CN102643400B - Meta-xylene formaldehyde resin and producing method thereof - Google Patents
Meta-xylene formaldehyde resin and producing method thereof Download PDFInfo
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- CN102643400B CN102643400B CN201210133726.3A CN201210133726A CN102643400B CN 102643400 B CN102643400 B CN 102643400B CN 201210133726 A CN201210133726 A CN 201210133726A CN 102643400 B CN102643400 B CN 102643400B
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- xylene
- formaldehyde resin
- xylene formaldehyde
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Abstract
The invention provides a synthetic method for producing a meta-xylene formaldehyde resin. The meta-xylene formaldehyde resin is preparing by subjecting organic sulfoacid which serves as a catalyst and meta-xylene and formaldehyde which serve as materials to a condensation polymerization. The molecular formula of the organic sulfoacid is R-SO3H, wherein the R is methyl. Compared with sulfuric acid serving as the catalyst, the meta-xylene formaldehyde resin produced by the method has the advantages of high solid and small viscosity.
Description
Technical field
The present invention relates to a kind of production method of polymkeric substance, relate in particular to a kind of production method of m-xylene formaldehyde resin.
Background technology
M-xylene formaldehyde resin (being also referred to as xylene formaldehyde resin, xylene resin) is a kind of conventional softening agent, utilize its good feature such as consistency, stopping property, make an addition in the various synthetic resins such as PVC, epoxy resin, urethane, acrylic resin, unsaturated polyester, to improve its plasticity, there is the features such as little, non-volatile, the long-range plasticization effect excellence of transport property, and can improve toughness, hydrophobicity, erosion resistance and the electrical property etc. of modifier; All there is important effect in multiple fields such as antifouling paste, insullac and tackiness agents.As m-xylene formaldehyde resin being used as and leading static corrosion resistant coating together with epoxy resin in CN10117511A; In CN102086318A, xylene formaldehyde resin is used as together with epoxy resin to solvent impregnated resin, to reach desirable insulation effect; In CN102276775A, xylene formaldehyde resin is used for to modified phenolic resins.
M-xylene formaldehyde resin is under acid catalyst existence condition, to carry out polycondensation by m-xylene and formaldehyde to obtain thickness resin, and generally catalyzer all uses sulfuric acid.Using sulfuric acid as catalyzer, one ton of resin of every production, can generate the waste acid water of 1.5 tons of left and right, and the resin generating need to wash to neutrality with a large amount of washing water, causes the quantity discharged of spent acid and waste water large.And sulfuric acid is as catalyzer, the resin viscosity obtaining is too high, is unfavorable for the post-treatment of product.
As disclosed dimethylbenzene, formaldehyde polycondensation under sulfuric acid existence condition in patent CN1569915A, prepare m-xylene formaldehyde resin, but product color is more yellow, viscosity is still higher.
In patent CN1231549C, disclose synthetic m-xylene formaldehyde resin can with catalyzer also comprise hydrochloric acid, tosic acid, oxalic acid etc., but above-mentioned catalyzer just has good catalytic activity when the phenols condensation reaction; Applicant find, adopt the catalyzer such as the disclosed tosic acid of this patent, Catalyzed m-xylene with prepare m-xylene formaldehyde resin with formaldehyde condensation polymer, productive rate is too low, cannot separate.
Summary of the invention
Carry out the production of m-xylene formaldehyde resin for sulfuric acid as catalyzer and have waste discharge and the too high problem of viscosity, the invention provides a kind of method of new production m-xylene formaldehyde resin.
First aspect of the present invention is to provide a kind of method of producing m-xylene formaldehyde resin, taking m-xylene, formaldehyde as raw material, with CH
3-SO
3h(methylsulfonic acid) be catalyzer, carry out polycondensation.
In aforesaid method of the present invention, described polycondensation can be to carry out in solution, emulsion or suspension.According to a kind of preferred embodiment of the method for the invention, described polycondensation is carried out in water.
In aforesaid method of the present invention, polycondensation temperature is controlled at 90 ~ 120 DEG C, more preferably 95 ~ 110 DEG C.
In aforesaid method of the present invention, the mass ratio of formaldehyde and m-xylene is preferably 1:4 ~ 7.
In aforesaid method of the present invention, the mass ratio of formaldehyde and catalyzer is preferably 1:0.3 ~ 2.5.
In foregoing of the present invention, described formaldehyde can be also the material that can generate formaldehyde, as paraformaldehyde or formaldehyde solution, its consumption taking generate formaldehyde quality as benchmark.
A kind of preferred embodiment of aforesaid method according to the present invention, step comprises:
Step 1, taking formaldehyde, m-xylene as raw material, adds CH
3-SO
3h reacts in water;
Step 2, reaction finishes rear stratification, by the CH of lower floor
3-SO
3h reclaims.
Second aspect of the present invention is to provide the m-xylene formaldehyde resin that a kind of aforesaid method is produced, in the m-xylene formaldehyde resin of producing, and solid content >=90%, viscosity≤60cps, oxygen level is 9% ~ 11%.
Wherein, described solid content refer to 105 DEG C, insulation within 3 hours, under condition, record.
Third aspect of the present invention is to provide a kind of methylsulfonic acid in the application catalyzing and synthesizing in m-xylene formaldehyde resin, and described methylsulfonic acid molecular formula is CH
3-SO
3h.
The production method of above-mentioned m-xylene formaldehyde resin provided by the invention, as compared with catalyzer, under identical polymerizing condition, gained resin viscosity reduces by more than 50 with sulfuric acid, and that oxygen level changes is little.
Embodiment
The invention provides a kind of m-xylene formaldehyde resin and preparation method thereof, taking methylsulfonic acid as catalyzer, m-xylene and formaldehyde are that raw material carries out condensation, and the resin obtaining has lower viscosity.
Wherein, described methylsulfonic acid molecular formula is CH
3-SO
3h.
Below by specific embodiment, m-xylene formaldehyde resin of the present invention and production method thereof are described in detail and are described, so that better understand content of the present invention, but should be understood that, following embodiment does not limit the scope of the invention.
embodiment 1
Paraformaldehyde 80kg, m-xylene 400kg, methylsulfonic acid 205kg(concentration 40.3%), water 120kg, add in reactor.After feeding intake, at 95 ~ 110 DEG C of backflow 8h, reaction finishes.
By reaction system cooling, stratification, lower floor is aqueous methane sulfonic acid, by the methylsulfonic acid recycling of lower floor.
Upper strata mashes with 100kg water and 7kg calcium carbonate, neutralization, and acid number is less than after 0.2mgKOH/g, stratification, upper strata concentrates, and 80 DEG C of filtrations obtain m-xylene formaldehyde resin finished product 230kg.
embodiment 2
Paraformaldehyde 80kg, m-xylene 400kg, methylsulfonic acid 191kg(concentration 36.1%), water 120kg, add in reactor.After feeding intake, at 96 ~ 104 DEG C of backflow 8h, reaction finishes.
By reaction system cooling, stratification, lower floor is aqueous methane sulfonic acid, by the methylsulfonic acid recycling of lower floor.
Upper strata mashes with 100kg water and 7kg calcium carbonate, neutralization, and acid number is less than after 0.2mgKOH/g, stratification, upper strata concentrates, and 80 DEG C of filtrations obtain m-xylene formaldehyde resin finished product 190kg.
embodiment 3
Paraformaldehyde 80kg, m-xylene 400kg, methylsulfonic acid 197kg(concentration 38.5%), water 120kg, add in reactor.After feeding intake, at 90 ~ 105 DEG C of backflow 8h, reaction finishes.
By reaction system cooling, stratification, lower floor is aqueous methane sulfonic acid, by the methylsulfonic acid recycling of lower floor.
Upper strata mashes with 100kg water and 7kg calcium carbonate, neutralization, and acid number is less than after 0.2mgKOH/g, stratification, upper strata concentrates, and 80 DEG C of filtrations obtain m-xylene formaldehyde resin finished product 210kg.
embodiment 4
Paraformaldehyde 80kg, m-xylene 400kg, methylsulfonic acid 240kg(concentration 34.5%), water 120kg, add in reactor.After feeding intake, at 93 ~ 106 DEG C of backflow 8h, reaction finishes.
By reaction system cooling, stratification, lower floor is aqueous methane sulfonic acid, by the methylsulfonic acid recycling of lower floor.
Upper strata mashes with 100kg water and 7kg calcium carbonate, neutralization, and acid number is less than after 0.2mgKOH/g, stratification, upper strata concentrates, and 80 DEG C of filtrations obtain m-xylene formaldehyde resin finished product 200kg.
embodiment 5
Paraformaldehyde 80kg, m-xylene 400kg, methylsulfonic acid 211kg(concentration 42.5%), water 120kg, add in reactor.After feeding intake, at 100 ~ 110 DEG C of backflow 8h, reaction finishes.
By reaction system cooling, stratification, lower floor is aqueous methane sulfonic acid, by the methylsulfonic acid recycling of lower floor.
Upper strata mashes with 100kg water and 7kg calcium carbonate, neutralization, and acid number is less than after 0.2mgKOH/g, stratification, upper strata concentrates, and 80 DEG C of filtrations obtain m-xylene formaldehyde resin finished product 240kg.
comparative example 1
Paraformaldehyde 80kg, m-xylene 400kg, sulfuric acid 80kg(concentration 98%), water 120kg, add in reactor.After feeding intake, at 100 ~ 110 DEG C of backflow 8h, reaction finishes.
By reaction system cooling, stratification, lower floor is aqueous methane sulfonic acid, by the methylsulfonic acid recycling of lower floor.
Upper strata mashes with 100kg water and 7kg calcium carbonate, neutralization, and acid number is less than after 0.2mgKOH/g, stratification, upper strata concentrates, and 80 DEG C of filtrations obtain m-xylene formaldehyde resin finished product 230kg.
comparative example 2
Paraformaldehyde 80kg, m-xylene 400kg, tosic acid 150kg(concentration 40%), water 120kg, add in reactor.After feeding intake, at 100 ~ 110 DEG C of backflow 8h, reaction finishes.
As a result, be difficult to compartment xylene formaldehyde resin and catalyst solution, cause catalyst recovery difficulty, thereby quantity of three wastes increases.
the mensuration of solid content
One
,operation steps:
Accurately take 2.2-2.3g sample (accurately to 0.0001g) in constant weight with in the tinned(sheet)iron ware of paper clip, in the baking oven of 105 DEG C after 3 hours, take out to be put in moisture eliminator and weigh to room temperature.
Two, calculate:
Total solids %=[(W
1-W
2)/W] × 100
In formula, W
1: the weight after oven dry; W
2: the weight of weighing bottle; W: sample weight.
the mensuration of viscosity
One
,operation steps:
Take 40g sample (accurately to 0.01g) and in beaker, add 10g toluene (accurately to 0.01g) wiring solution-forming, shake up, sample is dissolved completely.Insert thermometer, control temperature at 20 ± 0.5 DEG C, with rotational viscosimeter replicate(determination) twice, the difference of replicate(determination) result is not more than 0.5cps.
the mensuration of oxygen level
One
,operation steps:
Take respectively sample 50g phenol 50g(accurately to 0.02g), drop in there-necked flask, then add tosic acid 40g, put in oil bath and heat up, in the time that temperature rises to 80 DEG C, stop heating, treat that it is warming up to 100 ± 2 DEG C naturally, adds 100ml toluene, till temperature rising reflux to toluene is clarified again, the quality of water in metering water trap.
Two, calculate:
X=(16/18)×2×M
In formula, X: oxygen level; 16/18: the percentage ratio of oxygen in water molecules; 2: sample size reaches the multiple coefficient of definition regulation amount; M: the quality (unit: g) that distillates water.
The m-xylene formaldehyde resin test result that above-described embodiment and comparative example obtain is in table 1.
Table 1, the m-xylene formaldehyde resin physical parameter contrast that the present invention and comparative example obtain
| ? | Solid content | Viscosity | Oxygen level |
| Embodiment 1 | 92.1% | 40cps | 9.5% |
| Embodiment 2 | 93.0% | 35cps | 8.8% |
| Embodiment 3 | 91.8% | 35cps | 9.2% |
| Embodiment 4 | 92.7% | 41cps | 9.3% |
| Embodiment 5 | 92.8% | 50cps | 10.5% |
| Comparative example 1 | 91.5% | 100cps | 10.5% |
Can find out by above-mentioned contrast, the m-xylene formaldehyde resin that production method of the present invention obtains is in the case of keeping high solid content and preferably oxygen level, and as compared with catalyzer (prior art), viscosity significantly reduces with sulfuric acid.
Above specific embodiments of the invention be have been described in detail, but it is just as example, the present invention is not restricted to specific embodiment described above.To those skilled in the art, any equivalent modifications that the present invention is carried out and alternative also all among category of the present invention.Therefore, equalization conversion and the amendment done without departing from the spirit and scope of the invention, all should contain within the scope of the invention.
Claims (2)
1. a method of producing m-xylene methyl resin, is characterized in that, taking m-xylene, formaldehyde as raw material, with CH
3-SO
3h is catalyzer, carries out polycondensation in water, and temperature is controlled at 90～120 DEG C; Reaction finishes rear stratification, by the CH of lower floor
3-SO
3h reclaims.
2. the m-xylene formaldehyde resin that method is produced as claimed in claim 1, is characterized in that, solid content >=90%, and viscosity≤60cps 20 DEG C time, oxygen level is 9%～11%.
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| CN102643400B true CN102643400B (en) | 2014-10-22 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103145939A (en) * | 2013-04-02 | 2013-06-12 | 开滦（集团）有限责任公司 | Modification method of xylene formaldehyde resin |
| CN103923287B (en) * | 2014-05-13 | 2016-06-29 | 山东圣泉新材料股份有限公司 | A kind of method preparing xylene formaldehyde resin |
| CN110317559A (en) * | 2019-05-22 | 2019-10-11 | 广西大学 | A kind of meta-xylene modified phenolic resin adhesive and preparation method thereof |
| CN113045720B (en) * | 2019-12-26 | 2022-09-13 | 山东圣泉新材料股份有限公司 | Meta-xylene resin, preparation method thereof and insulating paint |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1511857A (en) * | 2002-06-28 | 2004-07-14 | 黄观明 | Process for synthesizing m-dimethyl benzene phenolic resin and use |
| CN1569915A (en) * | 2003-07-21 | 2005-01-26 | 苏州特种化学品有限公司 | Xylene formaldehyde resin production method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60123519A (en) * | 1984-11-05 | 1985-07-02 | Hitachi Chem Co Ltd | Production of cured article of odorless or low odor crosslinking compound |
| JPH0684414B2 (en) * | 1985-04-11 | 1994-10-26 | 三菱瓦斯化学株式会社 | Process for producing phenol-modified aromatic hydrocarbon formaldehyde resin |
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2012
- 2012-05-03 CN CN201210133726.3A patent/CN102643400B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1511857A (en) * | 2002-06-28 | 2004-07-14 | 黄观明 | Process for synthesizing m-dimethyl benzene phenolic resin and use |
| CN1569915A (en) * | 2003-07-21 | 2005-01-26 | 苏州特种化学品有限公司 | Xylene formaldehyde resin production method |
Non-Patent Citations (2)
| Title |
|---|
| JP昭60-123519A 1985.07.02 |
| JP昭61-235413A 1986.10.20 |
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Effective date of registration: 20200731 Address after: No.1559 Canggong Road, Fengxian District, chemical industry zone, Fengxian District, Shanghai 201400 Patentee after: SHANGHAI YOU CHUANG CHEMICALS Co.,Ltd. Address before: 201512 Shanghai City, Jinshan District Jinshanwei town Qiushi Road No. 688 Building 1, unit 5, Room 305 Patentee before: SHANGHAI HONESTY FINE CHEMICAL TECHNOLOGY Co.,Ltd. |
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