CN109627468B - Organic acid metal salt phenolic resin compound and preparation method thereof - Google Patents
Organic acid metal salt phenolic resin compound and preparation method thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08J2361/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with polyhydric phenols
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Abstract
The invention relates to an organic acid metal salt phenolic resin compound and a preparation method thereof. The structure of the compound is characterized in that metal ions are taken as a coordination center, and carboxylate ions, hydroxide ions and phenoxy ions are taken as coordination ions, so that the phenolic resin is crosslinked in a coordination bond mode. The composite is prepared by compounding 100 parts of phenolic resin and 20-100 parts of organic acid metal salt together in a physical crushing and blending or chemical melting and blending mode, and a complex formed by phenolic hydroxyl and the organic acid metal salt is utilized to form a cross-linking bond in a coordination form in the phenolic resin. The structure of the coordination crosslinking bond can increase the strength and the heat resistance of the phenolic resin, and the structure of the organic acid can also increase the interface compatibility and the chemical reactivity of the phenolic resin and other materials (such as rubber, plastics and base materials). The organic acid metal salt phenolic resin composite can be applied to rubber, plastics and composite materials.
Description
Technical Field
The invention relates to the field of composite materials, in particular to an organic acid metal salt phenolic resin compound and a preparation method thereof.
Background
The chemical modification of phenolic resin is a kind of modification method which uses chemical reaction to change the molecular structure of ordinary phenol-formaldehyde resin, and aims at improving its brittleness, cohesiveness and heat resistance, and sometimes requires to improve other physical properties. Chemical modification of phenolic resins is often by the following route: (1) blocking phenolic hydroxyl groups. Etherifying or epoxidizing phenolic hydroxyl groups, which do not normally participate in chemical reactions during the resin manufacturing process. (2) Other components are introduced. When synthesizing phenolic resin, low molecular weight or high molecular weight compound which can be chemically reacted with phenols, aldehydes and phenolic resin active points is introduced to generate phenolic resin with special structure, thereby realizing specific modification effect. For example, alkylphenol, cardanol, tung oil, silicon compounds, boron compounds, and the like are added. This type of modification is the mainstream of chemical modification of phenolic resins. (3) The nonuniformity of the cross-linking state of the molecular chain is controlled. The molecular weight formed by crosslinking the resin through long-chain raw materials and special reaction is in bimodal distribution, and the phenolic resin is crosslinked into a non-uniform continuous structure by two methods of synthesis and blending. (4) Etherified modified phenolic resin is prepared into phenolic resin containing methylol. Common chemically modified phenolic resins include: alkylphenol modification, polyvinyl acetal modification, epoxy resin modification, melamine modification, silicone modification, boron modification, molybdenum phosphorus modification, xylene formaldehyde resin modification, tung oil modification, linseed oil bar modification, cashew nut shell oil modification, sulfonated phenol aldehyde, maleimide polymer modification, rosin modification, tall oil modification, alkynyl functionalization and the like (from the following: Tang Lulin, Linning, Wupexi. high performance phenol formaldehyde resin and its application technology [ M ]. chemical industry Press, 2008.). The active site of the phenolic resin is phenolic hydroxyl, ortho-position and para-position of the phenolic hydroxyl on a benzene ring or hydroxymethyl of the thermosetting phenolic aldehyde. The ortho-position and para-position of phenolic hydroxyl on a benzene ring can be crosslinked with HMT and HMMM curing agents to cure the resin, the methylol of thermosetting phenolic aldehyde can be further condensed to cure the resin, the reports of further crosslinking and curing by utilizing the phenolic hydroxyl are few, the phenolic hydroxyl of high-performance phenolic resin and application technology thereof are described in the book of high-performance phenolic resin and application technology thereof, the phenolic hydroxyl is generally not involved in chemical reaction in the resin manufacturing process, and the method for blocking the phenolic hydroxyl is to etherify or epoxidize the phenolic hydroxyl.
The paper of Zhang Wen Fang reports the research of high ortho phenolic resin, the weak acid salt catalyst of bivalent metal Ca, Mg, Zn, Cd, Pb, Cu, Co, Ni with ortho-position induction action is introduced into the phenolic reaction system, in the presence of proper phenol/formaldehyde molar ratio and ortho-position inducer, phenol and aldehyde react at ortho-position of phenolic hydroxyl group to form high ortho-position linear phenolic resin mainly using methylene to replace ortho-position hydrogen atom (from Zhang Wen Fang, Yingong, Liuchun Ling, et al. synthesis and characterization of high ortho-position thermoplastic phenolic resin [ J ]. Shanxi university report (from Kokai edition), 2015,43(1): 51-55.). These divalent metals are used only as catalysts for the preparation of high ortho phenolic resins, with lower catalyst loadings.
The high ortho phenolic resin polycondensation reaction equation is given in reports of Samply, Lingming, SAMPE China 2010 and the ninth advanced materials technical workshop, and the reaction mechanism is that phenolic hydroxyl-divalent metal carboxylate-formaldehyde forms a complex intermediate, so that the para-position reaction of formaldehyde and phenolic hydroxyl is limited (from the point of bath Lin, Lingming, a synthesis and performance research [ C ]// SAMPE China 2010 of the high ortho phenolic resin and the ninth advanced materials technical workshop, 2010.).
The doctor paper of Liuyang university at northeast suggests the concept of metal modified phenolic resin, wherein phenol or low-order phenolic resin reacts with some metal acid or metal halide, metal alcoholate or metal organic compound to obtain modified phenolic resin with enhanced heat resistance and flame retardance, and introduces molybdenum, titanium, tungsten and zirconium modified phenolic resin (introduced from Liuyang. grafting modification research on phenolic resin [ D ]. northeast university, 2013.).
Chinese patent CN103665284 proposes a method for preparing alkyl phenol-formaldehyde resin and an organic zinc salt modifier by compounding and an application thereof. Wherein the amount of the modifier zinc salt of organic acid is 0.5-10 parts by mass of the zinc salt of organic acid per 100 parts by mass of the alkyl phenolic resin. However, the softening point of the composite of the alkylphenol formaldehyde resin and the organic acid zinc salt is lower than that of the alkylphenol formaldehyde resin, which means that the crosslinking degree of the composite of the alkylphenol formaldehyde resin and the organic acid zinc salt is not enough, so that the performance of the composite cannot be reflected.
Disclosure of Invention
The present invention provides an organic acid metal salt phenolic resin compound and a preparation method thereof in order to solve the above problems.
It is an object of the present invention to provide an organic acid metal salt phenolic resin composite having the following structure:
wherein, R is1Is hydrogen (H) or hydroxymethyl (HOCH)2)；
R2Is hydrogen (H) Or Hydroxy (OH);
R3h, a linear or branched C4-C12 alkyl group, preferably tert-butyl, tert-octyl, nonyl, dodecyl, more preferably tert-butyl or tert-octyl;
R4is methylene (CH)2) Sulfur (S) having a single sulfur bond, sulfur (S-S) having a double sulfur bond or CH2-(S)m-CH2M is an integer of 1 to 4;
R5is a linear or branched C1-C30 saturated or unsaturated alkyl, C6-C20 saturated or unsaturated alicyclic group, or C6-C20 aryl;
m is an alkaline earth metal or a +2 valent transition metal, preferably Mg, Ca, Zn, Co, Mn, Fe, Pb, Ni, or the like;
n is an integer of 1 to 50, preferably an integer of 1 to 30, more preferably an integer of 1 to 20.
The organic acid metal salt phenolic resin compound is characterized in that the organic acid metal salt and phenolic hydroxyl of the phenolic resin form a complex, the central ion of the complex is a metal ion with coordination capacity, and the coordination ions surrounding the metal ion are carboxylate ions, hydroxide ions and phenoxy ions. The advantage of this structure is that the phenolic resin is further cross-linked by complexation of phenolic hydroxyl groups with metal ions, which is directly reflected by an increase in the glass transition temperature of the composite and an increase in the softening point of the resin. The coordination bond formed by the complex structure belongs to a dynamic cross-linking bond, and can be formed again after the coordination bond is broken, so that the function of reinforcing the resin matrix is achieved. In addition, the formation of such coordinate bonds is related to the phenolic hydroxyl groups of the phenolic resin, which generally do not participate in chemical reactions during the resin production process and the curing and crosslinking process of the resin.
The organic acid metal salt phenolic resin compound is prepared from the following raw materials in parts by weight:
100 parts of phenolic resin;
20-100 parts of organic acid metal salt; preferably 40 to 60 parts.
Wherein the phenolic resin has a structure shown as the following formula:
wherein R is1Is hydrogen or hydroxymethyl; r2Is hydrogen or hydroxy; r3Hydrogen, straight chain or branched C4-C12 alkyl; r4Is methylene, a sulfur, a disulfide bond or CH2-(S)m-CH2M is an integer of 1 to 4; n is an integer of 1 to 50.
The organic acid metal salt structure is represented by the following formula:
R5-COO-M-OOC-R5(formula 4) or R5-COO-M-OH (formula 5),
wherein R is5Is a linear or branched C1-C30 saturated or unsaturated alkyl, C6-C20 saturated or unsaturated alicyclic group, or C6-C20 aryl; m is an alkaline earth metal or a +2 valent transition metal.
The second purpose of the invention is to provide a preparation method of the organic acid metal salt phenolic resin compound.
The preparation method of the organic acid metal salt phenolic resin compound has two methods, namely physical crushing and blending and chemical melting and blending.
The physical crushing and blending method comprises the steps of crushing and mixing the raw materials according to the raw material amount to obtain an organic acid metal salt phenolic resin mixture, and heating the mixture to a molten state during use to form the organic acid metal salt phenolic resin compound.
The phenolic resin is crushed by a high-speed stirrer, the organic acid metal salt is added, the mixture is further crushed and mixed to obtain an organic acid metal salt phenolic resin mixture, and the mixture is heated to a molten state during use to form the organic acid metal salt phenolic resin compound.
Preferably, the physical pulverization blending method comprises the following steps: mixing the raw materials according to the raw material amount, stirring at a high speed at the temperature of 10-30 ℃ for crushing for more than 3 times at intervals of 30-180 seconds each time, and heating to a molten state in the using process to obtain the organic acid metal salt phenolic resin compound. More preferably, the temperature is heated to 100-150 ℃ in the using process.
The chemical melt blending process comprises the steps of: mixing the raw materials according to the raw material amount, heating the phenolic resin to 100-200 ℃ under the protection of nitrogen to enable the phenolic resin to reach a molten state, adding organic acid metal salt, raising the reaction temperature to 160-210 ℃, and stirring for reaction for 10-60 minutes to obtain the organic acid metal salt phenolic resin compound.
The temperature of the molten phenolic resin is preferably 130-200 ℃, the reaction temperature is preferably 180-200 ℃, and the stirring reaction time is preferably 20-40 minutes.
The chemical melt blending method may specifically include the following processes: adding phenolic resin into a four-mouth flask, and installing a reflux device, a digital display electric stirrer, a constant temperature electric jacket and an electronic energy-saving temperature controller. Under the protection of nitrogen, heating the phenolic resin to a molten state, wherein the heating temperature is higher than the softening point of the phenolic resin by 50 ℃. Adding organic acid metal salt under mechanical stirring, and stirring for reaction to obtain the organic acid metal salt phenolic resin compound.
Since the softening point of the composite formed by the organic acid metal salt and the phenolic resin is increased, which may influence the subsequent application, the invention provides two methods for preparing the organic acid metal salt phenolic resin composite. The physical pulverization blending method does not bring about an increase in the softening point of the resin matrix, but requires heating to form a complex of the organic acid metal salt and the phenol resin. The chemical melt blending can directly obtain the organic acid metal salt phenolic resin compound, but the softening point of the compound is higher than that of the phenolic resin.
The softening point and the glass transition temperature of the composite organic acid metal salt phenolic resin are increased, which can indicate that the phenolic resin and organic acid zinc react with each other in a melting state to generate chemical cross-linking, and the chemical cross-linking is a result of the complexation of the organic acid zinc and phenolic hydroxyl of the phenolic resin, and the movement of the molecular chain of the phenolic resin is limited. The chemical cross-linking bond can also bring about the increase of the maximum thermal decomposition temperature of the compound, and the improvement of the performance can widen the application field. Meanwhile, an organic molecular chain is introduced into the phenolic resin structure along with the complex reaction of the organic zinc and phenolic resin phenolic hydroxyl, and the organic molecular chain can increase the interface compatibility and even the chemical reactivity of the phenolic resin with rubber, plastics and base materials. In addition, the composite structure of the organic acid metal salt and the phenolic resin does not affect the further curing of the phenolic resin, and the phenolic resin can form a double cross-linked network, thereby improving the strength, toughness, heat resistance and the like of the phenolic resin.
The structure of the coordination crosslinking bond can increase the strength and the heat resistance of the phenolic resin, and the structure of the organic acid can also increase the interface compatibility and the chemical reactivity of the phenolic resin and other materials (such as rubber, plastics and base materials). The organic acid metal salt phenolic resin composite can be applied to rubber, plastics and composite materials.
In comparison with the doctor paper of the Liuyang university at northeast. The paper introduces the preparation processes of molybdenum modified phenolic resin, titanium modified phenolic resin, tungsten modified phenolic resin and zirconium modified phenolic resin, and the raw materials and the preparation processes of the molybdenum modified phenolic resin, the titanium modified phenolic resin, the tungsten modified phenolic resin and the zirconium modified phenolic resin are obviously different from those of the invention. The technology disclosed by the invention is that organic acid metal salt and phenolic resin are compounded, namely, metal ions are taken as a coordination center, carboxylate ions, hydroxide ions and phenoxy ions are taken as coordination ions, and the phenolic resin is crosslinked in a form of coordination bonds.
Compared with the technology of Chinese patent CN103665284, the addition amount of the organic acid metal salt in the technology disclosed by the invention is larger than that of the Chinese patent CN103665284, namely the dosage of the organic acid zinc salt serving as the modifier of the Chinese patent CN103665284 is 0.5-10 parts by mass of the organic acid zinc salt added to 100 parts by mass of the alkyl phenolic resin, and the dosage of the organic acid metal salt is 20-100 parts by mass of the organic acid metal salt added to 100 parts by mass of the alkyl phenolic resin. The increased amount of metal salts of organic acids results in an increase in the glass transition temperature and softening point of the resin, whereas in chinese patent CN103665284 the softening point of the resin is decreased. In addition, chinese patent CN103665284 only discloses the compounding of zinc salts of organic acids with alkyl phenol-formaldehyde resins, but the present invention is applicable to a wider range of phenol-formaldehyde resins, including thermoplastic phenol-formaldehyde and thermosetting phenol-formaldehyde.
Detailed Description
The present invention is described in detail below with reference to specific examples. It should be understood that the practical use of the present invention is not limited to the embodiments.
1. Raw materials and reagents
TABLE 1 raw materials and reagents
2. Apparatus and device
TABLE 2 instruments and apparatus
3. Analysis and testing
(1) Softening point test: the softening point was tested according to ASTM D3461-14.
(2) Measurement of glass transition temperature
The Differential Scanning Calorimeter (DSC) was turned on, the software was run, and the system was purged with nitrogen at a constant flow rate of 50mL/min for not less than 20 min. An amount (typically 5-15mg, to the nearest 0.1mg) of the sample is weighed into a crucible. And (3) enabling the heating furnace body to reach the initial temperature, putting the sample crucible and the blank crucible on a sensor in the furnace body, and starting to measure after the temperature of the furnace body is stable. And (3) using a DSC program to control the temperature, increasing the furnace temperature from 20 ℃ to 200 ℃ at a speed of 10 ℃/min, keeping the constant temperature of 200 ℃ for 1min, then reducing the furnace temperature from 200 ℃ to 0 ℃ at a speed of 10 ℃/min, keeping the constant temperature of 0 ℃ for 1min, then increasing the furnace temperature from 0 ℃ to 200 ℃ at a speed of 10 ℃/min, and carrying out the measurement of the glass transition temperature of the sample. And finally, cooling the instrument program to the initial temperature, and obtaining the glass transition temperature of the sample according to the DSC curve.
(3) Thermogravimetric analysis
The thermogravimetric analyzer (TGA) was turned on, the software was run, and the balance was stabilized. An amount (typically 5-15mg, to the nearest 0.1mg) of the sample is weighed into a crucible on a sample pan of the balance. The furnace body was allowed to reach the starting temperature, and the system was purged with nitrogen at a constant flow rate of 50mL/min for a period of not shorter than 20 min. The sample was tested by raising the furnace temperature from 20 ℃ to 600 ℃ at a ramp rate of 10 ℃/min. And finally, cooling the instrument program to the initial temperature, and obtaining the maximum thermal decomposition temperature of the sample according to the thermal weight loss curve.
4. Sample preparation
Example 1, preparation of organic acid zinc phenolic resin complex by physical pulverization and blending method.
200g of SL2005 resin was pulverized with a portable high-speed universal pulverizer (model ZK-100B), 100g of zinc stearate was added, and further pulverized and mixed to obtain a zinc stearate-phenol resin mixture having a resin softening point of 117.2 ℃.
The experimental methods of examples 2 to 10 were the same as in example 1, except that the type of resin was changed and the type and amount of the organic acid metal salt were changed.
TABLE 3 examples 2-10 formulations
| Resin composition | Dosage of | Organic acid metal salt | Dosage of | |
| Example 2 | SL-2005 | 200g | Zinc monomethacrylate | 80g |
| Example 3 | SL-1401 | 200g | Zinc acetate | 60g |
| Example 4 | SL-1801 | 200g | Zinc monomethacrylate | 100g |
| Example 5 | SL-1801 | 200g | Zinc stearate | 80g |
| Example 6 | SL-3020 | 200g | Zinc benzoate | 160g |
| Example 7 | SL-3020 | 200g | Zinc monomethacrylate | 60g |
| Example 8 | SL-7015 | 200g | Zinc dimethacrylate | 100g |
| Example 9 | Sulfur-containing phenol resin 1 | 200g | Zinc benzoate | 140g |
| Example 10 | Sulfur-containing phenol resin 2 | 200g | Zinc stearate | 120g |
Example 11, preparation of organic acid zinc phenolic resin composite by chemical melt blending method.
Phenolic resin is added into a four-mouth flask, and a reflux device, a digital display electric stirrer (JJ-1), a constant temperature electric heating jacket (HDM-500) and an electronic energy-saving temperature control instrument (ZNHW-II type) are arranged. Under the protection of nitrogen, heating the phenolic resin to a molten state, wherein the heating temperature is higher than the softening point of the phenolic resin by 50 ℃. Adding organic acid metal salt under mechanical stirring, stirring and reacting for 30min to obtain the organic acid metal salt phenolic resin compound.
Examples 12 to 20 the experimental method was the same as in example 11, and the kind of the resin was changed and the kind and the amount of the organic acid metal salt were changed.
TABLE 4 examples 12-20 formulations
| Resin composition | Dosage of | Organic acid metal salt | Dosage of | |
| Example 12 | SL-2005 | 200g | Zinc monomethacrylate | 80g |
| Example 13 | SL-1401 | 200g | Zinc acetate | 60g |
| Example 14 | SL-1801 | 200g | Zinc monomethacrylate | 100g |
| Example 15 | SL-1801 | 200g | Zinc stearate | 80g |
| Example 16 | SL-3020 | 200g | Zinc benzoate | 160g |
| Example 17 | SL-3020 | 200g | Zinc monomethacrylate | 60g |
| Example 18 | SL-7015 | 200g | Zinc dimethacrylate | 100g |
| Example 19 | Sulfur-containing phenol resin 1 | 200g | Zinc benzoate | 140g |
| Example 20 | Sulfur-containing phenol resin 2 | 200g | Zinc stearate | 120g |
Test results 1 physical crush blending
A calorimetric System (FP900) to measure softening point, a differential scanning calorimeter (DSC1 start System) to measure glass transition temperature, a thermogravimetric and simultaneous thermal analyzer (TGA/DSC1 start System) to measure maximum thermal decomposition temperature.
TABLE 5 test results of examples 1 to 10
The softening point of the organic acid zinc salt phenolic resin compound prepared by the physical crushing and blending method is not obviously increased, and the processing window of the compound is consistent with that of the original resin. The glass transition temperature of the compound rises by 2-7 ℃, and the maximum thermal decomposition temperature rises by 10-20 ℃. The glass transition temperature of a test sample needs to be raised to a sample molten state to eliminate thermal history, then the temperature is lowered to enable the sample to reach a crystalline state, and then the glass transition test is carried out. The glass transition temperature of the compound is increased, which indicates that the phenolic resin and the organic acid zinc react with each other in a molten state to generate chemical cross-linking bonds, and the chemical cross-linking bonds limit the movement of molecular chains of the phenolic resin. The organic acid zinc salt phenolic resin composite has undergone cross-linking of the organic acid zinc and the salt phenolic resin before the decomposition temperature is reached, with the result that the maximum thermal decomposition temperature of the composite is increased.
Test results 2 chemical melt blending method
A calorimetric System (FP900) to measure softening point, a differential scanning calorimeter (DSC1 start System) to measure glass transition temperature, a thermogravimetric and simultaneous thermal analyzer (TGA/DSC1 start System) to measure maximum thermal decomposition temperature.
TABLE 6 test results of examples 11 to 20
The softening point of the organic acid zinc salt phenolic resin compound prepared by the chemical melting blending method is increased by 5-10 ℃, and the increasing trends of the glass transition temperature and the maximum thermal decomposition temperature are consistent with the compound prepared by the physical crushing blending method. The compound prepared by the chemical melt blending method has a crosslinking reaction with the phenolic resin in the preparation process, so that the softening point of the compound is higher than that of the original resin, and the processing window is also adjusted.
The above examples of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (7)
1. An organic acid metal salt phenolic resin composite, characterized in that said composite has the following structure:
Wherein R is1Is hydrogen or hydroxymethyl; r2Is hydrogen or hydroxy;
R3hydrogen, straight chain or branched C4-C12 alkyl;
R4is methylene, a sulfur, a disulfide bond or CH2-(S)m-CH2M is an integer of 1 to 4;
R5is a linear or branched C1-C30 saturated or unsaturated alkyl group, a C6-C20 saturated or unsaturated alicyclic group, a C6-C20 aryl group;
m is Zn; n is an integer of 1 to 50;
the compound is prepared from the following raw materials by a physical crushing blending method or a chemical melting blending method, wherein the raw materials comprise the following components in parts by weight:
100 parts of phenolic resin;
40-100 parts of organic acid metal salt;
the physical crushing and blending method comprises the following steps: crushing and mixing the raw materials according to the amount of the raw materials to obtain an organic acid metal salt phenolic resin mixture, and heating the mixture to a molten state in the using process to form an organic acid metal salt phenolic resin compound;
the chemical melt blending process comprises the steps of: heating the phenolic resin to 100-200 ℃ under the protection of nitrogen to enable the phenolic resin to reach a molten state, adding organic acid metal salt, raising the reaction temperature to 160-210 ℃, and stirring for reaction for 10-60 minutes to obtain the organic acid metal salt phenolic resin compound.
2. The organic acid metal salt phenolic resin composite of claim 1, wherein:
R3is tert-butyl, tert-octyl, nonyl or dodecyl; n is an integer of 1 to 30.
3. The organic acid metal salt phenolic resin composite of claim 1, characterized in that the composite is prepared from raw materials comprising, in parts by weight:
100 parts of phenolic resin;
40-60 parts of organic acid metal salt.
4. The organic acid metal salt phenolic resin composite of claim 1, wherein:
the structure of the phenolic resin is shown as the following formula:
wherein R is1Is hydrogen or hydroxymethyl; r2Is hydrogen or hydroxy;
R3hydrogen, straight chain or branched C4-C12 alkyl;
R4is methylene, a sulfur, a disulfide bond or CH2-(S)m-CH2M is an integer of 1 to 4;
n is an integer of 1 to 50;
the organic acid metal salt structure is represented by the following formula:
wherein R is5Is a linear or branched C1-C30 saturated or unsaturated alkyl group, a C6-C20 saturated or unsaturated alicyclic group, a C6-C20 aryl group; m is Zn.
5. A method for preparing the organic acid metal salt phenolic resin composite according to any one of claims 1 to 4, characterized in that:
the preparation method comprises a physical crushing blending method or a chemical melting blending method;
the physical crushing and blending method comprises the following steps: crushing and mixing the raw materials according to the amount of the raw materials to obtain an organic acid metal salt phenolic resin mixture, and heating the mixture to a molten state in the using process to form an organic acid metal salt phenolic resin compound;
the chemical melt blending process comprises the steps of: heating the phenolic resin to 100-200 ℃ under the protection of nitrogen to enable the phenolic resin to reach a molten state, adding organic acid metal salt, raising the reaction temperature to 160-210 ℃, and stirring for reaction for 10-60 minutes to obtain the organic acid metal salt phenolic resin compound.
6. The method of preparing an organic acid metal salt phenolic resin composite as claimed in claim 5, characterized in that the physical pulverization blending method comprises the steps of:
mixing the raw materials according to the raw material amount, stirring at a high speed at the temperature of 10-30 ℃ for crushing for more than 3 times at intervals of 30-180 seconds each time, and heating to a molten state in the using process to obtain the organic acid metal salt phenolic resin compound.
7. The method of producing an organic acid metal salt phenolic resin composite according to claim 5, characterized in that:
the temperature of the molten phenolic resin is 130-200 ℃, the reaction temperature is 180-200 ℃, and the stirring reaction time is 20-40 minutes.
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