CN114685742B - Preparation method of phenolic resin - Google Patents
Preparation method of phenolic resin Download PDFInfo
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- CN114685742B CN114685742B CN202011622018.7A CN202011622018A CN114685742B CN 114685742 B CN114685742 B CN 114685742B CN 202011622018 A CN202011622018 A CN 202011622018A CN 114685742 B CN114685742 B CN 114685742B
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 41
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title abstract description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 150000002989 phenols Chemical class 0.000 claims abstract description 20
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 20
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- -1 aldehyde compound Chemical class 0.000 claims abstract description 14
- 230000009471 action Effects 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000853 adhesive Substances 0.000 claims description 9
- 230000001070 adhesive effect Effects 0.000 claims description 9
- 239000002023 wood Substances 0.000 claims description 9
- 239000008098 formaldehyde solution Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 53
- 230000035484 reaction time Effects 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 6
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 abstract description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 abstract description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 abstract description 4
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 abstract description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 abstract description 4
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 238000004513 sizing Methods 0.000 description 5
- 238000007731 hot pressing Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- YCOXTKKNXUZSKD-UHFFFAOYSA-N 3,4-xylenol Chemical compound CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 241000219000 Populus Species 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- HFJRKMMYBMWEAD-UHFFFAOYSA-N dodecanal Chemical compound CCCCCCCCCCCC=O HFJRKMMYBMWEAD-UHFFFAOYSA-N 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical group [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 239000002783 friction material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention discloses a preparation method of phenolic resin. The preparation method of the phenolic resin comprises the following steps: under the action of a catalyst, carrying out polycondensation reaction on a phenolic compound and an aldehyde compound in a micro-channel reactor; wherein the phenolic compound is one or more of phenol, resorcinol, m-cresol, o-cresol, p-cresol and 3, 5-xylenol; the structural formula of the aldehyde compound is R-CHO, R is H, C 1 ～C 3 Alkyl group
Description
Technical Field
The invention relates to a preparation method of phenolic resin.
Background
At present, the production capacity, the process level and the product quality of the phenolic resin in China are greatly improved, the annual yield of the phenolic resin in China reaches 111.90 ten thousand tons, and exceeds 20 percent of the global yield of the phenolic resin. In 2018, in the main application fields of phenolic resin products in China, the proportions of three application fields of phenolic molding compounds, wood processing, laminated boards and grinding and friction materials in the total consumption amount are 22.5%, 20.5% and 20.0% respectively. The phenolic resin has the advantages of high bonding strength, good water resistance and good weather resistance due to the unique reticular cross-linked molecular structure, and the phenolic resin has increasingly used in the fields of wood processing and laminated boards. However, the reported phenolic resin still has the defects of high formaldehyde release and the like. For example, the chinese patent application No. 201710358550.4 provides a method for modifying phenolic resin adhesive, which modifies phenolic resin to reduce formaldehyde release to a certain extent, but has limited reduction, and still has formaldehyde release of 0.11-0.142 mg/L, and the reaction time is as long as 100min.
The microchannel reactor is a continuous pipe reactor, a reaction device with characteristic dimension between 10 and 1000 microns manufactured by micro-processing technology, and controls chemical reaction in micro space. Compared with the traditional batch reaction process, the microchannel reactor has the advantages of high-speed mixing, high-efficiency heat transfer, narrow residence time distribution, good repeatability, rapid system response, convenience in automatic control, no obvious amplification effect, high safety performance and the like. However, microchannel reactors are generally suitable for reactions with relatively short reaction times, and can only achieve desired reaction completion levels by controlling reaction temperatures, flow rates, residence times, and other critical parameters to desired conditions. It can be seen that not all reactions can be performed in a microchannel reactor. The reaction type for preparing the phenolic resin belongs to polycondensation reaction, and when the reaction is carried out in a micro-channel, a pipeline is easy to be blocked, equipment is damaged, and thus, the report on the aspect of synthesizing the phenolic resin by utilizing a micro-channel reactor in a continuous mode is not seen so far.
Therefore, there is a need in the art to develop a method for preparing phenolic resin with high reaction efficiency, short reaction time and low formaldehyde emission.
Disclosure of Invention
The invention aims to overcome the defects of long time consumption, low reaction efficiency, high formaldehyde release of the prepared product and the like of the method for preparing the phenolic resin in the prior art, and provides the preparation method of the phenolic resin. The preparation method can be completed in a short time, has high reaction efficiency, does not block a pipeline, has better application performance of the product, greatly reduces formaldehyde release amount and has better bonding strength; the whole reaction process is airtight, the volatilization amount of raw materials is small, and the smell is small; the stability of the phenolic resin is ensured, and the product quality is ensured.
The invention solves the technical problems through the following technical proposal.
The invention provides a preparation method of phenolic resin, which comprises the following steps: under the action of a catalyst, carrying out polycondensation reaction on a phenolic compound and an aldehyde compound in a micro-channel reactor; wherein the phenolic compound is one or more of phenol, resorcinol, m-cresol, o-cresol, p-cresol and 3, 5-xylenol; the structural formula of the aldehyde compound isR-CHO, R is H, C 1 ～C 3 Alkyl groupOne or more of the following; the time of the polycondensation reaction is 1-4 min.
In the present invention, the catalyst may be a basic catalyst conventionally used in the art for catalyzing polycondensation reaction, preferably one or more of a hydroxide catalyst, a carbonate catalyst and a sulfite catalyst, more preferably a hydroxide catalyst.
Wherein the hydroxide catalyst is preferably one or more of barium hydroxide, calcium hydroxide, copper hydroxide, ferric hydroxide, sodium hydroxide and potassium hydroxide, more preferably sodium hydroxide.
Wherein the carbonate catalyst is preferably one or more of sodium carbonate, potassium carbonate and sodium bicarbonate.
Wherein the sulfite catalyst is sodium sulfite.
In the present invention, the phenolic compound is preferably phenol.
In the present invention, the aldehyde compound is preferably formaldehyde.
In the present invention, when the aldehyde compound is formaldehyde, the formaldehyde may be added in the form of a formaldehyde solution according to the conventional art.
The solvent in the formaldehyde solution may be a solvent which is conventionally used in the art to completely solvent the formaldehyde, and is preferably water.
Wherein, in the formaldehyde solution, the mass percentage of formaldehyde can be conventional in the field and can be generally 36.7-37%.
In the present invention, the molar ratio of the phenolic compound to the aldehyde compound may be a molar ratio conventional in this type of reaction in the art, preferably 1: (1.5 to 2.2), more preferably 1: (2-2.2).
In the present invention, the molar ratio of the catalyst to the phenolic compound may be a molar ratio conventional in this type of reaction in the art, preferably 1: (0.4 to 0.9), more preferably 1: (0.7-0.9).
In the present invention, the temperature of the polycondensation reaction may be a temperature conventional in the art, preferably 110 to 180 ℃, more preferably 150 to 180 ℃.
In the present invention, the time of the polycondensation reaction is preferably 1 to 2 minutes. The polymerization time is the residence time of the reactants within the microchannel reactor.
In a preferred embodiment, the method for preparing the phenolic resin comprises the following steps: carrying out the polycondensation reaction of the mixture A and the mixture B in the microchannel reactor; wherein the mixed material A is a mixture of the phenolic compound, the aldehyde compound and a solvent; the mixture B is a mixture of the catalyst and a solvent.
Wherein, in the mixture A, the solvent can be a solvent conventionally used in the art for such reactions, preferably water.
The preparation method of the mixture A can be conventional in the field, and generally comprises the following steps: the phenolic compound, the aldehyde compound and the solvent are mixed.
Wherein the molar ratio of the phenolic compound to the solvent in the mixture a may be a molar ratio conventional in this type of reaction in the art, preferably 1: (1.5 to 3.5), more preferably 1: (1.7 to 3.4), for example, 1:3.2.
wherein, in the mixture B, the solvent may be a solvent which is conventionally used in the art to completely solvent the catalyst, preferably water.
Wherein the mass percent of the catalyst in the mixture B may be conventional in the art, preferably 30% to 35%, more preferably 32%.
In certain embodiments of the invention, the mixture a and the mixture B may be fed simultaneously in the microchannel reactor.
In a more preferred embodiment, the method for preparing the phenolic resin comprises the following steps: and the mixed material A and the mixed material B respectively enter the micro-channel reactor through a feeding controller at the same time to carry out the polycondensation reaction.
The flow rate of the mixed material A is within the allowable range of the flow rate of the micro-channel reactor, and the mixed material A and the mixed material B can be controlled to complete feeding at the same time.
The flow rate of the mixture B is within the allowable range of the flow rate of the micro-channel reactor, and the mixture A and the mixture B can be controlled to complete feeding at the same time.
In certain embodiments of the invention, the polycondensation reaction may be conducted in the reaction environment of the microchannel reactor. The reaction environment comprises one or more reaction units. The reaction environment is formed by connecting a plurality of reaction units in series or in parallel, and each reaction unit can realize feeding, mixing, heat exchange, reaction and discharging. Each reaction unit is provided with one or more material inlets and one or more material outlets.
In the present invention, the reaction environment of the microchannel reactor may have a capacity conventional in the art, and may be generally 70 to 90mL, preferably 70 to 80mL.
Each of the reaction units may be provided with a separate heating system for heating the reaction unit. The heating system may be an oil bath.
On the basis of conforming to the common knowledge in the field, the above preferred conditions can be arbitrarily combined to obtain the preferred examples of the invention.
The reagents and materials used in the present invention are commercially available.
The invention has the positive progress effects that: according to the invention, the phenolic resin is prepared in the microchannel reactor, so that the reaction is completed in a short time, the reaction efficiency is greatly improved, a pipeline is not blocked, the application performance of the product is better, the formaldehyde release amount is greatly reduced, and the bonding strength is better; the whole reaction process is airtight, the volatilization amount of raw materials is small, and the smell is small; the stability of the phenolic resin is ensured, and the product quality is ensured.
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
The microchannel reactor used in the examples below included a feed controller, a reaction unit, and a heating system. The liquid capacity of the reaction units is fixed, a plurality of reaction units form a reaction environment, the polycondensation reaction is carried out in the reaction environment, and the liquid capacity of the reaction environment is 80mL; the feed controller can control the feed speed and reaction time; the heating system heats the reaction unit for the oil bath.
The parts in the following examples and comparative examples are parts by mass.
Example 1
(1) Uniformly mixing 60.8 parts of deionized water, 100 parts of phenol and 129.38 parts of 37% formaldehyde aqueous solution according to a certain proportion to prepare a mixed material A; the molar ratio of phenol to formaldehyde is 1:1.5; the molar ratio of phenol to deionized water is 1:3.2;
53.19 parts of 32% sodium hydroxide aqueous solution by mass percent is prepared, namely a mixed material B; the molar ratio of phenol to sodium hydroxide is 1:0.4;
(2) The flow rate of the feeding controller is regulated, so that the mixed material A and the mixed material B can be added at the same time;
(3) Raising the temperature of the reaction environment to 110 ℃, starting feeding, and carrying out the reaction for 4min;
(4) Continuously reacting until the raw materials are used up to obtain phenolic resin; after the reaction, deionized water is used for cleaning the channel of the micro-reactor, and the reaction is closed.
Example 2
(1) Uniformly mixing 30.21 parts of deionized water, 94 parts of phenol and 178.38 parts of 37% formaldehyde aqueous solution according to a certain proportion to prepare a mixed material A; the molar ratio of phenol to formaldehyde is 1:2.2; the molar ratio of phenol to deionized water is 1:1.7;
112.5 parts of 32% sodium hydroxide aqueous solution by mass percentage is prepared, namely a mixed material B; the molar ratio of phenol to sodium hydroxide is 1:0.9;
(2) The flow rate of the feeding controller is regulated, so that the mixed material A and the mixed material B can be added at the same time;
(3) Raising the temperature of the reaction environment to 180 ℃, starting feeding, and carrying out the reaction for 1min;
(4) Continuously reacting until the raw materials are used up to obtain phenolic resin; after the reaction, deionized water is used for cleaning the channel of the micro-reactor, and the reaction is closed.
Example 3
(1) Uniformly mixing 60.78 parts of deionized water, 94 parts of phenol and 162.16 parts of 37% formaldehyde aqueous solution according to a certain proportion to prepare a mixed material A; the molar ratio of phenol to formaldehyde is 1:2; the molar ratio of phenol to deionized water is 1:3.4;
preparing 87.5 parts of 32% sodium hydroxide aqueous solution, namely a mixed material B; the molar ratio of phenol to sodium hydroxide is 1:0.7;
(2) The flow rate of the feeding controller is regulated, so that the mixed material A and the mixed material B can be added at the same time;
(3) Raising the temperature of the reaction environment to 150 ℃, starting feeding, and carrying out the reaction for 2min;
(4) Continuously reacting until the raw materials are used up to obtain phenolic resin; after the reaction, deionized water is used for cleaning the channel of the micro-reactor, and the reaction is closed.
Comparative example 1
The modified phenolic resin is prepared according to the following steps: 150g of phenolic resin adhesive is added into a reaction kettle, stirred, heated to 30 ℃ and kept at the temperature for 10min; adding liquid alkali into a reaction kettle to adjust the pH value to 12, heating to 80 ℃, adding 50g of lignin, and preserving the temperature for 90min; cooling to 25 ℃ and discharging to obtain the phenolic resin.
Comparative example 2
The difference compared to example 1 is only that the phenolic compound is 3, 4-xylenol, the other conditions being the same as in example 1.
Comparative example 3
The difference compared with example 1 is that the aldehyde compound is lauraldehyde, and other condition parameters are the same as example 1.
Comparative example 4
The difference compared to example 1 is only that the polycondensation reaction time is 0.5min, the other conditions parameters are the same as in example 1.
Comparative example 5
The difference compared to example 1 is only that the polycondensation reaction time is 6min, the other conditions parameters are the same as in example 1.
Effect example 1
And (3) glue preparation: the phenolic resins prepared in the examples and the comparative examples are uniformly mixed with industrial flour respectively, the sizing agent is prepared for standby, and the mass ratio of the phenolic resin to the industrial flour is 4:1.
sizing: respectively pouring the sizing agent prepared by the steps into a glue spreader, and controlling the sizing amount of the two sides of the poplar bark to be 350g/m 2 Paving into 5 layers of poplar plywood by using a interlayer sizing method;
cold pressing: placing the paved base material into a cold press, and cold pressing for 30-50 min under the condition of 0.6-0.8 MPa;
hot pressing: and (3) putting the base material subjected to cold pressing into a hot press, and performing hot pressing at the temperature of 140 ℃ and the pressure of 0.8-1 MPa, wherein the hot pressing speed is 1min/mm, the hot pressing time is 15min, and the pressure is released and exhausted for 3min until the pressure is 0.
The bonding strength of the plate prepared by the method is tested according to 4.17.5.2.3 in national standard GB/T17657-2013, and the specification of a test sample is 10 x 2.5cm; the formaldehyde release amount of the plate prepared by the method is tested according to the dryer method in national standard GB/T17657-2013, the specification of a test sample is 15 x 5cm, and the result is shown in Table 1.
TABLE 1
Claims (7)
1. A method for preparing phenolic resin used as wood adhesive, which is characterized by comprising the following steps: under the action of an alkaline catalyst, the mixed material A and the mixed material B carry out polycondensation reaction in a micro-channel reactor; wherein the mixed material A is a mixture of phenolic compounds, aldehyde compounds and solvents; the mixed material B is a mixture of a catalyst and a solvent;
wherein the phenolic compound is phenol;
the aldehyde compound is formaldehyde;
the alkaline catalyst is sodium hydroxide;
in the mixed material A, the solvent is water;
in the mixture A, the molar ratio of the phenolic compound to the solvent is 1: (1.5-3.5);
the molar ratio of the phenolic compound to the aldehyde compound is 1: (1.5-2.2);
the molar ratio of the phenolic compound to the catalyst is 1: (0.4 to 0.9);
the temperature of the polycondensation reaction is 110-180 ℃, and the time of the polycondensation reaction is 1-4 min.
2. The method for preparing a phenolic resin for wood adhesives according to claim 1, wherein the formaldehyde is added in the form of a formaldehyde solution;
and/or the time of the polycondensation reaction is 1-2 min.
3. The method for preparing a phenolic resin for wood adhesives according to claim 2, wherein the solvent in the formaldehyde solution is water;
and/or, in the formaldehyde solution, the mass percentage of formaldehyde is 36.7% -37%;
and/or the molar ratio of the phenolic compound to the aldehyde compound is 1: (2-2.2);
and/or the molar ratio of the phenolic compound to the catalyst is 1: (0.7 to 0.9);
and/or the temperature of the polycondensation reaction is 150-180 ℃.
4. The method for producing a phenolic resin for wood adhesives according to claim 1, wherein in the mixture B, the solvent is water;
and/or, in the mixed material B, the mass percentage of the catalyst is 30% -35%;
and/or, in the microchannel reactor, the mixture a and the mixture B are fed simultaneously.
5. The method of preparing phenolic resin for wood adhesives according to claim 1, wherein the molar ratio of phenolic compound to solvent in the mixture a is 1: (1.7-3.4);
and/or, in the mixed material B, the mass percentage of the catalyst is 32%.
6. The method of preparing phenolic resin for wood adhesives according to claim 5, wherein the molar ratio of phenolic compound to solvent in the mixture a is 1:3.2.
7. the method for preparing the phenolic resin used as the wood adhesive according to any one of claims 4 to 6, wherein the method for preparing the phenolic resin comprises the following steps: and the mixed material A and the mixed material B respectively enter the micro-channel reactor through a feeding controller at the same time to carry out the polycondensation reaction.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20060073836A (en) * | 2004-12-24 | 2006-06-29 | 한국화학연구원 | Process for preparing molecular weight-controlled resol type phenolic resin |
| CN104327227A (en) * | 2014-11-18 | 2015-02-04 | 西安元创化工科技股份有限公司 | Method for synthesizing phenolic resin |
| CN104828803A (en) * | 2015-03-23 | 2015-08-12 | 山东省科学院能源研究所 | A preparing method of a monodisperse phenolic resin carbon microbead |
| CN109354660A (en) * | 2018-11-23 | 2019-02-19 | 山东圣泉新材料股份有限公司 | A kind of automobile filter paper phenolic resin and preparation method thereof and automobile filter paper |
| CN110527041A (en) * | 2019-10-12 | 2019-12-03 | 山东阳谷华泰化工股份有限公司 | A kind of synthetic method of phenolic resin |
| CN110564346A (en) * | 2019-09-20 | 2019-12-13 | 上海昶法新材料有限公司 | Modified phenolic glue and preparation method thereof |
| CN111944464A (en) * | 2020-07-02 | 2020-11-17 | 上海昶法新材料有限公司 | Modified phenolic resin adhesive and preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8383703B2 (en) * | 2006-10-09 | 2013-02-26 | British American Tobacco (Investments) Limited | Making discrete solid particles of polymeric material |
| CN107501050A (en) * | 2017-08-28 | 2017-12-22 | 常州大学 | A kind of method that phenol is prepared using micro passage reaction |
-
2020
- 2020-12-31 CN CN202011622018.7A patent/CN114685742B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20060073836A (en) * | 2004-12-24 | 2006-06-29 | 한국화학연구원 | Process for preparing molecular weight-controlled resol type phenolic resin |
| CN104327227A (en) * | 2014-11-18 | 2015-02-04 | 西安元创化工科技股份有限公司 | Method for synthesizing phenolic resin |
| CN104828803A (en) * | 2015-03-23 | 2015-08-12 | 山东省科学院能源研究所 | A preparing method of a monodisperse phenolic resin carbon microbead |
| CN109354660A (en) * | 2018-11-23 | 2019-02-19 | 山东圣泉新材料股份有限公司 | A kind of automobile filter paper phenolic resin and preparation method thereof and automobile filter paper |
| CN110564346A (en) * | 2019-09-20 | 2019-12-13 | 上海昶法新材料有限公司 | Modified phenolic glue and preparation method thereof |
| CN110527041A (en) * | 2019-10-12 | 2019-12-03 | 山东阳谷华泰化工股份有限公司 | A kind of synthetic method of phenolic resin |
| CN111944464A (en) * | 2020-07-02 | 2020-11-17 | 上海昶法新材料有限公司 | Modified phenolic resin adhesive and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 柴春鹏等.高分子合成材料学.北京理工大学出版社,2019,291-296. * |
| 苯酚-尿素-甲醛三元共缩聚树脂合成工艺的研究;徐亮;杨建洲;;化学与粘合(第03期);197-199 * |
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