CN109181585A - A kind of lignin-base is without aldehyde adhesive and preparation method thereof - Google Patents
A kind of lignin-base is without aldehyde adhesive and preparation method thereof Download PDFInfo
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- CN109181585A CN109181585A CN201811117318.2A CN201811117318A CN109181585A CN 109181585 A CN109181585 A CN 109181585A CN 201811117318 A CN201811117318 A CN 201811117318A CN 109181585 A CN109181585 A CN 109181585A
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- lignin
- polyvinyl alcohol
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- adhesive
- base
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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
- C09J129/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
- C09J129/02—Homopolymers or copolymers of unsaturated alcohols
- C09J129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention relates to a kind of lignin-bases without aldehyde adhesive and preparation method thereof, which includes: that polyvinyl alcohol oxidation and lignin-base are prepared without aldehyde adhesive.The present invention selects polyvinyl alcohol and lignin to invent a kind of preparation method of the lignin-base without aldehyde adhesive for raw material with glutaraldehyde as cross linker.Lignin-base of the invention, not using formaldehyde as Material synthesis, greatly reduces the burst size of methanal of the wood-based plate using adhesive of the present invention compacting, to environment and human health without aldehyde adhesive.Lignin-base of the invention, with glutaraldehyde as cross linker, can make polyvinyl alcohol and lignin form closely cross-linked structure without aldehyde adhesive, enhance the bonding strength of the wood-based plate using adhesive of the present invention compacting.Preparation method of the invention is simple to operation, can promote the efficiency of factory's adhesive production, reduces production cost.
Description
Technical field
The invention belongs to adhesive fields, and in particular to a kind of lignin-base is without aldehyde adhesive and preparation method thereof.
Background technique
Epoch constantly advance, and as raw material of industry source important at this stage, petroleum coal etc., which is being presented, to fall sharply
Trend, this brings stern challenge to following industrial production.However, requirement of the people for green without subtracting therewith
It is few.With the rapid development of economy, the products such as wood furniture floor come into huge numbers of families, this is just to the environmental-protecting performance of wooden materials
More stringent requirements are proposed, and based Wood Adhesives are exactly most important one condition.Polyvinyl alcohol is that a kind of nontoxic and price is low
Honest and clean green product is a kind of biodegradable environment-friendly materials.Polyvinyl alcohol can be mass produced by Non oil-based route,
Therefore cheap.Since it has excellent performance in terms of bonding, therefore adhesive can be prepared as matrix using polyvinyl alcohol.
Lignin is to be widely present in one of wood materials high molecular polymer, and content is larger in plant, and
It can all regenerate every year.It is that new material and high-valued chemical industry new raw material have become a kind of new development trend by lignin conversion,
Its transformation technology and efficient utilize also have become current hot spot.The wooden presence for being known as complicated structure and phenolic hydroxyl group,
Therefore it can be used as adhesive preparation and modified important materials.The cost of adhesive is not only reduced, can also be made artificial
Board industry realizes Green Sustainable.
Lignin is modified the presence for needing crosslinking agent as additive to polyvinyl alcohol, and common crosslinking agent has isocyanide
Acid esters, borax, dibutyl phthalate, formaldehyde etc., however these crosslinking agents have the place of its relative deficiency: isocyanates
Viscosity is too high, is easy to react with the hydroxyl in water；Borax high temperature resistance is poor；Dibutyl phthalate has relatively strong
Volatility；Formaldehyde is all not friendly enough to environment and human body.Therefore, the crosslinking agent for selecting one kind environmentally protective is for adhesive
Prepare it is particularly important.A kind of crosslinking agent of the glutaraldehyde as green, cross-linking properties is superior, cheap, is widely transported
For various cross-linking reactions.With hydroxyl condensation reaction can occur for its essential groups aldehyde radical, form ehter bond, and then formed staggered
Network structure improves the adhesive property of adhesive.
Summary of the invention
The present invention adds lignin using polyvinyl alcohol as raw material, by cross-linking polymerization prepare it is a kind of environmentally protective and
The lignin-base of function admirable is without aldehyde adhesive.It can be used as preparation of the based Wood Adhesives for wood-based plate.
The object of the invention to solve the technical problems adopts the following technical solutions to realize:
A kind of lignin-base proposed according to the present invention is without aldehyde adhesive and preparation method thereof, comprising the following steps:
Polyvinyl alcohol oxidation: in the water for dispersing room temperature under stirring for polyvinyl alcohol.It is warming up to the first dissolution temperature
Degree, is kept stirring state, until polyvinyl alcohol is completely dissolved.It cools the temperature to the first oxidizing temperature, oxidant is added, carry out the
One reaction, obtains oxidic polyethylene alcohol, spare；
Lignin-base is prepared without aldehyde adhesive: lignin is dissolved in lye under stirring.It is wooden by what is dissolved
Element is added in oxidic polyethylene alcoholic solution, and crosslinking agent is added, and is carried out the second reaction, is cooled to room temperature, obtains after completion of the reaction
Lignin-base is without aldehyde adhesive.
The object of the invention to solve the technical problems also can be used following technical measures and further realize:
Preferably, preparation method above-mentioned, wherein the mass ratio of the polyvinyl alcohol and water is 1-3:10, the oxidant
It is 0.3-4.7:100 with the mass ratio of polyvinyl alcohol, the mass ratio of the lignin and lye is 1-5:8, the polyvinyl alcohol
It is 1-7:1 with the mass ratio of lignin, the mass ratio of the crosslinking agent and lignin is 1-13:100.
Preferably, preparation method above-mentioned, wherein the reaction condition of first reaction are as follows: 30-100 DEG C of temperature, the time
40-80min；The reaction condition of second reaction are as follows: 30-100 DEG C of temperature, time 40-80min；First solution temperature
It is 90-100 DEG C；First oxidizing temperature is 30-100 DEG C.
Preferably, preparation method above-mentioned, wherein the oxidant is in potassium peroxydisulfate, sodium peroxydisulfate or ammonium persulfate
At least one.
Preferably, preparation method above-mentioned, wherein the lye is the sodium hydroxide solution of mass fraction 5-7%.
Preferably, preparation method above-mentioned, wherein the crosslinking agent is glutaraldehyde.
Also the following technical solution is employed for the object of the invention to solve the technical problems to realize.
A kind of lignin-base proposed according to the present invention is without aldehyde adhesive and preparation method thereof, and the lignin-base is without aldehyde
Adhesive is prepared by method described in any of the above embodiments.
By above-mentioned technical proposal, lignin-base of the invention at least has the advantage that without aldehyde adhesive
(1) lignin-base of the invention can have Non oil-based route extensive without aldehyde adhesive using polyvinyl alcohol as raw material
Production, it is low in cost.And formaldehyde is not added, and it is beneficial to human health, it is environmentally protective.
(2) lignin-base of the invention is added to partial lignin without aldehyde adhesive, and lignin derives from natural resources, produces
Amount is abundant, cheap.As additive, it can be reacted with polyvinyl alcohol and generate cross-linked structure abundant, while reduce gluing
The solidification temperature of agent.In addition, the addition of lignin can reduce adhesive cost, improve strong with the gluing of the wood-based plate of its preparation
Degree.
(3) lignin-base of the invention is without aldehyde adhesive using glutaraldehyde as crosslinking agent, and cross-linking properties is superior, price is low
It is honest and clean, it is environmentally protective.With hydroxyl condensation reaction can occur for essential groups aldehyde radical, form ehter bond, and then form staggered network knot
Structure improves the adhesive property of adhesive.
The above description is only an overview of the technical scheme of the present invention, in order to better understand the technical means of the present invention,
And can be implemented in accordance with the contents of the specification, with presently preferred embodiments of the present invention, detailed description is as follows below.
Specific embodiment
It is of the invention to reach the technical means and efficacy that predetermined goal of the invention is taken further to illustrate, below in conjunction with
Preferred embodiment, to a kind of lignin-base proposed according to the present invention without its specific embodiment party of aldehyde adhesive and preparation method thereof
Formula, feature and its effect, detailed description is as follows.In the following description, different " embodiment " or " embodiment " refers to different
It surely is the same embodiment.In addition, the special characteristic, structure or feature in one or more embodiments can be by any suitable form groups
It closes.
The embodiment of the present invention proposes a kind of lignin-base without aldehyde adhesive and preparation method thereof.
The preparation method the following steps are included:
Polyvinyl alcohol oxidation: in the water for dispersing room temperature under stirring for polyvinyl alcohol, the matter of polyvinyl alcohol and water
Amount is than being 1-3:10.It is warming up to 90-100 DEG C of dissolution, is kept stirring state, until polyvinyl alcohol is completely dissolved.It cools the temperature to
30-100 DEG C, oxidant is added, aoxidizes 40-80min, obtains oxidic polyethylene alcohol, it is spare；
Lignin-base is prepared without aldehyde adhesive: lignin is dissolved in the hydroxide of mass fraction 5-7% under stirring
In sodium solution, the mass ratio of lignin and sodium hydroxide solution is 1-5:8.The lignin dissolved is added to oxidic polyethylene
In alcoholic solution, crosslinking agent is added, 40-80min is reacted at 30-100 DEG C, is cooled to room temperature after completion of the reaction, lignin is obtained
Base is without aldehyde adhesive.
In the present embodiment, oxidant includes but is not limited to: at least one in potassium peroxydisulfate, sodium peroxydisulfate or ammonium persulfate
Kind.
In the present embodiment, crosslinking agent includes but is not limited to: glutaraldehyde.
Adhesive prepared by the present invention is liquid at normal temperature, in use, adhesive is sprayed directly on stand-by plate,
Carry out hot pressing.
Optionally, veneer spread is 220-280g/m2, hot pressing temperature is 135 DEG C, hot pressing pressure 1MPa, when hot pressing
Between be 15min.
With specific embodiment, the present invention will be further described below, but not as the limitation of the invention.
Embodiment 1
(1) it disperses 25g polyvinyl alcohol under stirring in the water of 100ml room temperature.After being uniformly dispersed, it is warming up to 90
DEG C dissolution, is kept stirring state, until polyvinyl alcohol is completely dissolved.50 DEG C are cooled the temperature to, polyvinyl alcohol mass fraction is added
2.5% oxidant potassium peroxydisulfate aoxidizes 60min, obtains oxidic polyethylene alcohol, spare；
(2) 13g lignin is dissolved under stirring in the sodium hydroxide solution of 30ml mass fraction 6%.It will dissolution
Good lignin is added in oxidic polyethylene alcoholic solution, the crosslinking agent glutaraldehyde of lignin quality score 5% is added, at 70 DEG C
Lower reaction 60min, is cooled to room temperature after completion of the reaction, obtains lignin-base without aldehyde adhesive.
Poplar three-layer glued board is suppressed using adhesive manufactured in the present embodiment, and tests its bonding strength, is as a result listed in
Table 1.
Embodiment 2
(1) it disperses 20g polyvinyl alcohol under stirring in the water of 100ml room temperature.After being uniformly dispersed, it is warming up to 90
DEG C dissolution, is kept stirring state, until polyvinyl alcohol is completely dissolved.60 DEG C are cooled the temperature to, polyvinyl alcohol mass fraction is added
2% oxidant potassium peroxydisulfate aoxidizes 70min, obtains oxidic polyethylene alcohol, spare；
(2) 5g lignin is dissolved under stirring in the sodium hydroxide solution of 30ml mass fraction 6%.It will dissolve
Lignin be added in oxidic polyethylene alcoholic solution, be added lignin quality score 5% crosslinking agent glutaraldehyde, at 70 DEG C
60min is reacted, is cooled to room temperature after completion of the reaction, obtains lignin-base without aldehyde adhesive.
Poplar three-layer glued board is suppressed using adhesive manufactured in the present embodiment, and tests its bonding strength, is as a result listed in
Table 1.
Embodiment 3
(1) it disperses 20mg polyvinyl alcohol under stirring in the water of 100ml room temperature.After being uniformly dispersed, it is warming up to
90 DEG C of dissolutions, are kept stirring state, until polyvinyl alcohol is completely dissolved.60 DEG C are cooled the temperature to, polyvinyl alcohol quality point is added
The oxidant potassium peroxydisulfate of number 2.5% aoxidizes 60min, obtains oxidic polyethylene alcohol, spare；
(2) 4mg lignin is dissolved under stirring in the sodium hydroxide solution of 30ml mass fraction 6%.It will dissolution
Good lignin is added in oxidic polyethylene alcoholic solution, the crosslinking agent glutaraldehyde of lignin quality score 5% is added, at 60 DEG C
Lower reaction 50min, is cooled to room temperature after completion of the reaction, obtains lignin-base without aldehyde adhesive.
Poplar three-layer glued board is suppressed using adhesive manufactured in the present embodiment, and tests its bonding strength, is as a result listed in
Table 1.
Embodiment 4
(1) it disperses 20mg polyvinyl alcohol under stirring in the water of 100ml room temperature.After being uniformly dispersed, it is warming up to
95 DEG C of dissolutions, are kept stirring state, until polyvinyl alcohol is completely dissolved.60 DEG C are cooled the temperature to, polyvinyl alcohol quality point is added
The oxidant potassium peroxydisulfate of number 2.5% aoxidizes 60min, obtains oxidic polyethylene alcohol, spare；
(2) 5mg lignin is dissolved under stirring in the sodium hydroxide solution of 30ml mass fraction 6.5%.It will be molten
The lignin solved is added in oxidic polyethylene alcoholic solution, the crosslinking agent glutaraldehyde of lignin quality score 5% is added, 70
60min is reacted at DEG C, is cooled to room temperature after completion of the reaction, obtains lignin-base without aldehyde adhesive.
Poplar three-layer glued board is suppressed using adhesive manufactured in the present embodiment, and tests its bonding strength, is as a result listed in
Table 1.
The bonding strength of 1 adhesive of table compacting poplar three-layer glued board
Note: the detection of above-mentioned adhesive: pH and solid content are detected according to the regulation in GB/T 14074-2006.
Above-mentioned glued board is poplar three-layer glued board, and veneer spread is 220-280g/m2, hot pressing temperature is 135 DEG C, heat
Pressure pressure is 1MPa, hot pressing time 15min.
Above-mentioned glued board detection: the glued board of compacting detects after being placed at room temperature for 5-7 days.
" wood-based plate and face artificial board are physical and chemical by GB/T 17657-2013 for the bonding strength of the adhesive prepared in case
Method for testing performance " it is measured.
The above described is only a preferred embodiment of the present invention, be not intended to limit the present invention in any form, according to
According to technical spirit any simple modification, equivalent change and modification to the above embodiments of the invention, this hair is still fallen within
In the range of bright technical solution.
Claims (6)
1. a kind of lignin-base is without aldehyde adhesive and preparation method thereof, which comprises the following steps:
Polyvinyl alcohol oxidation: in the water for dispersing room temperature under stirring for polyvinyl alcohol, being warming up to the first solution temperature, protects
Stirring is held, until polyvinyl alcohol is completely dissolved, the first oxidizing temperature is cooled the temperature to, oxidant is added, it is anti-to carry out first
It answers, obtains oxidic polyethylene alcohol, it is spare；
Lignin-base is prepared without aldehyde adhesive: lignin being dissolved in lye under stirring, the lignin dissolved is added
Enter into oxidic polyethylene alcoholic solution, crosslinking agent is added, carries out the second reaction, be cooled to room temperature, obtain wooden after completion of the reaction
Plain base is without aldehyde adhesive.
2. preparation method according to claim 1, which is characterized in that
The mass ratio of the polyvinyl alcohol and water is 1-3:10,
The mass ratio of the oxidant and polyvinyl alcohol is 0.3-4.7:100,
The mass ratio of the lignin and lye is 1-5:8,
The mass ratio of the polyvinyl alcohol and lignin is 1-7:1,
The mass ratio of the crosslinking agent and lignin is 1-13:100.
3. preparation method according to claim 1, which is characterized in that
The reaction condition of first reaction are as follows: 30-100 DEG C of temperature, time 40-80min；
The reaction condition of second reaction are as follows: 30-100 DEG C of temperature, time 40-80min；
First solution temperature is 90-100 DEG C；
First oxidizing temperature is 30-100 DEG C.
4. preparation method according to claim 1, which is characterized in that
The oxidant is at least one of potassium peroxydisulfate, sodium peroxydisulfate or ammonium persulfate.
5. preparation method according to claim 1, which is characterized in that
The lye is the sodium hydroxide solution of mass fraction 5-7%.
6. preparation method according to claim 1, which is characterized in that
The crosslinking agent is glutaraldehyde.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811117318.2A CN109181585B (en) | 2018-09-25 | 2018-09-25 | Lignin-based formaldehyde-free adhesive and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811117318.2A CN109181585B (en) | 2018-09-25 | 2018-09-25 | Lignin-based formaldehyde-free adhesive and preparation method thereof |
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| CN109181585A true CN109181585A (en) | 2019-01-11 |
| CN109181585B CN109181585B (en) | 2020-06-16 |
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Cited By (5)
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| CN112143458A (en) * | 2020-08-11 | 2020-12-29 | 湖南省春龙竹艺有限公司 | Aldehyde-free adhesive for bamboo summer sleeping mat and preparation method thereof |
| CN112538335A (en) * | 2020-12-08 | 2021-03-23 | 安徽芨智生物科技有限公司 | Bletilla striata wood glue powder and preparation method thereof |
| CN113122149A (en) * | 2020-01-10 | 2021-07-16 | 北京林业大学 | Environment-friendly high-performance geopolymer-based adhesive laminated wood and preparation method thereof |
| CN115401762A (en) * | 2022-07-11 | 2022-11-29 | 大亚人造板集团有限公司 | E NF Process for manufacturing grade flame-retardant hollow shaving board |
| CN116334950A (en) * | 2023-03-27 | 2023-06-27 | 安徽普尔德无纺科技有限公司 | Production process of glue for hand towel |
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Cited By (5)
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| CN113122149A (en) * | 2020-01-10 | 2021-07-16 | 北京林业大学 | Environment-friendly high-performance geopolymer-based adhesive laminated wood and preparation method thereof |
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| CN115401762A (en) * | 2022-07-11 | 2022-11-29 | 大亚人造板集团有限公司 | E NF Process for manufacturing grade flame-retardant hollow shaving board |
| CN116334950A (en) * | 2023-03-27 | 2023-06-27 | 安徽普尔德无纺科技有限公司 | Production process of glue for hand towel |
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