CN109749030A - A kind of production method of expandability flame-retardant phenolic resin - Google Patents
A kind of production method of expandability flame-retardant phenolic resin Download PDFInfo
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- CN109749030A CN109749030A CN201910159846.2A CN201910159846A CN109749030A CN 109749030 A CN109749030 A CN 109749030A CN 201910159846 A CN201910159846 A CN 201910159846A CN 109749030 A CN109749030 A CN 109749030A
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Abstract
The invention belongs to macromolecule chemical industry technical fields, and in particular to a kind of production method of expandable phenolic resin.The present invention provides a kind of production method of room temperature expandability flame-retardant phenolic resin, in this method synthesis process mainly using to raw material have phenol, formaldehyde, basic catalyst, formaldehyde catching agent, surfactant, fire retardant etc..In the synthesis process of phenolic resin, pass through the reasonable setting of reaction condition, control is distinguished into addition and polycondensation two-step reaction, reaction is not only made to become mild, easily operated, period short, and the content of free phenol and free aldehyde can also be significantly reduced, reduce subsequent product in the construction process to the damage of human body and to the pollution of environment, is conducive to industrialized production.Therefore the production method of room temperature expandability flame-retardant phenolic resin provided by the invention has good market and application prospect.
Description
Technical field
The invention belongs to macromolecule chemical industry technical fields, and in particular to a kind of production method of expandable phenolic resin.
Background technique
Currently, expandability flame-retardant phenolic resin contains the application or blank in the fields of grade in trickling fire.Phenolic resin is at this
The application in field is a kind of new technique, this investigative technique is more advanced in foreign countries, then just starts to start to walk at home, also
It is able to produce the fire that is suitable for trickling without a domestic enterprise and contains dedicated phenolic resin.The resin can be used for the technology evaluated
Index include it is active it is high, solid content is high, free phenol and content of free aldehyde are low, flame retardant property is good etc., these technical indicators
Exactly develop the difficult point that resin needs to break through.The production of country's phenolic resin foam mainly uses expandable phenolic resin at present
With foaming agent, curing agent, other auxiliary agents by being quickly stirred casting foamable, process characteristic be need mold, and
And could generally be cured by 12h or more under conditions of 60~80 DEG C, cause production efficiency low and higher cost, especially
Site operation field is needed used in some, there are technological difficulties.When construction environment is complicated or construction place is narrow, sent out using heat
Steep pre-formed method carry out construction serious inconvenience can be brought to construction.
Phenolic resin, which generally passes through the raw materials such as formaldehyde, phenol and reacts in a kettle, to be prepared, the polymerization of phenolic resin
It spends directly related with reaction temperature.Since reactant tends to occur the chemical reaction of Various Complex in a kettle, in general
Reaction temperature is higher, and the degree of polymerization is higher, so number molecular weight is smaller, water-soluble preferable phenolic resin in order to synthesize to obtain,
It often has to reduce reaction temperature, and at this moment will lead to new problem and occur, i.e., reaction raw materials are due to the too low difficulty of temperature
With fully reacting, leads to the too high levels of free aldehyde and free phenol in the phenolic resin being prepared, seriously affect construction personnel
Health.Patent No. CN201810611677 provides a kind of synthetic method of phenolic resin, poly- by phenol and formaldehyde crosslinking
A small amount of Pentaerythritols compound is directly added when conjunction, so that be crosslinked between Pentaerythritols compound participation phenol and formaldehyde,
The crosslink density of resin is significantly improved on three-dimensional space, so that the anti-flammability and smoke-suppressing of phenolic resin are improved in itself,
But this method is by the way that Pentaerythritols compound is added as additive in paraformaldehyde and phenol under certain conditions
It is reacted, the reaction process time is long and reaction not exclusively makes the content of free phenol and free aldehyde higher.
Summary of the invention
The present invention provides a kind of production methods of room temperature expandability flame-retardant phenolic resin, are produced by this method
Phenolic resin is for manufacturing phenol formaldehyde foam.The production of phenol formaldehyde foam needs a special slip casting pump and a hybrid gun, two kinds of groups
Reaction generates foam rapidly after dividing (resin, catalyst) to mix with the volume ratio of 4:1, then product meeting rapid expanding to substance
Long-pending 20~40 times.After expansion, phenolic aldehyde gently steeps rapid curing in a few minutes.Phenol formaldehyde foam is characterized in that reaction
Speed is fast, expansion rate is high, the high (60m of construction efficiency3/ h), this makes phenol formaldehyde foam contain a major product as trickling fire.
The product primarily can be used for following aspect:
1, the quick of trickling fire is intercepted；
2, permanent closed under the conditions of pressure-bearing；
3, work face goaf fire extinguishing；
3, gas exhaust lane, high-order drill site filling and closed；
4, wall-rock crack is blocked, air seepage flow is prevented；
5, fire dam and firewall are constructed in a certain range；
6, hollow filling and the roof fall filling in tunnel, working face；
7, the fender crack of the support with backfilling of gob side entry retaining bracket and gob side entry driving, which blocks, is used for hollow filling.
Therefore, it is good that low volatile matter, flame retardant property are researched and developed, can adapt to the fiery phenolic resin contained of trickling, is market hair
The inexorable trend of exhibition has good application prospect.
In order to overcome defect existing for expandability flame-retardant phenolic resin production method in the prior art, the purpose of the present invention exists
In providing, a kind of reaction is mild, operates the producer of room temperature expandability flame-retardant phenolic resin controllable, easy to industrialized production
Method.
The present invention provides a kind of production methods of expandability flame-retardant phenolic resin, method includes the following steps:
(1) by phenol and formaldehyde basic catalyst is added in vacuum mode sucting reaction kettle, be warming up to 65~85 DEG C into
Row reaction insulation reaction 20~50 minutes, by reasonably controlling reaction condition, such as temperature, catalyst, makes main in reaction kettle
Polycondensation reaction does not occur substantially for the addition reaction that formaldehyde and phenol occurs, therefore thermal discharge can be well controlled,
It is not in the danger such as bumping, slug.
(2) composite formaldehyde agent for capturing is added, is warming up to 85~100 DEG C, insulation reaction 30~50 minutes, controls Weight-average molecular
Amount is in MW500~700, at this moment by the control of reaction condition, so that polycondensation mainly occurs is anti-for intermediate reaction object in reaction kettle
It answers, controls the thermal discharge in reaction process, so that reaction is easily controllable, avoid addition in the prior art, polycondensation in this way
Occur while reaction, reduces the generation of amount of heat in reaction process, improve the utilization efficiency of raw material reactant.Meanwhile
By the way that composite formaldehyde agent for capturing is added during the reaction, that is, the content of free phenol and free aldehyde is reduced, average mark of getting back
Son measures relatively better resol.
(3) it cools for the first time, is neutralized to neutrality with acid, then carry out vacuum dehydration.
(4) it cools for the second time, fire retardant is added, first rank expandability flame-retardant phenolic resin can be obtained.
Further, phenol is pre- heat fusing.
Further, basic catalyst include sodium hydroxide or and potassium hydroxide, the concentration of basic catalyst be 50%, alkali
Property catalyst content be 1~5% (being calculated with the addition weight of phenol).
Further, acid is hydrochloric acid or sulfuric acid, and pH control after having adjusted pH, can be added in right amount 7.0~7.5 after adjusting
The surfactant of 20~40kg, the surfactant can for anionic surfactant, nonionic surfactant or
Organosiloxane class surfactant, preferably one or more of p-methyl benzenesulfonic acid, dodecyl phenol, nonyl phenol compounding.
Further, in step (3) vacuum degree control of vacuum dewatering process in -0.085~-0.09Mpa.
Further, the temperature to cool for the first time in step (3) is controlled at 50 DEG C hereinafter, second in step (4)
The temperature to cool is controlled at 40 DEG C or less.
Further, fire retardant can be also possible to nothing such as halogen-free flame-retardant, ammonium polyphosphate for organic fire-retardant
Machine fire retardant, such as one of triphenyl phosphate, decabromodiphenylethane, ammonium polyphosphate or a variety of.
Further, a kind of preparation method of expandability flame-retardant phenolic resin, this method are further comprising the steps of:
(1) by phenol and formaldehyde in vacuum mode sucting reaction kettle, to be subsequently added into 1~4% basic catalyst (with benzene
The addition poidometer of phenol), 70~80 DEG C are warming up to, is reacted, insulation reaction 20~40 minutes；
(2) composite formaldehyde agent for capturing is added, is warming up to 90~95 DEG C, insulation reaction 30~40 minutes, controls Weight-average molecular
Amount is in Mw 500~700；
(3) it cools for the first time, is down to 50 DEG C hereinafter, being neutralized to PH=7.0~7.2 with acid, then carry out vacuum dehydration
To appropriate viscosity.
(4) it cools for the second time, is down to 40 DEG C hereinafter, addition fire retardant, can be obtained first rank expandability flame-proof phenolic
Resin.
Further, a kind of preparation method of expandability flame-retardant phenolic resin, this method are further comprising the steps of:
(1) by phenol and formaldehyde to be subsequently added into 2~3% 50% sodium hydroxide alkali in vacuum mode sucting reaction kettle
Property catalyst (with the addition poidometer of phenol), is warming up to 70~75 DEG C, is reacted, and insulation reaction 30~35 minutes；
(2) composite formaldehyde agent for capturing is added, is warming up to 90~95 DEG C, insulation reaction 35~40 minutes, controls Weight-average molecular
Amount is in Mw 500~700；
(3) it cools for the first time, is down to 50 DEG C, be neutralized to PH=7.0~7.2 with acid, -0.085~-
0.09Mpa carries out vacuum dehydration, dehydration to appropriate viscosity.
(4) it cools for the second time, is down to 40 DEG C, triphenyl phosphate fire retardant is added, the resistance of first rank expandability can be obtained
Fire phenolic resin.
A kind of composition principle of room temperature expandability flame-retardant phenolic resin provided by the invention is as follows:
Room temperature expandability flame-retardant phenolic resin be phenol and formaldehyde under alkaline condition, through addition, polycondensation reaction, and control
Certain extent of reaction has obtained the fluid resin of certain molecular mass and viscosity.Its synthetic reaction course is as follows:
(1) base catalysis generates the benzene negative oxygen ion with stronger nucleophilicity:
(2) addition reaction is carried out with formaldehyde generate a hydroxymethylphenol:
(3) continue to react with formaldehyde, generate hydroxymethyl-phenol, tri hydroxy methyl phenol and be condensed into resol:
(4) it is complicated monokaryon and multicore with phenolic resin that the thermosetting property trickling fire being obtained by the polycondensation reaction, which is contained,
Acidic catalyst is added, then further occurrence cross-linking reaction in phenolic alcohol molecule mixture in the system:
The present invention is to provide a kind of room temperature expandability flame-proof phenolic tree on the basis of studying phenolic resin synthesis mechanism
The production method of rouge, by factors such as multiple exploratory response conditions such as temperature, pressure, reaction raw materials proportion, auxiliary agent, phenolic aldehyde tree
The synthesis step of rouge in the industrial production reasonably distinguishes control, i.e., first allows formaldehyde and phenol to be added under certain condition
At reaction, then conversion reaction condition, then condensation reaction occurs, such differentiation controls to be easy to regulate and control so that reacting, and is avoided existing
While having addition in technology, polycondensation reaction, the generation of amount of heat in reaction process is reduced, because without sudden and violent
The danger such as boiling, slug.
The present invention reduces containing for free phenol and free aldehyde by the way that composite formaldehyde agent for capturing is added during the reaction
Amount, the relatively better resol of average molecular weight of getting back.
Compared with prior art, a kind of production method of room temperature expandability flame-retardant phenolic resin provided by the invention have with
It is lower the utility model has the advantages that
(1) control reasonably is distinguished into addition and polycondensation two-step reaction in the industrial production, so that reaction is mild, is easy to grasp
Make, avoid in reaction process and the danger such as bumping, slug occur, reduce reaction in amount of heat generations cause react can not
Control；
(2) by distinguishing addition and polycondensation two-step reaction in control phenolic resin synthesis process, so that addition and condensation are anti-
Should more completely, the residual for improving reaction efficiency, saving reaction raw materials and reducing free phenol and free formaldehyde in product；
(3) composite formaldehyde agent for capturing is added in process of production, had both reduced containing for final products free phenol and free aldehyde
Amount, the relatively good resol of average molecular weight of having got back reduce the damage in work progress to workers ' health.
(4) it joined surfactant in process of production, played foam stabilizing in system, so that in foaming process
Foam structure is more complete.
(5) it joined fire retardant in process of production, provide a kind of room temperature expandability flame-proof phenolic tree haveing excellent performance
Rouge, the resin can produce one kind in room temperature by cooperatively forming phenolic resin foam with foaming agent, curing agent and other auxiliary agents
It is capable of the flame-retardant phenolic resin of fast foaming down, trickling fire can be performed well in and contain equal fields.
(6) the anti-flammability phenolic resin that production method provided by the invention is produced, can be sent out at normal temperature
Bubble has the characteristics that expansion rate is fast, construction rate is high, thus improves its application performance and expand its application field, has
Good market prospects.
Specific embodiment
The following describes the present invention further through the description of specific embodiments, but it is to limit of the invention that this, which is not,
System, those skilled in the art's basic thought according to the present invention can make various modifications or improvements, but without departing from this
The basic thought of invention, is all within the scope of the present invention.
Embodiment 1
(1) by the phenol 1000kg of pre- heat fusing and formaldehyde 1200kg to be subsequently added into vacuum mode sucting reaction kettle
50%NaOH catalyst 10kg is warming up to 85 DEG C and is reacted, and insulation reaction 20 minutes；
(2) composite formaldehyde agent for capturing 5kg is added, is warming up to 100 DEG C, insulation reaction 30 minutes, control weight average molecular weight existed
Mw 500~700；
(3) it cools for the first time to 50 DEG C hereinafter, be neutralized to PH=7.0~7.5 with 20% hydrochloric acid solution ,-
0.085~-0.09Mpa carries out vacuum dehydration, dehydration to appropriate viscosity.
(4) it cools for the second time to 40 DEG C or less addition triphenyl phosphates, first rank expandable phenolic resin can be obtained.
Embodiment 2
(1) by the phenol 1000kg and formaldehyde (1800kg) of pre- heat fusing in vacuum mode sucting reaction kettle, then plus
Enter 50%NaOH catalyst 50kg, is warming up to 65 DEG C and is reacted, insulation reaction 50 minutes；
(2) composite formaldehyde agent for capturing 20kg is added, is warming up to 85 DEG C, insulation reaction 50 minutes, control weight average molecular weight existed
Mw500~700；
(3) it cools for the first time to 45 DEG C hereinafter, being neutralized to PH=7.0~7.2, addition surface with 20% hydrochloric acid solution
Activating agent 20kg carries out vacuum dehydration, dehydration to appropriate viscosity at -0.085~-0.09Mpa；
(4) it cools for the second time to 35 DEG C or less addition triphenyl phosphates, first rank expandability flame-proof phenolic can be obtained
Resin.
Embodiment 3
(1) by the phenol 1000kg and formaldehyde (1400kg) of pre- heat fusing in vacuum mode sucting reaction kettle, then plus
Enter 50%KOH catalyst 20kg, is warming up to 80 DEG C and is reacted, insulation reaction 40 minutes；
(2) composite formaldehyde agent for capturing 20kg is added, is warming up to 90 DEG C, insulation reaction 40 minutes, control weight average molecular weight existed
Mw500~700；
(3) it cools for the first time to 50 DEG C hereinafter, be neutralized to PH=7.0~7.2 with 49% sulfuric acid solution ,-
Vacuum dehydration, dehydration to appropriate viscosity are carried out under 0.085~-0.09Mpa；
(4) it cools for the second time to 40 DEG C or less addition ammonium polyphosphates, first rank expandability flame-proof phenolic can be obtained
Resin.
Embodiment 4
(1) by the phenol 1000kg and formaldehyde (1600kg) of pre- heat fusing in vacuum mode sucting reaction kettle, then plus
Enter 50%KOH catalyst 30kg, is warming up to 70 DEG C and is reacted, insulation reaction 30 minutes；
(2) composite formaldehyde agent for capturing 15kg is added, is warming up to 95 DEG C, insulation reaction 35 minutes, control weight average molecular weight existed
Mw500~700；
(3) it cools for the first time to 50 DEG C hereinafter, being neutralized to PH=7.0~7.2 with 49% sulfuric acid solution, addition is to first
Benzene sulfonic acid 40kg carries out vacuum dehydration, dehydration to appropriate viscosity at -0.085~-0.09Mpa；
(4) it cools for the second time to 40 DEG C or less addition triphenyl phosphates, first rank expandability flame-proof phenolic can be obtained
Resin.
Embodiment 5
(1) by the phenol 1000kg and formaldehyde (1500kg) of pre- heat fusing in vacuum mode sucting reaction kettle, then plus
Enter 50%KOH catalyst 40kg, is warming up to 75 DEG C and is reacted, insulation reaction 35 minutes；
(2) composite formaldehyde agent for capturing 20kg is added, is warming up to 95 DEG C, insulation reaction 40 minutes, control weight average molecular weight existed
Mw 500~700；
(3) it cools for the first time to 40 DEG C hereinafter, being neutralized to PH=7.0~7.2, addition 12 with 49% sulfuric acid solution
Alkylphenol 30kg carries out vacuum dehydration, dehydration to appropriate viscosity at -0.085~-0.09Mpa；
(4) it cools for the second time to 40 DEG C or less addition ammonium polyphosphates, first rank expandability flame-proof phenolic can be obtained
Resin.Test example one foams first rank expandability flame-retardant phenolic resin obtained in above-described embodiment, detects its performance and refers to
Mark.
(1) test material: after the first rank expandability flame-retardant phenolic resin foaming in Examples 1 to 5, its performance is measured
Index, wherein include density (kg/m3), expansion multiple, flexural strength (kpa), oxygen index (OI) (%), ignition temperature (DEG C) and
The content of flame-retardant and anti-static performance, free phenol, free aldehyde.
(2) test method: where flame-retardant and anti-static performance passes through GB/T8333-2008 " standard rigid foamed plastics combustion
Burn method for testing performance vertical combustion " it is tested；
(3) index is required:
1 performance indicator of table
| Project | Index |
| Density (kg/m3) | 30-50 |
| Expansion multiple | 20-40 |
| Flexural strength (kPa) | > 40 |
| Oxygen index (OI) (%) | > 35 |
| Ignition temperature (DEG C) | > 400 |
| Flame-retardant and anti-static performance | Meet GB/T8333-2008 standard |
(4) test result is as shown in table 1:
The comparison of 2 Examples 1 to 4 results of property of table
According to table 2, good, all reality of first rank expandability flame-retardant phenolic resin foam performance in Examples 1 to 5
It applies the ignition temperature in example and is both greater than 400 DEG C, expansion multiple can meet industrial performance requirement.Wherein, oxygen index (OI) is high
Indicate that material is nonflammable, the low expression material of oxygen index (OI) is easy burning, by table 2 it is known that in embodiment 3 and embodiment 5
Oxygen index (OI) reached 40, show it with good flame retardant property.
In industrialized production, process is easy to control this production method.The production method provided according to the present invention is produced
First rank expandability flame-retardant phenolic resin, environmentally protective, performance stablizes, and free phenol (< 4%) and free aldehyde (<'s 0.2%) contains
It measures low, reduces the damage to construction personnel's health, while anti-flammability can reach A grades, there is more excellent flame retardant effect, energy
It is widely used in each technical field.
It should be understood by those skilled in the art that the above-described embodiments merely illustrate the principles and effects of the present invention,
And is not intended to limit the present invention.Any person skilled in the art all without departing from the spirit and scope of the present invention, to upper
It states embodiment and carries out modifications and changes.Therefore, such as those of ordinary skill in the art without departing from institute of the present invention
All equivalent modifications or change completed under the spirit and technical idea of announcement, should be contained by claim of the invention
Lid.
Claims (10)
1. a kind of production method of expandability flame-retardant phenolic resin, which is characterized in that method includes the following steps:
(1) phenol and formaldehyde are warming up to 65~85 DEG C, heat preservation so that basic catalyst is added in vacuum mode sucting reaction kettle
Reaction 20~50 minutes；
(2) composite formaldehyde agent for capturing is added, is warming up to 85~100 DEG C, insulation reaction 30~50 minutes；
(3) it cools for the first time, is neutralized to neutrallty condition with acid, then carry out vacuum dehydration；
(4) it cools for the second time, fire retardant is added, first rank expandability flame-retardant phenolic resin can be obtained.
2. the production method of expandability flame-retardant phenolic resin according to claim 1, which is characterized in that the phenol is pre-
Heat fusing.
3. the production method of expandability flame-retardant phenolic resin according to claim 1, which is characterized in that the base catalysis
Agent includes sodium hydroxide or potassium hydroxide.
4. the production method of expandability flame-retardant phenolic resin according to claim 3, which is characterized in that the base catalysis
The concentration of agent is 50%, and the content of the basic catalyst is 1~5%.
5. the production method of expandability flame-retardant phenolic resin according to claim 1, which is characterized in that the acid is hydrochloric acid
Or sulfuric acid, the neutrallty condition are that pH is controlled 7.0~7.5.
6. the production method of expandability flame-retardant phenolic resin according to claim 1, which is characterized in that the step (3)
The vacuum degree control of middle vacuum dewatering process is in -0.085~-0.09Mpa.
7. the production method of expandability flame-retardant phenolic resin according to claim 1, which is characterized in that the step (3)
The temperature that middle first time cools is controlled at 50 DEG C hereinafter, the temperature control to cool for the second time in the step (4) exists
40 DEG C or less.
8. the production method of expandability flame-retardant phenolic resin according to claim 1, which is characterized in that the fire retardant is
One of triphenyl phosphate, decabromodiphenylethane, ammonium polyphosphate are a variety of.
9. the production method of expandability flame-retardant phenolic resin described according to claim 1~any one of 8, which is characterized in that
It the described method comprises the following steps:
(1) by phenol and formaldehyde 1~4% basic catalyst is added, is warming up to 70~80 in vacuum mode sucting reaction kettle
DEG C, insulation reaction 20~40 minutes；
(2) composite formaldehyde agent for capturing is added, is warming up to 90~95 DEG C, insulation reaction 30~40 minutes；
(3) it cools for the first time, is down to 50 DEG C hereinafter, being neutralized to pH=7.0~7.2 with acid, then carry out vacuum dehydration；
(4) it cools for the second time, is down to 40 DEG C hereinafter, addition fire retardant, can be obtained first rank expandability flame-retardant phenolic resin.
10. the production method of expandability flame-retardant phenolic resin according to claim 9, which is characterized in that the method packet
Include following steps:
(1) by phenol and formaldehyde in vacuum mode sucting reaction kettle, 50% Sodium Hydroxide Alkaline for being subsequently added into 2~3% is urged
Agent is warming up to 70~75 DEG C, is reacted, and insulation reaction 30~35 minutes；
(2) composite formaldehyde agent for capturing is added, is warming up to 90~95 DEG C, insulation reaction 35~40 minutes；
(3) it cools for the first time, is down to 50 DEG C, pH=7.0~7.2 are neutralized to acid, at -0.085~-0.09Mpa
Carry out vacuum dehydration；
(4) it cools for the second time, is down to 40 DEG C, fire retardant is added, first rank expandability flame-retardant phenolic resin can be obtained.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111157670A (en) * | 2020-01-06 | 2020-05-15 | 天津理工大学 | Test device for testing multi-state foam to control flowing fire |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2260804C (en) * | 1996-07-17 | 2006-11-28 | Ashland Inc. | Benzylic ether phenolic resole resins, their preparation, and uses |
| CN102838771A (en) * | 2012-09-18 | 2012-12-26 | 中国林业科学研究院林产化学工业研究所 | Preparation method of halogen-free environmental-friendly synergistic flame retardant phenolic foam composite material |
| CN103073840A (en) * | 2013-01-29 | 2013-05-01 | 山东圣泉化工股份有限公司 | Phenolic aldehyde foam material |
| CN103524689A (en) * | 2012-07-06 | 2014-01-22 | 徐州龙田合成材料有限公司 | Production method of normal-temperature expandable phenolic resin |
-
2019
- 2019-03-04 CN CN201910159846.2A patent/CN109749030A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2260804C (en) * | 1996-07-17 | 2006-11-28 | Ashland Inc. | Benzylic ether phenolic resole resins, their preparation, and uses |
| CN103524689A (en) * | 2012-07-06 | 2014-01-22 | 徐州龙田合成材料有限公司 | Production method of normal-temperature expandable phenolic resin |
| CN102838771A (en) * | 2012-09-18 | 2012-12-26 | 中国林业科学研究院林产化学工业研究所 | Preparation method of halogen-free environmental-friendly synergistic flame retardant phenolic foam composite material |
| CN103073840A (en) * | 2013-01-29 | 2013-05-01 | 山东圣泉化工股份有限公司 | Phenolic aldehyde foam material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111157670A (en) * | 2020-01-06 | 2020-05-15 | 天津理工大学 | Test device for testing multi-state foam to control flowing fire |
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Application publication date: 20190514 |