CN108949078A - A kind of method of modified phenolic resin adhesive - Google Patents
A kind of method of modified phenolic resin adhesive Download PDFInfo
- Publication number
- CN108949078A CN108949078A CN201710358550.4A CN201710358550A CN108949078A CN 108949078 A CN108949078 A CN 108949078A CN 201710358550 A CN201710358550 A CN 201710358550A CN 108949078 A CN108949078 A CN 108949078A
- Authority
- CN
- China
- Prior art keywords
- phenolic resin
- resin adhesive
- modified phenolic
- temperature
- lignin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The present invention provides a kind of methods of modified phenolic resin adhesive, comprising the following steps: phenolic resin adhesive is added into reaction kettle, stirs, heat temperature raising, and keep the temperature；Liquid alkaline is added into reaction kettle and adjusts pH to alkalinity, after heat temperature raising, adds lignin, and keep the temperature；Cooling, discharging.The method integrated artistic of the modified phenolic resin adhesive is simple, and operating procedure is few, is suitable for industrialization large-scale production；Preparing modified phenolic resin adhesive according to the present invention, cost is relatively low; it is reacted by lignin with traditional the further of phenolic resin adhesive; bonding strength further increases; free phenolic aldehyde is greatly lowered simultaneously; substantially reduce the discharge of aldehyde, phenolic compound; be conducive to environmental protection, therefore, there is good market and application prospect.
Description
Technical field
The invention belongs to adhesive technology fields, and in particular to a kind of method of modified phenolic resin adhesive.
Background technique
As one of renewable resource the most abundant on the earth, lignin is widely present in seed plant, with cellulose
The basic framework of plant is constituted with hemicellulose.For content, tellurian lignin accounts for about plant next in number only to cellulose
The 20%~30% of weight of object is the second largest natural organic matter.Existing quantity is very huge in nature for lignin, estimates
It counts the annual whole world and 150,000,000,000 t lignin can produce by plant growth, wherein generated in the cooking waste liquor of pulp and paper industry
Industrial wood is known as 30,000,000 t.But current lignin is utilized well not yet, the whole world only about 6% lignin obtain
To effective recycling.By-product of the lignin as wood hydrolysis industry and paper industry will be by if being not fully utilized
One of the primary pollution source in paper industry is crossfaded into, then not only causes serious environmental pollution, but also also results in the huge of resource
Big waste.
With the rapid development of China's industry of artificial boards, the yield of wood-based plate is prepared also on constantly using phenolic resin
It rises.Synvaren adhesive strength is high, and has many advantages, such as excellent water resistance and weatherability, is suitable for production outdoor use
Wood-based plate.But simultaneously and there are hot pressing time length, solidification temperature and cost of material height and there is harmful substance release.With
Raw material phenol and formaldehyde to produce phenolic resin have the characteristics that non-renewable from petrochemical industry.Study renewable, performance
The raw material that high energy substitutes phenol or formaldehyde to produce phenolic resin is always the target of adhesive industry.Especially, traditional phenolic aldehyde
The preferable phenolic resin gluing of glue performance is made through polycondensation after a period of time under alkaline environment using formaldehyde, phenol in glue
Agent, but since phenol price is higher, and phenol is larger to human injury, to limit the development of phenolic resin adhesive and answer
With popularization.
Summary of the invention
In order to obtain the high-performance pnenolic aldehyde glue that a kind of bonding strength is high and free phenol aldehyde concentration is low, the present invention provides one kind
The phenolic resin gluing traditional with modification is compounded with appropriate lignin by phenolic resin adhesive appropriate under alkaline condition
The method of agent, the compound process react lignin further with free phenolic aldehyde, and it is (dense to can obviously reduce free phenolic content
Degree), while improving bonding strength.
Therefore, the present invention provides following technical schemes:
A kind of method of modified phenolic resin adhesive, comprising the following steps:
S1: phenolic resin adhesive being added into reaction kettle, stirring, heat temperature raising, and keeps the temperature；
S2: liquid alkaline is added into reaction kettle and adjusts pH to alkalinity, after heat temperature raising, adds lignin, and keep the temperature；
S3: cooling, discharging.
Preferably, in the method for above-mentioned modified phenolic resin adhesive, the phenolic resin adhesive with it is described wooden
The dry weight ratio of element is 1:3~1:8.For example, the dry weight ratio of the phenolic resin adhesive and the lignin is 1:
3, the dry weight ratio of the phenolic resin adhesive and the lignin is 1:4, further preferably 1:5, further excellent
It is selected as 1:6, is still more preferably 1:7, is still more preferably 1:8.
Preferably, the range of the pH value of the alkalinity described in the step S2 of the method for above-mentioned modified phenolic resin adhesive
It is 8 to 13, it is further preferred that the range of the pH value of the alkalinity is 9~12, most preferably 10~11.
Preferably, in the step S1 of the method for above-mentioned modified phenolic resin adhesive, 30 DEG C~50 DEG C are heated to,
And 5~20min is kept the temperature at 30 DEG C~50 DEG C；It is highly preferred that being heated to 35 DEG C~45 DEG C, and protected at 35 DEG C~45 DEG C
5~20min of temperature.In addition, in step sl, the duration of stirring is 10~15min.
Preferably, in the step S2 of the method for above-mentioned modified phenolic resin adhesive, 40 DEG C~120 DEG C are heated to
Afterwards, lignin is added, and keeps the temperature 20~90min at 40 DEG C~120 DEG C, further preferably 30~80min of heat preservation, more into one
Step 40~70min of preferred heat preservation, most preferably 50~60min of heat preservation.
Preferably, in the step S3 of the method for above-mentioned modified phenolic resin adhesive, 20~25 DEG C is cooled to, is then gone out
Material.
Therefore, compared with prior art, technical solution provided by the present invention at least has following advantageous effects:
(1) the method integrated artistic of modified phenolic resin adhesive of the present invention is simple, and operating procedure is few, to reaction environment require compared with
It is low, be suitable for industrialization large-scale production lower to worker's technical operation Capability Requirement；(2) wood used in the present invention
Quality rises new material (Shandong) Co., Ltd by east and provides, and can be directly used for various experiment reactions, without carrying out any pretreatment,
Meet Workshop Production requirement；(3) modified phenolic resin adhesive is prepared according to the present invention cost is relatively low, pass through lignin and tradition
The further reaction of phenolic resin adhesive, bonding strength further increase, while free phenolic aldehyde is greatly lowered, and substantially reduces
The discharge of aldehyde, phenolic compound is conducive to environmental protection, therefore, has good market and application prospect.
Specific embodiment
The present invention is further elaborated With reference to embodiment, but the present invention is not limited to following embodiment party
Formula.
A kind of method of modified phenolic resin adhesive, comprising the following steps:
S1: phenolic resin adhesive being added into reaction kettle, stirring, heat temperature raising, and keeps the temperature；
S2: liquid alkaline is added into reaction kettle and adjusts pH to alkalinity, after heat temperature raising, adds lignin, and keep the temperature；
S3: cooling, discharging.
In a preferred embodiment, the dry weight ratio of the phenolic resin adhesive and the lignin be 1:3~
1:8。
In a preferred embodiment, the range of the pH value of alkalinity described in step S2 is 8 to 13.
In a preferred embodiment, in step sl, 30 DEG C~50 DEG C are heated to, and is protected at 30 DEG C~50 DEG C
5~20min of temperature.
In a preferred embodiment, in step s 2, after being heated to 40 DEG C~120 DEG C, lignin is added, and
20~90min is kept the temperature at 40 DEG C~120 DEG C.
In a preferred embodiment, in step s3,20~25 DEG C are cooled to, is then discharged.
Phenolic resin adhesive rises new material (Shandong) Co., Ltd by east and provides, and solid content is 50wt% viscosity 450；
Lignin rises new material (Shandong) Co., Ltd by east and provides；Adjusting liquid alkaline content used in pH is 32%；Free phenol is according to GB/
3.13 detections in T14074-2006；Free aldehyde is according to 3.16 detections in GB/T14074-2006；Bonding strength uses poplar
Wood is pressed into three-ply board, and is detected according to a) the I class glued board in 4.15 in 17567-1999；Burst size of methanal is according to GB/
4.59 condensed steam waters detection in T17657-2013.
Embodiment 1
Modified phenolic resin adhesive is prepared according to the following steps:
S1: 150g phenolic resin adhesive being added into reaction kettle, and stirring is heated to 30 DEG C, and at this temperature
Keep the temperature 10min；
S2: being added liquid alkaline into reaction kettle and adjust pH to 12, after being heated to 80 DEG C, add 50g lignin, and
90min is kept the temperature at a temperature of this；
S3: 25 DEG C of dischargings are cooled to get modified phenolic resin adhesive 1.
Embodiment 2
Modified phenolic resin adhesive is prepared according to the following steps:
S1: 160g phenolic resin adhesive being added into reaction kettle, and stirring is heated to 30 DEG C, and at this temperature
Keep the temperature 10min；
S2: being added liquid alkaline into reaction kettle and adjust pH to 12, after being heated to 80 DEG C, add 40g lignin, and
90min is kept the temperature at a temperature of this；
S3: 25 DEG C of dischargings are cooled to get modified phenolic resin adhesive 2.
Embodiment 3
Modified phenolic resin adhesive is prepared according to the following steps:
S1: 167g phenolic resin adhesive being added into reaction kettle, and stirring is heated to 30 DEG C, and at this temperature
Keep the temperature 10min；
S2: being added liquid alkaline into reaction kettle and adjust pH to 12, after being heated to 80 DEG C, add 33g lignin, and
90min is kept the temperature at a temperature of this；
S3: 25 DEG C of dischargings are cooled to get modified phenolic resin adhesive 3.
Embodiment 4
Modified phenolic resin adhesive is prepared according to the following steps:
S1: 171g phenolic resin adhesive being added into reaction kettle, and stirring is heated to 30 DEG C, and at this temperature
Keep the temperature 10min；
S2: being added liquid alkaline into reaction kettle and adjust pH to 12, after being heated to 80 DEG C, add 29g lignin, and
90min is kept the temperature at a temperature of this；
S3: 25 DEG C of dischargings are cooled to get modified phenolic resin adhesive 4.
Embodiment 5
Modified phenolic resin adhesive is prepared according to the following steps:
S1: 175g phenolic resin adhesive being added into reaction kettle, and stirring is heated to 30 DEG C, and at this temperature
Keep the temperature 10min；
S2: being added liquid alkaline into reaction kettle and adjust pH to 12, after being heated to 80 DEG C, add 25g lignin, and
90min is kept the temperature at a temperature of this；
S3: 25 DEG C of dischargings are cooled to get modified phenolic resin adhesive 5.
Embodiment 6
Modified phenolic resin adhesive is prepared according to the following steps:
S1: 178g phenolic resin adhesive being added into reaction kettle, and stirring is heated to 30 DEG C, and at this temperature
Keep the temperature 10min；
S2: being added liquid alkaline into reaction kettle and adjust pH to 12, after being heated to 80 DEG C, add 22g lignin, and
90min is kept the temperature at a temperature of this；
S3: 25 DEG C of dischargings are cooled to get modified phenolic resin adhesive 6.
Meanwhile inventor has detected modified phenolic resin obtained in above embodiments 1~6 according further to relevant criterion respectively
The free phenol of rouge adhesive 1~6, dissociate aldehyde, bonding strength, Form aldehyde release figureofmerit, and testing result see the table below 1:
Table 1
Note: bonding strength is the average strength of 12 sample planks.
Specific embodiments of the present invention are described in detail above, but it is merely an example, the present invention is simultaneously unlimited
It is formed on particular embodiments described above.To those skilled in the art, any couple of present invention carries out equivalent modifications and
Substitution is also all among scope of the invention.Therefore, without departing from the spirit and scope of the invention made by equal transformation and
Modification, all should be contained within the scope of the invention.
Claims (6)
1. a kind of method of modified phenolic resin adhesive, which comprises the following steps:
S1: phenolic resin adhesive being added into reaction kettle, stirring, heat temperature raising, and keeps the temperature；
S2: liquid alkaline is added into reaction kettle and adjusts pH to alkalinity, after heat temperature raising, adds lignin, and keep the temperature；S3: cooling,
Discharging.
2. the method for modified phenolic resin adhesive according to claim 1, which is characterized in that the phenolic resin gluing
The dry weight ratio of agent and the lignin is 1:3~1:8.
3. the method for modified phenolic resin adhesive according to claim 1, which is characterized in that alkali described in step S2
Property pH value range be 8 to 13.
4. the method for modified phenolic resin adhesive according to claim 1, which is characterized in that in step sl, heating
30 DEG C~50 DEG C are warming up to, and keeps the temperature 5~20min at 30 DEG C~50 DEG C.
5. the method for modified phenolic resin adhesive according to claim 1, which is characterized in that in step s 2, heating
After being warming up to 40 DEG C~120 DEG C, lignin is added, and keeps the temperature 20~90min at 40 DEG C~120 DEG C.
6. the method for modified phenolic resin adhesive according to claim 1, which is characterized in that in step s3, cooling
To 20~25 DEG C, then discharge.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710358550.4A CN108949078A (en) | 2017-05-19 | 2017-05-19 | A kind of method of modified phenolic resin adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710358550.4A CN108949078A (en) | 2017-05-19 | 2017-05-19 | A kind of method of modified phenolic resin adhesive |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108949078A true CN108949078A (en) | 2018-12-07 |
Family
ID=64461599
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710358550.4A Pending CN108949078A (en) | 2017-05-19 | 2017-05-19 | A kind of method of modified phenolic resin adhesive |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108949078A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109680537A (en) * | 2018-12-12 | 2019-04-26 | 济宁明升新材料有限公司 | A kind of novel Coating combination glue and preparation method and its application in papermaking interlayer spray |
| WO2020132738A1 (en) * | 2018-12-28 | 2020-07-02 | Suzano S.A. | Resole phenolic resins, processes of synthesis of said resins and use thereof |
| CN113322035A (en) * | 2021-05-31 | 2021-08-31 | 江西亚太化工有限公司 | Environment-friendly modified resin and application thereof in bamboo forming |
| CN113717673A (en) * | 2021-09-28 | 2021-11-30 | 上海昶法新材料有限公司 | Method for improving opening time of phenolic resin adhesive |
| US12122882B2 (en) | 2020-11-13 | 2024-10-22 | Wilsonart Llc | Multi-part lignin-based resin system for decorative laminates |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101348698A (en) * | 2008-09-12 | 2009-01-21 | 中国林业科学研究院林产化学工业研究所 | Preparation method of alkali lignin-phenolic composite adhesive for wood industry |
| CN105754527A (en) * | 2016-03-21 | 2016-07-13 | 常州大学 | Phenolic resin adhesive containing demethylated lignin and preparation method of phenolic resin adhesive |
| US20160304757A1 (en) * | 2015-04-15 | 2016-10-20 | Fpinnovations | High residual content (hrc) kraft/soda lignin as an ingredient in wood adhesives |
-
2017
- 2017-05-19 CN CN201710358550.4A patent/CN108949078A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101348698A (en) * | 2008-09-12 | 2009-01-21 | 中国林业科学研究院林产化学工业研究所 | Preparation method of alkali lignin-phenolic composite adhesive for wood industry |
| US20160304757A1 (en) * | 2015-04-15 | 2016-10-20 | Fpinnovations | High residual content (hrc) kraft/soda lignin as an ingredient in wood adhesives |
| CN105754527A (en) * | 2016-03-21 | 2016-07-13 | 常州大学 | Phenolic resin adhesive containing demethylated lignin and preparation method of phenolic resin adhesive |
Non-Patent Citations (1)
| Title |
|---|
| 卢庆曾 等: "《国外木工胶粘剂文集》", 28 February 1991, 中国林业出版社 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109680537A (en) * | 2018-12-12 | 2019-04-26 | 济宁明升新材料有限公司 | A kind of novel Coating combination glue and preparation method and its application in papermaking interlayer spray |
| CN109680537B (en) * | 2018-12-12 | 2021-06-15 | 济宁明升新材料有限公司 | Novel interlayer bonding adhesive and preparation method thereof and application of novel interlayer bonding adhesive in spraying between papermaking layers |
| WO2020132738A1 (en) * | 2018-12-28 | 2020-07-02 | Suzano S.A. | Resole phenolic resins, processes of synthesis of said resins and use thereof |
| CN113728052A (en) * | 2018-12-28 | 2021-11-30 | 苏扎诺有限公司 | Resol-type phenolic resin, synthesis method and application thereof |
| US12122882B2 (en) | 2020-11-13 | 2024-10-22 | Wilsonart Llc | Multi-part lignin-based resin system for decorative laminates |
| CN113322035A (en) * | 2021-05-31 | 2021-08-31 | 江西亚太化工有限公司 | Environment-friendly modified resin and application thereof in bamboo forming |
| CN113717673A (en) * | 2021-09-28 | 2021-11-30 | 上海昶法新材料有限公司 | Method for improving opening time of phenolic resin adhesive |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108949078A (en) | A kind of method of modified phenolic resin adhesive | |
| Jin et al. | Preparation and characterization of phenol–formaldehyde adhesives modified with enzymatic hydrolysis lignin | |
| CN105504191B (en) | A kind of preparation method of eutectic ionic liquid Lignin-based phenolic | |
| CN101519572A (en) | Method for preparing phenol formaldehyde adhesive by bio oil | |
| CN108531116B (en) | Sulfate lignin modified urea-formaldehyde resin adhesive and preparation method thereof | |
| CN104087219A (en) | Preparation method of lignin-modified phenolic resin wood adhesive | |
| CN103497295B (en) | A kind of original position ultrasound polymerization preparation method of industrial alkali lignin modified phenolic resin | |
| CN103613727B (en) | Preparation method of lignin-modified phenol aldehyde resin adhesive | |
| CN108297519B (en) | Manufacturing method of paper-based copper-clad plate | |
| CN107641495B (en) | A kind of vegetable protein adhesive and its preparation method and application | |
| CN101348698A (en) | Preparation method of alkali lignin-phenolic composite adhesive for wood industry | |
| CN104130733B (en) | The preparation method of the modified biomass liquefied resin tackiness agent of enhanced water resistance | |
| Lin et al. | Study on preparation and properties of phenol-formaldehyde-chinese fir liquefaction copolymer resin | |
| CN101220251B (en) | Oxidized starch modified phenolic resin lumber adhesion agent, preparation method and application thereof | |
| CN102408673B (en) | Epoxidized soybean oil modified phenolic resin and method for producing non-fire-retardant paper based copper clad laminate by using same | |
| CN109370512A (en) | A kind of walnut cake meal protein adhesive for plywood and preparation method thereof | |
| CN106432655B (en) | A kind of epoxy soybean oil modified phenolic resin and its preparation method and application | |
| CN110499141A (en) | Camellia oleifera oil cake adhesive modified by biomass cross-linking agent and its preparation method and application | |
| CN101870856B (en) | Bark powder phenolic-resin adhesive and preparation method thereof | |
| CN109371752B (en) | Surface sizing agent for paper | |
| CN106085353A (en) | A kind of preparation method of formaldehydeless lignin-base based Wood Adhesives | |
| CN108948300A (en) | A kind of preparation method of lignin-base phenolic resin adhesive | |
| CN109679547A (en) | A kind of preparation method of modified phenolic resin adhesive and products thereof | |
| CN103952117A (en) | Crosslinking modified jatropha curcas cake meal adhesive and preparation method thereof | |
| CN103465339A (en) | Production method of high-strength formaldehyde-free environmentally friendly fiberboard |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181207 |