CN113461886B - Fast-curing phenolic resin and application thereof - Google Patents
Fast-curing phenolic resin and application thereof Download PDFInfo
- Publication number
- CN113461886B CN113461886B CN202110624059.8A CN202110624059A CN113461886B CN 113461886 B CN113461886 B CN 113461886B CN 202110624059 A CN202110624059 A CN 202110624059A CN 113461886 B CN113461886 B CN 113461886B
- Authority
- CN
- China
- Prior art keywords
- phenolic resin
- curing
- phenol
- mass
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000005011 phenolic resin Substances 0.000 title abstract description 22
- 229920001568 phenolic resin Polymers 0.000 title abstract description 22
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 65
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 53
- 238000006243 chemical reaction Methods 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 28
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 14
- 239000001913 cellulose Substances 0.000 claims description 14
- 229920002678 cellulose Polymers 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 12
- 239000008098 formaldehyde solution Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 238000007599 discharging Methods 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000006467 substitution reaction Methods 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 239000002023 wood Substances 0.000 abstract description 26
- 238000004519 manufacturing process Methods 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 12
- 239000000853 adhesive Substances 0.000 abstract description 7
- 230000001070 adhesive effect Effects 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000006872 improvement Effects 0.000 abstract description 2
- 231100000053 low toxicity Toxicity 0.000 abstract description 2
- 239000011120 plywood Substances 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000012986 modification Methods 0.000 description 11
- 230000004048 modification Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 238000005520 cutting process Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 238000009740 moulding (composite fabrication) Methods 0.000 description 9
- 238000003825 pressing Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 238000011282 treatment Methods 0.000 description 8
- 230000000087 stabilizing effect Effects 0.000 description 7
- 238000005452 bending Methods 0.000 description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 6
- 230000003068 static effect Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 150000001299 aldehydes Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 150000002895 organic esters Chemical class 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- HGRQXFSEUWLBTH-UHFFFAOYSA-N [Na].C1(OCC(C)O1)=O Chemical compound [Na].C1(OCC(C)O1)=O HGRQXFSEUWLBTH-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- -1 aldehyde compounds Chemical class 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 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
- C08G8/28—Chemically modified polycondensates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/34—Organic impregnating agents
- B27K3/50—Mixtures of different organic impregnating agents
-
- 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)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Forests & Forestry (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to a fast-curing phenolic resin and application thereof. The water-soluble rapid-curing modified phenolic resin prepared by the method has the advantages of high curing speed, energy consumption saving, production efficiency improvement, safety and environmental protection, and can be widely used on recombined wood, modified wood or plywood. The invention develops a novel phenolic resin adhesive with low toxicity and high curing speed, can reduce curing time, save energy consumption, reduce production cost of recombined wood and improve production efficiency in the production of recombined wood.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a fast-curing phenolic resin and application thereof.
Background
Phenolic resin (PF) refers to a resin formed by polycondensation of phenolic compounds and aldehyde compounds under the action of a catalyst, and the dosage of the phenolic resin is inferior to that of urea-formaldehyde resin adhesive. The phenolic resin has high adhesive strength, excellent environmental aging resistance, better high temperature resistance and water resistance, and is suitable for manufacturing adhesives for building, vehicle and ship structural materials and wood. The excellent weather resistance and boiling water resistance are recognized as the best glue species for producing outdoor-grade recombined wood from domestic and foreign countries.
However, phenolic resin adhesives also have the disadvantages of dark color, hard and brittle cured adhesive layers, high curing temperature, low curing speed and the like. In the production process of the recombined wood, the traditional phenolic resin adhesive is generally cured at 130-160 ℃ to obtain good bonding strength, so that the production efficiency is low, and the energy and equipment consumption is high. The characteristic of phenolic resins that require higher temperatures and longer times to cure creates the following problems: (1) The temperature is high, the heat energy consumption is high, the production cost is high, and the yield is low; (2) long time, resulting in low production efficiency; (3) The high temperature and uneven heat transfer limit the application range of the process.
In terms of accelerating the curing, it has been reported that the addition of some carbonates, salts containing divalent metal ions or some organic esters such as bases, acetates and carbonates can significantly accelerate the curing. But also has the defects of reduced mechanical property index and the like. Therefore, research and development of the novel phenolic resin adhesive with low toxicity, high curing speed and good mechanical index have important significance in reducing curing time, reducing energy consumption, reducing production cost of recombined wood, improving production efficiency and promoting development of wood-based wood processing companies.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a fast curing phenolic resin and application thereof. The water-soluble rapid-curing modified phenolic resin prepared by the method has the advantages of high curing speed, energy consumption saving, production efficiency improvement, safety and environmental protection, and can be widely used on recombined wood, modified wood or plywood.
The preparation method of the water-soluble fast-curing modified phenolic resin comprises the following steps:
and (3) fully mixing thiourea, cellulose sulfate, phenol and a catalyst, fully dissolving and mixing, adding formaldehyde solution, performing constant temperature control reaction at 40-60 ℃ for 1-3 hours, then performing reaction at 75-90 ℃ for 2-4 hours, and cooling and discharging after the reaction is finished to obtain the water-soluble rapid-curing modified phenolic resin.
Preferably, the temperature is reduced to 20-35 ℃ after the reaction is finished.
The catalyst is selected from one or two of ammonia water, sodium hydroxide and potassium hydroxide, and the addition amount is 2% -10% of the mass of phenol, preferably 4% -8%, and more preferably 6%.
The addition amount of the thiourea is 1% -5% of the mass of the phenol, preferably 2% -4%, and more preferably 3%.
Preferably, the substitution degree of the cellulose sulfate is 0.3-0.5; the addition amount is 10% -30% of the mass of phenol, preferably 15% -25%, more preferably 20%.
The addition amount of formaldehyde is 60% -90% of the mass of phenol, preferably 70% -80%; the formaldehyde is preferably added to the reaction in the form of an aqueous solution, the concentration of the aqueous formaldehyde solution preferably being 25 to 35% by weight.
In the invention, other reaction raw materials except phenol, which are not specially described, are added in the form of aqueous solution, and the concentration of the reaction raw materials is generally common solution concentration, and can be adjusted according to the solid content requirement. The material proportion relation in the invention is calculated according to pure substances.
The water-soluble fast-curing phenolic resin is applied to recombined wood, and the method comprises the following steps: immersing the thin veneer subjected to rotary cutting in resin for modification, drying, pressing at normal temperature for forming, thermally curing for a period of time, and demoulding and curing to obtain the recombined wood.
Compared with the preparation method of adding conventional curing agents such as carbonate, resorcinol or organic ester, the method provided by the invention has the advantages that the curing time is obviously shortened, and the mechanical property index is higher. According to the preparation method of the water-soluble fast-curing phenolic resin, after thiourea is added, a structure of a copolymethylene bridge-CH 2 NHCO-exists, condensation reaction can be carried out with the phenolic resin, and the copolycondensation speed is higher than that of polymerization reaction between phenolic hydroxyl groups; in addition, phenols and aldehydes can also polymerize with cellulose sulfate to increase cure speed.
Experiments prove that the curing time of the water-soluble fast-curing phenolic resin prepared by the method is shortened by more than 40%, the free phenol content is less than 1.0%, and the free formaldehyde content is less than 0.05%; the internal bonding strength is increased to 5.0MPa, which is improved by 66.7 percent compared with the prior modification; the average static bending strength is increased to 210.0 MPa, which is improved by 62.8 percent compared with the static bending strength before modification; the average value of the elastic modulus is increased to 25000MPa, and the elastic modulus is increased by 78.6% compared with that before modification. In conclusion, the water-soluble phenolic resin product obtained by the synthetic process has extremely low free phenol and free aldehyde, the wood curing time is greatly shortened, the internal bonding strength, static bending strength and elastic modulus are all improved, and the performance of the base material is obviously improved. Has important significance for reducing the production cost of the recombined wood and improving the production efficiency.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. For clarity, the following examples are provided in detail.
Example 1
Firstly adding a certain amount of pure phenol into a tank reactor, then respectively adding a thiourea solution with the concentration of 12% and a cellulose sulfate aqueous solution with the concentration of 0.5% and the substitution degree of 0.35 into the tank according to the concentration of 2% and 10% of the phenol mass, slowly dropwise adding ammonia water with the concentration of 25% into the tank, fully mixing and dissolving the ammonia water with the concentration of 10% of the phenol mass, dropwise adding a formaldehyde solution with the concentration of 35%, wherein the addition amount of formaldehyde is 90% of the phenol mass, carrying out a constant-temperature stable reaction for 1h at 50 ℃, heating to 85 ℃, carrying out a reaction for 3h, and rapidly cooling to 35 ℃ after the reaction is finished, and discharging.
And (3) using the obtained water-soluble rapid-curing modified phenolic resin to impregnate and modify the veneer subjected to the spin-cutting treatment, drying, pressing at normal temperature for forming, thermally curing at 140 ℃ for 13 hours, and demoulding and curing to obtain the recombined wood. And detecting the mechanical property index.
Example 2
Firstly adding a certain amount of pure phenol into a tank reaction, then respectively adding a 10% thiourea solution and a 1.0% cellulose sulfate aqueous solution with the substitution degree of 0.50 into the tank according to 3% and 30% of the phenol mass, slowly dropwise adding a 30% sodium hydroxide aqueous solution into the tank, fully mixing and dissolving the sodium hydroxide with the sodium hydroxide aqueous solution, dropwise adding a 32% formaldehyde solution, stabilizing the formaldehyde adding amount at 80% of the phenol mass at 45 ℃ for 2 hours after the completion of the reaction, heating to 75 ℃, reacting for 4 hours, and rapidly cooling to 30 ℃ for discharging after the reaction is completed.
And (3) using the obtained water-soluble rapid-curing modified phenolic resin to impregnate and modify the veneer subjected to the rotary cutting treatment, drying, pressing and forming at normal temperature, curing for 14h at 140 ℃, and demoulding and curing to obtain the recombined wood.
Example 3
Firstly adding a certain amount of pure phenol into a tank reaction, then respectively adding a 10% thiourea solution and a 1.2% cellulose sulfate aqueous solution with the substitution degree of 0.40 into the tank according to 5% and 20% of the phenol mass, slowly dropwise adding a 30% potassium hydroxide aqueous solution into the tank, fully mixing and dissolving the potassium hydroxide with the potassium hydroxide accounting for 8% of the phenol mass, dropwise adding a 30% formaldehyde solution, stabilizing the formaldehyde adding amount for 70% of the phenol mass at 40 ℃ for 3 hours after the completion of the reaction, heating to 90 ℃, reacting for 2 hours, and rapidly cooling to 20 ℃ for discharging after the reaction is finished.
And (3) using the obtained water-soluble rapid-curing modified phenolic resin to impregnate and modify the veneer subjected to the rotary cutting treatment, drying, pressing and forming at normal temperature, thermally curing at 140 ℃ for 14h, and demoulding and curing to obtain the recombined wood.
Example 4
Firstly adding a certain amount of pure phenol into a tank reaction, then respectively adding an 8% thiourea solution and a 1.5% cellulose sulfate aqueous solution with the substitution degree of 0.30 into the tank according to 4% and 15% of the phenol mass, slowly dropwise adding a 32% sodium hydroxide aqueous solution into the tank, fully mixing and dissolving the sodium hydroxide with the sodium hydroxide aqueous solution, dropwise adding a 25% formaldehyde solution, wherein the addition amount of formaldehyde is 60% of the phenol mass, stabilizing at 60 ℃ for 1h after the completion of the reaction, heating to 80 ℃, reacting for 4h, and rapidly cooling to 25 ℃ for discharging after the reaction is finished.
And (3) using the obtained water-soluble rapid-curing modified phenolic resin to impregnate and modify the veneer subjected to the rotary cutting treatment, drying, pressing and forming at normal temperature, thermally curing at 140 ℃ for 12 hours, and demolding and curing to obtain the recombined wood.
Comparative example 1
Firstly adding a certain amount of pure phenol into a tank reaction, then adding 25% ammonia water into the tank according to 10% of the mass of the phenol, fully mixing and dissolving, then dropwise adding 35% formaldehyde solution, wherein the addition amount of formaldehyde is 90% of the mass of the phenol, stabilizing at 50 ℃ for 1h after the completion of the reaction, heating to 80 ℃, reacting for 4h, and rapidly cooling to 25 ℃ for discharging after the reaction is completed.
And (3) using the obtained water-soluble rapid-curing modified phenolic resin to impregnate and modify the veneer subjected to the rotary cutting treatment, drying, pressing and forming at normal temperature, thermally curing at 140 ℃ for 22 hours, and demolding and curing to obtain the recombined wood.
Comparative example 2
Adding a certain amount of pure phenol into a tank reaction, adding pure resorcinol into the tank according to 5% of the phenol mass, adding a 32% sodium hydroxide aqueous solution into the tank according to 9% of the phenol mass, fully mixing and dissolving, dropwise adding a 32% formaldehyde solution, stabilizing at 60 ℃ for 1h after the completion of the reaction, heating to 75 ℃, reacting for 4h, and rapidly cooling to 30 ℃ for discharging after the reaction is completed.
And (3) using the obtained water-soluble rapid-curing modified phenolic resin to impregnate and modify the veneer subjected to the rotary cutting treatment, drying, pressing and forming at normal temperature, thermally curing at 140 ℃ for 17 hours, and demolding and curing to obtain the recombined wood.
Comparative example 3
Firstly adding a certain amount of pure phenol into a tank reaction, adding a 10% sodium carbonate aqueous solution into the tank according to 2% of the phenol mass, adding a 30% potassium hydroxide aqueous solution into the tank according to 8% of the phenol mass, fully mixing and dissolving, then dropwise adding a 30% formaldehyde solution, wherein the addition amount of formaldehyde is 70% of the phenol mass, stabilizing at 45 ℃ for 2 hours after finishing, heating to 90 ℃, reacting for 2 hours, and rapidly cooling to 20 ℃ after finishing the reaction, and discharging.
And (3) using the obtained water-soluble rapid-curing modified phenolic resin to impregnate and modify the veneer subjected to the rotary cutting treatment, drying, pressing and forming at normal temperature, thermally curing at 140 ℃ for 16 hours, and demolding and curing to obtain the recombined wood.
Comparative example 4
Adding a certain amount of pure phenol into a tank reaction, adding pure sodium carbonate propylene ester into the tank according to 2% of the phenol mass, adding 30% of sodium hydroxide aqueous solution into the tank according to 10% of the phenol mass, fully mixing and dissolving, dropwise adding 25% of formaldehyde solution, stabilizing for 3 hours at 40 ℃ after the addition of 60% of the phenol mass is completed, heating to 80 ℃, reacting for 4 hours, and rapidly cooling to 25 ℃ after the reaction is completed, and discharging.
And (3) using the obtained water-soluble rapid-curing modified phenolic resin to impregnate and modify the veneer subjected to the rotary cutting treatment, drying, pressing and forming at normal temperature, thermally curing at 140 ℃ for 17 hours, and demolding and curing to obtain the recombined wood.
Performance testing
The free phenol and free formaldehyde contents of the water-soluble rapid-curing modified phenolic resins prepared in examples 1 to 4 and comparative examples 1 to 4 were detected, wherein the detection of the free formaldehyde content was referred to 3.16 methods for measuring the free formaldehyde content in GB/T14074-2017, the detection of the internal bond strength was referred to 6.7 methods for measuring the internal bond strength in GB/T11718-2009, and the detection of the static bending strength and the elastic modulus was referred to 4.7 methods in GB/T17657-2013 after the preparation of the recombinant wood was completed. The test results are shown in Table 1:
TABLE 1 data for Water-soluble phenolic resins
| Name of the name | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| Free phenol wt% | 0.91 | 0.87 | 0.93 | 0.90 | 2.01 | 1.97 | 1.57 | 2.11 |
| Free formaldehyde content wt% | 0.04 | 0.03 | 0.03 | 0.04 | 0.18 | 0.21 | 0.19 | 0.21 |
| Internal bond strength MPa | 5.44 | 5.00 | 5.11 | 4.98 | 3.50 | 3.00 | 3.21 | 3.11 |
| Static bending strength MPa | 189 | 190 | 201 | 210 | 121 | 122 | 148 | 129 |
| Modulus of elasticity MPa | 21000 | 19000 | 23000 | 25000 | 13000 | 12000 | 13000 | 14000 |
| Time h of curing of the substrate | 13 | 14 | 13 | 12 | 22 | 17 | 16 | 17 |
The invention mixes thiourea, cellulose sulfate, phenol and catalyst uniformly, activates for a period of time, and combines thiourea and cellulose sulfate for use. Compared with the conventional curing agents such as carbonate, resorcinol or organic ester, the curing time is obviously shorter, and the mechanical property index is higher. Because of the presence of the copolymethylene bridge-CH after addition of thiourea 2 Structure of NHCO-. Its presence indicates that thiourea can undergo condensation reaction with phenolic resin and that copolycondensation rate is higher than that of polymerization reaction between phenolic hydroxyl groups. In addition, phenols and aldehydes can also polymerize with cellulose sulfate to increase cure speed. Not only can accelerate solidification and improve production efficiency, but also has important significance for reducing production cost of recombined wood.
The water-soluble phenolic resin obtained by the synthetic process has extremely low free phenol and free aldehyde, and the performance of the base material is obviously improved. The test results show that the curing time of the water-soluble fast curing modified phenolic resin prepared by the method is shortened by 40%, and the free phenol content is less than 1.0% and the free formaldehyde content is less than 0.05%. The internal bonding strength after modification is increased to 5.0MPa, 66.7% higher than that before modification, the static bending strength average value after modification is increased to 210.0 MPa, 62.8% higher than that before modification, and the elastic modulus average value after modification is increased to 25000MPa, 78.6% higher than that before modification.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (6)
1. The water-soluble fast-curing modified phenolic resin is characterized by comprising the following steps of: fully mixing thiourea, cellulose sulfate, phenol and a catalyst, fully dissolving and mixing, adding formaldehyde solution, controlling the temperature at 40-60 ℃ to react for 1-3 hours, then reacting at 75-90 ℃ for 2-4 hours, and cooling and discharging after the reaction is finished to obtain water-soluble fast-curing modified phenolic resin;
the catalyst is selected from one or two of ammonia water, sodium hydroxide and potassium hydroxide;
the addition amount of the catalyst is 2% -10% of the mass of phenol;
the addition amount of the thiourea is 1% -5% of the mass of the phenol;
the addition amount of the cellulose sulfate is 10% -30% of the mass of phenol;
the addition amount of formaldehyde is 60% -90% of the mass of phenol;
formaldehyde is added into the reaction in the form of aqueous solution, and the concentration of the aqueous solution of formaldehyde is 25-35 wt%.
2. The water-soluble fast-curing modified phenolic resin of claim 1, wherein the catalyst is added in an amount of 4% -8% of the mass of phenol.
3. The water-soluble rapid-curing modified phenolic resin of claim 1, wherein the addition amount of thiourea is 2% -4% of the mass of phenol.
4. The water-soluble fast-curing modified phenolic resin of claim 1, wherein the degree of substitution of cellulose sulfate is 0.3-0.5.
5. The water-soluble rapid-curing modified phenolic resin according to claim 1, wherein the addition amount of the cellulose sulfate is 15% -25% of the mass of phenol; the addition amount of formaldehyde is 70-80% of the mass of phenol.
6. The water-soluble fast curing modified phenolic resin according to claim 1, wherein the temperature is reduced to 20-35 ℃ after the reaction is completed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110624059.8A CN113461886B (en) | 2021-06-04 | 2021-06-04 | Fast-curing phenolic resin and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110624059.8A CN113461886B (en) | 2021-06-04 | 2021-06-04 | Fast-curing phenolic resin and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113461886A CN113461886A (en) | 2021-10-01 |
| CN113461886B true CN113461886B (en) | 2024-02-06 |
Family
ID=77872420
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110624059.8A Active CN113461886B (en) | 2021-06-04 | 2021-06-04 | Fast-curing phenolic resin and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113461886B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE716221C (en) * | 1936-04-26 | 1942-01-15 | Kalle & Co Ag | adhesive |
| CN105964882A (en) * | 2016-06-22 | 2016-09-28 | 马鞍山市创诚铸造有限公司 | Environment-friendly molding sand adopting cellulose sulfate modified animal glue as adhesive and preparation method thereof |
| CN106995525A (en) * | 2017-05-19 | 2017-08-01 | 江苏三木化工股份有限公司 | Daiamid epoxy curing agent and preparation method that a kind of thiocarbamide is modified |
| CN112552472A (en) * | 2020-11-13 | 2021-03-26 | 山东京博木基材料有限公司 | Preparation method of water-soluble toughened modified phenolic resin |
-
2021
- 2021-06-04 CN CN202110624059.8A patent/CN113461886B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE716221C (en) * | 1936-04-26 | 1942-01-15 | Kalle & Co Ag | adhesive |
| CN105964882A (en) * | 2016-06-22 | 2016-09-28 | 马鞍山市创诚铸造有限公司 | Environment-friendly molding sand adopting cellulose sulfate modified animal glue as adhesive and preparation method thereof |
| CN106995525A (en) * | 2017-05-19 | 2017-08-01 | 江苏三木化工股份有限公司 | Daiamid epoxy curing agent and preparation method that a kind of thiocarbamide is modified |
| CN112552472A (en) * | 2020-11-13 | 2021-03-26 | 山东京博木基材料有限公司 | Preparation method of water-soluble toughened modified phenolic resin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113461886A (en) | 2021-10-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Pizzi | Phenolic resin adhesives | |
| JP7511485B2 (en) | Process for preparing the binding resin | |
| CN102942888B (en) | Super adhesive for artificial boards and preparation method thereof | |
| CN103865018B (en) | A kind of matrix resin and a kind of structure laminated wood stick with glue agent | |
| CA2128912A1 (en) | Modified phenol-aldehyde resin and binder system | |
| CA1200336A (en) | Making composite articles | |
| CA2846002C (en) | Liquid kraft lignin compositions | |
| US6291558B1 (en) | Composition board binding material | |
| CN113461886B (en) | Fast-curing phenolic resin and application thereof | |
| US3927140A (en) | Adhesive composition | |
| RU2154652C2 (en) | Method of preparing urea-modified phenol resin binder intended for treating chip of middle layers of wood chip boards | |
| CN114015001B (en) | Preparation method of phenolic resin | |
| Fan et al. | Chemical structure and curing behavior of phenol–urea–formaldehyde cocondensed resins of high urea content | |
| US5342880A (en) | Phenolic resol plywood resin, manufacture and use | |
| CN111087956B (en) | Modified phenolic resin adhesive and preparation method and application thereof | |
| DE4030718A1 (en) | Lignin based binder prodn. from black liquor or thick liquor - by concn. of liquor, addn. of alkali, addn. of phenol and formaldehyde or para:formaldehyde and condensn. | |
| EP4077579A1 (en) | Novel process for preparing a bonding resin | |
| CN110625705A (en) | Bamboo-wood composite container bottom plate and manufacturing method thereof | |
| CN112662352A (en) | Special phenolic resin adhesive for bamboo gluing and preparation method thereof | |
| CN112300350B (en) | Urea-formaldehyde resin adhesive modifier and application thereof, modified urea-formaldehyde resin adhesive and application thereof | |
| CN106810656A (en) | A kind of phenol-formaldehyde resin modified and preparation method thereof | |
| JP7554140B2 (en) | Adhesive and its manufacturing method | |
| CN111303810B (en) | Preparation method of E0-grade modified urea-formaldehyde resin for bent plate | |
| SK86096A3 (en) | Binders for the production of lignocellulose-containing mouldings | |
| AT300368B (en) | Process for the production of plastic moldings reinforced with acid-resistant glass fibers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |