CN106590488A - Method for preparing oxidized lignin phenolic resin adhesive - Google Patents
Method for preparing oxidized lignin phenolic resin adhesive Download PDFInfo
- Publication number
- CN106590488A CN106590488A CN201611193561.3A CN201611193561A CN106590488A CN 106590488 A CN106590488 A CN 106590488A CN 201611193561 A CN201611193561 A CN 201611193561A CN 106590488 A CN106590488 A CN 106590488A
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- CN
- China
- Prior art keywords
- phenolic resin
- resin adhesive
- parts
- lignin
- formaldehyde
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Classifications
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- 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
- C09J161/14—Modified phenol-aldehyde condensates
-
- 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
Abstract
The invention relates to the field of industrial adhesive processing, in particular to a method for preparing an oxidized lignin phenolic resin adhesive. The method for preparing the oxidized lignin phenolic resin adhesive comprises steps as follows: solid powdery lignin is prepared firstly, and then lignin degradation and adhesive preparation are performed. The oxidized lignin phenolic resin adhesive has the beneficial effects as follows: the bonding strength is high, solid content is high, and uniform adhesive coating is facilitated; compared with a traditional phenolic resin adhesive, the oxidized lignin phenolic resin adhesive has the advantages that lignin replaces most phenol, the content of free formaldehyde is lower than 0.3%, and great significance in the aspects of saving of raw material cost, environmental protection and the like is realized.
Description
Technical field
The present invention relates to industrial adhesive manufacture field, more particularly to a kind of system of oxidative lignin's phenolic resin adhesive
Make method.
Background technology
At present, some wood-based plates (such as composite floor board, plywood, core-board) in process of production, have been used with first
Aldehyde for main component phenolic resin as adhesive, plywood product prepared by phenolic resin adhesive has bonding strength
The advantages of high, weather-proof, water-fast and corrosion resistance and good.As the deficient price of petroleum resources constantly rises, its primary raw material benzene
Phenol price also constantly rises, and directly results in phenolic resin adhesive on the high side.Simultaneously as the system of phenolic resin adhesive
Standby technique can also discharge a certain amount of formaldehyde during production and use, and formaldehyde can cause the various diseases of human body, such as roar
Breathe heavily, tracheitiies, dermatitis etc., Long Term Contact even can cause malignant tumor.These wood-based plates used in people decorate indoors
When, the free shape formaldehyde for having neither part nor lot in reaction remained in sheet material gradually can discharge to surrounding, so as to indoors environment is empty
The main body of formaldehyde is formed in gas.
Lignin yield is only second to cellulose, is the second substantial amounts of reproducible biomass resource in nature.In timber
Industrial adhesive field introduces lignin and launches research, is the important directions that lignin is develop and useedd.
At present, common lignin-base adhesive is typically lignin itself and prepares gluing by modified as primary raw material
Agent, but it is in hot pressing, existence time is longer, temperature is higher and the problems such as high acidity；At the same time, lignin adhesive
Also need to upon compression, through special processing technique, plywood color blackening, physical property, machine can be caused in process
Tool performance and resistance to water it is poor this, lignin prepares adhesive and needs further research and innovate for primary raw material.
The content of the invention
It is an object of the invention to provide a kind of manufacture method of oxidative lignin's phenolic resin adhesive, with modified wood
Quality part substitutes benzene cheese novolak resin adhesive, cost-effective solution problems of the prior art, the present invention
Concrete technical scheme is as follows：
A kind of manufacture method of oxidative lignin's phenolic resin adhesive, comprises the following steps：
Straw after drying and potassium hydroxide solid are dissolved in BDO solution, are placed in high pure nitrogen
In reactor, while opening stirring, temperature is 150～190 DEG C, reacts 3.5h；Reaction final vacuum, then to reacting liquid filtering 3
～5 times, filtrate pH value is adjusted to 1.8～2.1, centrifugation is repeatedly washed with deionized the sediment fraction after centrifugation into
Property, last dehydrate obtains pressed powder and is lignin.
It is anti-in 110～120 DEG C by the lignin, copper sulfate, potassium hydroxide solution and hydrogenperoxide steam generator mix homogeneously
1.5～2h is answered, 85～90 DEG C are then cooled to, keeping temperature simultaneously adds for the first time formalin, reacts 30～45min, again
60 DEG C are cooled to, second addition formalin, and phenol is added, and 85～90 DEG C are to slowly warm up to, 1.5～2h is reacted, cool down,
Obtain finished product, i.e. oxidative lignin's phenolic resin adhesive.
Further, the manufacture method of oxidative lignin's phenolic resin adhesive, the gross weight number of its raw material is：
50～65 parts of straw, 48～63 parts of formaldehyde, 18～24 parts of phenol, 18～30 parts of potassium hydroxide solid, copper sulfate 1.2
～3 parts, 0.3～0.9 part of hydrogenperoxide steam generator.
Further, the manufacture method of oxidative lignin's phenolic resin adhesive, the gross weight number of its raw material is：
52 parts of straw, 56 parts of formaldehyde, 21 parts of phenol, 20 parts of potassium hydroxide solid, 1.2 parts of copper sulfate, hydrogenperoxide steam generator
0.4 part.
Further, after the reactant liquor is filtered for the first time, filtering residue with 95～100 DEG C, pH value be 9.8～10.3 Isosorbide-5-Nitrae-
Butanediol solution is washed；Then carry out second filtration, from the beginning of filtering from second, filtering residue uses 80～85 DEG C, pH value for 9.8～
10.3 deionized water wash.
Further, the filtrate pH value dilute hydrochloric acid or dilute sulfuric acid are adjusted.
Further, the potassium hydroxide solution mass concentration is 8～9%.
Further, it is the 1/3 of the formaldehyde gross weight number that the first time adds the amount of formaldehyde, described to add for the second time
The amount for entering formaldehyde is the 2/3 of the formaldehyde gross weight number.
The present invention compared with prior art, has the advantages that：
Lignin of the present invention has boiling point high, and pressure is low, is ensuing lignin degradation the advantages of dissolubility is good
Process and adhesive preparation process provide good basis.Oxidation modification lignin phenol formaldehyde resin adhesive phase of the present invention
Bonding strength height, solid content are high for traditional phenolic resin, it is ensured that actual bonding demand, while being easy to uniform
Gluing, compared with traditional phenolic resin adhesive, lignin instead of most phenol, and the content of free formaldehyde is less than
0.3%, the aspects such as the cost that economizes in raw materials, environmental protection are had very important significance.
Specific embodiment
The embodiments described below are a part of embodiments of the invention, rather than the embodiment of whole.Based on the present invention
In embodiment, the every other enforcement that those of ordinary skill in the art are obtained under the premise of creative work is not made
Example, belongs to the scope of protection of the invention.
Embodiment 1
Described in the present embodiment, a kind of manufacture method of oxidative lignin's phenolic resin adhesive is comprised the following steps：
Straw after drying and potassium hydroxide solid are dissolved in BDO solution, are placed in high pure nitrogen
In reactor, while opening stirring, temperature is 150～190 DEG C, reacts 3.5h；Reaction final vacuum, then to reacting liquid filtering 3
～5 times, after reactant liquor is filtered for the first time, with 95～100 DEG C, pH value is 9.8～10.3 BDO solution washing to filtering residue；
Then second filtration is carried out, from the beginning of filtering from second, with 80～85 DEG C, pH value is the washing of 9.8～10.3 deionizations to filtering residue
Wash, merging filtrate, filtrate pH value is adjusted to 1.8～2.1, centrifugation is repeatedly washed with deionized water the sediment fraction after centrifugation
Wash to neutrality, last dehydrate obtains pressed powder and is lignin.
By the lignin, copper sulfate, potassium hydroxide solution and hydrogenperoxide steam generator mix homogeneously, the potassium hydroxide is molten
Liquid mass concentration is 8～9%, and in 110～120 DEG C 1.5～2h is reacted, and is then cooled to 85～90 DEG C, keeping temperature and first
Secondary addition formalin, the amount of formaldehyde is the 1/3 of the formaldehyde gross weight number, reacts 30～45min, and 60 are cooled to again
DEG C, second addition formalin, the amount of formaldehyde is the 2/3 of the formaldehyde gross weight number, and adds phenol, is to slowly warm up to
85～90 DEG C, 1.5～2h is reacted, cooling obtains finished product, i.e. oxidative lignin's phenolic resin adhesive.
Described in the present embodiment, the manufacture method of oxidative lignin's phenolic resin adhesive, the gross weight number of its raw material
For：
52 parts of straw, 56 parts of formaldehyde, 21 parts of phenol, 20 parts of potassium hydroxide solid, 1.2 parts of copper sulfate, hydrogenperoxide steam generator
0.4 part.
Embodiment 2
The present embodiment is improved on the basis of embodiment 1, and the content described in embodiment 1 is also the present embodiment institute
Have, no longer specifically repeat herein.
Described in the present embodiment, a kind of manufacture method of oxidative lignin's phenolic resin adhesive, the gross weight of its raw material
Number is：
65 parts of straw, 48 parts of formaldehyde, 19 parts of phenol, 30 parts of potassium hydroxide solid, 1.5 parts of copper sulfate, hydrogenperoxide steam generator
0.5 part.
Embodiment 3
The present embodiment is improved on the basis of embodiment 1, and the content described in embodiment 1 is also the present embodiment institute
Have, no longer specifically repeat herein.
Described in the present embodiment, a kind of manufacture method of oxidative lignin's phenolic resin adhesive, in terms of parts by weight, bag
Containing following components：
54 parts of straw, 63 parts of formaldehyde, 22 parts of phenol, 27 parts of potassium hydroxide solid, 2.5 parts of copper sulfate, hydrogenperoxide steam generator
0.9 part.
Embodiment 4
The present embodiment is improved on the basis of embodiment 1, and the content described in embodiment 1 is also the present embodiment institute
Have, no longer specifically repeat herein.
Described in the present embodiment, a kind of manufacture method of oxidative lignin's phenolic resin adhesive, in terms of parts by weight, bag
Containing following components：
50 parts of straw, 52 parts of formaldehyde, 18 parts of phenol, 22 parts of potassium hydroxide solid, 2.0 parts of copper sulfate, hydrogenperoxide steam generator
0.7 part.
Embodiment 5
The present embodiment is improved on the basis of embodiment 1, and the content described in embodiment 1 is also the present embodiment institute
Have, no longer specifically repeat herein.
Described in the present embodiment, a kind of manufacture method of oxidative lignin's phenolic resin adhesive, in terms of parts by weight, bag
Containing following components：
61 parts of straw, 50 parts of formaldehyde, 24 parts of phenol, 24 parts of potassium hydroxide solid, 3.0 parts of copper sulfate, hydrogenperoxide steam generator
0.6 part.
Embodiment 6
The present embodiment is improved on the basis of embodiment 1, and the content described in embodiment 1 is also the present embodiment institute
Have, no longer specifically repeat herein.
Described in the present embodiment, a kind of manufacture method of oxidative lignin's phenolic resin adhesive, in terms of parts by weight, bag
Containing following components：
63 parts of straw, 59 parts of formaldehyde, 23 parts of phenol, 18 parts of potassium hydroxide solid, 2.7 parts of copper sulfate, hydrogenperoxide steam generator
0.3 part.
To the oxidative lignin's phenolic resin adhesive obtained by above-described embodiment 1-6, with reference to standard GB/T/T
14074-2006, enters to free formaldehyde content, free phenol content, bonding strength in oxidative lignin's phenolic resin adhesive
Row test, test result such as following table：
| Project | Free formaldehyde content (%) | Free phenol content (%) | Bonding strength (MPa) |
| Embodiment 1 | 0.081 | 2.23 | 2.15 |
| Embodiment 2 | 0.080 | 2.22 | 2.22 |
| Embodiment 3 | 0.082 | 2.24 | 2.19 |
| Embodiment 4 | 0.082 | 2.23 | 2.20 |
| Embodiment 5 | 0.083 | 2.24 | 2.16 |
| Embodiment 6 | 0.082 | 2.24 | 2.18 |
As seen from the above table, oxidative lignin's phenolic resin adhesive meets in standard GB/T/T 14074-2006 and specifies
Relevant parameter.
Finally it should be noted that：Various embodiments above only to illustrate technical scheme, rather than a limitation；To the greatest extent
Pipe has been described in detail with reference to foregoing embodiments to the present invention, it will be understood by those within the art that：Its according to
So the technical scheme described in foregoing embodiments can be modified, either which part or all technical characteristic are entered
Row equivalent；And these modifications or replacement, do not make the essence disengaging various embodiments of the present invention technology of appropriate technical solution
The scope of scheme.
Claims (7)
1. a kind of manufacture method of oxidative lignin's phenolic resin adhesive, it is characterised in that comprise the following steps：
Straw after drying and potassium hydroxide solid are dissolved in BDO solution, the reaction with high pure nitrogen is placed in
In kettle, while opening stirring, temperature is 150～190 DEG C, reacts 3.5h；Reaction final vacuum, then to reacting liquid filtering 3～5
It is secondary, filtrate pH value is adjusted to 1.8～2.1, centrifugation is repeatedly washed with deionized the sediment fraction after centrifugation to neutrality,
Last dehydrate obtains pressed powder and is lignin.
By the lignin, copper sulfate, potassium hydroxide solution and hydrogenperoxide steam generator mix homogeneously, in 110～120 DEG C of reactions
1.5～2h, is then cooled to 85～90 DEG C, and keeping temperature simultaneously adds for the first time formalin, reacts 30～45min, drops again
Temperature adds formalin to 60 DEG C, for the second time, and adds phenol, is to slowly warm up to 85～90 DEG C, reacts 1.5～2h, and cooling is obtained
Obtain finished product, i.e. oxidative lignin's phenolic resin adhesive.
2. the manufacture method of oxidative lignin's phenolic resin adhesive as claimed in claim 1, it is characterised in that the gross weight of raw material
Measuring number is：
50～65 parts of straw, 48～63 parts of formaldehyde, 18～24 parts of phenol, 18～30 parts of potassium hydroxide solid, copper sulfate 1.2～3
Part, 0.3～0.9 part of hydrogenperoxide steam generator.
3. the manufacture method of oxidative lignin's phenolic resin adhesive as claimed in claim 2, it is characterised in that the gross weight of raw material
Measuring number is：
52 parts of straw, 56 parts of formaldehyde, 21 parts of phenol, 20 parts of potassium hydroxide solid, 1.2 parts of copper sulfate, hydrogenperoxide steam generator 0.4
Part.
4. the manufacture method of oxidative lignin's phenolic resin adhesive as claimed in claim 1, it is characterised in that the reactant liquor
After filtering for the first time, with 95～100 DEG C, pH value is 9.8～10.3 BDO solution washing to filtering residue；Then second is carried out
Secondary filtration, from the beginning of filtering from second, with 80～85 DEG C, pH value is 9.8～10.3 deionized water wash to filtering residue.
5. the manufacture method of oxidative lignin's phenolic resin adhesive as claimed in claim 1, it is characterised in that the filtrate PH
Value dilute hydrochloric acid or dilute sulfuric acid are adjusted.
6. the manufacture method of oxidative lignin's phenolic resin adhesive as claimed in claim 1, it is characterised in that the hydroxide
Potassium solution mass concentration is 8～9%.
7. the manufacture method of oxidative lignin's phenolic resin adhesive as claimed in claim 1, it is characterised in that the first time
The amount for adding formaldehyde is the 1/3 of the formaldehyde gross weight number, and the amount of second addition formaldehyde is the formaldehyde gross weight
The 2/3 of number.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611193561.3A CN106590488A (en) | 2016-12-21 | 2016-12-21 | Method for preparing oxidized lignin phenolic resin adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611193561.3A CN106590488A (en) | 2016-12-21 | 2016-12-21 | Method for preparing oxidized lignin phenolic resin adhesive |
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| Publication Number | Publication Date |
|---|---|
| CN106590488A true CN106590488A (en) | 2017-04-26 |
Family
ID=58602507
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611193561.3A Pending CN106590488A (en) | 2016-12-21 | 2016-12-21 | Method for preparing oxidized lignin phenolic resin adhesive |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112175558A (en) * | 2020-10-22 | 2021-01-05 | 彭娜 | Modified lignin weather-resistant adhesive and preparation method thereof |
| CN113773775A (en) * | 2021-11-11 | 2021-12-10 | 山东永创材料科技有限公司 | Preparation method of phenolic resin adhesive for wood |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112175558A (en) * | 2020-10-22 | 2021-01-05 | 彭娜 | Modified lignin weather-resistant adhesive and preparation method thereof |
| CN112175558B (en) * | 2020-10-22 | 2021-10-22 | 宁波赫革丽高分子科技有限公司 | Modified lignin weather-resistant adhesive and preparation method thereof |
| CN113773775A (en) * | 2021-11-11 | 2021-12-10 | 山东永创材料科技有限公司 | Preparation method of phenolic resin adhesive for wood |
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Application publication date: 20170426 |