CN111909332B - Solid thermosetting phenolic resin and preparation method thereof - Google Patents
Solid thermosetting phenolic resin and preparation method thereof Download PDFInfo
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- CN111909332B CN111909332B CN202010666951.8A CN202010666951A CN111909332B CN 111909332 B CN111909332 B CN 111909332B CN 202010666951 A CN202010666951 A CN 202010666951A CN 111909332 B CN111909332 B CN 111909332B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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Abstract
The application discloses a solid thermosetting phenolic resin and a synthetic method thereof, wherein the synthetic method comprises the following steps: taking divalent metal salt as a catalyst, reacting excessive phenol and formaldehyde at 90-110 ℃, and sequentially dehydrating under normal pressure, removing phenol under vacuum and cooling after the reaction is finished to obtain the solid thermosetting phenolic resin. Dehydrating at normal pressure to 115-125 ℃. The synthesis method of the solid thermosetting phenolic resin can obviously improve the stability among phenolic resin batches and the storage stability, the process is easy to control, and the gel risk can not occur.
Description
Technical Field
The application relates to the technical field of phenolic resin, in particular to solid thermosetting phenolic resin and a preparation method thereof.
Background
The solid thermosetting phenolic resin is mainly carried out by the following two ways:
(1) under the alkaline condition, excessive formaldehyde and phenol form phenolic resin which is blocked by a hydroxymethyl structure and is solid at normal temperature by controlling the synthesis speed of hydroxymethyl, and the curing process of the resin mainly comprises the condensation of hydroxymethyl among phenolic molecules;
(2) the excessive formaldehyde and phenol form high ortho solid thermosetting phenolic resin with dibenzyl ether and hydroxymethyl structure under the catalysis of divalent metal salt.
The existing solid thermosetting phenolic resin mainly has the following problems:
1. the process is complex and the industrial production difficulty is high.
Because the existing solid thermosetting phenolic resin has a hydroxymethyl structure, the process is difficult to control, the resin is easy to be directly gelated and cured in a reaction kettle, and the production can be carried out only in small batch.
2. The stability of the resin is poor, and the performance difference between the initial material and the final material is large in the discharging process of the resin.
If the discharging temperature is high, the resin viscosity is low, the discharging time is short, but the condensation between hydroxymethyl groups is quicker; if the discharging temperature is low, the viscosity of the resin is high, and the discharging time is long, the performance stability of the resin is poor.
3. The storage stability is poor. Due to the existence of hydroxymethyl structures in the resin, the hydroxymethyl groups are continuously subjected to slow condensation during storage.
Disclosure of Invention
The application provides a preparation method of solid thermosetting phenolic resin, which can obviously improve the stability among phenolic resin batches and the storage stability, is easy to control the process and can not generate the gel risk.
A preparation method of a solid thermosetting phenolic resin comprises the following steps:
taking divalent metal salt as a catalyst, reacting excessive phenol and formaldehyde at 90-110 ℃, and sequentially dehydrating under normal pressure, removing phenol under vacuum and cooling after the reaction is finished to obtain the solid thermosetting phenolic resin.
The application adopts divalent metal salt as a catalyst, excessive phenol reacts with formaldehyde to form a large amount of dibenzyl ether bonds, the structure is not decomposed at the temperature lower than 150 ℃, the structure is decomposed at the temperature higher than 150 ℃, methylene bonds are formed and formaldehyde is released when the dibenzyl ether bonds are decomposed, and the formaldehyde release can further condense phenolic resin chains to cause the resin to be cured.
Several alternatives are provided below, but not as an additional limitation to the above general solution, but merely as a further addition or preference, each alternative may be combined individually for the above general solution or between several alternatives without technical or logical contradictions.
Optionally, dehydrating to 115-125 ℃ under normal pressure.
The temperature control of atmospheric dehydration is an important process parameter at which solid thermosetting phenolic resins are formed.
Optionally, the molar ratio of phenol to formaldehyde is 1.5-2: 1.
optionally, the reaction time of the phenol and the formaldehyde is 4-10 h.
Optionally, the divalent metal salt is at least one of a divalent zinc salt, a divalent barium salt and a divalent calcium salt.
More preferably, the divalent metal salt is at least one of zinc acetate, barium acetate, calcium chloride and barium chloride.
Optionally, dephenolizing to 130-140 ℃ under vacuum. The vacuum dephenolization is carried out under the condition that the vacuum degree is less than 0.095 Mpa.
Optionally, the formaldehyde is an aqueous formaldehyde solution and/or paraformaldehyde.
The formaldehyde can be added in the form of aqueous formaldehyde solution or paraformaldehyde. In any form, the purpose is to introduce formaldehyde into the reaction system.
Optionally, the formaldehyde adopts a formaldehyde aqueous solution and paraformaldehyde, and the molar ratio of the formaldehyde aqueous solution to aldehyde groups in the paraformaldehyde is 1.5-2.0: 1.
optionally, the mass ratio of the catalyst to the phenol is 0.5-15: 1000.
the application also provides a solid thermosetting phenolic resin prepared by the preparation method.
Compared with the prior art, the application has the following beneficial effects:
(1) a new phenolic resin fixing mechanism is adopted, the phenolic resin is not cured at low temperature and is cured at high temperature;
(2) the solid thermosetting phenolic resin does not react at 130 ℃, and the resin stability among batches is good, and the storage stability is good.
(3) The process is simple, no gel risk occurs in the production process of the phenolic resin, and the mass production can be enlarged.
Detailed Description
The technical solution of the present application is described in detail below with reference to specific embodiments.
Example 1
Adding 1000kg of preheated and molten phenol into a high-level metering tank by using a special pump, metering into a reaction kettle, adding 500kg of formaldehyde aqueous solution with the mass fraction of 37% and 0.5kg of calcium chloride into the reaction kettle, heating to 100 ℃, and carrying out heat preservation and reflux for 6 hours. After the heat preservation is finished, the normal pressure dehydration temperature is up to 120 ℃, the vacuum dehydration is up to 130 ℃ (the vacuum degree is less than 0.095 Mpa), the reaction is stopped, the product is discharged, and the light yellow solid 980Kg is obtained after cooling.
Example 2
Adding 1000kg of preheated and molten phenol into a high-level metering tank by using a special pump, metering into a reaction kettle, adding 800kg of formaldehyde aqueous solution with the mass fraction of 37% and 1kg of calcium acetate into the reaction kettle, heating to 100 ℃, and carrying out heat preservation and reflux for 3 hours. And after the heat preservation is finished, dehydrating at normal pressure to 120 ℃, dehydrating in vacuum to 130 ℃ (the vacuum degree is less than 0.095 Mpa), stopping the reaction, discharging the product, and cooling to obtain 1020Kg of light yellow solid.
Example 3
Adding 1000kg of preheated and molten phenol into a high-level metering tank by using a special pump, metering into a reaction kettle, adding 200kg of paraformaldehyde and 15kg of zinc acetate into the reaction kettle, heating to 100 ℃, and carrying out heat preservation and reflux for 3 hours. After the heat preservation is finished, the normal pressure dehydration temperature is up to 120 ℃, the vacuum dehydration is up to 130 ℃ (the vacuum degree is less than 0.095 Mpa), the reaction is stopped, the product is discharged, and 940Kg of light yellow solid is obtained after cooling.
Example 4
Adding 1000kg of preheated and molten phenol into a high-level metering tank by using a special pump, metering into a reaction kettle, then adding 500kg of formaldehyde aqueous solution with the mass fraction of 37%, 100kg of paraformaldehyde and 5kg of barium chloride into the reaction kettle, heating to 100 ℃, and carrying out heat preservation and reflux for 5 hours. And after the heat preservation is finished, dehydrating at normal pressure to 120 ℃, dehydrating in vacuum to 130 ℃ (the vacuum degree is less than 0.095 Mpa), stopping the reaction, discharging the product, and cooling to obtain 980Kg of light yellow solid.
Example 5
Adding 1000kg of preheated and molten phenol into a high-level metering tank by using a special pump, metering into a reaction kettle, then adding 300kg of formaldehyde aqueous solution with the mass fraction of 37%, 100kg of paraformaldehyde, 90kg of trioxymethylene, 5kg of zinc acetate and 8kg of calcium chloride into the reaction kettle, heating to 100 ℃, and carrying out heat preservation and reflux for 4 hours. And after the heat preservation is finished, dehydrating at normal pressure to 120 ℃, dehydrating in vacuum to 130 ℃ (the vacuum degree is less than 0.095 Mpa), stopping the reaction, discharging the product, and cooling to obtain 980Kg of light yellow solid.
Comparative example 1
Adding 300kg of preheated and molten phenol into a high-level metering tank by using a special pump, metering into a reaction kettle, adding 375kg of formaldehyde aqueous solution with the mass fraction of 37% and 15kg of zinc acetate into the reaction kettle, heating to 100 ℃, and carrying out heat preservation and reflux for 6 hours. After the heat preservation is finished, the normal pressure dehydration temperature is up to 100 ℃, the vacuum dehydration temperature is up to 100 ℃ (the vacuum degree is less than 0.095 Mpa), the vacuum dehydration is carried out until the resin polymerization speed is 120s (the polymerization speed measuring temperature is 160 ℃)/, the reaction is stopped, the product is discharged within 30 minutes, and 305kg of light yellow solid is obtained after cooling.
Performance testing
The following tests were performed on the pale yellow solid resins of examples 1 to 5 and comparative example 1 of the present application, and the test results are shown in table 1:
TABLE 1
As can be seen from Table 1, the low methylol content of the solid thermosetting phenol resin of the present application as compared with comparative example 1 results in the prolonged polymerization rate of the examples of the present application, but the prolonged polymerization rate is not significant.
As can be seen from table 1, the molecular weight distribution of the solid thermosetting resin of the present application is narrower because the solid thermosetting phenol resin of comparative example 1 contains more methylol groups, which causes polymerization reaction between long chains of the phenol resin during dehydration of the resin, resulting in non-uniform molecular weight distribution of the resin.
The pale yellow solid resins of examples 1 to 5 and comparative example 1 were subjected to resin polymerization rate test under storage at different temperatures, and the results are shown in Table 2.
TABLE 2
The larger the change in polymerization rate, the poorer the storage stability of the resin, and it can be seen from table 2 that the storage stability of the solid thermosetting phenol-formaldehyde resins prepared in examples 1 to 5 is significantly better than that of the solid thermosetting phenol-formaldehyde resin in comparative example 1 at different temperatures.
As can be seen from the tests of examples 1 to 5 and comparative example 1 stored at 100 ℃ for 5h, the change of the polymerization rate of comparative example 1 is very obvious, the phenolic resin can not flow at the polymerization rate of 20s, and the change of the polymerization rate is not large in the application.
Application performance characterization
The thermosetting phenolic resins of examples 1-5 and comparative example 1 were used to prepare injection molding materials, and the injection molding materials comprise the following components in percentage by mass: 45% of phenolic resin, 30% of wood powder, 15% of calcium carbonate and 10% of other auxiliary agents.
The preparation process of the phenolic aldehyde injection molding material comprises the following steps:
the phenolic resin is crushed and uniformly mixed with other materials, the mixture is plasticated by a two-roll plasticator for a period of time, then the mixture is crushed and granulated to obtain the phenolic resin injection molding material, and the performance test is carried out on the phenolic resin injection molding material, and the test results are shown in table 3.
TABLE 3
As can be seen from Table 3, in examples 1 to 5, the bending properties and impact strength of the injection molded material samples were comparable to those of comparative example 1, but the flowability, curing time and retention time of the injection molded material samples of examples 1 to 5 were all longer than those of comparative example 1, which indicates that the workability of examples 1 to 5 was significantly better than that of comparative example 1.
The above-mentioned embodiments only express several embodiments of the present application, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the concept of the present application, and these are all within the scope of protection of the present application. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (9)
1. The preparation method of the phenolic resin solid is characterized by comprising the following steps:
the thermosetting phenolic resin starts to decompose when heated to the temperature higher than 150 ℃, methylene bonds are formed and formaldehyde is released when dibenzyl ether bonds are decomposed, and the release of the formaldehyde enables the phenolic resin chains to be further condensed to obtain the phenolic resin solid;
the synthesis of the thermosetting phenolic resin comprises the following steps:
taking divalent metal salt as a catalyst, reacting excessive phenol and formaldehyde at 90-110 ℃, dehydrating to 115-125 ℃ under normal pressure, removing phenol to 130-140 ℃ under vacuum, and cooling to obtain the solid thermosetting phenolic resin.
2. The method for preparing the phenolic resin solid as claimed in claim 1, wherein the molar ratio of the phenol to the formaldehyde is 1.5-2: 1.
3. the method for preparing the phenolic resin solid as claimed in claim 1, wherein the reaction time of the phenol and the formaldehyde is 4-10 h.
4. The method for preparing phenolic resin solids according to claim 1, wherein the divalent metal salt is at least one of a divalent zinc salt, a divalent barium salt, and a divalent calcium salt.
5. The method for producing phenolic resin solids according to claim 1 wherein the formaldehyde is an aqueous formaldehyde solution and/or paraformaldehyde.
6. The method for preparing the phenolic resin solid as claimed in claim 1, wherein the formaldehyde adopts formaldehyde aqueous solution and paraformaldehyde, and the molar ratio of the formaldehyde aqueous solution to the aldehyde group in the paraformaldehyde is 1.5-2.0: 1.
7. the method for preparing the phenolic resin solid as claimed in claim 1, wherein the mass ratio of the catalyst to the phenol is 0.5-15: 1000.
8. a phenolic resin solid prepared by the synthesis method according to any one of claims 1 to 7.
9. An injection molding compound prepared by using the phenolic resin solid as claimed in claim 8, wherein the injection molding compound comprises the following components in percentage by mass: 45% of solid phenolic resin, 30% of wood powder, 15% of calcium carbonate and 10% of other auxiliary agents.
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| CN111154054A (en) * | 2019-12-18 | 2020-05-15 | 杭摩新材料集团股份有限公司 | Method for modifying phenolic resin by using cardanol and rubber |
| CN111205799A (en) * | 2020-02-28 | 2020-05-29 | 杭摩新材料(嘉兴)有限公司 | Production process of cardanol modified phenolic resin adhesive |
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| US4097463A (en) * | 1977-01-10 | 1978-06-27 | Monsanto Company | Process for preparing high ortho novolac resins |
| US4299947A (en) * | 1980-06-11 | 1981-11-10 | Sumitomo Bakelite Company Limited | Process for producing quick-curing phenolic resin |
| CN101381439B (en) * | 2008-10-27 | 2010-09-29 | 北京玻钢院复合材料有限公司 | Thermosetting rapid curing phenolic resin and preparation method thereof |
| CN101597364B (en) * | 2009-06-30 | 2011-01-19 | 陕西师范大学 | Synthesis method of thermosetting phenol-formaldehyde resin in solid at normal temperature |
| CN101880367B (en) * | 2010-08-03 | 2012-07-25 | 山东圣泉化工股份有限公司 | Method for preparing high-ortho thermoplastic phenolic resin |
| CN106040966B (en) * | 2015-06-18 | 2019-02-05 | 济南圣泉集团股份有限公司 | Cold-box binder and casting and forming body |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111154054A (en) * | 2019-12-18 | 2020-05-15 | 杭摩新材料集团股份有限公司 | Method for modifying phenolic resin by using cardanol and rubber |
| CN111205799A (en) * | 2020-02-28 | 2020-05-29 | 杭摩新材料(嘉兴)有限公司 | Production process of cardanol modified phenolic resin adhesive |
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