CN109679547A - A kind of preparation method of modified phenolic resin adhesive and products thereof - Google Patents
A kind of preparation method of modified phenolic resin adhesive and products thereof Download PDFInfo
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- CN109679547A CN109679547A CN201811565427.0A CN201811565427A CN109679547A CN 109679547 A CN109679547 A CN 109679547A CN 201811565427 A CN201811565427 A CN 201811565427A CN 109679547 A CN109679547 A CN 109679547A
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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
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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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
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- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The present invention relates to preparation methods of a kind of modified phenolic resin adhesive and products thereof.The following steps are included: by phenol, catalyst is added in reaction kettle the preparation method, is warming up to 40~50 DEG C, the insulated and stirred first segment time；It is slowly added to first part's formaldehyde, insulated and stirred second segment time；70~100 DEG C are warming up to, second part formaldehyde, insulated and stirred third section time are slowly added to；Papermaking waste and deionized water, the 4th time of insulated and stirred is added；It is slowly added to Part III formaldehyde, the 5th time of insulated and stirred；Reaction system is cooled to 25 DEG C, the 6th time of insulated and stirred discharges.The present invention using papermaking waste without carry out it is any processing can be used directly, not only improve the reduction of production cost, and can achieve the purpose that biomass resource efficiently utilizes.In addition, the key indexes such as the free phenolic content of the modified phenolic resin adhesive, bonding strength meet national standard.
Description
Technical field
The invention belongs to technical field of polymer materials, in particular to a kind of preparation side of modified phenolic resin adhesive
Method further relates to the modified phenolic resin adhesive as made from the preparation method.
Background technique
About 4,800,000 tons of world's phenolic resin yield in 2010, wherein phenolic resin adhesive accounts for about 33%.It is well known that
China is the first big country of world's Wood-based Panel Production, and Wood-Based Panels in China yield in 2011 reaches 2.35 billion cubic meters, consumes timber glue
About 10,000,000 tons of glutinous agent, wherein based on phenolic aldehyde, ureaformaldehyde, melamine resin.Phenolic resin is because of its unique netted friendship
Join molecular structure, has the advantages that bonding strength height, water-tolerant, good weatherability.But with petroleum resources worsening shortages and
Petroleum base chemical industry increasing price of raw materials, the large-scale production and application of wood-based plate phenolic resin adhesive are increasingly limited
System.From the eighties in last century, people, which begin one's study, prepares phenol with the natural polyphenols raw material such as papermaking waste, tannin substitution phenol
Urea formaldehyde adhesive.The papermaking waste overwhelming majority is burnt up as fuel, and only 1%~2% papermaking waste is separated
High value added product is produced out, it is seen then that in actual production, the higher value application rate of papermaking waste is lower.
Summary of the invention
In order to overcome many disadvantages in the prior art, while in order to realize the high-valued recycling of papermaking waste, this
Invention first aspect provides a kind of preparation method of modified phenolic resin adhesive comprising following steps:
S1: by phenol, catalyst is added in reaction kettle, is warming up to 40~50 DEG C, the insulated and stirred first segment time；
S2: first part's formaldehyde, insulated and stirred second segment time are slowly added to；
S3: being warming up to 70~100 DEG C, is then slowly added into second part formaldehyde, insulated and stirred third section time；
S4: papermaking waste and deionized water, the 4th time of insulated and stirred is added；
S5: Part III formaldehyde, the 5th time of insulated and stirred are slowly added to；
S6: reaction system is cooled to 25 DEG C, the 6th time of insulated and stirred discharges to get the phenol-formaldehyde resin modified
Adhesive.
Preferably, in the above preparation method, the proportion by weight of each material is as follows:
Wherein, formaldehyde is made of first part's formaldehyde, the second part formaldehyde and the Part III formaldehyde.
Preferably, in the above preparation method, the papermaking waste is selected from following any one or more: corruption slurry, screenings,
Wood skin, grass end, pulping waste liquor, siliceous white clay.
Preferably, in the above preparation method, the catalyst is selected from following any one or more: barium hydroxide, hydrogen-oxygen
Change calcium, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium sulfite.
Preferably, in the above preparation method, the first segment time is 10~35min, and the second segment time is 20
~40min, the third section time are 40~60min, and the 4th time is 60~90min, and the 5th time is
20~30min, the 6th time are 5~10min.
Preferably, in the above preparation method, in step sl, in reaction system is warming up to 40~50 DEG C in 30min.
Preferably, in the above preparation method, in step s3, in reaction system is warming up to 70~100 in 40min
℃。
Preferably, in the above preparation method, first part's formaldehyde, second described is added dropwise respectively using pump is added dropwise
Divide formaldehyde and the Part III formaldehyde.
Also, second aspect of the present invention additionally provides a kind of modified phenolic resin adhesive, by described in first aspect
Preparation method be made.
Compared with prior art, technical solution provided by the present invention have it is following the utility model has the advantages that
In other words the post-processing skill that preparation method of the present invention uses papermaking waste is just added after phenol
Papermaking waste improves the reaction efficiency of phenol so that phenol is sufficiently activated, to significantly reduce in reaction product
The content of phenol, formaldehyde finally makes synthesized modified phenolic resin adhesive reach environmentally protective requirement.Wherein, originally
Invent utilized papermaking waste can be used directly without carrying out any processing, not only improves the reduction of production cost, has
Conducive to large-scale industrial production, and it can achieve the purpose that biomass resource efficiently utilizes.In addition, the modified alkyd resin glue
It sticks the key indexes such as free phenolic content, the bonding strength of agent and meets national standard.
Therefore, preparation method of modified phenolic resin adhesive provided by the present invention and products thereof has good market
Potentiality.
Specific embodiment
The present invention is further elaborated With reference to embodiment, but the present invention is not limited to following embodiment party
Formula.
Embodiment 1
Modified phenolic resin adhesive is prepared according to the following steps:
S1: by 100g phenol, 30g sodium hydroxide is added in reaction kettle, and starting stirring is uniformly mixed bottom reactant,
In reaction system is warming up to 50 DEG C in 30min, insulated and stirred 30min；
S2: first part formaldehyde 180g is instilled by reaction kettle, insulated and stirred with rate of addition appropriate using pump is added dropwise
30min；
S3: in reaction system is warming up to 80 DEG C in 40min, then using pump is added dropwise with rate of addition appropriate by second
Part formaldehyde 60g instills reaction kettle, insulated and stirred 50min；
S4: 10g papermaking waste and 50g deionized water, insulated and stirred 90min is added；
S5: Part III formaldehyde 10g is instilled by reaction kettle, insulated and stirred with rate of addition appropriate using pump is added dropwise
30min；
S6: being cooled to 25 DEG C for reaction system, and after insulated and stirred 10min, discharging is glutinous to get the modified alkyd resin glue
Agent.
Embodiment 2
Modified phenolic resin adhesive is prepared according to the following steps:
S1: by 50g phenol, 15g sodium hydroxide is added in reaction kettle, and starting stirring is uniformly mixed bottom reactant,
In reaction system is warming up to 50 DEG C in 30min, insulated and stirred 30min；
S2: first part formaldehyde 140g is instilled by reaction kettle, insulated and stirred with rate of addition appropriate using pump is added dropwise
30min；
S3: in reaction system is warming up to 80 DEG C in 40min, then using pump is added dropwise with rate of addition appropriate by second
Part formaldehyde 50g instills reaction kettle, insulated and stirred 50min；
S4: 100g papermaking waste and 50g deionized water, insulated and stirred 90min is added；
S5: Part III formaldehyde 10g is instilled by reaction kettle, insulated and stirred with rate of addition appropriate using pump is added dropwise
30min；
S6: being cooled to 25 DEG C for reaction system, and after insulated and stirred 10min, discharging is glutinous to get the modified alkyd resin glue
Agent.
Embodiment 3
Modified phenolic resin adhesive is prepared according to the following steps:
S1: by 10g phenol, 1g sodium hydroxide is added in reaction kettle, and starting stirring is uniformly mixed bottom reactant, in
Reaction system is warming up to 50 DEG C in 30min, insulated and stirred 30min；
S2: first part formaldehyde 14g is instilled by reaction kettle, insulated and stirred with rate of addition appropriate using pump is added dropwise
30min；
S3: in reaction system is warming up to 80 DEG C in 40min, then using pump is added dropwise with rate of addition appropriate by second
Part formaldehyde 4g instills reaction kettle, insulated and stirred 50min；
S4: 150g papermaking waste and 200g deionized water, insulated and stirred 90min is added；
S5: Part III formaldehyde 2g is instilled by reaction kettle, insulated and stirred with rate of addition appropriate using pump is added dropwise
30min；
S6: being cooled to 25 DEG C for reaction system, and after insulated and stirred 10min, discharging is glutinous to get the modified alkyd resin glue
Agent.
Comparative example
Existing phenolic resin adhesive is prepared according to the following steps:
S1: by 50g phenol, 15g sodium hydroxide is added in reaction kettle, and starting stirring is uniformly mixed bottom reactant,
In reaction system is warming up to 50 DEG C in 30min, insulated and stirred 30min；
S2: first part formaldehyde 140g is instilled by reaction kettle, insulated and stirred with rate of addition appropriate using pump is added dropwise
30min；
S3: in reaction system is warming up to 80 DEG C in 40min, then using pump is added dropwise with rate of addition appropriate by second
Part formaldehyde 50g instills reaction kettle, insulated and stirred 50min；
S4: 120g deionized water, insulated and stirred 90min is added；
S5: Part III formaldehyde 10g is instilled by reaction kettle, insulated and stirred with rate of addition appropriate using pump is added dropwise
30min；
S6: being cooled to 25 DEG C for reaction system, after insulated and stirred 10min, discharges to get the phenolic resin adhesive.
In addition, inventor also has detected the modified phenolic resin adhesive and comparative example system of Examples 1 to 3 preparation respectively
The key index of standby phenolic resin adhesive, specific testing result are as shown in table 1 below:
The burst size of methanal and bonding strength testing result of 1 sample of table
| Sample source | Burst size of methanal mg/L | Bonding strength MPa |
| Embodiment 1 | 0.31 | 1.51 |
| Embodiment 2 | 0.19 | 0.90 |
| Embodiment 3 | 0.10 | 0.80 |
| Comparative example | 0.20 | 1.23 |
Burst size of methanal and bonding strength in upper table are according to GB/T17657-2013 standard examinations；Pass through data
Comparison is it is found that the free phenolic content of modified phenolic resin adhesive provided by the present invention, bonding strength meet national mark
Standard, and identical index is similar with traditional phenolic resin.
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 (9)
1. a kind of preparation method of modified phenolic resin adhesive, which comprises the following steps:
S1: by phenol, catalyst is added in reaction kettle, is warming up to 40~50 DEG C, the insulated and stirred first segment time；
S2: first part's formaldehyde, insulated and stirred second segment time are slowly added to；
S3: being warming up to 70~100 DEG C, is then slowly added into second part formaldehyde, insulated and stirred third section time；
S4: papermaking waste and deionized water, the 4th time of insulated and stirred is added；
S5: Part III formaldehyde, the 5th time of insulated and stirred are slowly added to；
S6: reaction system is cooled to 25 DEG C, the 6th time of insulated and stirred, discharging is glutinous to get the modified alkyd resin glue
Agent.
2. preparation method according to claim 1, which is characterized in that the proportion by weight of each material is as follows:
Wherein, formaldehyde is made of first part's formaldehyde, the second part formaldehyde and the Part III formaldehyde.
3. preparation method according to claim 1, which is characterized in that the papermaking waste is selected from following any or more
Kind: corruption slurry, screenings, wood skin, grass end, pulping waste liquor, siliceous white clay.
4. preparation method according to claim 1, which is characterized in that the catalyst is selected from following any one or more:
Barium hydroxide, calcium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium sulfite.
5. preparation method according to claim 1, which is characterized in that the first segment time is 10~35min, described the
Two times are 20~40min, and the third section time is 40~60min, and the 4th time is 60~90min, described
5th time is 20~30min, and the 6th time is 5~10min.
6. preparation method according to claim 1, which is characterized in that in step sl, in 30min by reaction system liter
Temperature is to 40~50 DEG C.
7. preparation method according to claim 1, which is characterized in that in step s3, in 40min by reaction system liter
Temperature is to 70~100 DEG C.
8. preparation method according to claim 1, which is characterized in that first part's first is added dropwise respectively using pump is added dropwise
Aldehyde, the second part formaldehyde and the Part III formaldehyde.
9. a kind of modified phenolic resin adhesive, which is characterized in that the modified phenolic resin adhesive according to right by wanting
Preparation method described in any one of 1-8 is asked to be made.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811565427.0A CN109679547A (en) | 2018-12-20 | 2018-12-20 | A kind of preparation method of modified phenolic resin adhesive and products thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811565427.0A CN109679547A (en) | 2018-12-20 | 2018-12-20 | A kind of preparation method of modified phenolic resin adhesive and products thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111087563A (en) * | 2019-12-25 | 2020-05-01 | 上海昶法新材料有限公司 | Modified phenolic resin, preparation method and refractory material containing modified phenolic resin |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101492522A (en) * | 2009-02-27 | 2009-07-29 | 中国林业科学研究院林产化学工业研究所 | Method of preparing alkali lignin modified phenolic resin |
| CN103113840A (en) * | 2013-02-25 | 2013-05-22 | 广西大学 | Method for producing wood adhesive by using papermaking black liquor |
| CN103555237A (en) * | 2013-10-24 | 2014-02-05 | 嘉善中林胶粘剂科技有限公司 | Method for preparing environment-friendly adhesive for biomass wood materials |
-
2018
- 2018-12-20 CN CN201811565427.0A patent/CN109679547A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101492522A (en) * | 2009-02-27 | 2009-07-29 | 中国林业科学研究院林产化学工业研究所 | Method of preparing alkali lignin modified phenolic resin |
| CN103113840A (en) * | 2013-02-25 | 2013-05-22 | 广西大学 | Method for producing wood adhesive by using papermaking black liquor |
| CN103555237A (en) * | 2013-10-24 | 2014-02-05 | 嘉善中林胶粘剂科技有限公司 | Method for preparing environment-friendly adhesive for biomass wood materials |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111087563A (en) * | 2019-12-25 | 2020-05-01 | 上海昶法新材料有限公司 | Modified phenolic resin, preparation method and refractory material containing modified phenolic resin |
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Application publication date: 20190426 |