CN106750060B - A kind of biomass accelerates phenolic resin cured and preparation method thereof - Google Patents
A kind of biomass accelerates phenolic resin cured and preparation method thereof Download PDFInfo
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- CN106750060B CN106750060B CN201611159935.XA CN201611159935A CN106750060B CN 106750060 B CN106750060 B CN 106750060B CN 201611159935 A CN201611159935 A CN 201611159935A CN 106750060 B CN106750060 B CN 106750060B
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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
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
-
- 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
- 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
- C09J11/08—Macromolecular additives
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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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)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention discloses a kind of biomass to accelerate phenolic resin cured and its Preparation Method, compared with prior art, the acceleration solidified reagents that the present invention uses are biological materials, it is cheap, introducing in phenolic resin simultaneously has degradable biological material, middle may improve through microbial action degradation when material scrap is placed into the soil；The preparation process of phenolic resin of the present invention is also relatively easy, and the acceleration solidified reagents used only need to use preceding addition in phenolic resin, more simple in operation；Phenolic resin curing temperature prepared by the present invention is lower and curing time is shorter, is suitable for Wood-based Panel Production and Furniture manufacture.
Description
Technical field
The present invention relates to based Wood Adhesives preparation technical field more particularly to a kind of biomass accelerate it is phenolic resin cured and
Preparation method.
Background technique
Phenolic resin (PF) is earliest industrialized synthesis high molecular material, has more than 100 years history so far.In wood
In material industry, PF is most important outdoor stages adhesive of artificial board kind, and dosage is only second to Lauxite, is timber industry neck
Domain the second major class adhesive made of synthetic resin has more excellent stability, water resistance and weatherability [Huang Farong, Jiao Yangsheng phenol
Urea formaldehyde and its application Beijing [M]: Chemical Industry Press, 2003].Although PF has common Lauxite unrivaled
Excellent properties, but it is there is also some inherent shortcomings, such as glue-line color is deep, glue-line is easily cracked, and especially solidification temperature is high, solid
The features such as changing speed slow (when general hot pressing temperature is 130~150 DEG C, hot pressing time 1.2min/mm), limits PF extensive use
[Chen Yuzhu, Chu Fuxiang, Fan Dongbin wait research [J] the Nanjing Forestry University journal of composite phenolic resin curing accelerator
(natural science edition), 2015,39 (1): 109-113].
For this purpose, many researchers propose the method for improving phenolic resin curing rate, phenolic resin curing can be accelerated
Substance include carbonate (sodium carbonate, sodium bicarbonate etc.), carbonic ester, high reaction activity substance (resorcinol, isocyanates
Deng) [[J] forest products is compared in the formation of Lei Hong, Du Guanben, A.Pizzi, et al. phenol-urea-formaldehyde condensation copolymerization resin structure
It learns and industry, 2009,29 (2): 73-78].Meanwhile copolycondensation phenol-formaldehyde resin modified is also a kind of cured method of acceleration, wherein
Typical Representative include that [Du Guanben, Lei Hong, A.Pizzi, et al. urea add urea-phenol-formaldehyde co-condensation polymer resin (PUF)
Measure research [J] the Beijing Forestry University journal that Pyrogentisinic Acid-urea-formaldehyde condensation copolymerization resin influences, 2009,31 (2): 122-
127].Currently, part research achievement has been generally to approve in the industry, and adopted extensively in practical application in industry.
It is patent " a kind of thermosetting rapid curing phenolic resin and preparation method thereof " (ZL 200810224194.8), " modified
Thermoset type quick solidified phenol-formaldehyde resin " (ZL 1916071) " converts phenolic resin to the side of rapid curing timber structure adhesive
Method " (103834337 A of ZL) describes phenolic resin correlation and accelerates cured preparation method.By comparing, above 3 inventions
Three aspects are embodied in main difference of the invention:
(1) 3 inventions solidify price from acceleration used in the present invention more than and cost is different.Above 3 inventions use
Accelerating solidified reagents is all petroleum chemicals, and price is relatively high, and the acceleration solidified reagents that the present invention uses are biological materials,
It is cheap, at the same in phenolic resin introduce have degradable biological material, when material scrap place into the soil it is middle through micro- life
Object effect degradation may improve；
(2) 3 inventions accelerate the adding manner of solidified reagents different with the present invention more than.Above 3 inventions, which use, to be added
Fast solidified reagents are to add during phenolic resin synthesis, and the acceleration solidified reagents that the present invention uses only need to be in phenolic aldehyde tree
Rouge uses preceding addition, more simple in operation；
(3) 3 inventions are different with phenolic resin service performance prepared by the present invention more than.Above 3 inventions, which use, to be added
Fast solidified reagents are added during phenolic resin synthesis, and the degree of polymerization and viscosity of phenolic resin can also change；And this hair
The bright acceleration solidified reagents used only need to use preceding addition a small amount of in phenolic resin, will not change the degree of polymerization of phenolic resin and stick
Degree.
By literature search, open report same as the present invention is had no.
Summary of the invention
The object of the invention is that solve the above-mentioned problems and provide a kind of biomass accelerate it is phenolic resin cured and
Preparation method.
The present invention through the following technical solutions to achieve the above objectives:
A kind of biomass acceleration phenolic resin cured, the raw material proportioning and biomass solid promotor of the phenolic resin
Dosage are as follows: the molar ratio of formaldehyde and phenol is 1.8:1.0~2.2:1.0, and it is solid that biomass solid promotor dosage accounts for phenolic resin
The 2-7% of body content.
Based on foregoing teachings, accelerate phenolic resin cured preparation method the present invention also provides the biomass, including with
Lower step:
(1) 37wt% formalin and phenol are added in reaction kettle, adjusting pH value with aqueous slkali is 8.5~9.0,
It is heated to 90 DEG C or so；
(2) adjusting pH value with aqueous slkali after 15min is 8.5~9.0；
(3) after 15min, adjusting pH value with aqueous slkali is 8.5~9.0；
(4) reaction is cooled to 40 DEG C, adjusting pH value with aqueous slkali is 8.5~9.0, cooling to water Combination 200% or so
Blowing obtains phenolic resin；
(5) before the use, biomass solid promotor is added in phenolic resin.
Further, in step (1), the molar ratio of the formaldehyde and phenol is 1.8:1.0~2.2:1.0.Step (1)-(4)
In, the alkali is one or both of NaOH, KOH.In step (1)-(4), the alkali concentration is 20%, 30% and 40%.
In step (5), the biomass solid promotor is pretreatment tannin, dialdehyde starch, pretreatment wood powder, pretreatment hemalbumin
In two or more；In step (5), the biomass solid promotor additional amount accounts for the 2- of solids phenol-formaldehyde resin content
7%.
The beneficial effects of the present invention are:
It is phenolic resin cured and preparation method thereof that the present invention is that a kind of biomass accelerates, compared with prior art, the present invention
The acceleration solidified reagents used are biological materials, cheap, while being introduced in phenolic resin with degradable biological matter
Material middle may be improved when material scrap is placed into the soil through microbial action degradation；The preparation of phenolic resin of the present invention
Technique is also relatively easy, and the acceleration solidified reagents used only need to use preceding addition in phenolic resin, more simple in operation；This
The phenolic resin curing temperature for inventing preparation is lower shorter with curing time, is suitable for Wood-based Panel Production and Furniture manufacture.
Specific embodiment
The invention will be further described below:
A kind of biomass of the present invention accelerates phenolic resin cured, the raw material proportioning and biomass solid of the phenolic resin
Promotor dosage are as follows: the molar ratio of formaldehyde and phenol is 1.8:1.0~2.2:1.0, and biomass solid promotor dosage accounts for phenolic aldehyde
The 2-7% of resin solid content.
A kind of biomass of the present invention accelerates phenolic resin cured preparation method, comprising the following steps:
(1) 37wt% formalin and phenol are added in reaction kettle, adjusting pH value with aqueous slkali is 8.5~9.0,
It is heated to 90 DEG C or so；
(2) adjusting pH value with aqueous slkali after 15min is 8.5~9.0；
(3) after 15min, adjusting pH value with aqueous slkali is 8.5~9.0；
(4) reaction is cooled to 40 DEG C, adjusting pH value with aqueous slkali is 8.5~9.0, cooling to water Combination 200% or so
Blowing obtains phenolic resin；
(5) before the use, biomass solid promotor is added in phenolic resin.
Further, in step (1), the molar ratio of the formaldehyde and phenol is 1.8: 1.0~2.2: 1.0.Step (1)-(4)
In, the alkali is one or both of Na0H, KOH.In step (1)-(4), the alkali concentration is 20%, 30% and 40%.
In step (5), the biomass solid promotor is pretreatment tannin, dialdehyde starch, pretreatment wood powder, pretreatment hemalbumin
In two or more；In step (5), the biomass solid promotor additional amount accounts for the 2- of solids phenol-formaldehyde resin content
7%.
Embodiment 1:
(1) 146 parts and 98 parts of phenol of 37wt% formalin are added in reaction kettle, with 30%Na0H aqueous slkali tune
Saving pH value is 8.5~9.0, is heated to 90 DEG C or so；
(2) adjusting pH value with 30%Na0H aqueous slkali after 15min is 8.5~9.0；
(3) after 15min, adjusting pH value with 30%KOH aqueous slkali is 8.5~9.0；
(4) reaction is cooled to 40 DEG C to water Combination 200% or so, with 30%Na0H aqueous slkali adjust pH value be 8.5~
9.0, cooling blowing obtains phenolic resin.
(5) phenolic resin before the use, is added 4.6 parts of biomass solid promotor.
By differential scanning calorimetric analysis instrument DSC (heating rate 10K/min) to add (PF1) before curing accelerator, after
(PF2) solidification temperature of phenolic resin and curing time test index are as follows:
| Phenolic resin | Curing time/min | Curing initiation temperature/DEG C | Cure peak temperature/DEG C |
| PF1 | 14.1 | 153.3 | 161.0 |
| PF2 | 12.7 | 143.0 | 156.7 |
Embodiment 2:
(1) 162 parts and 98 parts of phenol of 37wt% formalin are added in reaction kettle, with 30%KOH aqueous slkali tune
Saving pH value is 8.5~9.0, is heated to 90 DEG C or so；
(2) adjusting pH value with 30%KOH aqueous slkali after 15min is 8.5~9.0；
(3) after 15min, adjusting pH value with 30%NaOH aqueous slkali is 8.5~9.0；
(4) reaction is cooled to 40 DEG C to water Combination 200% or so, with 30%KOH aqueous slkali adjust pH value be 8.5~
9.0, cooling blowing obtains phenolic resin.
(5) phenolic resin before the use, is added 5.8 parts of biomass solid promotor.
By differential scanning calorimetric analysis instrument DSC (heating rate 10K/min) to add (PF1) before curing accelerator, after
(PF2) solidification temperature of phenolic resin and curing time test index are as follows:
| Phenolic resin | Curing time/min | Curing initiation temperature/DEG C | Cure peak temperature/DEG C |
| PF1 | 13.2 | 149.1 | 155.6 |
| PF2 | 11.3 | 138.7 | 152.4 |
Basic principles and main features and advantages of the present invention of the invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (7)
1. a kind of biomass accelerates phenolic resin cured, it is characterised in that: the raw material proportioning and biomass of the phenolic resin
Curing accelerator dosage are as follows: the molar ratio of formaldehyde and phenol is 1.8:1.0~2.2:1.0, and biomass solid promotor dosage accounts for
The 2-7% of solids phenol-formaldehyde resin content.
2. biomass described in claim 1 accelerates phenolic resin cured preparation method, which is characterized in that including following step
It is rapid:
(1) 37wt% formalin and phenol are added in reaction kettle, adjusting pH value with aqueous slkali is 8.5~9.0, heating
It is warming up to 90 DEG C；
(2) adjusting pH value with aqueous slkali after 15min is 8.5~9.0；
(3) after 15min, adjusting pH value with aqueous slkali is 8.5~9.0；
(4) reaction is cooled to 40 DEG C, adjusting pH value with aqueous slkali is 8.5~9.0, and cooling blowing obtains to water Combination 200%
Phenolic resin；
(5) before the use, biomass solid promotor is added in phenolic resin.
3. biomass according to claim 2 accelerates phenolic resin cured preparation method, it is characterised in that: step (1)
In, the molar ratio of the formaldehyde and phenol is 1.8:1.0~2.2:1.0.
4. biomass according to claim 2 accelerates phenolic resin cured preparation method, it is characterised in that: step (1)-
(4) in, the alkali is one or both of NaOH, KOH.
5. biomass according to claim 2 accelerates phenolic resin cured preparation method, it is characterised in that: step (1)-
(4) in, the alkali concentration is 20%, 30% and 40%.
6. biomass according to claim 2 accelerates phenolic resin cured preparation method, it is characterised in that: step (5)
In, the biomass solid promotor be pre-process tannin, dialdehyde starch, pretreatment wood powder, pretreatment hemalbumin in two
Kind is a variety of.
7. biomass according to claim 2 accelerates phenolic resin cured preparation method, it is characterised in that: step (5)
In, the biomass solid promotor additional amount accounts for the 2-7% of solids phenol-formaldehyde resin content.
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| CN201611159935.XA CN106750060B (en) | 2016-12-15 | 2016-12-15 | A kind of biomass accelerates phenolic resin cured and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109134798A (en) * | 2018-08-07 | 2019-01-04 | 枣阳市众成化工有限公司 | A kind of preparation method of high solidification rate phenolic resin |
| CN110591281A (en) * | 2019-04-01 | 2019-12-20 | 洛阳双瑞橡塑科技有限公司 | Grid and preparation method thereof |
| CN110591282A (en) * | 2019-04-01 | 2019-12-20 | 洛阳双瑞橡塑科技有限公司 | Fireproof grating and preparation method thereof |
| CN114891278B (en) * | 2022-06-13 | 2023-05-16 | 西南林业大学 | Full biomass-based building material and preparation method thereof |
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|---|---|---|---|---|
| CN101037527A (en) * | 2007-03-29 | 2007-09-19 | 上海交通大学 | Method for preparing bakelite by using nonmetal material in waste printing circuit board |
| CN103834337A (en) * | 2014-03-21 | 2014-06-04 | 南京林业大学 | Method for converting ordinary phenolic resin into quick-curing wood structure adhesive |
| CN106220800A (en) * | 2016-08-31 | 2016-12-14 | 四川国能高科生物树脂有限公司 | A kind of fast curing type bio-oil phenol-formaldehyde resin modified and preparation method thereof |
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2016
- 2016-12-15 CN CN201611159935.XA patent/CN106750060B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101037527A (en) * | 2007-03-29 | 2007-09-19 | 上海交通大学 | Method for preparing bakelite by using nonmetal material in waste printing circuit board |
| CN103834337A (en) * | 2014-03-21 | 2014-06-04 | 南京林业大学 | Method for converting ordinary phenolic resin into quick-curing wood structure adhesive |
| CN106220800A (en) * | 2016-08-31 | 2016-12-14 | 四川国能高科生物树脂有限公司 | A kind of fast curing type bio-oil phenol-formaldehyde resin modified and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 酚醛树脂胶粘剂研究进展;马玉峰等;《粘结》;20140210(第2期);第033-039页 |
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