CN1865308A - Method for catalyzing and producing phenyl phenol formaldehyde resin using macropore strong acid cation exchange resin - Google Patents
Method for catalyzing and producing phenyl phenol formaldehyde resin using macropore strong acid cation exchange resin Download PDFInfo
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- CN1865308A CN1865308A CNA2006100400692A CN200610040069A CN1865308A CN 1865308 A CN1865308 A CN 1865308A CN A2006100400692 A CNA2006100400692 A CN A2006100400692A CN 200610040069 A CN200610040069 A CN 200610040069A CN 1865308 A CN1865308 A CN 1865308A
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- strong acid
- phenyl phenol
- orthoxenol
- exchange resin
- acid cation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
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- Phenolic Resins Or Amino Resins (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a phenyl phenol formaldehyde resin of large-hole strong acid cationic exchange resin catalyst, which is characterized by the following: adapting orthoxenol phenol and oxymethylene as raw material; proceeding condensation reaction under solid acid catalyst; filtering in the final point to remove catalyst; distilling the filtrate to obtain the product. The invention saves several medium procedures, which is easy to operate to produce high quality product.
Description
Technical field
The invention belongs to the preparation method of phenyl phenol formaldehyde resin.Being particularly related to a kind of is raw material with orthoxenol and formaldehyde, under the exchange resin catalyzed effect of macropore strong acid cation, makes thermoplasticity phenyl phenol formaldehyde resin through catalyzing and condensing, suction filtration, distillation.The method that belongs to the phenyl phenol formaldehyde resin.
Background technology
Thermoplasticity phenyl phenol formaldehyde rosin products can make life-span length and to water and the fabulous varnish of alkaline stability energy, this varnish has extremely strong weather resistance and weathering resistance, is specially adapted to moist cold and marine vessel use.Especially marine paint has splendid weather resistance, is specially adapted to marine vessel.
The at present domestic existing mineral acid (hydrochloric acid that utilizes, phosphoric acid, oxalic acid, sulfuric acid, Phenylsulfonic acid), mineral alkali (sodium hydroxide, hydrated barta, ammoniacal liquor, zinc oxide), solid acid (macropore strong acid cation exchange resin) catalytic preparation phenols is that the document of resin is reported for work, have and utilize the document of sodium hydroxide catalytic preparation phenyl phenol formaldehyde resin to report for work, existing phenyl phenol formaldehyde rosin products production technique is a raw material with orthoxenol and formaldehyde, through the sodium hydroxide catalyzing and condensing, neutralization, washing, extraction, vacuum distilling makes, but wastewater flow rate is big in the art production process, serious environment pollution, and the neutralization of pH value adjusting operation easier is big, and quality product is relatively poor.
Summary of the invention
The object of the present invention is to provide a kind of new method of producing the phenyl phenol formaldehyde resin, to overcome existing preparation method's deficiency.
Technical scheme of the present invention is as follows: present method is a raw material with orthoxenol and formaldehyde, carries out condensation reaction under the exchange resin catalyzed effect of macropore strong acid cation, filters the back filtrate distillation is made product.
The present invention includes following steps:
1) orthoxenol, solvent, formaldehyde metering are joined in the there-necked flask successively, begin to stir, heat temperature raising, rotating speed is controlled at 50-100r/min;
Add catalyzer when 2) mixeding liquid temperature is raised to 50 ℃ in the flask, make catalyzer and solution thorough mixing, catalyzer is the macropore strong acid cation exchange resin, and its consumption (weight ratio) is 5～15% of an orthoxenol;
3) heated and stirred is carried out back flow reaction, and temperature of reaction remains on 80-110 ℃, reaction times 2-3h;
4) will react back solution suction filtration;
5) filtrate is put into a new there-necked flask, 50-100r/min stirs, and adds thermal distillation, after 110-120 ℃ of no distillate slips out, stops heating, stops water coolant;
6) will distill leftover materials and be cooled to 50-60 ℃, and stop to stir, obtain the phenyl phenol formaldehyde rosin products.
Above-mentioned orthoxenol is that 99% technical grade product, formaldehyde are 37% technical grade product, orthoxenol and formaldehyde solid-liquid weight ratio 1: 0.55～0.6;
Above-mentioned solvent is anhydrous butanols, and grade is chemical pure or technical grade, and consumption is the 35%-45% of two kinds of main raw materials.
The invention has the beneficial effects as follows:
Present method is a raw material with orthoxenol and formaldehyde, carries out condensation reaction under the exchange resin catalyzed effect of macropore strong acid cation, filters the back filtrate distillation is made product.Present method has saved middle operation such as neutralization, washing, extraction, catalyzer and unreacted reactant are recycling, there is not newly-increased discharge of wastewater, reduce environmental pollution, and pH value need not regulated, easy handling, good product quality detect with digital rotational viscosimeter NDJ-5S, and product viscosity reaches 8000cp above (20 ℃).
Description of drawings
Be described further below in conjunction with embodiment and accompanying drawing.
Fig. 1 is a process flow sheet of the present invention;
Fig. 2 is device for carrying out said and the instrument of embodiment.
Embodiment
Further illustrate the solution of the present invention and effect below in conjunction with embodiment.
As shown in Figure 2, a is a reaction unit, and b is a water distilling apparatus.
Shown in Fig. 2 a, the exsiccant there-necked flask is put into shell type electrically heated thermostatted fix and install stirring 5, two mouths of there-necked flask are loaded onto ball-type reflux condensing tube 3 and thermometer 4 respectively, then the industrial formol of the orthoxenol of main raw material 99% and 37% and solvent are put in the there-necked flask by prescription (seeing Table 1) metering successively, start and stir and heating, rotating speed is controlled at 50-100
Table 1
In the r/min, when temperature rise to 50 ℃, add catalyzer, continue heated and stirred then and carry out back flow reaction, temperature remains on 85-95 ℃ in the there-necked flask, stops heating behind the reaction 2.5h, stopped reaction, open water-ring vacuum pump suction filtration machine (filter flask is equipped with B, replaces filter paper with copper wire gauze), filter out catalyzer earlier, catalyzer is poured in the returnable bottle, obtained muddy dark clear look filtrate.This process reaction equation is as follows:
| Title material | Phenylphenol (g) | Formaldehyde (ml) | Catalyzer (g) | Butanols (ml) |
| Consumption | 100 | 55 | 12 | 85 |
Orthoxenol and formaldehyde carry out the carbonylation condensation reaction under the solid acid catalyst effect, generate bisphenols or three phenolic compounds earlier, and further polycondensation becomes the macromolecule polymkeric substance.
Filtrate is poured in the water distilling apparatus, shown in Fig. 2 b.Filtrate is carried out the heated and stirred distillation, rotating speed is controlled in the 50-100r/min, distillation dehydration and solvent heat up, distillate when rising to 85 ℃, temperature is arranged, about 110 ℃ of latter temperatures, distillate is less behind about 60～90min, temperature begins to raise, be controlled at 110-120 ℃ till do not have a distillate, when no distillate oozes, stop heating and cooling water, remove prolong and heating unit, when dropping to 50-60 ℃, the leftover materials temperature stops to stir and pouring into prior oven dry, in the reagent bottle 6 of weighing, obtaining product is the reddish-brown thick liquid, and tested viscosity is 10000cp (20 ℃).
Claims (4)
1, a kind of with the exchange resin catalyzed method of producing the phenyl phenol formaldehyde resin of macropore strong acid cation, it is characterized in that it may further comprise the steps:
1) orthoxenol, solvent, formaldehyde metering are joined in three mouthfuls of containers or the flask successively, begin to stir, heat temperature raising, rotating speed is controlled at 50-100r/min;
Add catalyzer when 2) mixeding liquid temperature is raised to 50 ℃ in the flask, make catalyzer and solution thorough mixing;
3) heated and stirred is carried out back flow reaction: temperature of reaction 80-110 ℃, reaction times 2-3h;
4) will react back solution suction filtration;
5) filtrate is put into a new there-necked flask, 50-100r/min stirs, and adds thermal distillation, after 110-120 ℃ of no distillate, stops heating and cooling water;
6) will distill leftover materials and be cooled to 50-60 ℃, and stop to stir, obtain the phenyl phenol formaldehyde rosin products.
2, described a kind of according to claim 1 with the exchange resin catalyzed method of producing the phenyl phenol formaldehyde resin of macropore strong acid cation, it is characterized in that described catalyzer macropore strong acid cation exchange resin, its ion-exchange equivalent 〉=4, its consumption (weight ratio) is 5～15% of an orthoxenol;
3 is described a kind of with the exchange resin catalyzed method of producing the phenyl phenol formaldehyde resin of macropore strong acid cation according to claim 1, it is characterized in that described orthoxenol is that 99% technical grade product, formaldehyde are 37% technical grade product, orthoxenol and formaldehyde solid-liquid weight ratio are 1: 0.55～0.6;
4, described a kind of according to claim 1 with the exchange resin catalyzed method of producing the phenyl phenol formaldehyde resin of macropore strong acid cation, it is characterized in that described solvent is anhydrous butanols, grade is chemical pure or technical grade, and consumption is the 35%-45% of orthoxenol and formaldehyde gross weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100400692A CN100347212C (en) | 2006-04-25 | 2006-04-25 | Method for catalyzing and producing phenyl phenol formaldehyde resin using macropore strong acid cation exchange resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100400692A CN100347212C (en) | 2006-04-25 | 2006-04-25 | Method for catalyzing and producing phenyl phenol formaldehyde resin using macropore strong acid cation exchange resin |
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| Publication Number | Publication Date |
|---|---|
| CN1865308A true CN1865308A (en) | 2006-11-22 |
| CN100347212C CN100347212C (en) | 2007-11-07 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2006100400692A Expired - Fee Related CN100347212C (en) | 2006-04-25 | 2006-04-25 | Method for catalyzing and producing phenyl phenol formaldehyde resin using macropore strong acid cation exchange resin |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102190768A (en) * | 2010-03-06 | 2011-09-21 | 徐州工业职业技术学院 | Method for preparing cumylphenol formaldehyde resin through catalysis of macroporous strongly acidic cation exchange resin |
| CN115260844A (en) * | 2022-08-24 | 2022-11-01 | 无锡新而奇化工科技有限公司 | Preparation method of polyester coating for household appliances |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1017053B (en) * | 1989-12-29 | 1992-06-17 | 天津大学 | Phenol resin synthesis catalyzed by ion-exchange resin |
| CN1050882A (en) * | 1990-12-07 | 1991-04-24 | 徐州化肥厂 | Large hole cation exchanger resin catalysis is produced right-tertiary phenol methylene oxide resin |
| US5686561A (en) * | 1994-08-23 | 1997-11-11 | Hoechst Celanese Corporation | Metal ion reduction in novolak resin solution using an anion exchange resin |
-
2006
- 2006-04-25 CN CNB2006100400692A patent/CN100347212C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102190768A (en) * | 2010-03-06 | 2011-09-21 | 徐州工业职业技术学院 | Method for preparing cumylphenol formaldehyde resin through catalysis of macroporous strongly acidic cation exchange resin |
| CN115260844A (en) * | 2022-08-24 | 2022-11-01 | 无锡新而奇化工科技有限公司 | Preparation method of polyester coating for household appliances |
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| Publication number | Publication date |
|---|---|
| CN100347212C (en) | 2007-11-07 |
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