CN101831042B - Preparation method of thermoplastic phenolic resin with high solid content - Google Patents
Preparation method of thermoplastic phenolic resin with high solid content Download PDFInfo
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- CN101831042B CN101831042B CN2010101854379A CN201010185437A CN101831042B CN 101831042 B CN101831042 B CN 101831042B CN 2010101854379 A CN2010101854379 A CN 2010101854379A CN 201010185437 A CN201010185437 A CN 201010185437A CN 101831042 B CN101831042 B CN 101831042B
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Abstract
The invention relates to a preparation method of a thermoplastic phenolic resin with high solid content, which is technically characterized by comprising the following steps of: adding phenol in a three-neck flask; heating for a period of time; adding an acidic catalyst A to fully and evenly mix with phenol; adding formaldehyde B to the mixture at 65 DEG C in a mol percentage of 5:4; reacting for 1h; and then, reacting for 3h at 75-85 DEG C to obtain the resin, wherein the volatility of the resin is less than 15 percent at the temperature below 100 DEG C within 2h. The environment-friendly thermoplastic phenolic resin which is prepared from paraformaldehyde by a method of stably reacting to the end by controlling temperature by stages has solid content larger than 80 percent without dewatering sewage containing phenol and aldehyde, is environment-friendly, time-saving, energy-saving and economic.
Description
Technical field
The present invention relates to a kind of preparation method of thermoplastic phenolic resin with high solid content, belong to the synthesis technique in the novolac resin commercial process.
Background technology
100 parts of the suitability for industrialized production employing phenol of novolac resin or phenols (content 100%); 26.5～27.5 parts of formaldehyde solutions (content 100%); The proportioning that hydrochloric acid (content 100%) is 0.056 part is come synthetic resins, need dehydrate afterwards again and pulverize.Can produce a large amount of phenolic wastewater because phenol is excessive in the production process, environment not caused serious pollution, even entail dangers to is human, vegeto-animal existence if do not add the direct discharging meeting of processing.Treatment technology commonly used has three types of physico-chemical process, chemical method and biochemical processs on the domestic industry, and what wherein have better effect is that the precipitator method, N-503 kerosin Centrifugical extraction, YXA-8005 type polymeric adsorbent, copolycondensation method, ozone oxidation method, liquid-film method etc. are boiled in acid.Reach more than 95% though physico-chemical process can make except that phenol efficient, processing power does not reach the demand of large-batch industrial.Chemical method relatively is fit to the demand of suitability for industrialized production, but this method or needing to throw in cause the material of secondary pollution and phenols to carry out polycondensation, or can not reclaim raw material phenol, all a kind of waste of resource concerning the environment and the producer.Though biochemical process processing efficiency height receives gas condition to influence little but floor space is bigger, and can not reclaim raw material phenol, can only match with second-stage treatment and carry out the processing of phenolic wastewater.In addition, existing people reclaims phenol and does not introduce other materials through analog calculation heat pump distillation method Phenol-Containing Wastewater Treatment and forms secondary pollution, but the open steam heat energy of waste water consumption per ton also has 26.9kJ.The somebody work out under acidic conditions cryptomelane almost completely in the oxidative degradation water body concentration be 100mg/L phenol, but long reaction time, process are complicated.
Summary of the invention
The technical problem that solves
For fear of the weak point of prior art, the present invention proposes a kind of preparation method of thermoplastic phenolic resin with high solid content, can overcome in the production process can produce a large amount of phenolic wastewater because phenol is excessive; To environment and biological harm; Reduce production costs simultaneously, the present invention synthetic thermoplastic phenolic, technology is simple, the energy-and time-economizing, need not to dehydrate; No phenolic wastewater discharging, the resin solid content height can directly apply to production.
Thought of the present invention is: utilize Paraformaldehyde 96 instead of formaldehyde solution, the moisture that reaction process is introduced significantly reduces, thereby guarantees that product has higher solids content.In addition, need seethe with excitement for some time when the present invention adopts the method for temperature control to make reaction unlike former industrial production, but smooth reaction is until terminal point.
Technical scheme
A kind of preparation method of thermoplastic phenolic resin with high solid content is characterized in that step is following:
Step 1: in there-necked flask, drop into phenol 100 mass parts;
Step 2: drop into catalyzer hydrochloric acid 0.01～0.05 mass parts, be heated to 55 ℃ and stir, add Paraformaldehyde 96 25～30 mass parts at 65 ℃ and react 1h;
Step 3: be warming up to the interior sustained reaction 3h of 75-85 ℃ of scope again and obtain thermoplastic phenolic resin with high solid content.
Beneficial effect
The preparation method of the thermoplastic phenolic resin with high solid content that the present invention proposes, characteristics are: one of starting material that (1) the present invention adopts formaldehyde is replaced by Paraformaldehyde 96, thereby has reduced the introducing of water in the building-up process; (2) taking sectional temperature-controlled mode in the reaction process, is that ladder is given birth to temperature, from low temperature to high temperature, makes the reaction under the hydrochloric acid catalysis need not pass through the boiling stage smooth reaction until terminal point.With the Paraformaldehyde 96 be raw material take sectional temperature-controlled smooth reaction method preparation to terminal highly filled environment-protecting thermoplastic resol solids content greater than 80%, need not take off and contain free phenol, aldehyde sewage, environmental protection, time-saving energy-saving, economy.
Graph of molecular weight distribution, infrared spectrogram and the thermogravimetric curve of the highly filled environment-protecting thermoplastic resol of employing the inventive method preparation are respectively like Fig. 1, Fig. 2 and shown in Figure 3.
Description of drawings
Fig. 1: (with DMF/LiCl is moving phase to the resin that the present invention produced through gel permeation chromatography/multi-angle laser light scattering (SEC/MALLS) combined instrument; Under 40 ℃, measure; Sample size 0.2mL; Solvent take-off rate 0.5mL/min) records number-average molecular weight and reach 1577 (3%), narrow molecular weight distribution (the Mw/Mn value is 1.127 (4%)).
Fig. 2: because water cut is few, infared spectrum signify hydroxy peak is not obvious, and 1624 and 1475 is the phenyl ring peak, after hexamethylenetetramine solidifies, has 2849,2918 methylene peak to occur.
Fig. 3: the thermal weight loss of this resol can be divided into three phases: the fs (about＜150 ℃); In this temperature range; Thermolysis speed maximum value occurs near 100 ℃, the minimizing of resin quality mainly comes from oligopolymer in the resol and weak end group (like-CH
2Removing and formaldehyde that methylene radical changes into, hydrogen etc. OH); Subordinate phase (150 ℃～300 ℃), in this stage, the rate of weight loss of resin reaches 20%, and mass loss mainly is by-OH and-CH
2-wait the weak bond thermolysis to generate a spot of H
2, CO, CO
2Cause; Phase III (＞300 ℃) mainly is the carbonization process (when atmosphere is rare gas element) of resol, and the phenyl ring in the resin decomposes in a large number, and thermolysis speed peak occurs near 500 ℃, and mass loss increases rapidly.
Embodiment
Combine embodiment, accompanying drawing that the present invention is further described at present:
Embodiment 1
Step 1: in there-necked flask, drop into 100 parts of phenol;
Step 2: drop into 0.01 part of catalyzer hydrochloric acid, be heated to 55 ℃ and stir, add Paraformaldehyde 96 65 ℃ of scopes and react 1h for 30 parts;
Step 3: be warming up to 85 ℃ of sustained reaction 3h again and can obtain the target resin.
Embodiment 2
Step 1: in there-necked flask, drop into 100 parts of phenol;
Step 2: drop into 0.03 part of catalyzer hydrochloric acid, be heated to 55 ℃ and stir, add Paraformaldehyde 96 at 65 ℃ and react 1h for 28 parts;
Step 3: be warming up to the interior sustained reaction 3h of 80 ℃ of scopes again and can obtain the target resin.
Embodiment 3
Step 1: in there-necked flask, drop into 100 parts of phenol;
Step 2: drop into 0.05 part of catalyzer hydrochloric acid, be heated to 55 ℃ and stir, add Paraformaldehyde 96 at 65 ℃ and react 1h for 25 parts;
Step 3: be warming up to the interior sustained reaction 3h of 75 ℃ of scopes again and can obtain the target resin.
Claims (1)
1. the preparation method of a thermoplastic phenolic resin with high solid content is characterized in that step is following:
Step 1: in there-necked flask, drop into phenol 100 mass parts;
Step 2: drop into catalyzer hydrochloric acid 0.01～0.05 mass parts, be heated to 55 ℃ and stir, add Paraformaldehyde 96 25～30 mass parts at 65 ℃ and react 1h;
Step 3: be warming up to the interior sustained reaction 3h of 75-85 ℃ of scope again and obtain thermoplastic phenolic resin with high solid content.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN2010101854379A CN101831042B (en) | 2010-05-27 | 2010-05-27 | Preparation method of thermoplastic phenolic resin with high solid content |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101854379A CN101831042B (en) | 2010-05-27 | 2010-05-27 | Preparation method of thermoplastic phenolic resin with high solid content |
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| CN101831042A CN101831042A (en) | 2010-09-15 |
| CN101831042B true CN101831042B (en) | 2012-07-04 |
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| CN2010101854379A Active CN101831042B (en) | 2010-05-27 | 2010-05-27 | Preparation method of thermoplastic phenolic resin with high solid content |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102108115B (en) * | 2011-01-13 | 2012-05-23 | 济南鲁东耐火材料有限公司 | Phenolic resin for environment-friendly thermoplastic refractory material and preparation method thereof |
| CN103992497B (en) * | 2014-04-22 | 2016-07-13 | 南京林业大学 | Utilize the method that natural fiber biological material prepares biomass-based foamed materials |
| CN112574371A (en) * | 2020-12-14 | 2021-03-30 | 陕西科技大学 | Bisphenol A paraformaldehyde phenolic resin and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1483749A (en) * | 2002-09-20 | 2004-03-24 | 山东省分析测试中心 | Method for preparing normal temp solidified high stvength glass fire reinforced plastics |
| CN1566172A (en) * | 2003-06-27 | 2005-01-19 | 上海尖端工程材料有限公司 | Foam type phenol-formaldehyde resin and its production technology |
| CN101307124A (en) * | 2008-07-14 | 2008-11-19 | 江苏九鼎新材料股份有限公司 | Thermoplastic phenolic resin and production process thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0597947A (en) * | 1991-10-07 | 1993-04-20 | Hitachi Chem Co Ltd | Production of phenolic resin |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1483749A (en) * | 2002-09-20 | 2004-03-24 | 山东省分析测试中心 | Method for preparing normal temp solidified high stvength glass fire reinforced plastics |
| CN1566172A (en) * | 2003-06-27 | 2005-01-19 | 上海尖端工程材料有限公司 | Foam type phenol-formaldehyde resin and its production technology |
| CN101307124A (en) * | 2008-07-14 | 2008-11-19 | 江苏九鼎新材料股份有限公司 | Thermoplastic phenolic resin and production process thereof |
Non-Patent Citations (2)
| Title |
|---|
| JP特开平5-97947A 1993.04.20 |
| 董瑞玲等."环保型酚醛树脂的研制".《工程塑料应用》.2001,第29卷(第10期),第1-3页. |
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