CN106750060A - A kind of biomass accelerate phenolic resin curing and preparation method of phenolic resin - Google Patents
A kind of biomass accelerate phenolic resin curing and preparation method of phenolic resin Download PDFInfo
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- CN106750060A CN106750060A CN201611159935.XA CN201611159935A CN106750060A CN 106750060 A CN106750060 A CN 106750060A CN 201611159935 A CN201611159935 A CN 201611159935A CN 106750060 A CN106750060 A CN 106750060A
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- phenolic resin
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- phenol
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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
Accelerate phenolic resin curing and preparation method of phenolic resin the invention discloses a kind of biomass, compared with prior art, the acceleration solidified reagents that the present invention is used are biological materials, it is cheap, introducing in phenolic resin simultaneously has degradable biological material, middle may be improved through microbial action degradation when material scrap is placed into the soil；The preparation technology of phenolic resin of the present invention is also relatively easy, and the acceleration solidified reagents for using only need to use preceding addition in phenolic resin, more simple in operation；Phenolic resin curing temperature prepared by the present invention is relatively low and hardening time is shorter, it is adaptable to Wood-based Panel Production and Furniture manufacture.
Description
Technical field
The present invention relates to based Wood Adhesives preparing technical field, more particularly to a kind of biomass accelerate phenolic resin curing and
Preparation method of phenolic resin.
Background technology
Phenolic resin (PF) is earliest industrialized synthesis macromolecular material, so far the existing history of more than 100 years.In wood
In material industry, PF is topmost outdoor stages adhesive of artificial board kind, and its consumption is only second to Lauxite, is timber industry neck
Domain the second major class adhesive made of synthetic resin, with more excellent stability, water resistance and weatherability [Huang Farong, burnt Yang Sheng phenol
Urea formaldehyde and its application [M] Beijing:Chemical Industry Press, 2003].Although PF has common Lauxite unrivaled
Excellent properties, but it there is also some inherent shortcomings, and such as glue-line color depth, glue-line is easily cracked, and especially solidification temperature is high, solid
The features such as changing speed slow when hot pressing time 1.2min/mm (general hot pressing temperature is 130~150 DEG C), limits PF extensive uses
[Chen Yuzhu, Chu Fuxiang, Fan Dongbin wait research [J] the Nanjing Forestry University journal of composite phenolic resin curing accelerators
(natural science edition), 2015,39 (1):109-113].
Therefore, many researchers propose the method for improving phenolic resin curing speed, phenolic resin curing can be accelerated
Material include carbonate (sodium carbonate, sodium acid carbonate etc.), carbonic ester, high reaction activity material (resorcinol, isocyanates
Deng) [Lei Hong, Du Guanben, A.Pizzi, et al. phenol-urea-formaldehyde condensation copolymerization resins structure are formed and compares [J] forest productss
Learn and industry, 2009,29 (2):73-78].Meanwhile, copolycondensation phenol-formaldehyde resin modified is also a kind of method for accelerating solidification, wherein
Typical Representative include urea-phenol-formaldehyde co-condensation polymer resin (PUF) [Du Guanben, Lei Hong, A.Pizzi, et al. urea add
Research [J] the Beijing Forestry University journal of amount Pyrogentisinic Acid-urea-formaldehyde condensation copolymerization resin influence, 2009,31 (2):122-
127].At present, part achievement in research has been generally to approve in the industry, and is able to adopt 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), " phenolic resin is converted into the side of rapid curing timber structure adhesive
Method " (A of ZL 103834337) describes the related preparation method for accelerating to solidify of phenolic resin.By comparing, 3 inventions of the above
Three aspects are embodied in main difference of the invention：
(1) 3 inventions more than accelerate solidification price and cost different from used in the present invention.3 inventions of the above are used
It is all petroleum chemicals to accelerate solidified reagents, and price is of a relatively high, and the acceleration solidified reagents that the present invention is used 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
Thing effect degradation may be improved；
(2) 3 inventions more than accelerate the feed postition of solidified reagents different with the present invention.3 inventions of the above are used and added
Fast solidified reagents are added during phenolic resin synthesizes, and the acceleration solidified reagents that the present invention is used only need to be in phenolic aldehyde tree
Fat uses preceding addition, more simple in operation；
(3) 3 inventions are different with phenolic resin performance prepared by the present invention more than.3 inventions of the above are used and added
Fast solidified reagents are added during phenolic resin synthesizes, and the degree of polymerization and viscosity of phenolic resin can also change；And this hair
The bright acceleration solidified reagents for using 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, to have no and disclose report with identical of the present invention.
The content of the invention
The purpose of the present invention be that provided to solve the above problems a kind of biomass accelerate phenolic resin curing and
Preparation method of phenolic resin.
The present invention is achieved through the following technical solutions above-mentioned purpose：
A kind of biomass of the present invention accelerate phenolic resin to consolidate, and the raw material proportioning and biomass solid of described phenolic resin promote
Entering agent dosage is：The mol ratio of formaldehyde and phenol is 1.8:1.0~2.2:1.0, biomass solid accelerator dosage accounts for phenolic aldehyde tree
The 2-7% of fat solids content.
A kind of biomass of the present invention accelerate the Preparation Method of phenolic resin, comprise the following steps：
(1) 37wt% formalins and phenol are added in reactor, it is 8.5~9.0 to adjust pH value with aqueous slkali,
It is heated to 90 DEG C or so；
(2) it is 8.5~9.0 to adjust pH value with aqueous slkali after 15min；
(3) after after 15min, it is 8.5~9.0 to adjust pH value with aqueous slkali；
(4) reaction is cooled to 40 DEG C to water Combination 200% or so, and it is 8.5~9.0 to adjust pH value with aqueous slkali, cooling
Blowing obtains phenolic resin；
(5) phenolic resin before the use, adds biomass solid accelerator.
Further, in step (1), the formaldehyde is 1.8 with the mol ratio of phenol:1.0~2.2:1.0.Step (1)-(4)
In, the alkali be NaOH, KOH in one or two.In step (1)-(4), the alkali concn is 20%, 30% and 40%.
In step (5), described biomass solid accelerator is pretreatment tannin, dialdehyde starch, pretreatment wood powder, pretreatment hemalbumin
In two or more；In step (5), described biomass solid accelerator addition accounts for the 2- of solids phenol-formaldehyde resin content
7%.
The beneficial effects of the present invention are：
The present invention is that a kind of biomass accelerate phenolic resin curing and preparation method of phenolic resin, compared with prior art,
The acceleration solidified reagents that the present invention is used are biological materials, cheap, while being introduced with degradable in phenolic resin
Biological material, middle may improve when material scrap is placed into the soil through microbial action degradation；Phenolic resin of the present invention
Preparation technology it is also relatively easy, and the acceleration solidified reagents for using only need to use preceding addition in phenolic resin, in operation more
Simply；Phenolic resin curing temperature prepared by the present invention is relatively low and hardening time is shorter, it is adaptable to Wood-based Panel Production and furniture system
Make.
Specific embodiment
The invention will be further described below：
A kind of biomass of the present invention accelerate phenolic resin to consolidate, and the raw material proportioning and biomass solid of described phenolic resin promote
Entering agent dosage is：The mol ratio of formaldehyde and phenol is 1.8:1.0~2.2:1.0, biomass solid accelerator dosage accounts for phenolic aldehyde tree
The 2-7% of fat solids content.
A kind of biomass of the present invention accelerate the Preparation Method of phenolic resin, comprise the following steps：
(5) 37wt% formalins and phenol are added in reactor, it is 8.5~9.0 to adjust pH value with aqueous slkali,
It is heated to 90 DEG C or so；
(6) it is 8.5~9.0 to adjust pH value with aqueous slkali after 15min；
(7) after after 15min, it is 8.5~9.0 to adjust pH value with aqueous slkali；
(8) reaction is cooled to 40 DEG C to water Combination 200% or so, and it is 8.5~9.0 to adjust pH value with aqueous slkali, cooling
Blowing obtains phenolic resin；
(5) phenolic resin before the use, adds biomass solid accelerator.
Further, in step (1), the formaldehyde is 1.8 with the mol ratio of phenol:1.0~2.2:1.0.Step (1)-(4)
In, the alkali be NaOH, KOH in one or two.In step (1)-(4), the alkali concn is 20%, 30% and 40%.
In step (5), described biomass solid accelerator is pretreatment tannin, dialdehyde starch, pretreatment wood powder, pretreatment hemalbumin
In two or more；In step (5), described biomass solid accelerator addition accounts for the 2- of solids phenol-formaldehyde resin content
7%.
Embodiment 1：
(1) 98 parts of 146 parts of 37wt% formalins and phenol are added in reactor, are adjusted with 30%NaOH aqueous slkalis
Section pH value is 8.5~9.0, is heated to 90 DEG C or so；
(2) it is 8.5~9.0 to adjust pH value with 30%NaOH aqueous slkalis after 15min；
(3) after after 15min, it is 8.5~9.0 to adjust pH value with 30%KOH aqueous slkalis；
(4) reaction to water Combination 200% or so, be cooled to 40 DEG C, with 30%NaOH aqueous slkalis adjust pH value be 8.5~
9.0, cooling blowing obtains phenolic resin.
(5) phenolic resin before the use, adds 4.6 parts of biomass solid accelerator.
By (PF1) before differential scanning calorimetric analysis instrument DSC (heating rate 10K/min) pair plus curing accelerator, after
(PF2) solidification temperature of phenolic resin and hardening time test index are as follows：
| Phenolic resin | Hardening 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：
(6) 98 parts of 162 parts of 37wt% formalins and phenol are added in reactor, are adjusted with 30%KOH aqueous slkalis
Section pH value is 8.5~9.0, is heated to 90 DEG C or so；
(7) it is 8.5~9.0 to adjust pH value with 30%KOH aqueous slkalis after 15min；
(8) after after 15min, it is 8.5~9.0 to adjust pH value with 30%NaOH aqueous slkalis；
(9) reaction to water Combination 200% or so, be cooled to 40 DEG C, with 30%KOH aqueous slkalis adjust pH value be 8.5~
9.0, cooling blowing obtains phenolic resin.
(10) phenolic resin before the use, adds 5.8 parts of biomass solid accelerator.
By (PF1) before differential scanning calorimetric analysis instrument DSC (heating rate 10K/min) pair plus curing accelerator, after
(PF2) solidification temperature of phenolic resin and hardening time test index are as follows：
| Phenolic resin | Hardening 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 |
General principle of the invention and principal character and advantages of the present invention has been shown and described above.The technology of the industry
Personnel it should be appreciated that the present invention is not limited to the above embodiments, simply explanation described in above-described embodiment and specification this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appending claims and its
Equivalent thereof.
Claims (7)
1. a kind of biomass accelerate phenolic resin curing, it is characterised in that：The raw material proportioning and biomass of described phenolic resin
Curing accelerator dosage is：The mol ratio of formaldehyde and phenol is 1.8:1.0~2.2:1.0, biomass solid accelerator dosage is accounted for
The 2-7% of solids phenol-formaldehyde resin content.
2. a kind of biomass accelerate the Preparation Method of phenolic resin, it is characterised in that comprise the following steps：
(1) 37wt% formalins and phenol are added in reactor, it is 8.5~9.0 to adjust pH value with aqueous slkali, heating
It is warming up to 90 DEG C or so；
(2) it is 8.5~9.0 to adjust pH value with aqueous slkali after 15min；
(3) after after 15min, it is 8.5~9.0 to adjust pH value with aqueous slkali；
(4) reaction is cooled to 40 DEG C to water Combination 200% or so, and it is 8.5~9.0 to adjust pH value with aqueous slkali, cools down blowing
Obtain phenolic resin；
(5) phenolic resin before the use, adds biomass solid accelerator.
3. biomass according to claim 2 accelerate the Preparation Method of phenolic resin, it is characterised in that：It is described in step (1)
Formaldehyde is 1.8 with the mol ratio of phenol:1.0~2.2:1.0.
4. biomass according to claim 2 accelerate the Preparation Method of phenolic resin, it is characterised in that：In step (1)-(4),
The alkali be NaOH, KOH in one or two.
5. biomass according to claim 2 accelerate the Preparation Method of phenolic resin, it is characterised in that：In step (1)-(4),
The alkali concn is 20%, 30% and 40%.
6. biomass according to claim 2 accelerate the Preparation Method of phenolic resin, it is characterised in that：It is described in step (5)
Biomass solid accelerator be pre-process tannin, dialdehyde starch, pretreatment wood powder, pretreatment hemalbumin in two kinds or many
Kind.
7. biomass according to claim 2 accelerate the Preparation Method of phenolic resin, it is characterised in that：It is described in step (5)
Biomass solid accelerator addition account for the 2-7% of solids phenol-formaldehyde resin content.
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| Application Number | Priority Date | Filing Date | Title |
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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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| CN106750060A true CN106750060A (en) | 2017-05-31 |
| CN106750060B CN106750060B (en) | 2019-03-29 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN114891278A (en) * | 2022-06-13 | 2022-08-12 | 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 |
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| 马玉峰等: "酚醛树脂胶粘剂研究进展", 《粘结》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN114891278A (en) * | 2022-06-13 | 2022-08-12 | 西南林业大学 | Full biomass-based building material and preparation method thereof |
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| CN106750060B (en) | 2019-03-29 |
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