CN1031512C - Chinese black wattle tannin gum using active Bakelite as cross-linker - Google Patents
Chinese black wattle tannin gum using active Bakelite as cross-linker Download PDFInfo
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- CN1031512C CN1031512C CN 92107343 CN92107343A CN1031512C CN 1031512 C CN1031512 C CN 1031512C CN 92107343 CN92107343 CN 92107343 CN 92107343 A CN92107343 A CN 92107343A CN 1031512 C CN1031512 C CN 1031512C
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Abstract
The present invention relates to a Chinese black wattle tannin glue using active phenolic resin with low molecular weight as a crosslinking agent, which can be used for manufacturing outdoor veneer boards. The present invention is characterized in that the active phenolic resin with low molecular weight, which has the P/F molar ratio of 1/2.2 to 1/3.4 is prepared and is used for replacing paraformaldehyde as the crosslinking agent to prepare the black wattle tannin glue. The phenolic resin comprises a certain amount of free formaldehyde and more methylol, and thus, the phenolic resin can be used as the crosslinking agent and simultaneously perform the function of a reinforcing agent. The veneer boards manufactured by the prepared black wattle tannin glue according to the gluing pressure process of the common phenolic glue are consistent with the bonding strength requirements of veneer boards GB9846.4-88I, and the cost of the Chinese black wattle tannin glue is lower than that of phenolic glue.
Description
The present invention relates to a kind of is the Chinese black wattle tanning gum that can be used for making outdoor grade plywood of linking agent with the lower molecular weight reactive phenolic resin.
In actual applications, the black wattle tanning gum prescription all is to make linking agent with Paraformaldehyde 96, and to add 10～20% phenolic glues be toughener, in order to make outdoor grade plywood.Because China's Paraformaldehyde 96 output is few, price is expensive, is difficult to promote for the tannin glue of linking agent with it.We are used to make concrete form with phenolic glue commonly used and black chaste tree tannin extract preparation tannin one phenolic glue, and its bonding strength and wood failure rate are all good, put into production.But black chaste tree tannin extract consumption can only account for 20～30% weight, increases the tannin extract consumption, the viscosity of tannin one phenolic glue generation gel out of control.
The purpose of this invention is to provide a kind of lower molecular weight reactive phenolic resin that contains a certain amount of free aldehyde and more methylol, replace Paraformaldehyde 96 preparation black wattle tanning gum, this tannin glue can be made outdoor grade plywood by the gluing pressure craft of phenolic glue commonly used.It is lower than phenolic glue to make the outdoor grade plywood cost with black wattle tanning gum of the present invention, and raw material is easy to get and is adapted at China and promotes.
The present invention is achieved in that the Acacia extract solution that is mixed with soluble in water, adds an amount of special lower molecular weight reactive phenolic resin and flour, stir evenly black wattle tanning gum, this glue can by with the same usage compacting of phenolic glue outdoor grade plywood.
The quality index of used China Dark chaste tree tannin extract is: moisture 6.7～12.6% weight, tannin 69.3～73.5% weight, non-tannis 23.3～25.9% weight, the concentration of insolubles 1.5～4.9% weight formaldehyde condensation values 80～85% weight Acacia extract solution is that 40～50% weight are preferably between 44～46% weight.The reactive phenolic resin prescription of using as linking agent is 1/2.2～1/3.4 for the phenol/formaldehyde mol ratio, be preferably between 1/2.6～1/3.0, the preparation method is for adding 35～50% weight (the formaldehyde amount that is equivalent to phenol/formaldehyde mol ratio 1/0.8～1/1.2) of whole phenol and formaldehyde total amount earlier, 90 ℃ of stirring reactions 50～60 minutes, add remaining whole formaldehyde again, and the reaction solution pH value is transferred to 8～10 with 30% weight NaOH solution, continuation was 90 ℃ of stirring reactions 10～80 minutes, preferably continued stirring reaction 20～50 minutes, cooling promptly becomes reactive phenolic resin.The reactive phenolic resin solid content that makes is 40～50% weight, and free phenol content is 0.2～2.6% weight, and content of free aldehyde is 2.3～7.7% weight, and viscosity is 1～2 second (20 ℃ of GARDNER steep formula viscometer A).
The modulation of black wattle tanning gum: in the black chaste tree evergreen chinquapin sol solution of 100 weight parts, add 30-50 weight part reactive phenolic resin, preferably add 35-45 weight part reactive phenolic resin, the flour that adds total rubber (tannin extract solution and resol total amount) 5～10% weight is again made filler, stirs evenly the black wattle tanning gum that promptly becomes pH value about 7.The pH value of also can be as required adjusting black wattle tanning gum with acetic acid or sodium hydroxide solution is 5～9, and the black wattle tanning gum vitality about PH7 (30 ℃) is 4 hours, and the black wattle tanning gum vitality in PH5～7 scopes is 4～6 hours.
The processing condition of black wattle tanning gum compacting glued board: this tannin glue is applicable to linden, multiple veneers such as Cortex Fraxini mandshuricae, Pinus massoniana Lamb, birch and Liu An, when using different veneer according to the coarse situation of plate face at 230～400g/m
2Adjust Amount of spread in (two-sided) scope.With 0.7mPa pressure precompressed 10 minutes, closure was displayed after 0～24 hour and is carried out hot pressing behind the gluing.Heat pressing process condition: pressure 1.0～1.2mpa (pressure is looked differing materials and is different), 140～150 ℃ of temperature; The thick veneer of the every mm of hot pressing time 50～70 seconds (as the thick three-ply-wood hot pressing of 3mm 3 minutes).
Embodiment 1
The preparation of reactive phenolic resin: with the resol of eight kinds of different mol ratio of three-necked flask preparation of putting belt stirrer, reflux exchanger and thermometer in the heated water bath.Under agitation add 104.4g90% phenol and 82.3g36.46% weight formaldehyde solution, be warmed up to 90 ℃, be incubated 1 hour.Add 82.3,98.7,115.2,131.7,148.1,164.6,181.0 and 197.5g36.46% weight formaldehyde solution then respectively, and the pH value of reaction solution is transferred between 8～10 with 30% weight NaOH solution, 15～17g, continued stirring reaction 20 minutes at 90 ℃, cooling, promptly become the reactive phenolic resin of using as linking agent, its analytical data sees Table 1.
Table 1 different mol ratio reactive phenolic resin is analyzed the free aldehyde viscosity phenol of data mol ratio solid content free phenol: formaldehyde % % by weight % by weight weight second (20 ℃) 1: 2.0 50.9 2.62 1.03 1.1～1.21: 2.2 49.4 2.22 2.29 1.11: 2.4 46.3 1.31 2.55 1.1～1.21: 2.6 45.1 0.89 3.56 1.0～1.11: 2.8 42.0 0.8 4.41 1.1～1.21: 3.0 40.7 0.66 6.32 1.0～1.21: 3.2 40.0 0.51 7.191: 3.4 39.6 0.27 7.70
Annotate: solid content press LY228-83 and is detected, and free phenol content press the LY235-83 detection, and content of free aldehyde is pressed the LY238-83 detection, and viscosity is steeped formula viscosity instrumentation with GARDNER, is equivalent to GARDNER A in 1～2 second.
The modulation of black wattle tanning gum:, add the black chaste tree evergreen chinquapin sol solution that obtains concentration 45% in the 500g water under stirring with the Acacia extract of 500g (moisture 10%).Get the black chaste tree evergreen chinquapin sol solution of 8 parts of 84g45%, add phenol/formaldehyde mol ratio 1/2.0,1/2.2,1/2.4,1/2.6,1/2.81/3.0,1/3.2 and 1/3.4 reactive phenolic resin 36g respectively, and respectively add 9.6g flour, stir evenly and promptly get 8 parts of black wattle tanning gums.
The glued board pressing conditions: be the examination material with the thick 1.08mm linden of 30 * 30cm veneer (water ratio 7～8%), manual roller coat tannin glue, single spreading amount 12.6～14.4g (is equivalent to single face 140～160g/m).Behind the gluing 10～60 minutes, on the QC-120T testing press, with 0.7mPa pressure precompressed 10 minutes.After closure is displayed 3～4 hours, at 140～150 ℃, under the 1.0mPa pressure, with 2 blocks of thick three-ply-wood of 3.24mm hot pressing together 6 minutes.Every part of tannin glue laminated system 4 Zhang San's plywood are pressed GB9846.9-88 and are made the glued board test specimen, and every glued board is got 4 test specimens, after boiling water boils 3 hours, with LY-500 type tension testing machine test bonding strength, the results are shown in Table 2.
Table 2 is the tannin glue of linking agent with the reactive phenolic resin of different mol ratio
Pressing plate is mol ratio bonding strength wood failure rate remarks phenol as a result: formaldehyde N/mm
2%1: 9 test specimens in 2.0 0.77 6 15 test specimens
(60%) intensity＞0.7N/mm
2In 1: 2.2 1.20 56 16 test specimen (100%)
Intensity＞0.7N/mm
21: 2.4 1.34 39 the same 1: 2.6 1.66 71 the same 1: 2.8 1.63 52 the same 1: 3.0 1.49 31 the same 1: 3.2 1.35 53 the same 1: 3.4 1.19 37 the same
Annotate: bonding strength is the mean value that multiply by behind 0.9 coefficient in the table, below each table all with, notes in addition.
Embodiment 2
As embodiment 1, the reactive phenolic resin of preparation 334g phenol/formaldehyde mol ratio 1/2.6, solid content 45.1% weight, free phenol 0.67% weight, free aldehyde 3.73% weight, viscosity 1.1～1.2 seconds.
The modulation of black wattle tanning gum: with the Acacia extract of 250g (moisture 10%), stir down and add in the 250g water, obtain concentration 45% weight Acacia extract solution, get the black chaste tree evergreen chinquapin sol solution of 4 parts of 100g45%, add 20,30,40 respectively, the reactive phenolic resin and 9.6,10.4,11.2 of 50g phenol/formaldehyde mol ratio 1/2.6,12.0g flour, stir evenly 4 parts of tannin glue that dosage of crosslinking agent is different.
Press the identical method of embodiment 1,, and detect bonding strength, the results are shown in Table 3 with 4 blocks of linden three-ply-wood of every part of tannin glue laminated system.
The tannin glue laminated of table 3 different amounts reactive phenolic resin hardens fruit PF resin demand bonding strength wood failure rate remarks to 100 parts of tannin extract solution N/mm
2In 20 0.66 0 16 test specimens of %, 1
(6%) intensity＞0.7N/mm
230 1.02 29 15 test specimens (100%)
Intensity＞0.7N/mm
240 1.63 53 16 test specimens (100%)
Intensity＞0.7N/mm
250 1.53 46 is the same
Embodiment 3
Carry out the impregnation pressing plate with phenol/formaldehyde mol ratio 1/2.6 reactive phenolic resin of embodiment 2 preparations and the Acacia extract solution of concentration 45%.
The modulation of black wattle tanning gum: get the black chaste tree evergreen chinquapin sol solution of 5 parts of 84g 45% weight, each adds the 36g reactive phenolic resin and 8.8g flour stirs evenly, and this moment, the pH value of black wattle tanning gum was 7.0 ± 0.1.Get two parts of tannin glue and pH value is transferred to 5.0 ± 0.1 and 6.0 ± 0.1 respectively with acetic acid.Other gets two parts of tannin glue and with 40%NaOH solution pH value is transferred to 8.0 ± 0.1 and 9.0 ± 0.1 respectively.The vitality of the black wattle tanning gum of PH9.0 ± 0.1 and PH8.0 ± 0.1 (20～25 ℃) be respectively 1 hour and the vitality of the black wattle tanning gum that 2 hours PH7.0 ± 0.1 are following greater than 4 hours.
Press the identical method of embodiment 1,, and detect bonding strength, the results are shown in Table 4 with 4 blocks of linden three-ply-wood of every part of tannin glue laminated system.
The pressing plate of table 4 different PH black wattle tanning gum is pH value bonding strength wood failure rate remarks as a result
N/mm
2%5.0 ± 0.1 1.38 67 15 test specimen (100%) intensity＞0.7N/mm
26.0 ± 0.1 1.46 53 the same 7.0 ± 0.1 1.47 69 16 test specimens (100%)
Intensity＞0.7N/mm
28.0 ± 0.1 1.62 93 the same 9.0 ± 0.1 1.53 61 the same embodiment 4
As embodiment 1 preparation 334g phenol/formaldehyde mol ratio 1/2.6 reactive phenolic resin, its solid content 45.2% weight, free phenol 0.67% weight, free aldehyde 3.32% weight, viscosity 1.1～1.2 seconds.
The modulation of black wattle tanning gum: the stirring of 300g (moisture 10%) Acacia extract is added in the 300g water down, obtain concentration 45% weight Acacia extract solution.Get 560g tannin extract solution and add 240g reactive phenolic resin and 64g flour, stir evenly into the 864g black wattle tanning gum.
With embodiment 1 same veneer, Amount of spread, precompressed and hot pressing condition, only closure is displayed 6 groups of (every group of 4 blocks of plates) linden three-ply-wood of compacting in 0～0.5,4,8,12,16,24 hour, is pressed GB9846.9-88 making test specimen after the precompressed, boiling water boiled 3 hours, detected bonding strength, the results are shown in Table 5.
Table 5 black wattle tanning gum is to the adaptability assembly time bonding strength wood failure rate remarks hour N/mm of different assembly times
2%0～0.5 1.59 73 15 test specimen (100%)
Intensity＞0.7N/mm
24 1.66 71 16 test specimens (100%)
Intensity＞0.7N/mm
28 1.41 88 the same 12 1.46 75 the same 16 1.55 91 the same 24 1.55 77 is the same
Embodiment 5
Reactive phenolic resin as embodiment 1 preparation 334g phenol/formaldehyde mol ratio 1/2.6 closes solid amount 44.6% weight, free phenol 0.80% weight, free aldehyde 3.07% weight viscosity 1.1～1.2 seconds.
The modulation of black wattle tanning gum: the stirring of 350g (moisture 10%) Acacia extract is added in the 350g water down, obtain the tannin extract solution of concentration 45%.Get 630g tannin extract solution and add 270g reactive phenolic resin and 72g flour, stir evenly into black wattle tanning gum.
Suppress two groups of linden three-ply-wood with embodiment 1 same veneer, Amount of spread, prefabricating condition, assembly time and hot pressing pressure (1.0mPa).One group fixedly hot pressing temperature be 140～150 ℃, hot pressing time was got respectively 4,5,6,7 minutes; Another group fixedly hot pressing time is 6 minutes, and hot pressing temperature is got 115 ± 5 ℃ 125 ± 5 ℃, 135 ± 5 ℃, 145 ± 5 ℃ respectively.Each condition is pressed 4 blocks of linden three-ply-wood, and the method detected intensity of pressing embodiment 1 the results are shown in Table 6 and table 7.
The different hot pressing time pressing plates of table 6 hot pressing time bonding strength wood failure rate remarks as a result divide N/mm
29 of 4 0.71 0 16 test specimens of % (56%)
Intensity＞0.7N/mm
25 1.04 0 16 test specimens (100%)
Intensity＞0.7N/mm
26 1.40 53 the same 7 1.56 55 is the same
The different hot pressing temperature pressing plates of table 7 are hot pressing temperature bonding strength wood failure rate remarks as a result
N/mm
2%110～120 00 16 test specimen is all boiled 120～130 0.37 0 16 test specimens and is boiled 3,1
(6%) intensity＞0.7N/mm
2130～140 0.84 0 16 test specimens, 11 (69%)
Intensity＞0.7N/mm
2140～150 1.40 53 16 test specimens (100%)
Intensity＞0.7N/mm
2
By table 6 and table 7 as seen, be the tannin glue of linking agent with the reactive phenolic resin, 140～150 ℃ of every mm thick plywood of hot pressing temperature hot pressing 1 minute, the intensity of glued board meets the requirement of GB9864.4-88I class plate, and the wood failure rate is greater than 50%.Hot pressing temperature is lower than 140 ℃, and then crosslinking curing is incomplete, and intensity is defective, no wood failure.
Embodiment 6
As embodiment 4 preparation 334g phenol/cresols mol ratio 1/2.6 reactive phenolic resins, modulation 864g black wattle tanning gum.
Compacting glued board: press the same Amount of spread of embodiment 1, prefabricating condition, assembly time, hot pressing temperature (140～150 ℃), compacting 30 * 30cm linden three-ply-wood (the thick 1.08mm of veneer): respectively 4 on Cortex Fraxini mandshuricae three-ply-wood (the thick 1.04mm of veneer), Pinus massoniana Lamb three-ply-wood (the thick 1.33mm of veneer), birch three-ply-wood (the thick 1.5mm of veneer), Liu An three-ply-wood (the thick 2.0mm of veneer).The hot pressing pressure of linden three-ply-wood is 1.0mpa, and the hot pressing pressure of other glued boards is 1.2mPa, 2 on each same assortment three-ply-wood of hot pressing, the every mm thick plywood of hot pressing time 1 minute.Press the method for embodiment 1, detect bonding strength, every block of plate is got 6 test specimens, the results are shown in Table 8
Table 8 is suppressed different assortment three-ply-wood detected result assortment hot pressing time bonding strength wood failure rate remarks with black wattle tanning gum
Divide N/mm
26 1.58 54 24 test specimens of % linden (100%)
Intensity＞0.7N/mm
222 of 6 1.23 44 24 test specimens of Cortex Fraxini mandshuricae (92%)
Intensity＞0.8N/mm
2Pinus massoniana Lamb 8 1.24 57 9 1.28 0 24 test specimens of the same birch (100%)
Intensity＞1.0N/mm
221 of 12 0.95 35 24 test specimens of Liu An
Intensity＞0.7N/mm
2
Claims (2)
1. reactive phenolic resin is the preparation method of the Chinese black wattle tanning gum of linking agent, it is characterized in that the Acacia extract solution that is made into concentration 40-50% weight soluble in water, in the black chaste tree evergreen chinquapin sol solution of 100 weight parts, add 30-50 weight part reactive phenolic resin, the flour that adds 5-10 weight parts again in the mixture of the tannin extract solution of 100 weight parts and resol, stir evenly into tannin glue, wherein the preparation method of reactive phenolic resin is that the mol ratio of phenol/formaldehyde is 1/2.2-1/3.4, add whole phenol and the formaldehyde that accounts for 35-50% weight of total formaldehyde earlier, this is equivalent to the formaldehyde amount of phenol/formaldehyde mol ratio 1/0.8-1/1.2, under 90C, reacted 50-60 minutes, add remaining whole formaldehyde again, and the pH value of reaction solution is transferred to 8-10 with sodium hydroxide solution, under 90 ℃ of agitation conditions, continue reaction 10-80 minutes, cool off the reactive phenolic resin of solid content 40-50% weight.
2. reactive phenolic resin according to claim 1 is the preparation method of the Chinese black wattle tanning gum of linking agent, it is characterized in that the pH value of black wattle tanning gum is transferred to 5-9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92107343 CN1031512C (en) | 1992-03-31 | 1992-03-31 | Chinese black wattle tannin gum using active Bakelite as cross-linker |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92107343 CN1031512C (en) | 1992-03-31 | 1992-03-31 | Chinese black wattle tannin gum using active Bakelite as cross-linker |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1065476A CN1065476A (en) | 1992-10-21 |
| CN1031512C true CN1031512C (en) | 1996-04-10 |
Family
ID=4942834
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92107343 Expired - Fee Related CN1031512C (en) | 1992-03-31 | 1992-03-31 | Chinese black wattle tannin gum using active Bakelite as cross-linker |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1031512C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1064067C (en) * | 1995-05-07 | 2001-04-04 | 柴万知 | Method for producing tannin-extract adhesive |
| CN1040763C (en) * | 1995-05-26 | 1998-11-18 | 内蒙古牙克石木材加工栲胶联合厂 | Larch tannin adhesive |
| CN101328252B (en) * | 2008-07-29 | 2010-04-14 | 武汉理工大学 | Preparation of low free monomer, degradable persimmon tannin modified phenolic resin |
| CN102134614B (en) * | 2010-11-04 | 2012-07-11 | 张家港市华昌药业有限公司 | Method for extracting D-galactose in black wattle gum |
| CN104802277B (en) * | 2014-11-20 | 2016-11-09 | 东华大学 | A kind of Corchorus olitorius L. strengthens the preparation method of tannic extract resin medium density fibre board (MDF) |
-
1992
- 1992-03-31 CN CN 92107343 patent/CN1031512C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1065476A (en) | 1992-10-21 |
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