CN106589801A - Synthetic method for high-oxygen index phenolic resin - Google Patents
Synthetic method for high-oxygen index phenolic resin Download PDFInfo
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- CN106589801A CN106589801A CN201611207579.4A CN201611207579A CN106589801A CN 106589801 A CN106589801 A CN 106589801A CN 201611207579 A CN201611207579 A CN 201611207579A CN 106589801 A CN106589801 A CN 106589801A
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- 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
- C08L61/14—Modified phenol-aldehyde condensates
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- 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
- C08G8/28—Chemically modified polycondensates
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/141—Hydrocarbons
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08J2361/14—Modified phenol-aldehyde condensates
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/02—Polyalkylene oxides
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- C08L2201/02—Flame or fire retardant/resistant
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- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
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Abstract
The invention discloses a synthetic method for high-oxygen index phenolic resin, and relates to the synthetic method for the high-oxygen index phenolic resin capable of achieving the high-grade fireproof performance of a phenolic resin cellular insulant. The synthetic method comprises the steps of modified synthesis of expandable phenolic resin and curing of foamed phenolic resin. Specifically, a boron-containing compound for internal modification is added into a system of phenol, paraformaldehyde and an alkaline polymerization catalyst for performing a polymerization reaction, and the boron internally-modified expandable phenolic resin is obtained; a boron-containing compound for external modification and a silane coupling agent are subjected to preprocessing, the preprocessed externally-modified boron compound is added into boron internally-modified expandable phenolic resin, curing is performed after inorganic filler, a pore former, a foam stabilizer and a curing agent are added, and the high-oxygen index phenolic resin is obtained.
Description
Technical field
The present invention relates to phenolic resin, more particularly, to a kind of synthetic method of high oxygen index (OI) phenolic resin.
Background technology
China's fire of high-rise building takes place frequently, and causes huge property loss and casualties.At present, construction material is fire-retardant
Problem has become the focus of domestic and international concern.With China's construction material energy-conservation/insulation and fire resistance are required it is further
Improve, the demand of fire retardant exterior wall insulation material will further increase.Phenolic resin class A foam A insulation material has both fire-retardant, light just
The excellent characteristic such as matter, safety, is a kind of inexpensive self-flame-retardant foam plasticss, will not be melted in combustion
Melt, will not also produce drip.Add toward phenolic resin toughener be improve its fragility it is big the shortcomings of conventional method, but compare
In the phenolic resin for being not added with altered contents, the heat-resisting of phenolic resin, fire resisting and corrosion resistance can decline after toughness reinforcing.Mesh
It is front not yet to have A level phenolic foam materials to emerge.
Fire retardant is to improve material flame resistance, reduce material and be ignited probability and suppress helping of being propagated further of flame
Agent.Fire retardant can be divided into addition type and the big class of response type two, and the former is referred in polymerization and polycondensation process in the main chain of high polymer
Or the group with fire retardation is introduced on side chain to reach fire-retardant purpose；The latter referred in polymeric material forming process,
It is distributed in material by physical mixed, inorganic and organic two class is divided into again, due to organic fire-retardant catabolite toxicity greatly, cigarette
The shortcomings of mist is big, is just progressively replaced by inorganic combustion inhibitor such as Firebrake ZB.Firebrake ZB has significant fire-retardant and smoke suppressing effect, also
High temperature molten drop (high temperature molten drop is dangerous Ignition sources) can be reduced, contributes to generating porous carbon layer in material combustion, and this carbon
Layer can be B2O3Stablize, when with stibium oxide, halogen containing flame-retardant, aluminium hydroxide, magnesium hydroxide compounding use, with good
Synergism, can reduce the consumption of other fire retardants while oxygen index (OI) is improved.Additionally, Firebrake ZB has under nontoxic, high temperature
The features such as not producing toxic gas, is a kind of fire retardant of green non-pollution.
Boron and expandability phenol in the report being modified to phenolic resin using boron-containing compound, such as boron-containing compound
There is complexation reaction in urea formaldehyde, generate phenolic resin Chinese patent CN1844233, the Chinese patent CN101531769 of boron modification,
But the phenolic resin oxygen index (OI) obtained by the method improves limited, its fire resistance needs further raising.Also have in phenol in document
Boron-containing compound is added to carry out outer modified Chinese patent CN104650785A, Chinese patent in urea formaldehyde building-up process
CN104004319A, but in the work, boron-containing compound is not preprocessed and is directly added in system, causes boron-containing compound
Very weak with the interaction of phenolic aldehyde, most of boron-containing compound fails to be dispersed in phenolic system, greatly reduces and mixes
Miscellaneous modified effect.But these work are limited to the step such as solidification of the synthesis in expandable phenolic resin or phenolic resin
A certain step introduces boron and is modified, there is not yet being modified while carrying out inside and outside substep simultaneously to phenolic resin with boron.
The content of the invention
It is an object of the invention to provide being capable of achieving one kind of the high-grade fireproof performance of phenolic resin foam insulation material
The synthetic method of high oxygen index (OI) phenolic resin.
The present invention includes the modified synthesis of expandable phenolic resin and two steps of solidification of foamed phenolic resin, concrete step
It is rapid as follows：
1) will add in phenol, paraformaldehyde, the system of basic polymerization catalyst for interior modified boron-containing compound, enter
Row polyreaction, obtains the expandable phenolic resin being modified in boron；
2) pretreatment will be carried out for outer modified boron-containing compound and silane coupler, by pretreated outer modified boron
Compound is added to step 1) in the expandable phenolic resin that is modified in the boron that obtains, add inorganic filler, pore creating material, foam stabilizing
Solidified after agent, firming agent, obtained high oxygen index (OI) phenolic resin.
In step 1) in, it is described for interior modified boron-containing compound borate, the borate to be adopted to may be selected from boron
At least one in acid, Firebrake ZB, iron borate, calcium boride etc.；The phenol, paraformaldehyde, basic polymerization catalyst, for interior
The mass ratio of modified boron-containing compound can be：(20～60) ︰ (20～60) ︰ (10～40) ︰ (0.1～10)；The alkalescence is poly-
Close at least one that catalyst may be selected from potassium hydroxide, sodium hydroxide, calcium hydroxide, barium hydroxide, magnesium hydroxide etc.；It is described
Viscosity is the thick expandable phenolic resin of 1000～6000PaS when the expandable phenolic resin being modified in boron is 25 DEG C.
In step 2) in, it is described to may be selected from boron powder, boric acid, Firebrake ZB, iron borate, boron for outer modified boron-containing compound
At least one in sand, calcium boride, diboron trioxide etc.；The silane coupler may be selected from KH560, KH550, KH540,
At least one in KH530 etc.；Expandable phenolic resin, inorganic filler, pore creating material, foam stabilizer, the solidification being modified in the boron
The mass ratio of agent can be (20～70) ︰ (5～50) ︰ (0.1～5) ︰ (0.1～4) ︰ (0.1～10) ︰ (0.1～10)；It is described inorganic
Filler may be selected from least one in aluminium hydroxide, magnesium hydroxide, silicon dioxide, sodium silicate etc.；The pore creating material may be selected from just
At least one in pentane, hydrogen peroxide, AC foaming agent etc.；The foam stabilizer may be selected from tween, organic foam stabilizer, 12
At least one in alkyl sodium sulfate, dodecylbenzene sodium sulfonate, castor oil polyoxyethylene ether etc.；The optional bin cure of the firming agent
At least one in acid, phosphoric acid, p-methyl benzenesulfonic acid etc.；The temperature of the solidification can be 40～100 DEG C, and the time of solidification can be 5
～10min.
Although phenol formaldehyde foam will not be melted in combustion, will not also produce drip, with excellent anti-flammability,
The advantages of high thermal stability and low smoke density, fire retardant degree is steeped considerably beyond polystyrene, polyurethane etc. is currently being widely used
Foam material, and dense smoke and poison will not be distributed, but the rigid aromatic ring of its structure methylene connection closely piles up so that resin
Matrix becomes fragile, thus the slag-off phenomenon of phenol formaldehyde foam is serious, fragility is big, surface is also easy to produce the weakness such as stress crack, toward phenolic aldehyde tree
Add in fat toughener be improve its fragility it is big the shortcomings of conventional method, but compared to being not added with the phenolic aldehyde tree of altered contents
Fat, the heat-resisting of phenolic resin, fire resisting and corrosion resistance can decline after toughness reinforcing.Not yet there is A level high fire-retardances phenolic aldehyde to steep at present
Foam material emerges.
The present invention is on the basis of existing phenolic resin foam insulation material production technology, expandable phenolic resin to be entered
The intramolecular boron modification of row, and phenolic resin foam insulation material is carried out outward by addition boron-containing compound in the curing process
It is modified, prepare the foam resin insulation material with high flame resistance.
The main cause of phenol formaldehyde foam non-refractory is that the C-C key bond energys of connection phenyl ring in phenolic resin are relatively low, and phenol hydroxyl
Base stage is easily oxidized, therefore easy to crack under the high temperature conditions and decomposition.First important technique measure of the present invention is by boracic
Compound (such as boric acid, calcium boride, FeB or Firebrake ZB) carries out intramolecular to expandable phenolic resin and is modified, in room temperature
Lower boron compound just can occur the coordination compound that complexation reaction generates boron modified phenolic resin, its B-O key with expandable phenolic resin
Bond energy is higher than C-C key bond energys, and this contributes to the preparation of high oxygen index (OI) phenolic resin and the improvement of its resistance to elevated temperatures.
Second important technique measure of the present invention is introduced in the solidification process of foamed phenolic resin through silane idol
The connection pretreated boron-containing compound of agent carry out it is outer modified, through one layer of the pretreated Firebrake ZB Surface coating of silane coupler
Silane coupler, coupling agent plays a part of medium, and phenolic aldehyde and Firebrake ZB are coupled together in covalent bond form, obtains strong boundary
Face interacts.Additionally, boron-containing compound can absorb heat under ignition temperature by crystallization evaporation of water, thing temperature of catching fire is reduced
Degree, can generate nonvolatile B again2O3Glassy mass, is coated on polymer surfaces, and this fine and close glassy state protective layer also rises
Can promote to generate a large amount of carbon (increase of carbon means that flammable effusion thing is reduced) to the effect of isolating membrane, and boric acid, with fine
Flame-retardant smoke inhibition effect.
The invention has the beneficial effects as follows, on the basis of existing phenolic resin foam insulation material production technology, pair can send out
Property phenolic resin carry out intramolecular boron modification, and entered by adding boron-containing compound in the solidification process of foamed phenolic resin
Row is outer modified, develops the foam resin insulation material of high fire-retardance high intensity.The present invention is using organic and inorganic materials
It is compound, by being modified inside and outside boron-containing compound, the temperature classification of phenolic resin material is greatly improved, keep it higher again
Heat insulation effect, has the excellent heat-insulating property and high-grade fire resistance of phenol formaldehyde foam concurrently, light weight and fire retardant, can be widely applied to outer
In wall outer heat preservation system.
Specific embodiment
The present invention is on the basis of existing phenolic resin foam insulation material production technology, expandable phenolic resin to be entered
The intramolecular boron modification of row, and phenolic resin foam insulation material is carried out outward by addition boron-containing compound in the curing process
It is modified, prepare the foam resin insulation material with high flame resistance.
The main cause of phenol formaldehyde foam non-refractory is that the C-C key bond energys of connection phenyl ring in phenolic resin are relatively low, and phenol hydroxyl
Base stage is easily oxidized, therefore easy to crack under the high temperature conditions and decomposition.First important technique measure of the present invention is by boracic
Compound (such as boric acid, calcium boride, FeB or Firebrake ZB) carries out intramolecular to expandable phenolic resin and is modified, in room temperature
Lower boron compound just can occur the coordination compound that complexation reaction generates boron modified phenolic resin, its B-O key with expandable phenolic resin
Bond energy is higher than C-C key bond energys, and this contributes to the improvement of resistance to elevated temperatures.
The mass ratio of synthesis expandable phenolic resin is as follows：
Phenol 20～60；
Paraformaldehyde 20～60；
Basic polymerization catalyst 10～40；
For interior modified boron-containing compound 0.1～10.
It is described that at least one is selected in boric acid, Firebrake ZB, calcium boride or iron borate for interior modified boron-containing compound
Kind.
The basic polymerization catalyst is selected in potassium hydroxide, sodium hydroxide, calcium hydroxide, barium hydroxide, magnesium hydroxide
Select at least one.
Second important technique measure of the present invention is introduced in the solidification process of foamed phenolic resin through silane idol
The connection pretreated boron-containing compound of agent carry out it is outer modified, through one layer of the pretreated Firebrake ZB Surface coating of silane coupler
Silane coupler, coupling agent plays a part of medium, and phenolic aldehyde and Firebrake ZB are coupled together in covalent bond form, obtains strong boundary
Face interacts.Additionally, boron-containing compound can absorb heat under ignition temperature by crystallization evaporation of water, thing temperature of catching fire is reduced
Degree, can generate nonvolatile B again2O3Glassy mass, is coated on polymer surfaces, and this fine and close glassy state protective layer also rises
To the effect of isolating membrane, and boric acid can promote to generate a large amount of carbon (increase of carbon means that flammable effusion thing is reduced) with good
Flame-retardant smoke inhibition effect.
3rd important technique measure of the present invention is 30～90 mass parts of addition in the solidification process of phenolic resin
, used as filler, improving, phenolic resin material is strong for inorganic compound (such as aluminium hydroxide, magnesium hydroxide, silicon dioxide, sodium silicate)
While spending, temperature classification is remarkably improved.
The mass ratio of foam resin solidification process is as follows：
The inorganic filler selects at least one in aluminium hydroxide, magnesium hydroxide, silicon dioxide, sodium silicate.
The pore creating material selects at least one in pentane, hydrogen peroxide, AC foaming agent.
The foam stabilizer is in tween, organic foam stabilizer, sodium lauryl sulphate, dodecylbenzene sodium sulfonate, castor
Select in Oleum Sesami polyoxyethylene ether at least one.
The firming agent selects at least one in sulphuric acid, phosphoric acid, p-methyl benzenesulfonic acid.
It is described for outer modified boron-containing compound may be selected from boron powder, boric acid, Firebrake ZB, iron borate, Borax, calcium boride,
At least one in diboron trioxide etc..
Above component is sequentially added into mixing kettle, 15～60s of high-speed stirred, in being quickly poured into mould, at 40～100 DEG C
5～10min of foamed solidification, cooling, the demoulding.According to mold shape, the material of respective shapes is sent；According to mold thickness, send
The material of respective thickness；According to mould volume size, corresponding compound is added, send the material of corresponding density.
Main performance index：
Apparent density (kg/m3)≤50
Heat conductivity (W/mK) 0.025～0.030
The fire retardant B1 levels of combustibility
Below with 4 embodiments, the invention will be further described.
Embodiment 1：
1000g phenol, 570g paraformaldehydes, 36g sodium hydroxide and 5g boric acid are sequentially added into mixing kettle, high-speed stirred
3min, is warming up to 85 DEG C of reaction 2.5h, obtains the expandable phenolic resin of boron modification.
Embodiment 2：
Firebrake ZB 10g is added into ultrasonic disperse 0.5h in 100mL95% ethanol, plus 3wt%KH560, flow back 2h, centrifugation point
From washing is dried to obtain the Firebrake ZB of pretreatment.
Embodiment 3：
By 50g expandable phenolic resins, 10g aluminium hydroxide, 10g magnesium hydroxide, 0.4g tween 80s, the boron of 8g pretreatment
Sour zinc, 6g pentanes and 10g sulphuric acid/phosphoric acid mixed acid sequentially add mixing kettle, and high-speed stirred 15s is quickly poured into 0.004m3's
In template die, the thick glass mats of 3mm are spread, closed die, the foamed solidification 10min at 80 DEG C, cooling, the demoulding obtains density
For 55kg/m3The high temperature resistance phenolic aldehyde foam insulating composite material of left and right.Referred to the oxygen of the phenolic foam sheet obtained by the method
Number may be up to 90.
Embodiment 4：
Change the Firebrake ZB in above-described embodiment 2 into boric acid, remaining steps are with embodiment 2 and embodiment 3.Use the method institute
The oxygen index (OI) of the phenolic foam sheet for obtaining may be up to 85.
Claims (10)
1. a kind of synthetic method of high oxygen index (OI) phenolic resin, it is characterised in that modified synthesis including expandable phenolic resin and
Two steps of solidification of foamed phenolic resin, comprise the following steps that：
1) will add in phenol, paraformaldehyde, the system of basic polymerization catalyst for interior modified boron-containing compound, gathered
Reaction is closed, the expandable phenolic resin being modified in boron is obtained；
2) pretreatment will be carried out for outer modified boron-containing compound and silane coupler, pretreated outer modified boronation is closed
Thing is added to step 1) in the expandable phenolic resin that is modified in the boron that obtains, add inorganic filler, pore creating material, foam stabilizer, solid
Solidified after agent, obtained high oxygen index (OI) phenolic resin.
2. a kind of synthetic method of high oxygen index (OI) phenolic resin as claimed in claim 1, it is characterised in that in step 1) in, institute
State and adopt borate, the borate to may be selected from boric acid, Firebrake ZB, iron borate, calcium boride for interior modified boron-containing compound
In at least one.
3. a kind of synthetic method of high oxygen index (OI) phenolic resin as claimed in claim 1, it is characterised in that in step 1) in, institute
Stating phenol, paraformaldehyde, basic polymerization catalyst, the mass ratio for interior modified boron-containing compound is：(20～60) ︰ (20
～60) ︰ (10～40) ︰ (0.1～10).
4. a kind of synthetic method of high oxygen index (OI) phenolic resin as claimed in claim 1, it is characterised in that in step 1) in, institute
State at least one of the basic polymerization catalyst in potassium hydroxide, sodium hydroxide, calcium hydroxide, barium hydroxide, magnesium hydroxide；
Viscosity is the thick expandability phenolic aldehyde tree of 1000～6000PaS when the expandable phenolic resin being modified in the boron is 25 DEG C
Fat.
5. a kind of synthetic method of high oxygen index (OI) phenolic resin as claimed in claim 1, it is characterised in that in step 2) in, institute
State for outer modified boron-containing compound in boron powder, boric acid, Firebrake ZB, iron borate, Borax, calcium boride, diboron trioxide
At least one.
6. a kind of synthetic method of high oxygen index (OI) phenolic resin as claimed in claim 1, it is characterised in that in step 2) in, institute
State at least one of the silane coupler in KH560, KH550, KH540, KH530.
7. a kind of synthetic method of high oxygen index (OI) phenolic resin as claimed in claim 1, it is characterised in that in step 2) in, institute
State in boron be modified expandable phenolic resin, inorganic filler, pore creating material, foam stabilizer, firming agent mass ratio be (20～70) ︰ (5
～50) ︰ (0.1～5) ︰ (0.1～4) ︰ (0.1～10) ︰ (0.1～10).
8. a kind of synthetic method of high oxygen index (OI) phenolic resin as claimed in claim 1, it is characterised in that in step 2) in, institute
State at least one of the inorganic filler in aluminium hydroxide, magnesium hydroxide, silicon dioxide, sodium silicate；The pore creating material may be selected from
At least one in pentane, hydrogen peroxide, AC foaming agent.
9. a kind of synthetic method of high oxygen index (OI) phenolic resin as claimed in claim 1, it is characterised in that in step 2) in, institute
Foam stabilizer is stated selected from tween, organic foam stabilizer, sodium lauryl sulphate, dodecylbenzene sodium sulfonate, Oleum Ricini polyoxy
At least one in vinyl Ether；The firming agent may be selected from least one in sulphuric acid, phosphoric acid, p-methyl benzenesulfonic acid.
10. a kind of synthetic method of high oxygen index (OI) phenolic resin as claimed in claim 1, it is characterised in that in step 2) in,
The temperature of the solidification is 40～100 DEG C, and the time of solidification is 5～10min.
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Cited By (5)
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| CN108912290A (en) * | 2018-06-14 | 2018-11-30 | 新疆美克思新材料股份有限公司 | A kind of phenolic resin, phenolic foam material and its synthetic method |
| CN109575210A (en) * | 2018-11-30 | 2019-04-05 | 湖北中烟工业有限责任公司 | A kind of preparation method of heat-insulated compound resin |
| CN110817835A (en) * | 2018-08-14 | 2020-02-21 | 中国科学院上海硅酸盐研究所 | Porous carbon material and preparation method thereof |
| CN111040375A (en) * | 2019-12-27 | 2020-04-21 | 华东理工大学 | Nano-pore antioxidant resin-based composite material and preparation method thereof |
| CN114907741A (en) * | 2022-04-27 | 2022-08-16 | 首航科环(泉州)纳米涂料有限公司 | Environment-friendly hydrophobic nano coating and preparation method and use method thereof |
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