CN108299787A - A kind of preparation method of the water soluble phenol resin composite material of casting - Google Patents
A kind of preparation method of the water soluble phenol resin composite material of casting Download PDFInfo
- Publication number
- CN108299787A CN108299787A CN201810030050.2A CN201810030050A CN108299787A CN 108299787 A CN108299787 A CN 108299787A CN 201810030050 A CN201810030050 A CN 201810030050A CN 108299787 A CN108299787 A CN 108299787A
- Authority
- CN
- China
- Prior art keywords
- phenol
- formaldehyde
- casting
- preparation
- added
- 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
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Mold Materials And Core Materials (AREA)
Abstract
The invention discloses a kind of water soluble phenol resin composite material and preparation method of casting low formaldehyde content, which belongs to thermosetting resin, can have lower content of formaldehyde, viscosity as binder for bonding casting sand.Due to having used a large amount of alkali lignin in resin, cost can be not only reduced, the burst size of formaldehyde and phenol in casting process can more be greatly reduced so that compared with similar products, more environmentally-friendly low toxicity contributes to casting industry to continue the development of health to this resin.
Description
Technical field
The invention belongs to technical field of organic chemistry, and in particular to the adhesive techniques field used in casting industry, especially
Phenolic resin middle reaches can be reduced by the synthetic method by being related to a kind of preparation method of water soluble phenol resin composite material
Content from formaldehyde and production cost.
Background technology
Phenolic resin is widely applied to casting industry due to its preferable caking property, is used as the glue of casting shell mold
Glutinous agent.Its casting sand collapsibility is good, gas-forming property is low, therefore is widely used in high-end casting industry.The phenol that casting industry uses
Urea formaldehyde, is broadly divided into thermosetting phenolic resin and thermoplastic phenolic resin, thermoplastic phenolic resin in process of production, phenol
It is generally higher than 1 with the molar ratio of formaldehyde, therefore free formaldehyde content is very low.And the thermosetting phenolic resin that foundry industry uses, it is
A kind of water soluble phenol resin mainly catalyzes and synthesizes under alkaline condition, and in the raw material of synthetic resin, formaldehyde and phenol rub
You are than generally higher than 1, and formaldehyde is excessive, therefore in this water-soluble phenolic resin, and the comparision contents of free formaldehyde are high, will produce
Larger formaldehyde taste, causes foundry's content of formaldehyde exceeded, seriously endangers the health of worker, causes a variety of diseases.Such as
What reduces the content of formaldehyde to dissociate in water soluble phenol resin, is a very great project.
Lignin is a kind of phenol polymer being present in plant, and there is aromatic radical, phenolic hydroxyl group, alcohol in molecular structure
Hydroxyl, carbonyl, methoxyl group, carboxyl, conjugated double bond isoreactivity group.It can be reacted under alkaline condition with formaldehyde, and in acid
It, can be with phenol reactant under the conditions of property.However lignin dissolution is poor, is added directly into phenolic resin, causes dispersion uneven,
And settle, influence the quality of phenolic resin.Alkali lignin has been selected to be added in phenolic resin herein, alkali lignin is easy
It is dissolved in alkaline aqueous solution, under alkaline condition there are more active sites to be reacted with formaldehyde so that lignin methylolation, because
This can be used for reducing the removing residue formaldehyde in water soluble phenol resin, reach the mesh for reducing free formaldehyde in water soluble phenol resin
, while the production cost of phenolic resin can also be reduced.
Although many documents and patent report cross lignin addition in phenolic resin, it is used for phenol-formaldehyde resin modified, is reduced
Cost.But before document the method production phenolic resin, be mainly used for artificial plate bond (CN105694779A and
CN105111394A), cohesive molding sand is not particularly suited for apply in casting industry, and production process and manner described herein
It is entirely different.The phenolic resin that casting industry uses needs lower viscosity, and it is mixed that highly viscous phenolic resin is unfavorable for molding sand
It closes.
Invention content
Technical problem to be solved by the present invention lies in order to reduce the content of free formaldehyde in phenolic resin, reduce simultaneously
The cost of phenolic resin provides a kind of water soluble phenol resin composite material can be used for casting industry.
In order to solve the above technical problem, the present invention provides technical solution be a kind of the water-soluble of casting low formaldehyde content
Property phenolic resin composite, preparation method comprise the steps of：
(1) basic catalyst and water are added into phenol, is heated with stirring to 65~75 DEG C of temperature, pre-reaction 1~30 minute,
Obtain mixed liquor A, the molar ratio of water and phenol is 7~10, and basic catalyst additive amount is the 5%~10% of gross mass；
(2) it is added dropwise formalin into above-mentioned mixed liquor A, the molar ratio of formaldehyde and phenol is 1.5~2.5, heat preservation 65~
75 DEG C are reacted 30-60 minutes, and solution B is obtained；
(3) above-mentioned solution B temperature is increased to 85~95 DEG C of temperature, the reaction was continued 30 minutes,
(4) it is added alkali lignin into reaction system, 85~95 DEG C of thermotonuses 30 minutes obtain solution C；
(5) 70 DEG C are cooled the temperature to hereinafter, acetylacetone,2,4-pentanedione is added into solution C, stirring is obtained to discharging after 20~50 DEG C
To the water soluble phenol resin composite material of the present invention.
Preferably, the basic catalyst is sodium hydroxide or potassium hydroxide.
Preferably, the step (1) is pre-reaction, and during this, phenol molecule is activated under alkaline condition, generates parent
With the very strong benzene negative oxygen ion of property, it is more prone to react with formaldehyde, generates a hydroxymethylphenol.
Preferably, lignin additive amount is the 1%-20% of phenol quality.
Preferably, the lignin is alkali lignin.Compared with common lignin, alkali lignin is soluble easily in water.In alkali
Property under the conditions of, alkali lignin have higher reactivity, can with formaldehyde react so that lignin in aromatic rings methylol
Change, the formaldehyde in reaction solution can be consumed, while the usage amount of phenol can also be reduced, reduce cost.
And after the reaction the phase be added alkali lignin, can to avoid lignin reaction's time too long, cause viscosity increase it is too fast,
Influence its effect mixed with molding sand.
Preferably, acetylacetone,2,4-pentanedione additive amount is the 0.1~0.5% of solution C total weight.Step (5) is：Stop drop in reaction
Thermophase, a small amount of acetylacetone,2,4-pentanedione, acetylacetone,2,4-pentanedione under alkaline condition, become carbanion, are easy to react with remaining formaldehyde, into
One step reduces the concentration of free formaldehyde in phenolic resin, and product free formaldehyde content is less than 0.1%.
Preferably, a kind of water soluble phenol resin composite material of casting low formaldehyde content, preparation method include with
Lower step：
(1) phenol is added in reactor and be stirred, basic catalyst and water is added, be heated to 65~75 DEG C of pre-reactions 1~
30 minutes, in reaction process, solution colour gradually deepened, and catalyst is sodium hydroxide or potassium hydroxide.
(2) under the conditions of 65~75 DEG C, formalin is added dropwise into reactor, is reacted 1 hour at 65~75 DEG C；
(3) temperature of reactor is increased to 85~95 DEG C, the reaction was continued 30 minutes.
(4) alkali lignin is added into reactor, 85~95 DEG C are reacted 30 minutes.
(5) reactor heating function is closed, 70 DEG C is down to hereinafter, addition acetylacetone,2,4-pentanedione, stirring to 20~50 in temperature
It discharges after DEG C, obtains water-soluble, low formaldehyde content alkaline thermosetting phenolic resin, can be used for bonding the type of casting
Sand.
The step (1) is pre-reaction process, and during this, phenol molecule is activated under alkaline condition, is generated affine
Property very strong benzene negative oxygen ion, be more prone to react with formaldehyde, generate a hydroxymethylphenol.
The molar ratio of formaldehyde and phenol is 1.5~2.5, and the molar ratio of water and phenol is 7~10 in reaction system.Catalyst
Additive amount is the 5%~10% of gross mass.Lignin additive amount is the 1%-20% of phenol quality, and acetylacetone,2,4-pentanedione additive amount is total
The 0.1~0.5% of weight.
The step (4) is：Compared with common lignin, alkali lignin is soluble easily in water.Under alkaline condition, alkali is wooden
Element has higher reactivity, and the aromatic rings methylolation so that in lignin can be reacted with formaldehyde, can consume reaction
Formaldehyde in liquid, while the usage amount of phenol can also be reduced, reduce cost.Alkali wood is added in the phase to the step (4) after the reaction
Quality can cause viscosity to increase too fast, influence its effect mixed with molding sand to avoid lignin reaction's time too long.
The step (5) is：Stop temperature-fall period, a small amount of acetylacetone,2,4-pentanedione in reaction, acetylacetone,2,4-pentanedione under alkaline condition, becomes
It at carbanion, is easy to react with remaining formaldehyde, further decreases the concentration of free formaldehyde in phenolic resin, product dissociates first
Aldehyde is less than 0.1%.
Alkali lignin has been selected to be added in phenolic resin in the present invention, alkali lignin is soluble in alkaline aqueous solution, alkali
Property under the conditions of there are more active sites to be reacted with formaldehyde so that lignin methylolation, therefore can be used for reducing water-soluble
Property phenolic resin in removing residue formaldehyde, achieve the purpose that reduce free formaldehyde in water soluble phenol resin, while can also reduce
The production cost of phenolic resin.
The preparation method of the present invention, need not pre-process lignin, improve synthesis technology so that production process
Simply.It is added due to directly using soluble alkali lignin, and in the final stage of phenolic resin building-up process, it not only can be with
Using under alkaline condition, the hydroxymethylation of lignin and formaldehyde reduces concentration of formaldehyde, while also controlling phenolic resin
The rising of composite emulsion viscosities.So that the phenolic resin composite of this low viscosity is more useful in casting industry.
The phenolic resin composite that the present invention is prepared, free formaldehyde content, viscosity and production cost are all relatively low,
Viscosity is smaller, good fluidity, and the tensile strength for bonding molding sand is big, can cohere molding sand as binder, be highly suitable for casting
Industry.
Specific implementation mode
Said program is described further below in conjunction with specific embodiment.It should be understood that these embodiments are for illustrating
The present invention and be not limited to limit the scope of the invention.The implementation condition used in embodiment can be done according to the condition of specific producer
Further adjustment, the implementation condition being not specified is usually the condition in routine experiment.
Embodiment 1：It is prepared by phenolic resin
A kind of water soluble phenol resin composite material of casting low formaldehyde content, preparation method comprise the steps of：
90g phenol is added in reactor and is stirred, 10g sodium hydroxides and 54g water is added, is heated to 65~75 DEG C of pre-reactions
1~30 minute, in reaction process, solution colour gradually deepened.
Under the conditions of 65~75 DEG C, the formalin of 150g 37wt% is added dropwise into reactor, reacts 1 at 65~75 DEG C
Hour.
Temperature of reactor is increased to 85~90 DEG C, the reaction was continued 30 minutes.
5g alkali lignins are added into reactor, 85~90 DEG C are reacted 30 minutes.
Reactor heating function is closed, 70 DEG C are down to hereinafter, addition 1mL acetylacetone,2,4-pentanediones, stirring to 20~50 in temperature
It discharges after DEG C.Water-soluble, low formaldehyde content alkaline thermosetting phenolic resin is obtained, can be used for bonding the type of casting
Sand.
In reaction system, the molar ratio of formaldehyde and phenol is 1.5~2.5, and the molar ratio of water and phenol is 7~10.Catalysis
Agent additive amount is the 5%~10% of gross mass.Lignin additive amount is the 1%-20% of phenol quality, and acetylacetone,2,4-pentanedione additive amount is
For gross mass 0.1%, product free formaldehyde content is less than 0.1%.
Embodiment 2：It is prepared by phenolic resin
A kind of water soluble phenol resin composite material of casting low formaldehyde content, preparation method comprise the steps of：
90g phenol is added in reactor and is stirred, 11g sodium hydroxides and 54g water is added, is heated to 65~75 DEG C of pre-reactions
1~30 minute, in reaction process, solution colour gradually deepened.
Under the conditions of 65~75 DEG C, the formalin of 167g 37wt% is added dropwise into reactor, reacts 1 at 65~75 DEG C
Hour.
Temperature of reactor is increased to 85~90 DEG C, the reaction was continued 30 minutes.
5g alkali lignins are added into reactor, 85~90 DEG C are reacted 30 minutes.
Reactor heating function is closed, 70 DEG C are down to hereinafter, addition 2mL acetylacetone,2,4-pentanediones, stirring to 20~50 in temperature
It discharges after DEG C.Water-soluble, low formaldehyde content alkaline thermosetting phenolic resin is obtained, can be used for bonding the type of casting
Sand.
Embodiment 3：It is prepared by phenolic resin
A kind of water soluble phenol resin composite material of casting low formaldehyde content, preparation method comprise the steps of：
90g phenol is added in reactor and is stirred, 11g sodium hydroxides and 54g water is added, is heated to 65~75 DEG C of pre-reactions
1~30 minute, in reaction process, solution colour gradually deepened.
Under the conditions of 65~75 DEG C, the formalin of 144g 37wt% is added dropwise into reactor, reacts 1 at 65~75 DEG C
Hour.
Temperature of reactor is increased to 85~90 DEG C, the reaction was continued 30 minutes.
10g alkali lignins are added into reactor, 85~90 DEG C are reacted 30 minutes.
Reactor heating function is closed, 70 DEG C are down to hereinafter, addition 1mL acetylacetone,2,4-pentanediones, stirring to 20~50 in temperature
It discharges after DEG C.Water-soluble, low formaldehyde content alkaline thermosetting phenolic resin is obtained, can be used for bonding the type of casting
Sand.
Embodiment 4：It is prepared by phenolic resin
A kind of water soluble phenol resin composite material of casting low formaldehyde content, preparation method comprise the steps of：
90g phenol is added in reactor and is stirred, 10g sodium hydroxides and 54g water is added, is heated to 65~75 DEG C of pre-reactions
1~30 minute, in reaction process, solution colour gradually deepened.
Under the conditions of 65~75 DEG C, the formalin of 144g 37wt% is added dropwise into reactor, reacts 1 at 65~75 DEG C
Hour.
Temperature of reactor is increased to 85~90 DEG C, the reaction was continued 30 minutes.
7g alkali lignins are added into reactor, 85~90 DEG C are reacted 30 minutes.
Reactor heating function is closed, 70 DEG C are down to hereinafter, addition 1mL acetylacetone,2,4-pentanediones, stirring to 20~50 in temperature
It discharges after DEG C.Water-soluble, low formaldehyde content alkaline thermosetting phenolic resin is obtained, can be used for bonding the type of casting
Sand.
Embodiment 5：The bonding of molding sand
1kg molding sand and 30g water soluble phenol resins are mixed evenly, is put into mold and is compacted, temperature 150~
200 DEG C of drying.The mold of tensile strength measurement is by GB/T 2684《Foundry sand and test mixture method》Requirement into
Row.As described in Table 1, the content of formaldehyde of several groups of phenolic resin of Examples 1 to 4 is glued in 0.1% or so, viscosity 100mPa.s or so
Knotting strength is higher, and major product index can meet the requirement of casting sand bonding.
The adhesion strength and leading indicator of phenolic resin described in 1 Examples 1 to 4 of table
The foregoing examples are merely illustrative of the technical concept and features of the invention, its object is to allow person skilled in the art's energy
Solution present disclosure much of that is simultaneously implemented according to this, and it is not intended to limit the scope of the present invention.It is all according to spirit of that invention
The equivalent transformation or modification that essence is done, should be covered by the protection scope of the present invention.
Claims (4)
1. a kind of preparation method of the water soluble phenol resin composite material of casting, it includes following steps：
(1) basic catalyst and water are added into phenol, is heated with stirring to 65~75 DEG C of temperature, pre-reaction 1~30 minute obtains
The molar ratio of mixed liquor A, water and phenol is 7~10, and basic catalyst additive amount is the 5%~10% of gross mass；
(2) it is added dropwise formalin into above-mentioned mixed liquor A, the molar ratio of formaldehyde and phenol is 1.5~2.5, keeps the temperature 65~75 DEG C
Reaction 30-60 minutes, obtains solution B；
(3) above-mentioned solution B temperature is increased to 85~95 DEG C of temperature, the reaction was continued 30 minutes,
(4) it is added alkali lignin into reaction system, 85~95 DEG C of thermotonuses 30 minutes obtain solution C；
(5) 70 DEG C are cooled the temperature to hereinafter, acetylacetone,2,4-pentanedione is added into solution C, stirring obtains this to discharging after 20~50 DEG C
The water soluble phenol resin composite material of invention.
2. preparation method according to claim 1, which is characterized in that the basic catalyst is sodium hydroxide or hydrogen-oxygen
Change potassium.
3. preparation method according to claim 1, which is characterized in that lignin additive amount is the 1%- of phenol quality
20%.
4. preparation method according to claim 1, which is characterized in that the lignin is alkali lignin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810030050.2A CN108299787A (en) | 2018-01-12 | 2018-01-12 | A kind of preparation method of the water soluble phenol resin composite material of casting |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810030050.2A CN108299787A (en) | 2018-01-12 | 2018-01-12 | A kind of preparation method of the water soluble phenol resin composite material of casting |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108299787A true CN108299787A (en) | 2018-07-20 |
Family
ID=62868736
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810030050.2A Pending CN108299787A (en) | 2018-01-12 | 2018-01-12 | A kind of preparation method of the water soluble phenol resin composite material of casting |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108299787A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US12122882B2 (en) | 2021-11-10 | 2024-10-22 | Wilsonart Llc | Multi-part lignin-based resin system for decorative laminates |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4817755B1 (en) * | 1970-08-12 | 1973-05-31 | ||
| JPH04371343A (en) * | 1991-06-20 | 1992-12-24 | Kaou Quaker Kk | Binder composition for sand core for high-pressure casting |
| US20020065400A1 (en) * | 2000-04-06 | 2002-05-30 | Mikhail Raskin | Resin material and method of producing same |
| JP2008213370A (en) * | 2007-03-06 | 2008-09-18 | Toyota Auto Body Co Ltd | Fibrous formed body and its manufacturing method |
| CN101607297A (en) * | 2009-07-22 | 2009-12-23 | 福州大学 | The preparation method of modified phenolic resin binder for casting |
| CN104193932A (en) * | 2014-08-13 | 2014-12-10 | 宁夏共享装备有限公司 | Production method for casting alkaline phenolic resin |
| CN104403068A (en) * | 2014-12-08 | 2015-03-11 | 济南圣泉集团股份有限公司 | Organic ester-hardened alkaline phenolic resin and preparation method thereof |
| KR20160080692A (en) * | 2014-12-30 | 2016-07-08 | 코오롱인더스트리 주식회사 | Phenol Resin Composition and Process of Preparing for the Same |
| CN106180537A (en) * | 2016-08-26 | 2016-12-07 | 蚌埠市北晨微型机床厂 | The precoated sand that a kind of casting cracking resistance is the most easy to stick |
| CN107428946A (en) * | 2015-04-02 | 2017-12-01 | 斯道拉恩索公司 | Activated wooden promotor composition, for its manufacture method with and application thereof |
| CN107775549A (en) * | 2016-08-29 | 2018-03-09 | 青岛天地铸造有限公司 | A kind of casting method of resin wheel |
-
2018
- 2018-01-12 CN CN201810030050.2A patent/CN108299787A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4817755B1 (en) * | 1970-08-12 | 1973-05-31 | ||
| JPH04371343A (en) * | 1991-06-20 | 1992-12-24 | Kaou Quaker Kk | Binder composition for sand core for high-pressure casting |
| US20020065400A1 (en) * | 2000-04-06 | 2002-05-30 | Mikhail Raskin | Resin material and method of producing same |
| JP2008213370A (en) * | 2007-03-06 | 2008-09-18 | Toyota Auto Body Co Ltd | Fibrous formed body and its manufacturing method |
| CN101607297A (en) * | 2009-07-22 | 2009-12-23 | 福州大学 | The preparation method of modified phenolic resin binder for casting |
| CN104193932A (en) * | 2014-08-13 | 2014-12-10 | 宁夏共享装备有限公司 | Production method for casting alkaline phenolic resin |
| CN104403068A (en) * | 2014-12-08 | 2015-03-11 | 济南圣泉集团股份有限公司 | Organic ester-hardened alkaline phenolic resin and preparation method thereof |
| KR20160080692A (en) * | 2014-12-30 | 2016-07-08 | 코오롱인더스트리 주식회사 | Phenol Resin Composition and Process of Preparing for the Same |
| CN107428946A (en) * | 2015-04-02 | 2017-12-01 | 斯道拉恩索公司 | Activated wooden promotor composition, for its manufacture method with and application thereof |
| CN106180537A (en) * | 2016-08-26 | 2016-12-07 | 蚌埠市北晨微型机床厂 | The precoated sand that a kind of casting cracking resistance is the most easy to stick |
| CN107775549A (en) * | 2016-08-29 | 2018-03-09 | 青岛天地铸造有限公司 | A kind of casting method of resin wheel |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US12122882B2 (en) | 2021-11-10 | 2024-10-22 | Wilsonart Llc | Multi-part lignin-based resin system for decorative laminates |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Pizzi | Bioadhesives for wood and fibres: a critical review | |
| CN105694781A (en) | Preparation and application methods of lignin-base green adhesive | |
| US3296159A (en) | Waste sulfite liquor aliphatic aldehyde reaction products | |
| US5646219A (en) | Method of preparing binder system and product thereof | |
| JP2019534345A (en) | Glyoxalized lignin composition | |
| EP0027333A1 (en) | Foundry moulding compositions and method of making foundry moulds and cores | |
| CN102604021A (en) | Method for synthesizing urea-formaldehyde resin containing micro free formaldehyde for E0-level artificial boards | |
| CN104311767A (en) | Modified urea-formaldehyde resin adhesive and preparation method thereof | |
| CN102443369A (en) | Timber adhesive and preparation method thereof | |
| CN103242500B (en) | Preparation method of phenol modified urea resin | |
| CN105694779A (en) | Phenolic resin adhesive and preparation method and application method thereof | |
| CN107586461A (en) | A kind of preparation method of formaldehydeless flame retardant type fiberboard | |
| CN108299787A (en) | A kind of preparation method of the water soluble phenol resin composite material of casting | |
| CN102585129A (en) | Urea-formaldehyde resin for artificial board and modification modulation method thereof | |
| CN112142936A (en) | Additive manufacturing rapid prototyping furan resin and preparation method thereof | |
| US2781328A (en) | Phenolic resin glue compositions containing hydrolyzed ligno-cellulosic degradation products | |
| JP6216637B2 (en) | Self-hardening mold manufacturing method, mold binder kit, and mold composition | |
| CN102134280A (en) | Biomass phenolic resin and preparation thereof | |
| JP2009292952A (en) | Binder for molding material and molded article | |
| CN104151513A (en) | Epoxy-modified urea-formaldehyde resin adhesive for artificial plates and preparation method of adhesive | |
| US12071518B2 (en) | Process for preparing a resin | |
| CN107964080A (en) | Myrica extract phenol-formaldehyde resin modified and its preparation method and application | |
| US3471420A (en) | Acetone-formaldehyde and phenol-acetone-formaldehyde resins extended with animal blood or soy flour and oil-in-water emulsion | |
| CN112778478A (en) | Furan resin and preparation method and application thereof | |
| CN107400494A (en) | A kind of wheat stalk-konjaku flour composite adhesive and preparation method thereof |
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: 20180720 |