CN102850499A - Modified urea formaldehyde resin and preparation method thereof - Google Patents
Modified urea formaldehyde resin and preparation method thereof Download PDFInfo
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- CN102850499A CN102850499A CN2012100765822A CN201210076582A CN102850499A CN 102850499 A CN102850499 A CN 102850499A CN 2012100765822 A CN2012100765822 A CN 2012100765822A CN 201210076582 A CN201210076582 A CN 201210076582A CN 102850499 A CN102850499 A CN 102850499A
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Abstract
The invention relates to a modified urea formaldehyde resin and a preparation method thereof; the modified urea formaldehyde resin of the invention has viscosity of 30-1000 pa.s at 25 DEG C, and is prepared from aldehyde, phenol and urea, wherein the molar ratio of aldehyde, phenol and urea is 5:(0.1-1):(2-4); the modified urea formaldehyde resin prepared by the invention not only has excellent mechanical properties, but also has very good waterproof performance; and the formaldehyde release amount is low.
Description
Technical field
The present invention relates to the urea-formaldehyde resin field, be specifically related to a kind of modified urea-formaldehyde resin and preparation method thereof.
Background technology
Since the wood industry successful Application, just with advantages such as its higher bonding strength, fast curing, low cost, raw material are easy to get, become the main flow tackiness agent of domestic and international timber industry from urea-formaldehyde resin, and for a long time in occupation of based Wood Adhesives market.But urea-formaldehyde resin itself is because the constraint such as release formaldehyde, acid and alkali-resistance, water resistance be bad restricts the further expansion of its range of application always.Along with social progress, the mankind more and more pay close attention to surrounding environment, product cost performance, and the inferior position of urea-formaldehyde resin highlights.
Phenol-modified urea-formaldehyde resin is partly to substitute urea-formaldehyde resin as guiding theory, with good weather-proof, the corrosion-resistant urea-formaldehyde resin that improves of resol take resol.But traditional technology adds cost consideration because of its technological design, and the phenols input amount is limited, and its performance is increased substantially.
Summary of the invention
In order to overcome defects, the invention provides a kind of phenols and drop into the phenol-modified urea-formaldehyde resin that ratio is little, technique is simple, with low cost, water tolerance significantly improves.
Modified urea-formaldehyde resin of the present invention under 25 ℃ viscosity be 30～100pa.s.
Modified urea-formaldehyde resin of the present invention mainly is prepared from by aldehyde, phenol, urea, and the mol ratio of described aldehyde, phenol, urea is 5: (0.1～1): (2～4).
Wherein, described aldehyde is one or more in formaldehyde, acetaldehyde, butyraldehyde, Paraformaldehyde 96, the trioxymethylene.
In addition, described phenol is one or more in phenol, cresols, xylenol, nonylphenol, dihydroxyphenyl propane, Bisphenol F, Resorcinol, the cardanol.
The present invention also provides a kind of preparation method of described modified urea-formaldehyde resin, and it comprises the steps:
(1) aldehyde, phenol are dosed in the reactor, stir;
(2) adding an acidic catalyst in the reactor, to regulate the pH value be 0.5～2.0;
(3) add part urea, the control temperature is no more than 70 ℃, is down to room temperature behind 0.5～1.5h;
(4) add residue urea, regulating the pH value is 7.5～9.0;
(5) be warming up to 80～90 ℃ of reactions 2～4 hours;
(6) dewater to solid content be 40～75%, get modified urea-formaldehyde resin.
Wherein, the part urea that adds in the step (3) is 40～75% of urea gross weight.
In addition, in step (3), described temperature is 50～70 ℃.
In addition, described an acidic catalyst is one or more in formic acid, oxalic acid, sulfuric acid, hydrochloric acid, phosphoric acid, the tosic acid.
In addition, in step (4), regulate the pH value with mineral alkali.
In addition, described mineral alkali is one or more in sodium hydroxide, potassium hydroxide, the ammoniacal liquor.
Modified urea-formaldehyde resin of the present invention, take phenol as example, its reaction mechanism is as follows:
In strong acidic environment, addition reaction occurs in aldehyde and ureagenetic outstanding army, hydroxyurea and the hydroxyl phenol that generates with phenol each other, and various small molecules interosculate in the later stage condensation course, form the water-fast structure of many rings of internal structure complexity.Because hydroxyl quantity reduces in the resin system, methylene bridge quantity showed increased is so after resin solidification, its water resistance significantly improves.
In addition, in the present invention, after adding first part urea, the macromole polycondensation for the very exothermic reaction, if temperature of reaction is too high, then can occurs and produce gel under strong acidic condition in aldehyde and urea, for avoiding vigorous reaction, the present invention controls its temperature of reaction and is no more than 70 ℃, preferably between 50～70 ℃, reacts and is down to room temperature after 0.5～1.5 hour.
Used formaldehyde, acetaldehyde, butyraldehyde, Paraformaldehyde 96, trioxymethylene, phenol, cresols, xylenol, nonylphenol, dihydroxyphenyl propane, Bisphenol F, Resorcinol, cardanol, formic acid, oxalic acid, sulfuric acid, hydrochloric acid, phosphoric acid, tosic acid etc. all can use the commercially available product of any specification or model among the present invention.
The present invention adopts the synthesis technique of weak base behind the first strong acid, compares with traditional alkali-acid-alkali technique, and technological design is simply unique, the stable easily control of reaction process, react automatic heat evolution early stage does not need concurrent heating, and whole building-up process does not need pressurization, so the common response still just can satisfy production requirement.Resin is through phenol-modified, outstanding army structure participates in, great variety has occured in its structure, water resistance has obtained increasing substantially, solved the difficult problem of common urea-formaldehyde resin complex process, weathering resistance, poor heat resistance, and the modified urea-formaldehyde resin phenols input amount that the present invention makes is little, burst size of methanal is little, economic environmental protection.
Embodiment
Following examples are used for explanation the present invention, but are not used for limiting the scope of the invention.
Embodiment 1
50mol formaldehyde, 5mol phenol are dropped in the reactor, with oxalic acid adjust pH to 1.0; Under the whipped state, first drops into 12mol urea, and the control temperature is no more than 70 ℃, is down to room temperature behind the reaction 1h; Drop into residue 18mol urea, with 40% sodium hydroxide solution adjust pH to 8.5, be warming up to 85 ℃ of reaction 3h; Carrying vacuum hydro-extraction to solid content is 40%, makes modified urea-formaldehyde resin, and the NDJ-7 type rotational viscosimeter of producing take Shanghai balance equipment factory records viscosity as 31pa.s under 25 ℃.According to GB-9846-2004 it is carried out performance test, the result is as shown in table 1.
Embodiment 2
50mol acetaldehyde, 1mol dihydroxyphenyl propane are dropped in the reactor, are 20% hydrochloric acid soln adjust pH to 2.0 with massfraction; Under the whipped state, first drops into 15mol urea, and hierarchy of control temperature is no more than 70 ℃, is down to room temperature behind the reaction 0.5h; Drop into residue 5mol urea, with 40% potassium hydroxide solution adjust pH to 9.0, be warming up to 80 ℃ of reaction 4h; Propose vacuum hydro-extraction to admittedly containing 45%, make modified urea-formaldehyde resin, the NDJ-7 type rotational viscosimeter of producing take Shanghai balance equipment factory is in 25 ℃ of lower viscosity of surveying as 55pa.s.According to GB-9846-2004 it is carried out performance test, the result is as shown in table 1.
Embodiment 3
50mol formaldehyde, 3mol phenol are dropped in the reactor, are 30% phosphoric acid solution adjust pH to 1.5 with massfraction; Under the whipped state, first drops into 24mol urea, and the temperature when control begins to react is not less than 50 ℃, but the upper limit is no more than 70 ℃, makes its natural thermopositive reaction, is down to room temperature behind the reaction 1.5h; Dropping into residue 16mol urea, is 30% ammoniacal liquor adjust pH to 7.5 with massfraction, is heated to 90 ℃ of reaction 2.5h; Propose vacuum hydro-extraction to admittedly containing 55%, make modified urea-formaldehyde resin, under 25 ℃, measure viscosity as 70pa.s take the NDJ-7 type rotational viscosimeter that balance equipment factory in Shanghai produces.According to GB-9846-2004 it is carried out performance test, the result is as shown in table 1.
Embodiment 4
50mol butyraldehyde, 10mol phenol are dropped in the reactor sulphuric acid soln adjust pH to 0.5 with 30%; Under the whipped state, first drops into 10mol urea, and the temperature when control begins to react is not less than 50 ℃, but the upper limit is no more than 70 ℃, makes its natural thermopositive reaction, is down to room temperature behind the reaction 0.5h; Dropping into residue 10mol urea, is 30% sodium hydroxide solution adjusting pH value to 8.0 with massfraction, is heated to 90 ℃ of reaction 4h; Propose vacuum hydro-extraction to admittedly containing 65%, make modified urea-formaldehyde resin, under 25 ℃, measure viscosity as 48pa.s take the NDJ-7 type rotational viscosimeter that balance equipment factory in Shanghai produces.According to GB-9846-2004 it is carried out performance test, the result is as shown in table 1.
Embodiment 5
50mol trioxymethylene, 1mol nonyl phenol are dropped in the reactor, with oxalic acid adjust pH to 2.0; Under the whipped state, first drops into 30mol urea, and the control temperature is no more than 70 ℃, is down to room temperature behind the reaction 1.5h; Dropping into residue 10mol urea, is 30% potassium hydroxide solution adjust pH to 8.0 with massfraction, is heated to 85 ℃ of reaction 2h; Propose vacuum hydro-extraction to admittedly containing 75%, make modified urea-formaldehyde resin, under 25 ℃, measure viscosity 92pa.s with the NDJ-7 type rotational viscosimeter that balance equipment factory in Shanghai produces.According to GB-9846-2004 it is carried out performance test, the result is as shown in table 1.
Embodiment 6
50mol formaldehyde, 8mol cardanol are dropped in the reactor, with formic acid adjust pH to 2.0; Under the whipped state, first drops into 12.8mol urea, and hierarchy of control temperature is no more than 70 ℃, is down to room temperature behind the reaction 1.5h; Dropping into residue 19.2mol urea, is 20% ammoniacal liquor adjust pH to 7.5 with massfraction, is heated to 80 ℃ of reaction 2.5h; Propose vacuum hydro-extraction to admittedly containing 55%, make modified urea-formaldehyde resin, under 25 ℃, measure viscosity as 67pa.s take the NDJ-7 type rotational viscosimeter that balance equipment factory in Shanghai produces.According to GB-9846-2004 it is carried out performance test, the result is as shown in table 1.
Embodiment 7
50mol formaldehyde, 6mol phenol are dropped in the reactor, with oxalic acid adjust pH to 0.5; Under the whipped state, first drops into 21.6mol urea, and hierarchy of control temperature is no more than 70 ℃, is down to room temperature behind the reaction 0.5h; Dropping into residue 11.6mol urea, is 25% ammoniacal liquor adjust pH to 9.0 with massfraction, is heated to 90 ℃ of reaction 2h; Propose vacuum hydro-extraction to admittedly containing 75%, make modified urea-formaldehyde resin, under 25 ℃, measure viscosity as 100pa.s take the NDJ-7 type rotational viscosimeter that balance equipment factory in Shanghai produces.According to GB-9846-2004 it is carried out performance test, the result is as shown in table 1.
The performance test results of the modified urea-formaldehyde resin that table 1. embodiment 1～7 makes
By above-mentioned experimental result, can find out, it is higher that the modified urea-formaldehyde resin glue that the present invention makes closes intensity, burst size of methanal is low, and after boiling experiment in 28 hours, all do not come unglued, have good water resistance, so the modified urea-formaldehyde resin that makes of the present invention better mechanical property not only, and water resistance is excellent, the phenols input amount is little, burst size of methanal is low, i.e. again environmental protection of economy.
Claims (10)
1. a modified urea-formaldehyde resin is characterized in that, the viscosity of described modified urea-formaldehyde resin under 25 ℃ is 30～100pa.s.
2. modified urea-formaldehyde resin according to claim 1 is characterized in that, described urea-formaldehyde resin mainly is prepared from by aldehyde, phenol, urea, and the mol ratio of described aldehyde, phenol, urea is 5: (0.1～1): (2～4).
3. modified urea-formaldehyde resin according to claim 1 is characterized in that, described aldehyde is one or more in formaldehyde, acetaldehyde, butyraldehyde, Paraformaldehyde 96, the trioxymethylene.
4. modified urea-formaldehyde resin according to claim 1 is characterized in that, described phenol is one or more in phenol, cresols, xylenol, nonylphenol, dihydroxyphenyl propane, Bisphenol F, Resorcinol, the cardanol.
5. the preparation method of arbitrary described modified urea-formaldehyde resin is characterized in that according to claim 1～4, comprises the steps:
(1) aldehyde, phenol are dosed in the reactor, stir;
(2) adding an acidic catalyst in the reactor, to regulate the pH value be 0.5～2.0;
(3) add part urea, the control temperature is no more than 70 ℃, is down to room temperature behind 0.5～1.5h;
(4) add residue urea, regulating the pH value is 7.5～9.0;
(5) be warming up to 80～90 ℃ of reactions 2～4 hours;
(6) dewater to solid content be 40～75%, get modified urea-formaldehyde resin.
6. preparation method according to claim 5 is characterized in that, the part urea that adds in the step (3) is 40～75% of urea gross weight.
7. preparation method according to claim 5 is characterized in that, in step (3), described temperature is 50～70 ℃.
8. preparation method according to claim 5 is characterized in that, described an acidic catalyst is one or more in formic acid, oxalic acid, sulfuric acid, hydrochloric acid, phosphoric acid, the tosic acid.
9. preparation method according to claim 5 is characterized in that, regulates the pH value with mineral alkali in step (4).
10. preparation method according to claim 9 is characterized in that, described mineral alkali is one or more in sodium hydroxide, potassium hydroxide, the ammoniacal liquor.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210076582.2A CN102850499B (en) | 2012-03-21 | 2012-03-21 | Modified urea formaldehyde resin and preparation method thereof |
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| CN201210076582.2A CN102850499B (en) | 2012-03-21 | 2012-03-21 | Modified urea formaldehyde resin and preparation method thereof |
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| CN102850499B CN102850499B (en) | 2014-09-03 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104073205A (en) * | 2014-06-25 | 2014-10-01 | 安徽神舟飞船胶业有限公司 | Formula and preparation process of urea improved phenol-formaldehyde resin adhesive |
| CN105585993A (en) * | 2016-03-11 | 2016-05-18 | 广西大学 | Method for preparing isobutyl aldehyde modified urea-formaldehyde resin adhesive |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85109503A (en) * | 1985-11-22 | 1986-07-23 | 中国石油化工总公司岳阳石油化工总厂 | The preparation method of phenol modified urea-formaldehyde resins and application |
| CN1057852A (en) * | 1990-06-28 | 1992-01-15 | 北京林业大学 | Modified urea aldehyde resin adhesive |
-
2012
- 2012-03-21 CN CN201210076582.2A patent/CN102850499B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85109503A (en) * | 1985-11-22 | 1986-07-23 | 中国石油化工总公司岳阳石油化工总厂 | The preparation method of phenol modified urea-formaldehyde resins and application |
| CN1057852A (en) * | 1990-06-28 | 1992-01-15 | 北京林业大学 | Modified urea aldehyde resin adhesive |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104073205A (en) * | 2014-06-25 | 2014-10-01 | 安徽神舟飞船胶业有限公司 | Formula and preparation process of urea improved phenol-formaldehyde resin adhesive |
| CN105585993A (en) * | 2016-03-11 | 2016-05-18 | 广西大学 | Method for preparing isobutyl aldehyde modified urea-formaldehyde resin adhesive |
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| CN102850499B (en) | 2014-09-03 |
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Owner name: SHANDONG SHENGQUAN NEW MATERIALS CO., LTD. Free format text: FORMER NAME: SHANDONG SHENGQUAN CHEMICAL INDUSTRY CO., LTD. |
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