CN111349202A - Preparation method of phenolic resin and phenolic foam material - Google Patents
Preparation method of phenolic resin and phenolic foam material Download PDFInfo
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- CN111349202A CN111349202A CN202010365461.4A CN202010365461A CN111349202A CN 111349202 A CN111349202 A CN 111349202A CN 202010365461 A CN202010365461 A CN 202010365461A CN 111349202 A CN111349202 A CN 111349202A
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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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- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
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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
- C08J2361/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with monohydric phenols
- C08J2361/10—Phenol-formaldehyde condensates
Abstract
The invention discloses a preparation method of phenolic resin, which comprises the following steps: s1: adding phenol and paraformaldehyde into a reaction container, uniformly mixing, adding an amine catalyst for the first time, heating to 45-60 ℃, and carrying out heat preservation reaction; s2: adding an amine catalyst for the second time, heating to 65-75 ℃, and carrying out heat preservation reaction; s3: adding an inorganic base catalyst solution into a reaction system, heating, carrying out heat preservation reaction until the phenolic resin in the reaction vessel reaches a preset viscosity, adding urea, and adjusting the pH value. By controlling different alkali catalysts and different reaction temperatures, the exotherms of depolymerization reaction, addition reaction and condensation reaction in a phenol and paraformaldehyde system are staggered, so that the temperature of the reaction system is more controllable, and the requirement of mass production is met. The invention also discloses a phenolic foam material.
Description
Technical Field
The invention relates to the technical field of phenolic foam materials, in particular to a preparation method of phenolic resin and a phenolic foam material.
Background
Phenolic foam is widely used in the construction industry and the like due to its excellent fire resistance, thermal insulation and dimensional stability. Phenolic foam is generally produced by mixing, foaming and curing phenolic resin, a foaming agent, a surfactant, a curing agent or other additives, and the phenolic resin has a high specific gravity of the foaming material and is required to have an appropriate viscosity. The viscosity is too high, and the foaming multiplying power of the prepared phenolic foam is smaller; too low a viscosity results in failure to produce a formed phenolic foam.
The viscosity of the phenolic resin prepared by the reaction of conventional phenol and formaldehyde under the condition of alkali catalysis needs to be controlled by vacuum dehydration treatment. The wastewater generated by vacuum dehydration contains harmful substances such as phenol, aldehyde and low molecular polymer, and increases the environmental protection pressure and treatment cost of production. The improved technical scheme is that paraformaldehyde is used as a formaldehyde raw material and reacts with phenol under the alkali catalysis condition, such as CN103848951A, CN102936325A, CN1955206A, CN102838771A and the like, and the method has the beneficial effect that no wastewater is generated. However, the paraformaldehyde solid is added in batches, and the addition at a certain temperature has certain operation difficulty, so that the method is not suitable for batch production.
The depolymerization of paraformaldehyde is an exothermic reaction, and in a phenolic reaction system, the activation energy of the hydroxymethyl condensation reaction is higher than that of the phenolic addition reaction, so that the addition reaction is mainly carried out at low temperature, and the rates of the addition reaction and the condensation reaction at high temperature are correspondingly improved. CN102766243A discloses a room temperature expandable phenolic resin, wherein phenol is added into a reaction system, the temperature is raised to 50-60 ℃, then paraformaldehyde and a modifier are added, the temperature is raised to 65-70 ℃, the temperature is kept, and heating is adopted in the process to promote depolymerization of the paraformaldehyde. The temperature rise is obvious after the paraformaldehyde is fed for a period of time, so that aldehyde addition reaction and hydroxymethyl condensation reaction can be rapidly carried out, and the phenolic resin with preset viscosity is not obtained favorably.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a preparation method of phenolic resin, which is beneficial to formation of hydroxymethyl at low temperature in the presence of amine catalyst, and can quickly generate hydroxymethyl condensation to reach the required viscosity of phenolic resin at the condition of temperature rise after adding inorganic base catalyst.
In order to achieve the technical effects, the technical scheme of the invention is as follows: a preparation method of phenolic resin comprises the following steps:
s1: adding phenol and paraformaldehyde into a reaction container, uniformly mixing, adding an amine catalyst for the first time, heating to 45-60 ℃, and carrying out heat preservation reaction;
s2: adding an amine catalyst for the second time, heating to 65-75 ℃, and carrying out heat preservation reaction;
s3: adding an inorganic base catalyst solution into a reaction system, heating, carrying out heat preservation reaction until the phenolic resin in the reaction vessel reaches a preset viscosity, adding urea, and adjusting the pH value.
The preferable technical scheme is that the mole ratio of phenol to paraformaldehyde is 1: (1.5-3.0), wherein the predetermined viscosity of the phenolic resin in the S3 is 2000-8000 mPa.s. Further, the molar ratio of phenol to paraformaldehyde is 1: (1.7-2.5), and more preferably, the molar ratio of phenol to paraformaldehyde is 1: (1.8-2.5).
The preferable technical scheme is that the amine catalyst is one or the combination of more than two of triethylamine, dimethylethanolamine, triethylene diamine, cyclohexylamine and triethanolamine.
The preferable technical scheme is that the inorganic base catalyst is one or the combination of more than two of sodium hydroxide, potassium hydroxide and barium hydroxide.
The preferable technical scheme is that the adding mass of the amine catalyst in S1 is 1-5% of the mass of phenol, and the adding mass of the amine catalyst in S2 is 0.5-3% of the mass of phenol.
The preferable technical proposal is that the mass of the inorganic base catalyst is 0.075 to 0.375 percent of the mass of the phenol. Preferably, the mass of the inorganic base catalyst is 0.125-0.375% of the mass of the phenol.
The preferable technical scheme is that the heat preservation reaction temperature in S3 is 85-95 ℃.
The invention also aims to provide a phenolic foam material, wherein the foaming raw material of the phenolic foam material mainly comprises phenolic resin, a surfactant, a foaming agent, urea and an acid curing catalyst, the phenolic resin is prepared by the preparation method of the phenolic resin, and the foaming temperature of the foaming raw material is 70-80 ℃.
The preferable technical scheme is that the foaming raw material mainly comprises, by weight, 100 parts of phenolic resin, 2-8 parts of surfactant, 3-15 parts of foaming agent, 2-8 parts of urea and 5-30 parts of acid curing catalyst.
The invention has the advantages and beneficial effects that:
according to the preparation method of the phenolic resin, the amine catalyst is added in batches, the paraformaldehyde begins to depolymerize at about 50 ℃ in a mixed system of phenol and the amine catalyst, and the paraformaldehyde can be promoted to depolymerize at a proper reaction rate under the condition of 45-60 ℃ in S1, and the reaction system can be maintained in the temperature range;
the alkalescence of the amine catalyst is weak, the paraformaldehyde in S1 is fully depolymerized under the alkalescence condition, and the temperature in the depolymerization process cannot be increased rapidly; in the S2 reaction, phenol and formaldehyde are subjected to nucleophilic addition to generate 2, 4-dimethylol phenol and 2, 6-dimethylol phenol which contain more hydroxymethyl; carrying out the condensation reaction catalyzed by strong base of S3; through the control of different alkali catalysts, different reaction temperatures and different reaction times, the exotherms of depolymerization reaction, addition reaction and condensation reaction in a phenol and paraformaldehyde system are staggered, so that the temperature of the reaction system is more controllable, and the requirement of mass production is met.
The amine catalyst is mainly beneficial to controlling the depolymerization process of the paraformaldehyde, and other alkaline catalysts are not beneficial to controlling the depolymerization temperature. Inorganic alkali such as sodium hydroxide has stronger catalytic performance on the phenol formaldehyde polycondensation reaction, not only can shorten the reaction time, but also the obtained phenolic foam has better performance. The final viscosity and activity of the resin are controlled by reaction temperature and time, the reaction time is short, the molecular weight of the resin is small, the viscosity of the resin is small, the resin is not beneficial to foaming, the reaction time is too long, the viscosity of the resin is large, the activity is reduced, the mixing of materials is not beneficial during foaming, and the leveling property is poor; different reaction times can affect the structure of the resin, the reaction temperature is too high, the condensation reaction rate is accelerated, the molecular weight distribution of the resin is not uniform, and the foaming is not facilitated.
Detailed Description
The following further describes embodiments of the present invention with reference to examples. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Foaming raw material of phenolic resin
The basic composition of the foaming raw material comprises thermosetting starch modified phenolic resin, a surfactant, a foaming agent and an acid curing agent, and other functional auxiliary agents such as a toughening agent, a smoke suppressant, a flame retardant, a filler and the like which are known in the foaming raw material of the phenolic foam can be selectively added, so that the foam has corresponding functions.
Foam piece made of phenolic foam
Phenolic foam may be used in the manufacture of related products including, but not limited to, panels, coils, and coated products having a predetermined structure. Furthermore, the foaming body can be compounded and foamed with metal foil, color steel, non-woven fabric and glass fiber fabric to prepare a composite product in which the foaming body and the materials are integrally connected.
In the steps of the preparation method of the phenolic resin, reaction end points of S1 and S2 are obtained through sampling detection, specifically, the reaction time of S1 is 40-100 min, and preferably 60-80 min; the reaction time of S2 is 50-90 min, preferably 60-80 min.
Example 1
Adding 100 parts of phenol and 57 parts of paraformaldehyde solution (the molar ratio of the phenol to the paraformaldehyde is 1: 1.8 in terms of formaldehyde) into a reactor in sequence, then adding 1.5 parts of dimethylethanolamine, slowly heating to 55 ℃, continuously adding 1.0 part of dimethylethanolamine after reacting for 60min, slowly heating to 65 ℃, reacting for 60min, adding 0.5 part of 25% sodium hydroxide solution, heating to 85 ℃, reacting to reach the resin viscosity of 3000mPa & s/25 ℃ (adding the sodium hydroxide solution until the reaction time reaching the resin viscosity is 90min), adding 5 parts of urea, cooling the reaction solution, adding acid to adjust the pH value of the system to 7, and obtaining the phenolic resin.
Example 2
Adding 100 parts of phenol and 57 parts of paraformaldehyde solution (the molar ratio of the phenol to the paraformaldehyde is 1: 1.8 in terms of formaldehyde) into a reactor in sequence, then adding 1.5 parts of dimethylethanolamine, slowly heating to 55 ℃, continuously adding 1.0 part of dimethylethanolamine after reacting for 60min, slowly heating to 65 ℃, reacting for 75min, adding 0.5 part of 25% potassium hydroxide aqueous solution, heating to 85 ℃, keeping the temperature and reacting for 105min, adding 5 parts of urea, cooling the reaction solution, and adding acid to adjust the pH value of the system to 7 to obtain the phenolic resin.
Example 3
Adding 100 parts of phenol and 57 parts of paraformaldehyde solution into a reactor in sequence, then adding 1.0 part of dimethylethanolamine, slowly heating to 55 ℃, continuously adding 0.5 part of dimethylethanolamine after reacting for 60min, slowly heating to 65 ℃, reacting for 60min, adding 1.5 parts of 25% sodium hydroxide aqueous solution, heating to 85 ℃, preserving heat, reacting for 85min, adding 5 parts of urea, cooling the reaction solution, and adding acid to adjust the pH value of the system to 7 to obtain the phenolic resin.
Example 4
Adding 100 parts of phenol and 64 parts of paraformaldehyde solution (the molar ratio of the phenol to the paraformaldehyde is 1: 2 in terms of formaldehyde) into a reactor in sequence, then adding 1.0 part of dimethylethanolamine, slowly heating to 55 ℃, continuously adding 3.0 parts of dimethylethanolamine after reacting for 60min, slowly heating to 65 ℃, reacting for 60min, adding 0.5 part of 25% sodium hydroxide aqueous solution, heating to 95 ℃, keeping the temperature, reacting for 85min, adding 5 parts of urea, cooling the reaction solution, and adding acid to adjust the pH value of the system to 7 to obtain the phenolic resin.
Example 5
Adding 100 parts of phenol and 64 parts of paraformaldehyde solution into a reactor in sequence, then adding 1.0 part of triethylamine, slowly heating to 60 ℃, continuously adding 1.0 part of triethylamine after reacting for 60min, slowly heating to 70 ℃, reacting for 60min, adding 0.5 part of 25% sodium hydroxide aqueous solution, heating to 90 ℃, reacting to reach the resin viscosity of 4000mPa & s/25 ℃, adding 5 parts of urea, cooling the reaction solution, and adding acid to adjust the pH value of the system to 7 to obtain the phenolic resin.
Example 6
Adding 100 parts of phenol and 80 parts of paraformaldehyde solution (the molar ratio of the phenol to the paraformaldehyde is 1: 2.5 in terms of formaldehyde) into a reactor in sequence, then adding 5.0 parts of dimethylethanolamine, slowly heating to 55 ℃, continuously adding 1.5 parts of dimethylethanolamine after reacting for 80min, slowly heating to 70 ℃ for reacting for 80min, adding 0.5 part of 25% sodium hydroxide aqueous solution, heating to 90 ℃, keeping the temperature for reacting for 95min, adding 5 parts of urea, cooling the reaction solution, and adding acid to adjust the pH value of the system to 7 to obtain the phenolic resin.
Comparative example 1
Comparative example is based on example 1 with the difference that in comparative example 1, instead of sodium hydroxide in aqueous sodium hydroxide solution, equimolar dimethylethanolamine was added to the reaction system, likewise heated to 85 ℃ to react to a resin viscosity of 3000 mPas/25 ℃, and dimethylethanolamine was added until the reaction time to reach the resin viscosity was 115 min.
Comparative examples 2 to 3
Comparative examples 2-3 are based on example 1 except that the first and second additions of dimethylethanolamine to the reaction system of comparative example 2 are combined in the first addition; the dimethylethanolamine added in the first and second additions to the reaction system in comparative example 3 were combined in the second addition.
The amine of comparative example 2 and the amine of comparative example 3 are added together, and the temperature of the phenolic resin reaction system rises too fast due to the concentrated release of the depolymerization temperature, so that the reaction liquid is sprayed out of the kettle, and the reaction cannot be carried out.
The phenolic resins of examples 1-6 and comparative example 1 were used as raw materials to prepare phenolic resins according to the following formulation and process: mixing phenolic resin 100 parts, castor oil polyoxyethylene ether 4 parts, urea powder 4 parts, isopentane/1-chloro-3.3.3-trifluoropropene (80/20 by weight) in advance; 20 parts of liquid p-toluenesulfonic acid/phenolsulfonic acid (weight ratio 70/30) with the concentration of 80 percent are quickly and uniformly stirred at the temperature of 20 ℃ and are placed in an oven at the temperature of 75 ℃ for 30min to obtain the phenolic foam.
The low thermal conductivity phenolic foam materials prepared by the phenolic resins of the examples and the comparative examples are tested by the following performances:
1) coefficient of thermal conductivity: a foam sample having a length of 30cm and a width of 30cm was placed between a hot plate at 35 ℃ and a cold plate at 15 ℃ of a thermal conductivity meter to perform measurement. According to GB/T10294/ISO 8032:1991, the thermal properties of phenolic foam boards are determined by means of a hot plate protection device;
2) compressive strength: the measurements were performed according to GB/T8813: the compressive stress at which the relative deformation of the rigid foam became 10% was measured.
The results of the performance tests obtained in the examples and comparative examples are shown in the following table:
| test specimen | Thermal conductivity/W/mK | Compressive strength/kPa |
| Example 1 | 0.0215 | 170 |
| Example 2 | 0.0204 | 185 |
| Example 3 | 0.0224 | 168 |
| Example 4 | 0.0222 | 175 |
| Example 5 | 0.0208 | 180 |
| Example 6 | 0.0215 | 175 |
| Comparative example 1 | 0.0254 | 155 |
In the comparative example 1, the amine catalyst is used for replacing the inorganic base catalyst to catalyze the polycondensation reaction of phenol and formaldehyde, the reaction time for reaching the preset viscosity is longer, the activity of the phenolic resin is reduced, and based on the same foaming raw material formula, the thermal conductivity coefficient of the obtained phenolic foam material is obviously higher than that of the embodiment, and the compression strength is poorer.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the technical principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. The preparation method of the phenolic resin is characterized by comprising the following steps:
s1: adding phenol and paraformaldehyde into a reaction container, uniformly mixing, adding an amine catalyst for the first time, heating to 45-60 ℃, and carrying out heat preservation reaction;
s2: adding an amine catalyst for the second time, heating to 65-75 ℃, and carrying out heat preservation reaction;
s3: adding an inorganic base catalyst solution into a reaction system, heating, carrying out heat preservation reaction until the phenolic resin in the reaction vessel reaches a preset viscosity, adding urea, and adjusting the pH value.
2. The method for preparing a phenol-formaldehyde resin according to claim 1, wherein the molar ratio of phenol to paraformaldehyde is 1: (1.5-3.0), wherein the predetermined viscosity of the phenolic resin in the S3 is 2000-8000 mPa.s.
3. The method for preparing phenolic resin according to claim 1, wherein the amine catalyst is one or more selected from triethylamine, dimethylethanolamine, triethylenediamine, cyclohexylamine, and triethanolamine.
4. The method for producing the phenol resin according to claim 1, wherein the inorganic base catalyst is one or a combination of two or more of sodium hydroxide, potassium hydroxide and barium hydroxide.
5. The method for producing a phenol resin according to claim 1, wherein the mass of the amine catalyst added in S1 is 1 to 5% of the mass of phenol, and the mass of the amine catalyst added in S2 is 0.5 to 3% of the mass of phenol.
6. The method for preparing phenolic resin according to claim 1, wherein the mass of the inorganic base catalyst is 0.075-0.375% of the mass of phenol.
7. The method for preparing the phenolic resin according to claim 1, wherein the temperature of the heat preservation reaction in S3 is 85-95 ℃.
8. A phenolic foam material is characterized in that a foaming raw material of the phenolic foam material mainly comprises phenolic resin, a surfactant, a foaming agent, urea and an acid curing catalyst, wherein the phenolic resin is prepared by the preparation method of the phenolic resin according to any one of claims 1 to 7, and the foaming temperature of the foaming raw material is 70-80 ℃.
9. The phenolic foam material of claim 8, wherein the foaming raw material comprises, by weight, 100 parts of phenolic resin, 2-8 parts of surfactant, 3-15 parts of foaming agent, 2-8 parts of urea, and 5-30 parts of acid curing catalyst.
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| CN202010365461.4A CN111349202A (en) | 2020-04-30 | 2020-04-30 | Preparation method of phenolic resin and phenolic foam material |
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| CN202010365461.4A CN111349202A (en) | 2020-04-30 | 2020-04-30 | Preparation method of phenolic resin and phenolic foam material |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4539338A (en) * | 1982-07-09 | 1985-09-03 | Koppers Company, Inc. | Phenol formaldehyde resoles for making phenolic foam |
| CN101885818A (en) * | 2010-07-02 | 2010-11-17 | 北京化工大学 | Method for synthesizing expandable phenolic resin |
| CN102766243A (en) * | 2012-07-25 | 2012-11-07 | 胡玉 | Room-temperature foamable phenolic resin and method for preparing phenolic foams by same |
| CN103865016A (en) * | 2014-03-20 | 2014-06-18 | 新疆科西嘉新材料有限公司 | Preparation method of expandable phenolic resin |
-
2020
- 2020-04-30 CN CN202010365461.4A patent/CN111349202A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4539338A (en) * | 1982-07-09 | 1985-09-03 | Koppers Company, Inc. | Phenol formaldehyde resoles for making phenolic foam |
| CN101885818A (en) * | 2010-07-02 | 2010-11-17 | 北京化工大学 | Method for synthesizing expandable phenolic resin |
| CN102766243A (en) * | 2012-07-25 | 2012-11-07 | 胡玉 | Room-temperature foamable phenolic resin and method for preparing phenolic foams by same |
| CN103865016A (en) * | 2014-03-20 | 2014-06-18 | 新疆科西嘉新材料有限公司 | Preparation method of expandable phenolic resin |
Non-Patent Citations (1)
| Title |
|---|
| 左继成等: "氢氧化钠催化多聚甲醛与苯酚缩聚工艺对树脂性能的影响", 《化学与黏合》 * |
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Application publication date: 20200630 |