation method thereof |
| CN116855157A (en) * | 2023-07-21 | 2023-10-10 | 深圳市普利凯新材料股份有限公司 | Coiled steel coating containing EEP and preparation method thereof |
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