CN103555237B - Method for preparing environment-friendly adhesive for biomass wood materials - Google Patents

Method for preparing environment-friendly adhesive for biomass wood materials Download PDF

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CN103555237B
CN103555237B CN201310507343.2A CN201310507343A CN103555237B CN 103555237 B CN103555237 B CN 103555237B CN 201310507343 A CN201310507343 A CN 201310507343A CN 103555237 B CN103555237 B CN 103555237B
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add
phenol
formaldehyde
reaction
caustic soda
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CN103555237A (en
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石建军
俞阳
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JIASHAN ZHONGLIN ADHESIVE TECHNOLOGY Co Ltd
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JIASHAN ZHONGLIN ADHESIVE TECHNOLOGY Co Ltd
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Abstract

The invention realizes industrial production of an environment-friendly adhesive for biomass wood materials by using industrial alkali lignin which is not subjected to processing treatment instead of 30-40 percent of phenol based on the existing water-soluble phenolic resin adhesive production process and equipment. The reaction is mild and smooth, and operation and control are easy; a plywood pressed by the adhesive accords with the requirement for national I-order plates, and the formaldehyde release amount reaches E0 grade.

Description

The preparation method of biomass wood environment-protective adhesive
Technical field
The present invention relates to a kind of preparation method of biomass wood environment-protective adhesive, particularly relate to a kind of preparation method of low-cost environment-friendly alkali lignin modified phenolic resin sizing agent, specifically with alkaline process reclaim alkali lignin for raw material, Substitute For Partial phenol makes modified phenolic resin adhesive, belongs to based Wood Adhesives field.
Background technology
Domestic current outdoor use Artificial Plate Adhesive, mainly based on resol, be secondly melamine modified urea-formaldehyde resin, but the main raw material of these sizing agents all derives from petrochemicals.In recent years, due to the minimizing of prospective oil and rising steadily of oil price, the resol production cost taking petrochemicals as raw material is high, therefore, utilize the biomass renewable resources Substitute For Partial phenol such as alkali lignin, produce low cost environmental protection and biomass wood sizing agent stable and reliable for performance is the development trend of wooden industry sizing agent industry from now on.Along with national environmental protection regulation is gradually improved, development environmental protection sizing agent is imperative, and wherein resol mainly finds development to low toxic and environment-friendly and low cost.
Xylogen is extensively present in the natural phenolic in natural plant body, it is a kind of reproducible biomass resource, it is the main component of pulp and paper industry waste liquid, whole world annual output is about 5,000 ten thousand tonnages, wherein only be utilized effectively less than 10%, the overwhelming majority is all burnt or is entered rivers, contaminate environment, waste resource.Xylogen has phenol structure and is conducive to preparing based Wood Adhesives, by nontoxic alkali lignin Substitute For Partial phenol, can save phenol usage and reduce residual formaldehyde amount.Substitute the phenol of 11000 yuan/ton with the alkali lignin of 1500 yuan/ton, sizing agent cost obviously reduces.So, be the developing direction of phenolic resin adhesive from now on the biomass wood sizing agent of alkali lignin Substitute For Partial phenol.
The preparation method of alkali lignin modified phenolic resin sizing agent, is also in alkali lignin applied research stage in sizing agent, and distance realizes industrial utilization and industrialization is also far away, still rests in laboratory at present.
The present invention with the industrial soda xylogen without any processing treatment for raw material, substitute the phenol amount of 30-40%, the basis that original water-soluble phenolic resin adhesive sticks agent producing process and equipment realizes the suitability for industrialized production of biomass wood environment-protective adhesive, reaction relaxes steadily, easy operation control, meet the requirement of national I class plate with the glued board that this sizing agent is pressed into, burst size of methanal reaches E0 level.
Summary of the invention
The object of the invention is the deficiency in order to solve above-mentioned technology and while a kind of can ensuring the quality of products is provided, reduce phenol usage quantity, and also reducing the preparation method of the biomass wood environment-protective adhesive of free phenol and aldehyde in product.
In order to achieve the above object, the preparation method of the biomass wood environment-protective adhesive designed by the present invention, comprises the following steps:
A) water, phenol, first liquid caustic soda, alkali lignin, first formaldehyde solution add 2 cubes of reactors, are warming up to 80-90 DEG C, reaction times 50-70min after stirring;
B) add toughener and second batch formaldehyde solution, be warming up to 80-90 DEG C and continue reaction 50-70min;
C) add second batch liquid caustic soda and the 3rd batch of formaldehyde solution, be warming up to 80-90 DEG C and continue reaction 50-70min;
When d) being cooled to 75 DEG C, add formaldehyde-trapping agent and the 3rd batch of liquid caustic soda, at 65-75 degree reaction 20-40min, tested viscosity is 20-40s/60 DEG C, cools immediately, is cooled to 40 DEG C with bottom discharge.
Wherein in whole production process, the mol ratio of formaldehyde and phenol is 1: 0.4-0.45, and wherein formaldehyde solution adds in three batches, and the mass ratio of each batch is 1: 0.9: 0.8, and the add-on of liquid caustic soda is the 45-55% of phenol, and the mass ratio added in three batches is 1: 4: 15; Alkali lignin add-on is the phenol amount of alternative 30-40%; Toughener add-on is the 10-15% of phenol; Formaldehyde-trapping agent add-on is the 10-15% of phenol amount; Water add-on will ensure that biomass wood sizing agent solid content controls at 45-50%.
Described alkali lignin is paper mill sulphate process, the soda spent liquor powder after concentrate drying, and wherein the content of effective ingredient xylogen is greater than 20%, pH value 10-12.
Described liquid caustic soda refers to that mass concentration is the sodium hydroxide solution of 30%.
The mass concentration of described formaldehyde solution is 37%.
Described toughener is trimeric cyanamide.
Described formaldehyde-trapping agent is urea.
The preparation method of the biomass wood environment-protective adhesive designed by the present invention is utilized to produce the biomass wood environment-protective adhesive obtained, solids content: 45-50%; PH:10-12; Viscosity: 100-300mpa.s25 DEG C; Free formaldehyde content :≤0.3%, is applicable to the glued board manufacturing various structure.
Wherein said alkali lignin substitutes phenol amount=(alkali lignin consumption)/(phenol usage+alkali lignin consumption); And above-mentioned per-cent is all mass percent.
The present invention compared with prior art has following outstanding advantages
1. to stick agent similar for production technique of the present invention and existing water-soluble phenolic resin adhesive, and equipment and process does not need large change.
2., under the catalysis of liquid caustic soda, formaldehyde divides to feed intake for three times and carries out polycondensation with phenol, controls temperature of reaction and reaction times simultaneously, slow down the heating naturally produced in reaction, make reaction be easy to control, be conducive to reducing free phenol, free aldehyde simultaneously, improve sizing agent quality.
3. the present invention adds gluing toughener trimeric cyanamide in reaction process, and trimeric cyanamide and formaldehyde carry out hydroxymethylation, generate various melamine methylol; Alkali lignin and formaldehyde reaction generate hydroxymethylated lignin, and these methylol compounds and phenol and formaldehyde reaction generate between various hydroxymethyl phenol and carry out condensation reaction, form copolymer resins, enhance bonding strength, provide water tolerance and thermotolerance.
4. the present invention adopts industrial soda xylogen to be raw material, do not need to process purification processes, directly can substitute phenol, product viscosity is moderate, stability in storage is good, free aldehyde is low, improves the utilising efficiency of biomass renewable resource, advances the commercial application of the biomass renewable resource such as alkali lignin in sizing agent field.
In sum, the present invention with the industrial soda xylogen without any processing treatment for raw material, substitute the phenol amount of 30-40%, the basis that original water-soluble phenolic resin adhesive sticks agent producing process and equipment realizes the suitability for industrialized production of biomass wood environment-protective adhesive, reaction relaxes steadily, easy operation control, use the present invention to the glued board that is pressed into of sizing agent meet the requirement of national I class plate, burst size of methanal reaches E0 level.
Accompanying drawing explanation
Fig. 1 be five embodiments to product and utilize the table with test results of this products production glued board.
Embodiment
Below by embodiment, the invention will be further described by reference to the accompanying drawings.
Embodiment 1:
The preparation method of the biomass wood environment-protective adhesive that the present embodiment describes comprises following steps:
1. water 200kg, phenol 400kg, first liquid caustic soda 10kg, alkali lignin 175kg, first formaldehyde solution 300kg in 2 cubes of reactors, be warming up to 85 DEG C, reaction 60min;
2. add trimeric cyanamide 50kg, second batch formaldehyde solution 270kg, be warming up to 85 DEG C, reaction 60min;
3. add second batch liquid caustic soda 40kg, the 3rd crowd of formaldehyde solution 240kg, be warming up to 85 DEG C, reaction 60min;
4., when being cooled to 75 DEG C, add urea 50kg and the 3rd crowd liquid caustic soda 150kg, 65-75 DEG C of reaction 20-40min; Then, time to be coated with that in 4 glasss, tested viscosity is for 20-40s/60 DEG C, reach requirement and cool stopped reaction immediately, be cooled to 40 DEG C with bottom discharge.
Embodiment 2:
The preparation method of the biomass wood environment-protective adhesive that the present embodiment describes comprises following steps:
1. in 2 cubes of reactors, the 200kg that adds water, phenol 400kg, first liquid caustic soda 10kg, alkali lignin 200kg, first formaldehyde solution 300kg, be warming up to 85 DEG C, reaction 60min;
2. add trimeric cyanamide 50kg, second batch formaldehyde solution 270kg, be warming up to 85 DEG C, reaction 60min;
3. add second batch liquid caustic soda 40kg, the 3rd crowd of formaldehyde solution 240kg, be warming up to 85 DEG C, reaction 60min;
4., when being cooled to 75 DEG C, adding urea 50kg and the 3rd crowd liquid caustic soda 150kg, 65-75 DEG C of reaction 20-40min, during to be coated with that in 4 glasss, tested viscosity is for 20-40s/60 DEG C, to reach requirement and cool stopped reaction immediately, be cooled to 40 degree with bottom discharge.
Embodiment 3:
The preparation method of the biomass wood environment-protective adhesive that the present embodiment describes comprises following steps:
1. in 2 cubes of reactors, add water 250kg, phenol 400kg, first liquid caustic soda 10kg, alkali lignin 250kg, first formaldehyde solution 300kg, be warming up to 85 DEG C, reaction 60min;
2. add trimeric cyanamide 50kg, second batch formaldehyde solution 270kg, be warming up to 85 DEG C, reaction 60min;
3. add second batch liquid caustic soda 40kg, the 3rd crowd of formaldehyde solution 240kg, be warming up to 85 DEG C, reaction 60min;
4., when being cooled to 75 DEG C, adding urea 50kg and the 3rd crowd liquid caustic soda 150kg, 65-75 DEG C of reaction 20-40min, during to be coated with that in 4 glasss, tested viscosity is for 20-40s/60 DEG C, to reach requirement stopped reaction immediately, be cooled to 40 degree with bottom discharge.
Embodiment 4:
That the present embodiment describes is the preparation method of sizing agent of the prior art, comprises following steps:
1. in 2 cubes of reactors, add water 50kg, phenol 400kg, first liquid caustic soda 10kg, do not add alkali lignin, first formaldehyde solution 280kg, be warming up to 85 DEG C, reaction 50min;
2. add trimeric cyanamide 25kg, second batch formaldehyde solution 240kg, be warming up to 85 DEG C, reaction 60min;
3. add the 3rd crowd of liquid caustic soda 40kg, the 3rd crowd of formaldehyde solution 210kg, be warming up to 85 DEG C, reaction 60min;
4. when being cooled to 75 DEG C, add urea 50kg and the 3rd crowd liquid caustic soda 150kg, 65 DEG C-75 DEG C, reaction 20-40min, with to be coated with in 4 glasss tested viscosity for 20-40s/60 spend time, reach requirement and stop cooling reaction immediately, be cooled to 40 DEG C with bottom discharge.
Embodiment 5
The preparation method of the biomass wood environment-protective adhesive that the present embodiment describes comprises following steps:
1. in 2 cubes of reactors, the 250kg that adds water, phenol 400kg, first liquid caustic soda 10kg, alkali lignin 275kg, first formaldehyde solution 300kg, be warming up to 85 DEG C, reaction 60min;
2. add trimeric cyanamide 50kg, second batch formaldehyde solution 270kg, be warming up to 85 DEG C, reaction 60min;
3. add second batch liquid caustic soda 40kg, the 3rd crowd of formaldehyde solution 240kg, be warming up to 85 DEG C, reaction 60min;
4. when being cooled to 75 DEG C, add urea 50kkg and the 3rd crowd liquid caustic soda 150kg, 65-75 DEG C, reaction 20-40min, during to be coated with that in 4 glasss, tested viscosity is for 20-40s/60 DEG C, to reach requirement stopped reaction immediately, is cooled to 40 DEG C with bottom discharge.
The sizing agent five embodiments obtained detects by the regulation of standard GB/T/T14074-2006.
The sizing agent simultaneously utilizing five embodiments to obtain is produced poplar plywood and is detected, and detection mode is as follows:
1. detect after first the poplar plywood room temperature be pressed into being placed 5 days;
2. bonding strength-by the type Ⅰ plywood bonding strength testing method in GB GB/T9846.12-88;
3. burst size of methanal-measure by the desiccating method in GB GB/T1765-1999;
4. dipping and stripping performance-detect by the regulation of GB GB/T1765-1999.
Have Fig. 1 known, the product obtained by the present invention, indices all meets national standard.

Claims (1)

1. a preparation method for biomass wood environment-protective adhesive, is characterized in that comprising the following steps:
A) water, phenol, first liquid caustic soda, alkali lignin, first formaldehyde solution add 2 cubes of reactors, are warming up to 80-90 DEG C, reaction times 50-70min after stirring;
B) add toughener and second batch formaldehyde solution, be warming up to 80-90 DEG C and continue reaction 50-70min;
C) add second batch liquid caustic soda and the 3rd batch of formaldehyde solution, be warming up to 80-90 DEG C and continue reaction 50-70min;
When d) being cooled to 75 DEG C, add formaldehyde-trapping agent and the 3rd batch of liquid caustic soda, at 65-75 DEG C of reaction 20-40min, tested viscosity is 20-40s/60 DEG C, cools immediately, is cooled to 40 DEG C with bottom discharge;
In whole production process, the mol ratio of formaldehyde and phenol is 1: 0.4-0.45, and wherein formaldehyde solution adds in three batches, and the mass ratio of each batch is 1: 0.9: 0.8, and the add-on of liquid caustic soda is the 45-55% of phenol, and the mass ratio added in three batches is 1: 4: 15; Alkali lignin add-on is the phenol amount of alternative 30-40%; Toughener add-on is the 10-15% of phenol; Formaldehyde-trapping agent add-on is the 10-15% of phenol amount; Water add-on will ensure that biomass wood sizing agent solid content controls at 45-50%;
Described alkali lignin is paper mill sulphate process, the soda spent liquor powder after concentrate drying, and wherein the content of effective ingredient xylogen is greater than 20%, pH value 10-12;
Described liquid caustic soda refers to that mass concentration is the sodium hydroxide solution of 30%;
The mass concentration of described formaldehyde solution is 37%;
Described toughener is trimeric cyanamide;
Described formaldehyde-trapping agent is urea.
CN201310507343.2A 2013-10-24 2013-10-24 Method for preparing environment-friendly adhesive for biomass wood materials Active CN103555237B (en)

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CN104087219A (en) * 2014-06-09 2014-10-08 德华兔宝宝装饰新材股份有限公司 Preparation method of lignin-modified phenolic resin wood adhesive
CN105348460B (en) * 2015-11-25 2017-11-17 北华大学 A kind of cellulosic ethanol lignin modification Phenolic resin wood adhesive and preparation method thereof
CN107236500A (en) * 2016-03-29 2017-10-10 中国林业科学研究院林产化学工业研究所 The preparation method of lignin sulfonate modified urea-phenolic resin
SE543103C2 (en) * 2018-11-27 2020-10-06 Stora Enso Oyj Process for preparing a solution of lignin in an aqueous medium by partial methylolation
CN109679547A (en) * 2018-12-20 2019-04-26 上海昶法新材料有限公司 A kind of preparation method of modified phenolic resin adhesive and products thereof
CN109679548A (en) * 2018-12-20 2019-04-26 上海昶法新材料有限公司 A kind of modified phenolic resin adhesive and preparation method thereof
CN109679549A (en) * 2018-12-21 2019-04-26 上海昶法新材料有限公司 A kind of preparation method suitable for building the modified phenolic resin adhesive of bond paper
CN110564346A (en) * 2019-09-20 2019-12-13 上海昶法新材料有限公司 Modified phenolic glue and preparation method thereof
CN114058302A (en) * 2021-12-30 2022-02-18 仁化县奥达胶合板有限公司 Adhesive for bamboo-wood composite plywood and synthetic method

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US4303562A (en) * 1980-07-24 1981-12-01 American Can Company Lignin-containing resin adhesive
CN101358120B (en) * 2008-09-18 2012-02-01 华南理工大学 Environment-friendly type alkali lignin modified phenolic resin adhesive and preparation method thereof
CN101544878B (en) * 2009-05-05 2012-01-04 浙江林学院 Alkali lignin oxidized starch modified phenolic glue and production method thereof
CN102061141B (en) * 2009-11-11 2013-10-16 青岛生物能源与过程研究所 Method for preparing environmentally-friendly adhesive for lignin-based timber

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