CN104194254B - Phenolic foam resin solidifying agent and synthetic method thereof - Google Patents
Phenolic foam resin solidifying agent and synthetic method thereof Download PDFInfo
- Publication number
- CN104194254B CN104194254B CN201410428537.8A CN201410428537A CN104194254B CN 104194254 B CN104194254 B CN 104194254B CN 201410428537 A CN201410428537 A CN 201410428537A CN 104194254 B CN104194254 B CN 104194254B
- Authority
- CN
- China
- Prior art keywords
- solidifying agent
- parts
- foam resin
- phenolic foam
- resin solidifying
- 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.)
- Expired - Fee Related
Links
Abstract
The present invention discloses a kind of phenolic foam resin solidifying agent and synthetic method thereof, employing aromatic hydrocarbons is raw material, add sulfuric acid and carry out sulfonation reaction, also Vanadium Pentoxide in FLAKES is added with in described sulfonation reaction step, described sulfuric acid to be concentration be 70% ~ 98% the vitriol oil or oleum, or the mixture of said two devices.Compared with prior art, the present invention adds Vanadium Pentoxide in FLAKES when sulfonation reaction, become phosphoric acid as dewatering agent dehydration when sulfonation reaction and become the effective constituent of solidifying agent, waste water can not be produced, waste residue or waste gas etc., sulfonation reaction is more easily carried out simultaneously, the temperature of particularly reacting is lower than the boiling point of toluene, thus reduce the equipment investment of generation process, toluene in addition, Vanadium Pentoxide in FLAKES, sulfuric acid market value is also far below the price of tosic acid, make the tosic acid of manufacturing cost lower than equal volume of gained phenolic foam resin solidifying agent of the present invention, phosphoric acid, sulfuric acid mixture.
Description
Technical field
The present invention relates to the phenolic foam resin of building materials field, particularly relate to a kind of phenolic foam resin solidifying agent and synthetic method thereof.
Background technology
Phenol formaldehyde foam is a kind of porous plastics obtained by foaming by resol.Compared with the material such as polystyrene foam, polyvinyl chloride foam, polyurethane foam accounting for leading market status in early days, in fire-retardant, it has special excellent victory energy.It is lightweight, and rigidity is large, good stability of the dimension, resistance to chemical attack, good heat resistance, difficult combustion, puts out certainly, low smog, flame resistant penetrates, and meets fire without unrestrained thing, cheap, be the ideal insulated heat lagging material of the industries such as electrical equipment, instrument, building, petrochemical complex, thus attract widespread attention.Pnenolic aldehyde foam material is generally made up of main components such as expandable phenolic resin, whipping agent, emulsifying agent, solidifying agent, and wherein solidifying agent plays a crucial role to resin solidification is shaping.
When solidifying agent is made in acid, acid can accelerate the polycondensation between molecular resin, and reaction liberated heat impels whipping agent anxious according to gasification, and emulsifying resins is swelled, cured resin simultaneously.The type of solidifying agent and quantity are extremely important to acquisition good quality froth at a certain temperature.The acid strong cured speed of mineral acid is fast but to metal by very strong corrosive nature, organic acid curing speed can reach inhibition to mineral acid slowly.Therefore only have organic acid and mineral acid reasonably combined, just can obtain the solidifying agent being suitable for actual production.
Solidifying agent based on present employing aromatic sulfonic acid is very general, this is because its corrodibility is little, and has plastification, and itself and mineral acid is used in combination, and solidification effect is better.When organic acid adopt tosic acid, mineral acid adopt phosphoric acid, sulfuric acid by a certain percentage composite form time, curing speed and the expansion rate of solidifying agent match, so adopted by some manufacturers in production practice.
Solid-state organic sulfonic acid is made into the aqueous solution of high density by tosic acid in use, therefore needs a large amount of tosic acid.And the cost of tosic acid is higher, marketable value is not generally at 10000 yuan/ton to 12000 yuan/ton etc., along with developing rapidly of phenol formaldehyde foam, its range of application constantly expands, also quite active to the research and development of its solidifying agent, wherein production cost problem is that those skilled in the art urgently wish to solve and the technical problem that never solves.
Summary of the invention
In view of this, the invention provides a kind of phenolic foam resin solidifying agent and synthetic method thereof, under the condition of low cost, synthesize desirable phenolic foam resin special curing agent.
The synthetic method of phenolic foam resin solidifying agent in the present invention, comprising: employing aromatic hydrocarbons is raw material, and add sulfuric acid and carry out sulfonation reaction, technological core of the present invention is: be also added with Vanadium Pentoxide in FLAKES in described sulfonation reaction step.
The synthetic method of above-mentioned phenolic foam resin solidifying agent, concrete operations are as follows:
Taking 100 parts, aromatic hydrocarbons by weight adds in reactor, adds Vanadium Pentoxide in FLAKES 20 ~ 100 parts; Preferably divide 2 ~ 5 times to add.
Start agitator, be added dropwise to 150 ~ 300 parts of sulfuric acid, sulfuric acid preferably carries out dropwise reaction still, and at the temperature of 80 DEG C ~ 170 DEG C, sulfonation reaction 1 ~ 24 is little both obtains phenolic foam resin solidifying agent up to reacting completely.
Aromatic hydrocarbons to be preferably in benzene,toluene,xylene, naphthalene any one or two or more mixtures, and hydroxyl, alkyl derivative.
Sulfuric acid is preferably the vitriol oil and/or the oleum that concentration is 70% ~ 98%; Be preferably the vitriol oil and/or the oleum of 90% ~ 98%.
Following one or both can also be added in described phenolic foam resin solidifying agent: dibasic alcohol 5 ~ 15 parts, diprotic acid 5 ~ 15 parts, and react 1 ~ 8 hour at the temperature of 100 DEG C ~ 200 DEG C.
Described dibasic alcohol preferably in water miscible ethylene glycol, propylene glycol, polyoxyethylene glycol in any one or more mixture.
Described diprotic acid preferably in water miscible adipic acid, Tetra hydro Phthalic anhydride in any one or more mixture.
Inhibiter can also be added in above-mentioned phenolic foam resin solidifying agent, add-on is 0.5 ~ 1% of phenolic foam resin solidifying agent gross weight, described inhibiter is organic amine inhibiter, is preferably one or more in thiocarbamide, hexamethyl tetramine, tetrahydroglyoxaline.
Compared with prior art, the present invention adds Vanadium Pentoxide in FLAKES when sulfonation reaction, becomes phosphoric acid and becomes the effective constituent of solidifying agent, can not produce waste water, waste residue or waste gas etc. as dewatering agent dehydration when sulfonation reaction, the water that simultaneously stability sulfonation reaction produces, solves the problem that sulfonation reaction generation water needs to remove, sulfonation reaction is more easily carried out, but applicant's main purpose when studying of the present invention reduces production cost, namely core content of the present invention, when adopting toluene sulfonation reaction to add Vanadium Pentoxide in FLAKES, as long as the temperature of sulfonation reaction reaches 80 DEG C ~ 170 DEG C can generate tosic acid, lower than the boiling point of toluene, thus reduce the equipment investment of generation process, toluene in addition, Vanadium Pentoxide in FLAKES, sulfuric acid market value is also far below the price of tosic acid, make the tosic acid of manufacturing cost lower than equal volume of gained phenolic foam resin solidifying agent of the present invention, phosphoric acid, 30% to 60% of sulfuric acid mixture.
Embodiment
In order to make those skilled in the art understand technical scheme of the present invention better, below in conjunction with specific embodiment, the present invention is described in further detail.
Following examples only for technical scheme of the present invention is clearly described, and can not limit the scope of the invention with this.
embodiment 1:taking toluene 100 parts by weight adds in reactor, adds Vanadium Pentoxide in FLAKES 20 parts disposable time; Start agitator, dripping 150 parts of concentration is the vitriol oil of 70%, and at the temperature of 80 DEG C, sulfonation reaction 24 is little both obtains phenolic foam resin solidifying agent up to reacting completely.
embodiment 2:taking toluene 100 parts by weight adds in reactor, adds Vanadium Pentoxide in FLAKES 20 parts disposable time; Start agitator, dripping 160 parts of concentration is the vitriol oil of 98%, and at the temperature of 85 DEG C, sulfonation reaction 15 is little of reacting completely; Add ethylene glycol 5 parts, adipic acid 5 parts again, and reaction obtains phenolic foam resin solidifying agent in 2 hours at the temperature of 110 DEG C.Sulfonation reaction can add one or more in thiocarbamide, hexamethyl tetramine, tetrahydroglyoxaline completely in phenolic foam resin solidifying agent, and add-on is 0.5% of phenolic foam resin solidifying agent gross weight.
embodiment 3:taking toluene 100 parts by weight adds in reactor, adds Vanadium Pentoxide in FLAKES totally 40 parts at twice; Start agitator, dripping 170 parts of concentration is the vitriol oil of 86%, and at the temperature of 90 DEG C, sulfonation reaction 12 is little of reacting completely; Sulfonation reaction can add the mixture of thiocarbamide, hexamethyl tetramine completely in phenolic foam resin solidifying agent, and add-on is 0.8% of phenolic foam resin solidifying agent gross weight.
embodiment 4:taking dimethylbenzene 100 parts by weight adds in reactor, divides and adds Vanadium Pentoxide in FLAKES totally 60 parts for three times; Start agitator, dripping 180 parts of concentration is the vitriol oil of 95%, and at the temperature of 95 DEG C, sulfonation reaction 8 is little of reacting completely; Sulfonation reaction can add tetrahydroglyoxaline in phenolic foam resin solidifying agent completely, and add-on is 0.9% of phenolic foam resin solidifying agent gross weight.
embodiment 5:taking dimethylbenzene 100 parts by weight adds in reactor, divides and adds Vanadium Pentoxide in FLAKES totally 70 parts for three times;
Start agitator, dripping 182 parts of concentration is the vitriol oil of 90%, and at the temperature of 150 DEG C, sulfonation reaction 5 is little of reacting completely; Add 10 parts, the mixture of ethylene glycol and polyoxyethylene glycol, Tetra hydro Phthalic anhydride 10 parts again, and reaction obtains the solidification of phenolic foam resin for 6 hours at the temperature of 150 DEG C.Sulfonation reaction can add the mixture of thiocarbamide, hexamethyl tetramine, tetrahydroglyoxaline completely in phenolic foam resin solidifying agent, and add-on is 1% of phenolic foam resin solidifying agent gross weight.
embodiment 6:taking toluene 100 parts by weight adds in reactor, divides and adds Vanadium Pentoxide in FLAKES totally 80 parts for four times; Start agitator, dripping 230 parts of concentration is the vitriol oil of 96%, and at the temperature of 100 DEG C, sulfonation reaction 9 is little of reacting completely; Sulfonation reaction can add tetrahydroglyoxaline in phenolic foam resin solidifying agent completely, and add-on is 0.5% of phenolic foam resin solidifying agent gross weight.
embodiment 7:taking toluene 100 parts by weight adds in reactor, divides and adds Vanadium Pentoxide in FLAKES totally 100 parts for five times; Start agitator, dripping 250 parts of concentration is the vitriol oil of 98%, and at the temperature of 165 DEG C, sulfonation reaction 5 is little of reacting completely; Add polyoxyethylene glycol 15 parts, Tetra hydro Phthalic anhydride 15 parts again, and reaction obtains phenolic foam resin solidifying agent in 8 hours at the temperature of 190 DEG C.
embodiment 8:taking toluene 100 parts by weight adds in reactor, adds Vanadium Pentoxide in FLAKES 98 parts disposable time; Start agitator, dripping 300 parts of concentration is the vitriol oil of 95%, and at the temperature of 180 DEG C, sulfonation reaction 20 is little both obtains phenolic foam resin solidifying agent up to reacting completely.
embodiment 9:taking benzene 100 parts by weight adds in reactor, adds Vanadium Pentoxide in FLAKES 20 parts disposable time; Start agitator, dripping 150 parts of concentration is the vitriol oil of 70%, and at the temperature of 80 DEG C, sulfonation reaction 24 is little both obtains phenolic foam resin solidifying agent up to reacting completely.
embodiment 10:taking benzene 100 parts by weight adds in reactor, adds Vanadium Pentoxide in FLAKES 26 parts at twice; Start agitator, dripping 180 parts of concentration is the vitriol oil of 98%, and at the temperature of 88 DEG C, sulfonation reaction 15 is little of reacting completely; Add ethylene glycol 6 parts, adipic acid 6 parts again, and reaction obtains phenolic foam resin solidifying agent in 2 hours at the temperature of 110 DEG C.Sulfonation reaction can add one or more in thiocarbamide, hexamethyl tetramine, tetrahydroglyoxaline completely in phenolic foam resin solidifying agent, and add-on is 0.6% of phenolic foam resin solidifying agent gross weight.
embodiment 11:taking benzene 100 parts by weight adds in reactor, adds Vanadium Pentoxide in FLAKES totally 44 parts at twice; Start agitator, dripping 170 parts of concentration is the vitriol oil of 86%, and at the temperature of 93 DEG C, sulfonation reaction 12 is little of reacting completely; Add polyoxyethylene glycol 12 parts, Tetra hydro Phthalic anhydride 12 parts again, and reaction obtains phenolic foam resin solidifying agent in 8 hours at the temperature of 190 DEG C.Sulfonation reaction can add the mixture of thiocarbamide, hexamethyl tetramine completely in phenolic foam resin solidifying agent, and add-on is 0.9% of phenolic foam resin solidifying agent gross weight.
embodiment 12:taking benzene 100 parts by weight adds in reactor, divides and adds Vanadium Pentoxide in FLAKES totally 66 parts for three times; Start agitator, dripping 256 parts of concentration is the vitriol oil of 95%, and at the temperature of 150 DEG C, namely sulfonation reaction 2 is little obtains phenolic foam resin solidifying agent up to reacting completely.
embodiment 13:taking benzene 100 parts by weight adds in reactor, divides and adds Vanadium Pentoxide in FLAKES totally 84 parts for three times; Start agitator, dripping 280 parts of concentration is the vitriol oil of 93%, and at the temperature of 109 DEG C, sulfonation reaction 4 is little of reacting completely.
embodiment 14:taking benzene 100 parts by weight adds in reactor, divides and adds Vanadium Pentoxide in FLAKES totally 100 parts for four times; Start agitator, dripping 300 parts of concentration is the vitriol oil of 96%, and at the temperature of 160 DEG C, sulfonation reaction 2 is little of reacting completely; Add ethylene glycol, propylene glycol, 15 parts, polyoxyethylene glycol mixture again, 10 parts, adipic acid, Tetra hydro Phthalic anhydride mixture, and reaction obtains phenolic foam resin solidifying agent in 4 hours at the temperature of 180 DEG C.Sulfonation reaction can add tetrahydroglyoxaline in phenolic foam resin solidifying agent completely, and add-on is 1% of phenolic foam resin solidifying agent gross weight.
embodiment 15:taking dimethylbenzene 100 parts by weight adds in reactor, and a point secondary adds Vanadium Pentoxide in FLAKES totally 30 parts; Start agitator, dripping 270 parts of concentration is the vitriol oil of 76%, and at the temperature of 103 DEG C, sulfonation reaction 10 is little of reacting completely.
embodiment 16:taking dimethylbenzene 100 parts by weight adds in reactor, divides and adds Vanadium Pentoxide in FLAKES totally 96 parts for three times; Start agitator, dripping 104 parts of concentration is the vitriol oil of 88%, and at the temperature of 80 DEG C, sulfonation reaction 24 is little of reacting completely; Add 14 parts, the mixture of ethylene glycol 12 parts, adipic acid and Tetra hydro Phthalic anhydride again, and reaction obtains the solidification of phenolic foam resin for 9 hours at the temperature of 120 DEG C.Sulfonation reaction can add thiocarbamide in phenolic foam resin solidifying agent completely, and add-on is 0.5% of phenolic foam resin solidifying agent gross weight.
embodiment 17:taking naphthalene 100 parts by weight adds in reactor, adds Vanadium Pentoxide in FLAKES 20 parts disposable time; Start agitator, dripping 150 parts of concentration is the vitriol oil of 70%, and at the temperature of 80 DEG C, sulfonation reaction 24 is little both obtains phenolic foam resin solidifying agent up to reacting completely.
embodiment 18:taking naphthalene 100 parts by weight adds in reactor, adds Vanadium Pentoxide in FLAKES 26 parts at twice; Start agitator, dripping 180 parts of concentration is the vitriol oil of 98%, and at the temperature of 88 DEG C, sulfonation reaction 15 is little of reacting completely; Add ethylene glycol 6 parts, adipic acid 6 parts again, and reaction obtains phenolic foam resin solidifying agent in 2 hours at the temperature of 110 DEG C.Sulfonation reaction can add one or more in thiocarbamide, hexamethyl tetramine, tetrahydroglyoxaline completely in phenolic foam resin solidifying agent, and add-on is 0.6% of phenolic foam resin solidifying agent gross weight.
embodiment 19:taking naphthalene 100 parts by weight adds in reactor, adds Vanadium Pentoxide in FLAKES totally 44 parts at twice; Start agitator, dripping 170 parts of concentration is the vitriol oil of 86%, and at the temperature of 93 DEG C, sulfonation reaction 12 is little of reacting completely; Add polyoxyethylene glycol 12 parts, Tetra hydro Phthalic anhydride 12 parts again, and reaction obtains phenolic foam resin solidifying agent in 8 hours at the temperature of 190 DEG C.Sulfonation reaction can add the mixture of thiocarbamide, hexamethyl tetramine completely in phenolic foam resin solidifying agent, and add-on is 0.9% of phenolic foam resin solidifying agent gross weight.
embodiment 20:taking naphthalene 100 parts by weight adds in reactor, divides and adds Vanadium Pentoxide in FLAKES totally 66 parts for three times; Start agitator, dripping 256 parts of concentration is the vitriol oil of 95%, and at the temperature of 150 DEG C, namely sulfonation reaction 2 is little obtains phenolic foam resin solidifying agent up to reacting completely.
embodiment 21:taking naphthalene 100 parts by weight adds in reactor, divides and adds Vanadium Pentoxide in FLAKES totally 84 parts for three times; Start agitator, dripping 280 parts of concentration is the vitriol oil of 93%, and at the temperature of 109 DEG C, sulfonation reaction 4 is little of reacting completely.
embodiment 22:taking naphthalene 100 parts by weight adds in reactor, divides and adds Vanadium Pentoxide in FLAKES totally 100 parts for four times; Start agitator, dripping 300 parts of concentration is the vitriol oil of 96%, and at the temperature of 160 DEG C, sulfonation reaction 2 is little of reacting completely; Add ethylene glycol, propylene glycol, 15 parts, polyoxyethylene glycol mixture again, 10 parts, adipic acid, Tetra hydro Phthalic anhydride mixture, and reaction obtains phenolic foam resin solidifying agent in 4 hours at the temperature of 180 DEG C.Sulfonation reaction can add tetrahydroglyoxaline in phenolic foam resin solidifying agent completely, and add-on is 1% of phenolic foam resin solidifying agent gross weight.
Below be only the preferred embodiment of the present invention, it should be pointed out that above-mentioned preferred implementation should not be considered as limitation of the present invention, protection scope of the present invention should be as the criterion with claim limited range.For those skilled in the art, without departing from the spirit and scope of the present invention, some improvements and modifications can also be made and also should be considered as protection scope of the present invention.
Claims (8)
1. the synthetic method of a phenolic foam resin solidifying agent, comprise: the alkyl derivative adopting aromatic hydrocarbons or aromatic hydrocarbons is raw material, add sulfuric acid and carry out sulfonation reaction, it is characterized in that, also Vanadium Pentoxide in FLAKES is added with in described sulfonation reaction step, described sulfuric acid to be concentration be 70% ~ 98% the vitriol oil or oleum, or the mixture of said two devices.
2. the synthetic method of phenolic foam resin solidifying agent as claimed in claim 1, it is characterized in that, concrete operations are as follows:
Taking 100 parts, aromatic hydrocarbons by weight adds in reactor, disposable or point add Vanadium Pentoxide in FLAKES 20 ~ 100 parts for 2 ~ 5 times;
Start agitator, add 150 ~ 300 parts of sulfuric acid, at the temperature of 80 DEG C ~ 170 DEG C, sulfonation reaction 1 ~ 24 is little both obtains phenolic foam resin solidifying agent up to reacting completely.
3. the synthetic method of phenolic foam resin solidifying agent as claimed in claim 1 or 2, it is characterized in that, described aromatic hydrocarbons is any one in benzene, naphthalene, and the alkyl derivative of described aromatic hydrocarbons is any one in toluene, dimethylbenzene.
4. the synthetic method of phenolic foam resin solidifying agent as claimed in claim 1 or 2, is characterized in that, the vitriol oil of described sulfuric acid 90% ~ 98% or oleum, or the mixture of said two devices.
5. the synthetic method of phenolic foam resin solidifying agent as claimed in claim 1 or 2, it is characterized in that, following one or both are added: dibasic alcohol 5 ~ 15 parts in described phenolic foam resin solidifying agent, diprotic acid 5 ~ 15 parts, and react 1 ~ 8 hour at the temperature of 100 DEG C ~ 200 DEG C;
Any one or more mixture in the water miscible ethylene glycol of described dibasic alcohol, propylene glycol, polyoxyethylene glycol;
Any one or more mixture in the water miscible adipic acid of described diprotic acid, Tetra hydro Phthalic anhydride.
6. the synthetic method of phenolic foam resin solidifying agent as claimed in claim 3, it is characterized in that, add following one or both in described phenolic foam resin solidifying agent: dibasic alcohol 5 ~ 15 parts, diprotic acid 5 ~ 15 parts, and react 1 ~ 8 hour at the temperature of 100 DEG C ~ 200 DEG C;
Any one or more mixture in the water miscible ethylene glycol of described dibasic alcohol, propylene glycol, polyoxyethylene glycol;
Any one or more mixture in the water miscible adipic acid of described diprotic acid, Tetra hydro Phthalic anhydride.
7. the synthetic method of phenolic foam resin solidifying agent as claimed in claim 4, it is characterized in that, add following one or both in described phenolic foam resin solidifying agent: dibasic alcohol 5 ~ 15 parts, diprotic acid 5 ~ 15 parts, and react 1 ~ 8 hour at the temperature of 100 DEG C ~ 200 DEG C;
Any one or more mixture in the water miscible ethylene glycol of described dibasic alcohol, propylene glycol, polyoxyethylene glycol;
Any one or more mixture in the water miscible adipic acid of described diprotic acid, Tetra hydro Phthalic anhydride.
8. a phenolic foam resin solidifying agent, is characterized in that, according to any one of claim 1 to 7, method prepares.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410428537.8A CN104194254B (en) | 2014-08-28 | 2014-08-28 | Phenolic foam resin solidifying agent and synthetic method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410428537.8A CN104194254B (en) | 2014-08-28 | 2014-08-28 | Phenolic foam resin solidifying agent and synthetic method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104194254A CN104194254A (en) | 2014-12-10 |
| CN104194254B true CN104194254B (en) | 2016-02-24 |
Family
ID=52079637
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410428537.8A Expired - Fee Related CN104194254B (en) | 2014-08-28 | 2014-08-28 | Phenolic foam resin solidifying agent and synthetic method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104194254B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108080561A (en) * | 2017-11-09 | 2018-05-29 | 邦尼化工（天津）有限公司 | A kind of heat curing type environment friendly curing agent and preparation method thereof |
| CN109517330A (en) * | 2018-11-22 | 2019-03-26 | 山东莱芜润达新材料有限公司 | A kind of preparation method of phenol formaldehyde foam resin curing agent |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1834152A (en) * | 2006-03-21 | 2006-09-20 | 上海胜星树脂涂料有限公司 | Method of preparing phenolic foam insulation material via foaming at normal temp |
| CN101928442A (en) * | 2010-01-07 | 2010-12-29 | 上海雅达特种涂料有限公司 | Material for manufacturing modified phenolic fireproofing insulation board |
| CN103059338A (en) * | 2012-12-21 | 2013-04-24 | 上海大学 | Polymerizable organic strong acid / sulfuric acid composite curing agent and foamable phenolic resin combination thereof |
-
2014
- 2014-08-28 CN CN201410428537.8A patent/CN104194254B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1834152A (en) * | 2006-03-21 | 2006-09-20 | 上海胜星树脂涂料有限公司 | Method of preparing phenolic foam insulation material via foaming at normal temp |
| CN101928442A (en) * | 2010-01-07 | 2010-12-29 | 上海雅达特种涂料有限公司 | Material for manufacturing modified phenolic fireproofing insulation board |
| CN103059338A (en) * | 2012-12-21 | 2013-04-24 | 上海大学 | Polymerizable organic strong acid / sulfuric acid composite curing agent and foamable phenolic resin combination thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104194254A (en) | 2014-12-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104194254B (en) | Phenolic foam resin solidifying agent and synthetic method thereof | |
| CN103333457B (en) | A kind of height presses down cigarette, high oxygen index phenolic fireproof insulating plate and preparation method thereof | |
| CN102977401A (en) | High fire retardation phenol formaldehyde foam preparation method | |
| JP5885855B2 (en) | Foam material based on phenolic resin | |
| CN102746612A (en) | Preparation method for halogen-free flame-retardant toughened phenolic foamed plastics | |
| CN101768326B (en) | Preparation method of modified phenolic resin and application thereof | |
| CN104761865B (en) | A kind of method for preparing urea formaldehyde resin foam as raw material one-step method with urea-formaldehyde | |
| CN103254381A (en) | Preparation method of nitrogenous phenolic resin in one-step synthesis process | |
| CN101024681A (en) | Method for preparing fluorine-contained multi-function epoxy resin | |
| CN107083017A (en) | A kind of normal temperature can send out synthesis and the foaming method of phenolic resin | |
| JP6261697B2 (en) | Heavy anticorrosion epoxy coating composition containing styrenated phenol and method for producing the same | |
| CN104211889A (en) | Foaming lignin-modified phenolic resin and preparation method thereof | |
| CN109293941A (en) | A kind of depolymerization lignin and its preparation method and application | |
| CN101735552A (en) | Material for manufacturing modified phenolic fireproof insulating plate | |
| FI60881C (en) | SAETT ATT FRAMSTAELLA FENOL-ALDEHYDSKUMPLASTER | |
| CN105601855A (en) | Foaming phenolic resin composition | |
| CN102757619A (en) | Preparation method of high stability phenolic foams | |
| CN109517330A (en) | A kind of preparation method of phenol formaldehyde foam resin curing agent | |
| CN104327452B (en) | A kind of flame retardant type phenolic foam board | |
| CN106496479B (en) | A kind of tetraphenylcyclopentadienone copolymerization anacardol formaldehyde Foamex and preparation method thereof | |
| CN105623135A (en) | Polystyrene flame-retardant masterbatch | |
| CN103289302A (en) | Preparation method of energy-saving and environment-friendly modified phenolic resin fireproof insulation board | |
| CN107602906A (en) | A kind of preparation method of low-cost environment-friendly phenol-formaldehyde resin modified fireproof heated board | |
| CN106243539A (en) | Energy saving and environment friendly insulation material and preparation method thereof | |
| CN106366560A (en) | Epoxy modified pressure-proof phenolic foam plate and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160224 Termination date: 20170828 |