CN106854264A - A kind of rice husk sill quality modified phenolic resin adhesive preparation method - Google Patents
A kind of rice husk sill quality modified phenolic resin adhesive preparation method Download PDFInfo
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- CN106854264A CN106854264A CN201611093413.4A CN201611093413A CN106854264A CN 106854264 A CN106854264 A CN 106854264A CN 201611093413 A CN201611093413 A CN 201611093413A CN 106854264 A CN106854264 A CN 106854264A
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- Prior art keywords
- rice husk
- phenolic resin
- resin adhesive
- modified phenolic
- heating
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- 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
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
- C08G14/08—Ureas; Thioureas
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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
- C09J161/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C09J161/04, C09J161/18 and C09J161/20
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The present invention relates to a kind of preparation method of rice husk sill quality modified phenolic resin adhesive.Method is as follows：(1) rice husk, suction filtration drying first are heat-treated with sulfuric acid；(2) NaOH alkali cleanings are used again, and filtrate is standby after suction filtration；(3) above-mentioned filtrate is heated, promotes solvent to volatilize completely, obtain alkali lignin solid；(4) by alkali lignin solid, NaOH solids, phenol and water, heat modification reaction；(5) formalin, NaOH solids and water are added, polymerisation is heated；(6) urea, temperature reaction, dehydration discharging are added.The lignin portion fortified phenol contained in present invention rice husk, raw material sources are extensively, cheap, are also fully utilized by agricultural wastes, the destruction that its burning is caused to environment reduced, for the recycling of discarded object provides a feasible path.
Description
Technical field
The present invention relates to chemical technology field, a kind of rice husk sill quality modified phenolic resin adhesive preparation side is referred specifically to
Method.
Background technology
The world today, oil persistently skyrockets as non-renewable resources, price, causes being produced into for phenolic resin adhesive
This also more and more higher, and the phenol of one of important source material as phenolic resin adhesive, its price remain high for a long time.In order to
The production cost of phenolic resin adhesive is reduced, other more cheap raw materials is found instantly rather hot to become instead of phenol
The research topic of door.And continuing to develop with society, environmental protection is that this more must be used more required by social each side
Natural polymer replaces phenol and formaldehyde as a kind of trend.
There is substantial amounts of aldehyde radical and hydroxyl in its structure as a kind of natural polyphenol family macromolecule polymer in lignin, therefore
This can with phenol and formaldehyde novolak resin when reduce the consumption of phenol and formaldehyde.Meanwhile, pass through light on the earth every year
About 150,000,000,000 tons of the lignin of cooperation synthesis；Only in paper-making pulping production process, isolated by raw material of string
Xylogen by-product also have about 50,000,000 tons/year, also the form of " black liquor " is directly discharged into natural water mostly, portion of product
Burned after being concentrated, the lignin being utilized effectively is less than 20%.
Used as a large agricultural country, rice is the staple food of compatriots for China, and up to 200,000,000 tons, rice husk is generally accounted for annual rice yield
The 20% of paddy, calculates like this, and annual rice husk has more than 4,000 ten thousand tons, and rice husk resource is enriched very much.However, rice husk surface is hard
Firmly, silicone content is high, is difficult to be bacterially decomposed, and bulk density is small, discards welding, and the exploitation of rice husk are significant.
If there is a kind of method effectively to be utilized to the lignin in rice husk, then it can be reduced to ecological environment
Destruction；Meanwhile, lignin is cheap, one ton of only hundreds of unit, compared to the phenol higher than 5000 yuan/ton and 1000 yuan/ton
Formaldehyde for, economic benefit is especially high.Therefore, carry out rice husk sill quality modified phenolic resin adhesive research work from
Environment benefits and economic gains aspect is all significant.
The content of the invention
The present invention is to provide a kind of rice husk sill quality modified phenolic resin adhesive preparation method, by the present invention
The production method of offer, reaches the content for reducing residual phenol and residual aldehyde in production cost, reduction adhesive.
Technical scheme is as follows：
In order to solve problem of the prior art, a kind of rice husk sill quality modified phenolic resin adhesive preparation method, its
It is characterized in comprise the following steps：
(1) rice husk of crushing is taken, the sulfuric acid solution for plus 10%, agitating heating for a period of time, is then filtered, washs, dried
It is stand-by；
(2) the stand-by sample of drying in step (1) is dissolved in the NaOH solution of concentration 0.5mol/L, one section of agitating heating
Time, then filter, collect filtrate；
(3) filtrate in step (2) is placed in 100 DEG C of heating environments, the solvent in removal filtrate collects alkali lignin
Solid；
(4) the alkali lignin solid in step (3), phenol, NaOH solids and deionized water are mixed, agitating heating
For a period of time, phenolate lignin liquor is obtained；
(5) phenolate lignin liquor in step (4) is mixed with formalin, NaOH solids, agitating heating is polymerized
Reaction；
(6) to adding a small amount of urea in step (5) reaction solution, agitating heating for a period of time after, carry out vacuum distillation discharging.
Further, it is 3 that the step (1) crushes rice husk and the mass ratio of 10% sulfuric acid solution:1~1:1, heating-up temperature
It it is 50~70 DEG C, the time is 1~3h.
Further, rice husk sill quality modified phenolic resin adhesive preparation method according to claim 1, its
It is characterised by, step (3) the alkali lignin solid is 5 with the mass ratio of phenol:100~40:100, NaOH solids and alkali wood
The mass ratio of quality solid is 1:100~5:100, heating-up temperature is 40~70 DEG C, and the time is 1~3h.
Further, the mass fraction of step (4) formalin is 37%, formalin and alkali lignin solid
Mass ratio is 10:100~100:100, NaOH solids are 1 with the mass ratio of alkali lignin solid:100~5:100, heating-up temperature
It it is 40~80 DEG C, the time is 0.5~5h.
The present invention has following superiority：
(1) present invention is greatly reduced due to replacing phenol and formaldehyde as raw material using substantial amounts of rice husk sill quality
The cost of production phenolic resin adhesive, also protects environment to a certain extent, embodies the theory of Green Chemistry.
(2) it is of the invention when raw rice husk is processed, the polysaccharide or oligomeric being stripped of by way of acid treatment in lignin
Sugar so that the phenolic resin adhesive of preparation has preferable water resistance.
(3) the method activation rice husk base lignin modification in production process of the present invention using alkali process prepares phenolic resin glue
Glutinous agent, required phenol and formaldehyde amount is small, produces small toxicity, and product has water solubility higher.
(4) present invention comes from natural agriculture and forestry organic waste material due to the raw material for using, not metal ion in raw material, therefore
This, the product insulating properties for obtaining are preferable.
Specific embodiment
The present invention is described in further details with specific embodiment below, but the present invention is not only limited in detail below in fact
Apply example.
First illustrate how rice husk sill quality obtains, but illustrated embodiment is not necessarily referring to the lignin of optimal applicable elements
Solid：
(1) take the rice husk after 90g is crushed to be placed in there-necked flask with 10% sulfuric acid of 30g, 70 DEG C of heating stirring 3h.Then
Filtering, washing, are put into baking oven and dry 24h；
(2) solid after drying is placed in the NaOH solution of the 0.5mol/L of 1L, 80 DEG C of heating stirring 10h, then mistake
Filter, collects filtrate；
(3) filtrate is placed in 100 DEG C of thermal station and is heated, treat that all volatilization is finished solvent, obtains alkali lignin solid, i.e. rice
Shell sill quality.
Embodiment one
(1) lignin 4g, phenol 10g, NaOH solid 0.1g deionized water 20g are added in 250mL there-necked flasks, is heated up
To 50 DEG C, heating stirring 3h；
(2) formalin 4g, NaOH solid 0.2g, 60 DEG C of reaction 1h are added；
(3) urea 0.4g is added, vacuum distillation to required viscosity discharges after 70 DEG C of reaction 1.5h.Rice husk sill can be obtained
Quality modified phenolic resin adhesive.
Embodiment two
(1) lignin 3g, phenol 10g, NaOH solid 0.15g deionized water 20g are added in 250mL there-necked flasks, is risen
Temperature is to 50 DEG C, heating stirring 3h；
(2) formalin 3g, NaOH solid 0.1g, 60 DEG C of reaction 1h are added；
(3) urea 0.4g is added, vacuum distillation to required viscosity discharges after 70 DEG C of reaction 1.5h.Rice husk sill can be obtained
Quality modified phenolic resin adhesive.
Embodiment three
(1) lignin 2g, phenol 10g, NaOH solid 0.1g deionized water 20g are added in 250mL there-necked flasks, is heated up
To 50 DEG C, heating stirring 3h；
(2) formalin 2g, NaOH solid 0.1g, 60 DEG C of reaction 1h are added；
(3) urea 0.4g is added, vacuum distillation to required viscosity discharges after 70 DEG C of reaction 1.5h.Rice husk sill can be obtained
Quality modified phenolic resin adhesive.
Example IV
(1) lignin 1g, phenol 10g, NaOH solid 0.05g deionized water 20g are added in 250mL there-necked flasks, is risen
Temperature is to 50 DEG C, heating stirring 3h；
(2) formalin 1g, NaOH solid 0.05g, 60 DEG C of reaction 1h are added；
(3) urea 0.4g is added, vacuum distillation to required viscosity discharges after 70 DEG C of reaction 1.5h.Rice husk sill can be obtained
Quality modified phenolic resin adhesive.
Embodiment five
(1) lignin 4g, phenol 10g, NaOH solid 0.1g deionized water 20g are added in 250mL there-necked flasks, is heated up
To 70 DEG C, heating stirring 1h；
(2) formalin 4g, NaOH solid 0.2g, 60 DEG C of reaction 1h are added；
(3) urea 0.4g is added, vacuum distillation to required viscosity discharges after 70 DEG C of reaction 1.5h.Rice husk sill can be obtained
Quality modified phenolic resin adhesive.
Embodiment six
(1) lignin 4g, phenol 10g, NaOH solid 0.1g deionized water 20g are added in 250mL there-necked flasks, is heated up
To 60 DEG C, heating stirring 2h；
(2) formalin 4g, NaOH solid 0.2g, 60 DEG C of reaction 1h are added；
(3) urea 0.4g is added, vacuum distillation to required viscosity discharges after 70 DEG C of reaction 1.5h.Rice husk sill can be obtained
Quality modified phenolic resin adhesive.
Embodiment seven
(1) lignin 4g, phenol 10g, NaOH solid 0.1g deionized water 20g are added in 250mL there-necked flasks, is heated up
To 50 DEG C, heating stirring 3h；
(2) formalin 4g, NaOH solid 0.2g, 70 DEG C of reaction 0.5h are added；
(3) urea 0.4g is added, vacuum distillation to required viscosity discharges after 70 DEG C of reaction 1.5h.Rice husk sill can be obtained
Quality modified phenolic resin adhesive.
Above content is to combine specific preferred embodiment further description made for the present invention, it is impossible to assert
Specific implementation of the invention is confined to these explanations.For the personnel of the technical field of the invention, this is not being departed from
On the premise of inventive concept, many simple deduction or replace can be also made, should all be considered as belonging to protection scope of the present invention.
Claims (4)
1. a kind of rice husk sill quality modified phenolic resin adhesive preparation method, it is characterized in that, comprise the following steps：
(1) take the rice husk of crushing, the sulfuric acid solution for plus 10%, agitating heating for a period of time, then filter, wash, dry it is stand-by；
(2) the stand-by sample of drying in step (1) is dissolved in the NaOH solution of concentration 0.5mol/L, during one section of agitating heating
Between, then filter, collect filtrate；
(3) filtrate in step (2) is placed in 100 DEG C of heating environments, the solvent in removal filtrate is collected alkali lignin and consolidated
Body；
(4) the alkali lignin solid in step (3), phenol, NaOH solids and deionized water are mixed, one section of agitating heating
Time, obtain phenolate lignin liquor；
(5) phenolate lignin liquor in step (4) is mixed with formalin, NaOH solids, agitating heating, be polymerized instead
Should；
(6) to adding a small amount of urea in step (5) reaction solution, agitating heating for a period of time after, carry out vacuum distillation discharging.
2. rice husk sill quality modified phenolic resin adhesive preparation method according to claim 1, it is characterised in that institute
It is 3 to state step (1) and crush rice husk and the mass ratio of 10% sulfuric acid solution:1~1:1, heating-up temperature is 50~70 DEG C, and the time is 1
~3h.
3. rice husk sill quality modified phenolic resin adhesive preparation method according to claim 1, it is characterised in that institute
It is 5 that step (3) alkali lignin solid is stated with the mass ratio of phenol:100~40:The matter of 100, NaOH solids and alkali lignin solid
Amount is than being 1:100~5:100, heating-up temperature is 40~70 DEG C, and the time is 1~3h.
4. rice husk sill quality modified phenolic resin adhesive preparation method according to claim 1, it is characterised in that institute
It is 37% to state the mass fraction of step (4) formalin, and formalin is 10 with the mass ratio of alkali lignin solid:100~
100:100, NaOH solids are 1 with the mass ratio of alkali lignin solid:100~5:100, heating-up temperature is 40~80 DEG C, time
It is 0.5~5h.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611093413.4A CN106854264A (en) | 2016-12-02 | 2016-12-02 | A kind of rice husk sill quality modified phenolic resin adhesive preparation method |
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| CN201611093413.4A CN106854264A (en) | 2016-12-02 | 2016-12-02 | A kind of rice husk sill quality modified phenolic resin adhesive preparation method |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019104815A1 (en) * | 2017-11-28 | 2019-06-06 | 黄宇 | Method for preparing lignin-phenol-formaldehyde resin adhesive |
| CN111040689A (en) * | 2019-12-24 | 2020-04-21 | 江南大学 | Long-chain alkylphenol and phenol synergistic modified lignin-based phenolic resin adhesive |
| CN111205798A (en) * | 2020-03-10 | 2020-05-29 | 江南大学 | Lignin pyrolytic phenol-based resin adhesive and preparation method thereof |
| CN111484587A (en) * | 2019-01-25 | 2020-08-04 | 石河子大学 | Method for preparing lignin-based phenolic resin |
| CN115181365A (en) * | 2022-08-20 | 2022-10-14 | 太仓市华鼎塑料有限公司 | Heat-aging-resistant glass fiber reinforced PP (polypropylene) material for vehicle |
| CN115746784A (en) * | 2022-10-28 | 2023-03-07 | 山东百木生新材料科技有限公司 | Preparation method of all-lignin-based adhesive |
| CN116535810A (en) * | 2023-04-13 | 2023-08-04 | 江苏耀鸿电子有限公司 | Phenolic resin for producing environment-friendly paper-based copper-clad plate and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1680413A (en) * | 2005-01-05 | 2005-10-12 | 福州大学 | Preparation of high-boiling alcohol lignin from plant refuse |
| CN105348460A (en) * | 2015-11-25 | 2016-02-24 | 北华大学 | Cellulosic ethanol lignin modified phenolic resin wood adhesive and preparation method thereof |
| CN106010396A (en) * | 2016-07-15 | 2016-10-12 | 安吉威龙塑木环保材料有限公司 | Preparation method of liquefied bamboo based adhesive |
-
2016
- 2016-12-02 CN CN201611093413.4A patent/CN106854264A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1680413A (en) * | 2005-01-05 | 2005-10-12 | 福州大学 | Preparation of high-boiling alcohol lignin from plant refuse |
| CN105348460A (en) * | 2015-11-25 | 2016-02-24 | 北华大学 | Cellulosic ethanol lignin modified phenolic resin wood adhesive and preparation method thereof |
| CN106010396A (en) * | 2016-07-15 | 2016-10-12 | 安吉威龙塑木环保材料有限公司 | Preparation method of liquefied bamboo based adhesive |
Non-Patent Citations (1)
| Title |
|---|
| 陈洪卓: "木质素及其复合物在环氧树脂胶粘剂中的应用研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019104815A1 (en) * | 2017-11-28 | 2019-06-06 | 黄宇 | Method for preparing lignin-phenol-formaldehyde resin adhesive |
| CN111484587A (en) * | 2019-01-25 | 2020-08-04 | 石河子大学 | Method for preparing lignin-based phenolic resin |
| CN111040689A (en) * | 2019-12-24 | 2020-04-21 | 江南大学 | Long-chain alkylphenol and phenol synergistic modified lignin-based phenolic resin adhesive |
| CN111205798A (en) * | 2020-03-10 | 2020-05-29 | 江南大学 | Lignin pyrolytic phenol-based resin adhesive and preparation method thereof |
| US11214716B2 (en) | 2020-03-10 | 2022-01-04 | Jiangnan University | Phenol-based resin adhesive from lignin pyrolysis and its preparation method |
| CN115181365A (en) * | 2022-08-20 | 2022-10-14 | 太仓市华鼎塑料有限公司 | Heat-aging-resistant glass fiber reinforced PP (polypropylene) material for vehicle |
| CN115181365B (en) * | 2022-08-20 | 2023-10-17 | 太仓市华鼎塑料有限公司 | Glass fiber reinforced PP material for automobile heat aging resistance |
| CN115746784A (en) * | 2022-10-28 | 2023-03-07 | 山东百木生新材料科技有限公司 | Preparation method of all-lignin-based adhesive |
| CN116535810A (en) * | 2023-04-13 | 2023-08-04 | 江苏耀鸿电子有限公司 | Phenolic resin for producing environment-friendly paper-based copper-clad plate and preparation method thereof |
| CN116535810B (en) * | 2023-04-13 | 2024-01-02 | 江苏耀鸿电子有限公司 | Phenolic resin for producing environment-friendly paper-based copper-clad plate and preparation method thereof |
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