CN114836153A - Preparation method of blending modified resin adhesive - Google Patents
Preparation method of blending modified resin adhesive Download PDFInfo
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- CN114836153A CN114836153A CN202210596616.4A CN202210596616A CN114836153A CN 114836153 A CN114836153 A CN 114836153A CN 202210596616 A CN202210596616 A CN 202210596616A CN 114836153 A CN114836153 A CN 114836153A
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- acrylic acid
- acid solution
- ethyl acetate
- dimethylphenol
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- 239000000853 adhesive Substances 0.000 title claims abstract description 55
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 55
- 229920005989 resin Polymers 0.000 title claims abstract description 52
- 239000011347 resin Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 238000002156 mixing Methods 0.000 title claims abstract description 37
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 138
- 239000000243 solution Substances 0.000 claims abstract description 86
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 59
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229920005551 calcium lignosulfonate Polymers 0.000 claims abstract description 58
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 claims abstract description 41
- OSDLLIBGSJNGJE-UHFFFAOYSA-N 4-chloro-3,5-dimethylphenol Chemical compound CC1=CC(O)=CC(C)=C1Cl OSDLLIBGSJNGJE-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000011259 mixed solution Substances 0.000 claims abstract description 33
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 239000008098 formaldehyde solution Substances 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004202 carbamide Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000003860 storage Methods 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 6
- 239000003063 flame retardant Substances 0.000 abstract description 5
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- 238000004026 adhesive bonding Methods 0.000 abstract description 2
- OOCMUZJPDXYRFD-UHFFFAOYSA-L calcium;2-dodecylbenzenesulfonate Chemical compound [Ca+2].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O.CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O OOCMUZJPDXYRFD-UHFFFAOYSA-L 0.000 description 10
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000005011 phenolic resin Substances 0.000 description 8
- 229920001568 phenolic resin Polymers 0.000 description 8
- 239000004375 Dextrin Substances 0.000 description 7
- 229920001353 Dextrin Polymers 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- 235000019425 dextrin Nutrition 0.000 description 7
- 235000013312 flour Nutrition 0.000 description 7
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 7
- 229920001807 Urea-formaldehyde Polymers 0.000 description 6
- 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 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000002023 wood Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000002464 physical blending Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005464 sample preparation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a preparation method of a blending modified resin adhesive, belonging to the technical field of composite materials. The method comprises the following operation steps: preparing calcium lignosulfonate and an acrylic acid solution; mixing calcium lignosulfonate with ethyl acetate, mixing an acrylic acid solution with 4-chloro-3, 5-dimethylphenol, filtering a mixed solution of the calcium lignosulfonate and the ethyl acetate to obtain an ethyl acetate solution of the calcium lignosulfonate, and adjusting the pH value of the mixed solution of the acrylic acid solution and the 4-chloro-3, 5-dimethylphenol to 8; preparing a formaldehyde solution, adding all urea, fully stirring to obtain a feed liquid, then starting to increase the value to 90 ℃, dropwise adding the obtained ethyl acetate solution of calcium lignosulfonate, dropwise adding the obtained mixed solution of acrylic acid solution and 4-chloro-3, 5-dimethylphenol, adding alumina particles, finally cooling to room temperature, and testing the discharged material to obtain the calcium lignosulfonate-based composite material with high viscosity, adhesive bonding strength and flame retardant capability.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to an improved modified resin adhesive.
Background
The usage of UF adhesives has been increasing since the urea-formaldehyde resin (UF) adhesives were first synthesized in 1844, and it has become one of the main adhesives of wood-based panels (accounting for more than 90% of the total usage), and is also the adhesive with the largest usage in the wood industry (accounting for more than 60% of the total consumption). The pollution of the artificial board mainly comes from adhesives, and wood products glued by UF adhesives can continuously release free F (formaldehyde), so that various countries set a series of laws and regulations for the problem of F release amount. The low F release index of UF adhesive used by artificial board production enterprises is regulated by the mandatory standard limit of GB/T18580-2001 (limit of formaldehyde release in artificial boards of interior decoration and finishing materials and products thereof), and the limit index of F release amount of the artificial boards by the CarB regulation of California in the United states is improved by more than 70 times compared with the domestic standard (which is a challenge and a rare opportunity for the domestic wood processing industry). Therefore, it is imperative to reduce the free F delivery of UF adhesives and related products.
The patent of the prior invention, the publication number of which is CN104162624B, discloses a special glue for shell type bonding and a preparation process thereof, and the technical scheme is as follows:
the special glue for shell bonding consists of 25 wt% of phenolic resin, 15 wt% of urotropine, 10 wt% of dextrin, 20 wt% of flour and 30 wt% of water.
A preparation process of special glue for shell bonding sequentially comprises the following steps:
1) the raw materials of phenolic resin, urotropine, dextrin and flour are classified and stacked in a dry place and marked, and the temperature of the storage period is required to be less than or equal to 30 degrees;
2) accurately weighing 25% of phenolic resin, 15% of urotropine, 10% of dextrin, 20% of flour and 30% of water by weight percentage;
3) when in preparation, the raw materials of phenolic resin, urotropine, dextrin and flour which are weighed according to the weight percentage are uniformly mixed together, then the mixed raw materials of phenolic resin, urotropine, dextrin and flour are put into batches, then one batch is put into water with the weight percentage of 30 percent, after the raw materials of phenolic resin, urotropine, dextrin and flour are uniformly stirred, the mixture is put into a second batch, and the rest is done in the same way until all the raw materials of phenolic resin, urotropine, dextrin and flour are put into water;
4) observing the uniformly stirred glue, wherein no particle or powder is required to be generated;
5) and (3) blending the viscosity degree of the glue obtained in the step 4) according to the use requirement.
Comprehensive analysis shows, through its viscosity of analysis, curing time and adhesive strength isoparametric all be less than this application, and this application still possesses fire retardant efficiency.
Disclosure of Invention
1. Problems to be solved
Aiming at the problems in the prior art, the invention provides a preparation method of a blending modified resin adhesive, which has higher viscosity, bonding strength and flame retardant capability through tests, guessed that calcium lignosulfonate may also play a role in heat insulation and coating, and additional experiments (not provided) show that the preliminary oxidative decomposition phenomenon does not occur until about 330 ℃, the middle-period oxidative combustion occurs at about 570 ℃ and the later-period oxidative combustion occurs at 790 ℃.
2. Technical scheme
In order to solve the above problems, the present invention adopts the following technical solutions.
A preparation method of a blending modified resin adhesive comprises the following operation steps:
preparing calcium lignosulfonate and an acrylic acid solution;
mixing calcium lignosulfonate and ethyl acetate for the first time, mixing an acrylic acid solution and 4-chloro-3, 5-dimethylphenol for the second time, filtering a mixed solution of the calcium lignosulfonate and the ethyl acetate to obtain an ethyl acetate solution of the calcium lignosulfonate, and adjusting the pH value of the mixed solution of the acrylic acid solution and the 4-chloro-3, 5-dimethylphenol to 8;
preparing a formaldehyde solution, preheating to 40 ℃, adjusting the pH value to 8 by using sodium hydroxide, then adding all urea, fully stirring to obtain a feed liquid, then starting to increase the value to 90 ℃, dropwise adding the obtained ethyl acetate solution of calcium lignosulfonate, uniformly stirring, cooling to 60 ℃, dropwise adding the obtained mixed solution of the acrylic acid solution and 4-chloro-3, 5-dimethylphenol, heating to 95 ℃, uniformly stirring, adding alumina particles, finally cooling to room temperature, and discharging.
In the above-mentioned preparation method of modified resin adhesive,
the mass ratio of the calcium lignosulfonate to the acrylic acid solution is 3: 6, wherein the mass concentration of the acrylic acid solution is 60 percent;
the mass consumption of the ethyl acetate is 2.5 times of that of the calcium lignosulphonate, and the mass consumption of the 4-chloro-3, 5-dimethylphenol is 2 times of that of the acrylic acid solution;
wherein the mass concentration of the 4-chloro-3, 5-dimethylphenol is 99.0 percent.
In the above-mentioned preparation method of modified resin adhesive,
the temperature of the first mixing and the temperature of the second mixing are both 90 ℃.
In the above-mentioned preparation method of modified resin adhesive,
the storage temperature of the ethyl acetate solution of calcium lignosulphonate is 65 ℃, and a water bath mode is adopted;
the temperature of the mixed solution of the acrylic acid solution and 4-chloro-3, 5-dimethylphenol was controlled at 80 ℃.
In the above-mentioned preparation method of modified resin adhesive,
the mass concentration of the formaldehyde solution is 35 percent;
the mass ratio of the formaldehyde solution to the urea is 1: 0.6.
in the above-mentioned preparation method of modified resin adhesive,
the speed of rotation for thorough stirring was 2000 rpm.
In the above-mentioned preparation method of modified resin adhesive,
the adding mass of the ethyl acetate solution of the calcium lignosulphonate is 15 percent of the feed liquid,
the addition amount of the mixed solution of the acrylic acid solution and the 4-chloro-3, 5-dimethylphenol is 8 percent of the feed liquid.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
the modified resin is characterized and analyzed by FT-IR, and the sample is 1470cm -1 -1680cm -1 Has characteristic absorption peak of benzene ring skeleton, which shows4-chloro-3, 5-dimethylphenol participates in the formation of molecular chains of the resin material; meanwhile, a characteristic peak (stretching vibration peak) of the sulfonic acid group is not found, which indicates that the calcium lignosulfonate does not participate in the formation of the molecular chain, no grafting exists and the like, and the calcium lignosulfonate is presumed to play a role in physical blending. The reason is that the acrylic acid solution can promote the formation of dimer and trimer and the deepening of the crosslinking density, and meanwhile, the addition of calcium lignosulfonate and the like can promote the internal polycondensation of the resin material and improve various comprehensive capabilities.
Drawings
FIG. 1 is a FT-IR spectrum of the product of example 1 of the invention.
Detailed Description
The invention is further described with reference to specific examples.
It should be noted that the reagents involved in the present application were purchased from Shanghai Aladdin Biotechnology Ltd.
Example 1
The preparation method of the blending modified resin adhesive comprises the following operation steps:
preparing calcium lignosulfonate and an acrylic acid solution;
mixing calcium lignosulfonate and ethyl acetate for the first time, mixing an acrylic acid solution and 4-chloro-3, 5-dimethylphenol for the second time, filtering a mixed solution of the calcium lignosulfonate and the ethyl acetate to obtain an ethyl acetate solution of the calcium lignosulfonate, and adjusting the pH value of the mixed solution of the acrylic acid solution and the 4-chloro-3, 5-dimethylphenol to 8;
preparing a formaldehyde solution, preheating to 40 ℃, adjusting the pH value to 8 by using sodium hydroxide, then adding all urea, fully stirring to obtain a feed liquid, then starting to increase the value to 90 ℃, dropwise adding the obtained ethyl acetate solution of calcium lignosulfonate, uniformly stirring, cooling to 60 ℃, dropwise adding the obtained mixed solution of acrylic acid solution and 4-chloro-3, 5-dimethylphenol, heating to 95 ℃, uniformly stirring, adding aluminum oxide particles, finally cooling to room temperature, and discharging. The mass percentage of the alumina particles added was 15% of the other substances.
In the above-mentioned preparation method of modified resin adhesive,
the mass ratio of the calcium lignosulfonate to the acrylic acid solution is 3: 6, wherein the mass concentration of the acrylic acid solution is 60 percent;
the mass consumption of the ethyl acetate is 2.5 times of that of the calcium lignosulphonate, and the mass consumption of the 4-chloro-3, 5-dimethylphenol is 2 times of that of the acrylic acid solution;
wherein the mass concentration of the 4-chloro-3, 5-dimethylphenol is 99.0 percent.
In the above-mentioned preparation method of modified resin adhesive,
the temperature of the first mixing and the temperature of the second mixing are both 90 ℃.
In the above-mentioned preparation method of modified resin adhesive,
the storage temperature of the ethyl acetate solution of calcium lignosulphonate is 65 ℃, and a water bath mode is adopted;
the temperature of the mixed solution of the acrylic acid solution and 4-chloro-3, 5-dimethylphenol was controlled at 80 ℃.
In the above-mentioned preparation method of modified resin adhesive,
the mass concentration of the formaldehyde solution is 35 percent;
the mass ratio of the formaldehyde solution to the urea is 1: 0.6.
in the above-mentioned preparation method of modified resin adhesive,
the speed of rotation for thorough stirring was 2000 rpm.
In the above-mentioned preparation method of modified resin adhesive,
the adding mass of the ethyl acetate solution of the calcium lignosulphonate is 15 percent of the feed liquid,
the addition amount of the mixed solution of the acrylic acid solution and the 4-chloro-3, 5-dimethylphenol is 8 percent of the feed liquid.
It should be reminded that the above operation requires consideration of ventilation safety, avoiding harmful effects on the body.
The preparation method of the blending modified resin adhesive comprises the following operation steps:
preparing calcium dodecyl benzene sulfonate and acrylic acid solution;
mixing calcium dodecyl benzene sulfonate and ethyl acetate for the first time, mixing an acrylic acid solution and 4-chloro-3, 5-dimethylphenol for the second time, filtering a mixed solution of the calcium dodecyl benzene sulfonate and the ethyl acetate to obtain an ethyl acetate solution of the calcium dodecyl benzene sulfonate, and adjusting the pH value of the mixed solution of the acrylic acid solution and the 4-chloro-3, 5-dimethylphenol to 8;
preparing a formaldehyde solution, preheating to 40 ℃, adjusting the pH value to 8 by using sodium hydroxide, then adding all urea, fully stirring to obtain a feed liquid, then starting to increase the value to 90 ℃, dropwise adding the obtained ethyl acetate solution of calcium dodecyl benzene sulfonate, uniformly stirring, cooling to 60 ℃, dropwise adding the obtained mixed solution of acrylic acid solution and 4-chloro-3, 5-dimethylphenol, heating to 95 ℃, uniformly stirring, adding aluminum oxide particles, finally cooling to room temperature, and discharging.
In the above-mentioned preparation method of modified resin adhesive,
the mass ratio of the calcium dodecylbenzene sulfonate to the acrylic acid solution is 3: 6, wherein the mass concentration of the acrylic acid solution is 60 percent;
the mass consumption of the ethyl acetate is 2.5 times of that of the calcium dodecyl benzene sulfonate, and the mass consumption of the 4-chloro-3, 5-dimethylphenol is 2 times of that of the acrylic acid solution;
wherein the mass concentration of the 4-chloro-3, 5-dimethylphenol is 99.0 percent.
In the above-mentioned preparation method of modified resin adhesive,
the temperature of the first mixing and the temperature of the second mixing are both 90 ℃.
In the above-mentioned preparation method of modified resin adhesive,
the storage temperature of the ethyl acetate solution of calcium dodecyl benzene sulfonate is 65 ℃, and a water bath mode is adopted;
the temperature of the mixed solution of the acrylic acid solution and 4-chloro-3, 5-dimethylphenol was controlled at 80 ℃.
In the above-mentioned preparation method of modified resin adhesive,
the mass concentration of the formaldehyde solution is 35 percent;
the mass ratio of the formaldehyde solution to the urea is 1: 0.6.
in the above-mentioned preparation method of modified resin adhesive,
the speed of rotation for thorough stirring was 2000 rpm.
In the above-mentioned preparation method of modified resin adhesive,
the adding mass of the ethyl acetate solution of the calcium dodecyl benzene sulfonate is 15 percent of the feed liquid,
the addition amount of the mixed solution of the acrylic acid solution and the 4-chloro-3, 5-dimethylphenol is 8 percent of the feed liquid.
Method for changing calcium lignosulphonate into calcium dodecyl benzene sulfonate
The preparation method of the blending modified resin adhesive comprises the following operation steps:
preparing calcium lignosulfonate and an acrylic acid solution;
mixing calcium lignosulfonate and ethyl acetate for the first time, mixing an acrylic acid solution and phenol for the second time, filtering a mixed solution of the calcium lignosulfonate and the ethyl acetate to obtain an ethyl acetate solution of the calcium lignosulfonate, and adjusting the pH value of the mixed solution of the acrylic acid solution and the phenol to 8;
preparing a formaldehyde solution, preheating to 40 ℃, adjusting the pH value to 8 by using sodium hydroxide, then adding all urea, fully stirring to obtain a feed liquid, then starting to increase the value to 90 ℃, dropwise adding the obtained ethyl acetate solution of calcium lignosulfonate, uniformly stirring, cooling to 60 ℃, dropwise adding the obtained mixed solution of acrylic acid solution and phenol, heating to 95 ℃, uniformly stirring, adding aluminum oxide particles, finally cooling to room temperature, and discharging.
In the above-mentioned preparation method of modified resin adhesive,
the mass ratio of the calcium lignosulfonate to the acrylic acid solution is 3: 6, wherein the mass concentration of the acrylic acid solution is 60 percent;
the mass consumption of the ethyl acetate is 2.5 times of that of the calcium lignosulphonate, and the mass consumption of the phenol is 2 times of that of the acrylic acid solution;
wherein the mass concentration of phenol is 99.0%.
In the above-mentioned preparation method of modified resin adhesive,
the temperature of the first mixing and the temperature of the second mixing are both 90 ℃.
In the above-mentioned preparation method of modified resin adhesive,
the storage temperature of the ethyl acetate solution of calcium lignosulphonate is 65 ℃, and a water bath mode is adopted;
the temperature of the mixed solution of the acrylic acid solution and phenol was controlled at 80 ℃.
In the above-mentioned preparation method of modified resin adhesive,
the mass concentration of the formaldehyde solution is 35 percent;
the mass ratio of the formaldehyde solution to the urea is 1: 0.6.
in the above-mentioned preparation method of modified resin adhesive,
the speed of rotation for thorough stirring was 2000 rpm.
In the above-mentioned preparation method of modified resin adhesive,
the adding mass of the ethyl acetate solution of the calcium lignosulphonate is 15 percent of the feed liquid,
the addition amount of the mixed solution of the acrylic acid solution and the phenol is 8 percent of the feed liquid.
Comparative scheme 3
The preparation method of the blending modified resin adhesive comprises the following operation steps:
preparing calcium lignosulfonate and an acrylic acid solution;
mixing calcium lignosulfonate and ethyl acetate for the first time, mixing an acrylic acid solution and 4-chloro-3, 5-dimethylphenol for the second time, filtering a mixed solution of the calcium lignosulfonate and the ethyl acetate to obtain an ethyl acetate solution of the calcium lignosulfonate, and adjusting the pH value of the mixed solution of the acrylic acid solution and the 4-chloro-3, 5-dimethylphenol to 8;
adding the obtained ethyl acetate solution of calcium lignosulphonate into a mixed solution of an acrylic acid solution and 4-chloro-3, 5-dimethylphenol, heating to 95 ℃, uniformly stirring, adding alumina particles, finally cooling to room temperature, and discharging.
In the above-mentioned preparation method of modified resin adhesive,
the mass ratio of the calcium lignosulfonate to the acrylic acid solution is 3: 6, wherein the mass concentration of the acrylic acid solution is 60 percent;
the mass consumption of the ethyl acetate is 2.5 times of that of the calcium lignosulphonate, and the mass consumption of the 4-chloro-3, 5-dimethylphenol is 2 times of that of the acrylic acid solution;
wherein the mass concentration of the 4-chloro-3, 5-dimethylphenol is 99.0 percent.
In the above-mentioned preparation method of modified resin adhesive,
the temperature of the first mixing and the temperature of the second mixing are both 90 ℃.
In the above-mentioned preparation method of modified resin adhesive,
the storage temperature of the ethyl acetate solution of calcium lignosulphonate is 65 ℃, and a water bath mode is adopted;
the temperature of the mixed solution of the acrylic acid solution and 4-chloro-3, 5-dimethylphenol was controlled at 80 ℃.
In the above-mentioned preparation method of modified resin adhesive,
the adding mass of the ethyl acetate solution of the calcium lignosulphonate is 15 percent of the feed liquid,
the addition amount of the mixed solution of the acrylic acid solution and the 4-chloro-3, 5-dimethylphenol is 8 percent of the feed liquid.
Example 2
The modified resin (sample prepared in example 1, KBr film sample preparation method) was characterized and analyzed by FT-IR, as shown in FIG. 1 (test conducted by local college laboratories), wherein the upper diagram in FIG. 1 is a standard spectrum of phenolic resin, the lower diagram in FIG. 1 is a spectrum of a blended modified resin sample at 1470cm -1 -1680cm -1 The compound has a characteristic absorption peak of a benzene ring skeleton, which indicates that 4-chloro-3, 5-dimethylphenol participates in the formation of a molecular chain of a resin material; meanwhile, a characteristic peak (stretching vibration peak) of the sulfonic acid group is not found, which indicates that the calcium lignosulfonate does not participate in the formation of the molecular chain, no grafting exists and the like, and the calcium lignosulfonate is presumed to play a role in physical blending.
Example 3
Example 1, comparative scheme 2 and comparative scheme 3 were selected and tested as follows:
(1) viscosity:
the measurement was carried out using a 4-cup-Permeameter, and the time required for the resin to flow out of the orifice until the flow column was interrupted was used as a measure.
(2) Adhesive strength:
the measurement was carried out by an electronic universal tester (tensile rate 6000N/min, measurement at 25 ℃) in accordance with GB/T14074-2006 standard.
(3) Flame retardant Properties (oxygen index)
The material was tested for oxygen index (LOI) according to GB/T2406-2009.
TABLE 1 test results
| Viscosity/s | Adhesive bonding strength/MPa | LOI/％ | |
| Example 1 | 98.7 | 7.35 | 75.2 |
| |
91.2 | 5.82 | 64.9 |
| |
86.5 | 6.74 | 60.7 |
| Comparative scheme 3 | 70.8 | 3.14 | 24.7 |
As shown in Table 1, the viscosity of the product prepared by the method is as high as 98.7s, the bonding strength is 7.35MPa, and the product has high flame retardant property and excellent comprehensive performance.
While the invention has been described in further detail in connection with specific embodiments thereof, it will be understood that the invention is not limited thereto, and that various other modifications and substitutions may be made by those skilled in the art without departing from the spirit of the invention, which should be considered to be within the scope of the invention as defined by the appended claims.
Claims (7)
1. A preparation method of a blending modified resin adhesive is characterized by comprising the following steps:
the method comprises the following operation steps:
preparing calcium lignosulfonate and an acrylic acid solution;
mixing calcium lignosulfonate and ethyl acetate for the first time, mixing an acrylic acid solution and 4-chloro-3, 5-dimethylphenol for the second time, filtering a mixed solution of the calcium lignosulfonate and the ethyl acetate to obtain an ethyl acetate solution of the calcium lignosulfonate, and adjusting the pH value of the mixed solution of the acrylic acid solution and the 4-chloro-3, 5-dimethylphenol to 8;
preparing a formaldehyde solution, preheating to 40 ℃, adjusting the pH value to 8 by using sodium hydroxide, then adding all urea, fully stirring to obtain a feed liquid, then starting to increase the value to 90 ℃, dropwise adding the obtained ethyl acetate solution of calcium lignosulfonate, uniformly stirring, cooling to 60 ℃, dropwise adding the obtained mixed solution of acrylic acid solution and 4-chloro-3, 5-dimethylphenol, heating to 95 ℃, uniformly stirring, adding aluminum oxide particles, finally cooling to room temperature, and discharging.
2. The method for preparing a modified resin adhesive according to claim 1, wherein:
the mass ratio of the calcium lignosulfonate to the acrylic acid solution is 3: 6, wherein the mass concentration of the acrylic acid solution is 60 percent;
the mass amount of the ethyl acetate is 2.5 times that of the calcium lignosulphonate, and the mass amount of the 4-chloro-3, 5-dimethylphenol is 2 times that of the acrylic acid solution;
wherein the mass concentration of the 4-chloro-3, 5-dimethylphenol is 99.0 percent.
3. The method for preparing a modified resin adhesive according to claim 1, wherein:
the temperature of the first mixing and the temperature of the second mixing are both 90 ℃.
4. The method for preparing a modified resin adhesive according to claim 1, wherein:
the storage temperature of the ethyl acetate solution of calcium lignosulphonate is 65 ℃, and a water bath mode is adopted;
the temperature of the mixed solution of the acrylic acid solution and 4-chloro-3, 5-dimethylphenol was controlled at 80 ℃.
5. The method for preparing a modified resin adhesive according to claim 1, wherein:
the mass concentration of the formaldehyde solution is 35 percent;
the mass ratio of the formaldehyde solution to the urea is 1: 0.6.
6. the method for preparing a modified resin adhesive according to claim 1, wherein:
the speed of rotation for thorough stirring was 2000 rpm.
7. The method for preparing a modified resin adhesive according to claim 1, wherein:
the adding mass of the ethyl acetate solution of the calcium lignosulphonate is 15 percent of the feed liquid,
the addition amount of the mixed solution of the acrylic acid solution and the 4-chloro-3, 5-dimethylphenol is 8 percent of the feed liquid.
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| US3077458A (en) * | 1957-05-27 | 1963-02-12 | Alim Corp | Non-aqueous fire ret ardant composition comprising a urea formaldehyde condensate |
| CA2711182A1 (en) * | 2008-01-04 | 2009-07-16 | Guang Yang | A new lumber adhesive and the preparation thereof |
| CN105666632A (en) * | 2016-01-25 | 2016-06-15 | 新沂市大自然木业有限公司 | Manufacturing method for environment-friendly corrosion prevention medium-density fiberboard for door plate of security door |
| CN111087956A (en) * | 2019-12-09 | 2020-05-01 | 华南农业大学 | Modified phenolic resin adhesive and preparation method and application thereof |
| CN112625627A (en) * | 2020-12-11 | 2021-04-09 | 中南林业科技大学 | Preparation method of lignin modified environment-friendly urea-formaldehyde resin adhesive |
| CN113249070A (en) * | 2021-05-13 | 2021-08-13 | 广西国旭春天人造板有限公司 | Urea-formaldehyde resin adhesive suitable for glue spraying assembly process and preparation method thereof |
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Patent Citations (6)
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| US3077458A (en) * | 1957-05-27 | 1963-02-12 | Alim Corp | Non-aqueous fire ret ardant composition comprising a urea formaldehyde condensate |
| CA2711182A1 (en) * | 2008-01-04 | 2009-07-16 | Guang Yang | A new lumber adhesive and the preparation thereof |
| CN105666632A (en) * | 2016-01-25 | 2016-06-15 | 新沂市大自然木业有限公司 | Manufacturing method for environment-friendly corrosion prevention medium-density fiberboard for door plate of security door |
| CN111087956A (en) * | 2019-12-09 | 2020-05-01 | 华南农业大学 | Modified phenolic resin adhesive and preparation method and application thereof |
| CN112625627A (en) * | 2020-12-11 | 2021-04-09 | 中南林业科技大学 | Preparation method of lignin modified environment-friendly urea-formaldehyde resin adhesive |
| CN113249070A (en) * | 2021-05-13 | 2021-08-13 | 广西国旭春天人造板有限公司 | Urea-formaldehyde resin adhesive suitable for glue spraying assembly process and preparation method thereof |
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