CN104327452A - Flame-retardant phenolic foam plate - Google Patents

Flame-retardant phenolic foam plate Download PDF

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Publication number
CN104327452A
CN104327452A CN201410654772.7A CN201410654772A CN104327452A CN 104327452 A CN104327452 A CN 104327452A CN 201410654772 A CN201410654772 A CN 201410654772A CN 104327452 A CN104327452 A CN 104327452A
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China
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parts
phenolic foam
foam board
acid
flame retardant
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CN201410654772.7A
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CN104327452B (en
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陈枫
卢焕青
钱云翔
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JINZHOU HOWAR INSULATION MATERIAL Co Ltd
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JINZHOU HOWAR INSULATION MATERIAL Co Ltd
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Abstract

The invention relates to a flame-retardant phenolic foam plate which is prepared by mixing the following components in parts by weight: 50-70 parts of alkali phenolic resin, 7-30 parts of a flame retardant, 5-15 parts of a foaming agent, 15-30 parts of water and 10-30 parts of a curing agent, so as to obtain a phenolic resin foaming system, heating to foam the phenolic resin foaming system at one time, and performing curing formation and later curing treatment so as to obtain the phenolic resin foam plate, wherein heating for foaming is carried out for 2-4h at 40-80 DEG C under the humidity of 40-90%. As the phenolic resin is modified when foamed, on premise that the mechanical property of the phenolic resin is not reduced, the flame retardancy is improved, and the cost problem of large-scale production is solved.

Description

A kind of flame retardant type phenolic foam board
Technical field
The present invention relates to building energy conservation new material technology field, particularly relate to the technology and method of a kind of resol and fire retardant mixed foaming.
Background technology
Under global financial crisis impact, can Chinese national economy keep continual and steady high speed development, and energy problem has become an outstanding contradiction.There is at present maximum in the world construction market in China, existing building area 40,000,000,000 square metres, and annual newly-increased building measures 2,000,000,000 square metres, and more than 95% is still high energy consumption building in China's new building at present, and building energy consumption has reached 27% of whole society's energy consumption.If do not take conservation measures, 50% national energy consumption will be had architectural to the year two thousand twenty.According to the statistics made by the departments concerned, China's thermal insulation performance of building envelope is general lower, the bulk thermal conductivity constants of exterior wall and window is 3 ~ 4 times of equal developed country, the power consumption of exterior wall unit floor area of building will exceed 4 ~ 5 times, and China's construction unit area total heat is that the close developed country of weather condition exceeds 2 ~ 5 times.Show that the potential of China's building energy conservation is very large thus, overall goal according to Ministry of Construction's building energy conservation: realize energy-conservation 50% to national cities and towns new building in 2010, complete 25% to existing building reducing energy consumption big city, medium-sized city completes 15%, and small city completes 10%.Energy-conservation 65% is realized to the year two thousand twenty north and the new building of coastal economy developed regions.Show that building energy conservation has become the key factor affecting China's energy sustainable development strategic decision thus, the unshakable state basic policy that Ye Shi China is lasting.
In China's nearly 30 years building trades and industrial manufacturing development course, lagging material experienced by conventional inorganic material and two stages of organic synthesis material, and for China's building energy conservation has made tremendous contribution, but above-mentioned wall heat insulation material all exists shortcoming.Huge, the round-the-clock life-time service heat insulation effect instability of inorganic heat insulation material process of manufacture energy consumption, complicated construction technique, especially materials'use process and environment and human body are harmful to aftertreatment, to such an extent as to some occasion even some country be prohibited from using; The excellent heat insulation effect that traditional styrofoam, polyurethane foam board have, widely use in the wall heat insulation material market that China is current, but do not possess safe fire resistance, especially produce poison gas during burning, the use of this type of material is limited in minimum Application Areas already in developed country in fact.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is the technology and method providing a kind of resol and fire retardant mixed foaming, while the method can not reduce the mechanical property of phenolic foam board prepared by existing phenolic foam foaming technology, increase flame retardant properties, and conservation, reduce production cost.
A kind of flame retardant type phenolic foam board, comprises following raw material, by weight ratio: alkalescent phenol resin 50 ~ 70 parts; Fire retardant 7 ~ 30 parts; Whipping agent 5 ~ 15 parts; 15 ~ 30 parts, water; 10 ~ 30 parts, solidifying agent; Stablizer 3 ~ 10 parts;
Preferably, described stablizer is polyvinyl alcohol, Polyvinylpyrolidone (PVP), any one or a few combination of polyoxyethylene glycol.
Preferably, also comprise high activity modified dose of 3 ~ 20 weight parts, described high activity modified dose is any one or a few combination in urethane, base polyurethane prepolymer for use as, epoxy resin and modified epoxy.
Preferably, described fire retardant is any one or a few the combination in tetrabromo-bisphenol, eight bromo ether, decabromodiphynly oxide, TDE.
Preferably, described whipping agent is any one or a few the combination in Skellysolve A, isohexane, normal hexane, pentamethylene and sherwood oil.
Preferably, described solidifying agent is made up of organic acid and mineral acid, and described organic acid is one or more in P-TOLUENE SULFO ACID 99, sulfocarbolic acid, xylene monosulfonic acid and acetic acid, and described mineral acid is any one or a few combination in sulfuric acid, phosphoric acid and hydrochloric acid.
Preferably, described alkalescent phenol resin is prepared as follows: by phenol, formaldehyde, react containing amino organic compound with containing phosphorus base organic compound under the effect of basic catalyst, obtain alkalescent phenol resin.
A kind of preparation method of flame retardant type phenolic foam board, by the solidifying agent of the whipping agent of the fire retardant of the alkalescent phenol resin of 50 ~ 70 weight parts, 7 ~ 30 weight parts, 5 ~ 15 weight parts, the water of 15 ~ 30 weight parts and 10 ~ 30 weight parts, stablizer part mixing of 3 ~ 10 weight parts, obtains phenol resin foam system;
Above-mentioned phenol resin foam system is once carried out foamable, curing molding and post curing treatment and obtains phenolic foam board, the temperature of described foamable is 40 DEG C ~ 80 DEG C, and humidity is 40% ~ 90%, and the time is 2 ~ 4 hours.
Beneficial effect of the present invention: compared with prior art, the present invention adds fire retardant on the basis of original Foaming of phenolic resin, improves the flame retardant properties of phenolic foam board, temperature is controlled, at 40 DEG C ~ 80 DEG C, to reduce energy consumption during batch production greatly.Meanwhile, due to adding of fire retardant, increase the pore size of original Foaming of phenolic resin plate, its density is reduced, but more improves than original phenolic resin foamed board in flame retardant properties.Therefore, the present invention, under the prerequisite not reducing phenolic foam board mechanical property, improves its flame retardant properties, also reduces density simultaneously, reduce costs.Experiment shows, adopts phenolic foam board prepared by method provided by the invention, ultimate compression strength >0.15 MPa, tensile strength >0.1 MPa, thermal conductivity <0.025 W/m K.Keep good flame retardant rating to be B1 level (difficult combustion level) simultaneously.
Embodiment
A preparation method for flame retardant type phenolic foam board, comprises the following steps:
The solidifying agent of the whipping agent of the fire retardant of the alkalescent phenol resin of 50 ~ 70 weight parts, 7 ~ 30 weight parts, 5 ~ 15 weight parts, the water of 15 ~ 30 weight parts and 10 ~ 30 weight parts is mixed, it is 50 DEG C ~ 90 DEG C in temperature, humidity is foamable under the environment of 40% ~ 90%, curing molding, obtains phenolic foam board.
Preferably, the present invention is first by fire retardant, resol, stablizer mixing, then high-speed stirring evenly after, then add whipping agent and mix, then adding water, solidifying agent, pour into after mixing in mould, foamed solidification is shaping, and temperature of reaction is preferably 40 DEG C ~ 80 DEG C, be more preferably 50 DEG C ~ 70 DEG C, most preferably be 60 DEG C ~ 70 DEG C.
Resol used in the present invention is preferably alkalescent phenol resin, described alkalescent phenol resin is a kind of low water absorption modified phenolic resins, preparation method is: by phenol, formaldehyde, mix containing amino organic compound and organic phosphorus compound, react under the condition of basic catalyst, obtain alkalescent phenol resin.Described alkalescent phenol resin consumption is preferably 50 ~ 70 weight parts, is more preferably 60 ~ 70 weight parts.
Fire retardant used in the present invention be preferably in tetrabromo-bisphenol, eight bromo ether, decabromodiphynly oxide, TDE one or more.Use amount of flame-retardant agent to be preferably 7 ~ 30 weight parts, be more preferably 7 ~ 20 weight parts, most preferably be 12 ~ 20 weight parts.
Whipping agent is the important component producing phenol formaldehyde foam, and be the material making phenol formaldehyde foam produce microvoid structure, the present invention selects pneumatogen to exist, pneumatogen is in participation foaming process, not there is chemical transformation in itself, just by the change of physical condition, produces a large amount of gas.Whipping agent used in the present invention is preferably lower boiling alkane, is more preferably one or more in Skellysolve A, iso-pentane, normal hexane, pentamethylene, sherwood oil.Described foaming agent consumption is preferably 5 ~ 15 weight parts, is more preferably 10 ~ 15 weight parts.
Phenolic foam board needs to absorb heat in foamed solidification process, and curing cycle is longer, usually adds acid as solidifying agent, and solidifying agent effect promotes thermopositive reaction, accelerates foamed solidification.Mineral acid price is low, but due to purity high, curing speed is too fast, therefore the present invention select solidifying agent be the mineral acid of PH=2.Mineral acid is preferably sulfuric acid, phosphoric acid and hydrochloric acid, is more preferably sulfuric acid.
In order to make reaction carry out smoothly, the present invention also adds stablizer.Its one or composite of stablizer polyvinyl alcohol, Polyvinylpyrolidone (PVP), polyoxyethylene glycol.
Also can add high activity modified dose of 3 ~ 20 weight parts in phenol resin foam system, described high activity modified dose is preferably 5 ~ 15 weight parts, is more preferably 5 ~ 10 weight parts.High activity modified dose with the hydroxyl generation crosslinking reaction in resol, can increase the stress of resol inside, increases its intensity.Described high activity modified dose be preferably in ammonia ester, base polyurethane prepolymer for use as, epoxy resin and modified epoxy one or more, be more preferably base polyurethane prepolymer for use as.
The present invention is by resol, fire retardant, stablizer, high activity modified dose of mixing, then high-speed stirring evenly after, then add whipping agent and mix, then adding solidifying agent, then pour into after being mixed by mixture in mould, the condition of curing molding is that temperature of reaction controls to be 40 DEG C ~ 80 DEG C
In order to further illustrate the present invention, below in conjunction with case study on implementation, phenolic foam board provided by the invention is described in detail.
Embodiment 1:
Calculate by weight, each gram is a, weighs each constitutive material:
Can be foamed alkalescent phenol resin 70 parts, do not add fire retardant, Skellysolve A 12 parts, 20 parts, water, 20 parts, the sulfuric acid of PH=2, polyoxyethylene glycol 3 parts, polyurethane prepolymer 5 parts.
In a mold, at temperature 70 C, carry out the foamed solidification time length in the thermostat container of humidity 50% is 2 hours to raw mixture stirring obtained.After obtaining phenolic foam board, more at room temperature dry, obtain required pure phenolic foam board.
Embodiment 2:
Calculate by weight, each gram is a, weighs each constitutive material:
Can be foamed alkalescent phenol resin 63 parts, tetrabromo-bisphenol 7 parts, Skellysolve A 12 parts, 20 parts, water, 20 parts, the sulfuric acid of PH=2, polyoxyethylene glycol 3 parts, polyurethane prepolymer 5 parts.
In a mold, at temperature 70 C, carry out the foamed solidification time length in the thermostat container of humidity 50% is 2 hours to raw mixture stirring obtained.After obtaining phenolic foam board, more at room temperature dry, obtain the required phenolic foam board with fire retardant modification.
Embodiment 3:
Calculate by weight, each gram is a, weighs each constitutive material:
Can be foamed alkalescent phenol resin 56 parts, tetrabromo-bisphenol 14 parts, Skellysolve A 12 parts, 20 parts, water, 20 parts, the sulfuric acid of PH=2, polyoxyethylene glycol 3 parts, polyurethane prepolymer 5 parts.
In a mold, at temperature 70 C, carry out the foamed solidification time length in the thermostat container of humidity 50% is 2 hours to raw mixture stirring obtained.After obtaining phenolic foam board, more at room temperature dry, obtain the required phenolic foam board with fire retardant modification.
Embodiment 4:
Calculate by weight, each gram is a, weighs each constitutive material:
Can be foamed alkalescent phenol resin 49 parts, tetrabromo-bisphenol 21 parts, Skellysolve A 12 parts, 20 parts, water, 20 parts, the sulfuric acid of PH=2, polyoxyethylene glycol 3 parts, polyurethane prepolymer 5 parts.
In a mold, at temperature 70 C, carry out the foamed solidification time length in the thermostat container of humidity 50% is 2 hours to raw mixture stirring obtained.After obtaining phenolic foam board, more at room temperature dry, obtain the required phenolic foam board with fire retardant modification.
Embodiment 5:
Calculate by weight, each gram is a, weighs each constitutive material:
Can be foamed alkalescent phenol resin 42 parts, tetrabromo-bisphenol 28 parts, Skellysolve A 12 parts, 20 parts, water, 20 parts, the sulfuric acid of PH=2, polyoxyethylene glycol 3 parts, polyurethane prepolymer 5 parts.
In a mold, at temperature 70 C, carry out the foamed solidification time length in the thermostat container of humidity 50% is 2 hours to raw mixture stirring obtained.After obtaining phenolic foam board, more at room temperature dry, obtain the required phenolic foam board with fire retardant modification.
Affiliated phenolic foam board is tested, result see table 1, the test result of the phenolic foam board that table 1 provides for the embodiment of the present invention.
The test result of the phenolic foam board that table 1 embodiment of the present invention provides
As shown in Table 1, phenolic foam board provided by the invention carries out foaming according to different flame retardant addition, solidify and prepare, its density is first along with the increase of the addition of fire retardant presents rising tendency, downtrending is presented more than 30%, its compressive strength reduces along with the increase of fire retardant, but still can requirement be reached, the change of its tensile strength is little.The limiting oxygen index(LOI) of phenolic foam board increases along with the increase of fire retardant, and its flame retardant rating reaches B1.As can be seen here, in phenol formaldehyde foam, add fire retardant under the prerequisite not reducing its mechanical property, can greatly improve its flame retardant properties, more can reduce costs.
The explanation of above embodiment just understands the inventive method and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the claims in the present invention protection domain.

Claims (8)

1. a flame retardant type phenolic foam board, is characterized in that, comprises following raw material, by weight ratio: alkalescent phenol resin 50 ~ 70 parts; Fire retardant 7 ~ 30 parts; Whipping agent 5 ~ 15 parts; 15 ~ 30 parts, water; 10 ~ 30 parts, solidifying agent; Stablizer 3 ~ 10 parts.
2. a kind of flame retardant type phenolic foam board according to claim 1, is characterized in that: described stablizer is polyvinyl alcohol, Polyvinylpyrolidone (PVP), any one or a few combination of polyoxyethylene glycol.
3. a kind of flame retardant type phenolic foam board according to claim 1, it is characterized in that: also comprise high activity modified dose of 3 ~ 20 weight parts, described high activity modified dose is any one or a few combination in urethane, base polyurethane prepolymer for use as, epoxy resin and modified epoxy.
4. a kind of flame retardant type phenolic foam board according to claim 1, is characterized in that: described fire retardant is any one or a few the combination in tetrabromo-bisphenol, eight bromo ether, decabromodiphynly oxide, TDE.
5. a kind of flame retardant type phenolic foam board according to claim 1, is characterized in that: described whipping agent is any one or a few the combination in Skellysolve A, isohexane, normal hexane, pentamethylene and sherwood oil.
6. a kind of flame retardant type phenolic foam board according to claim 1, it is characterized in that: described solidifying agent is made up of organic acid and mineral acid, described organic acid is one or more in P-TOLUENE SULFO ACID 99, sulfocarbolic acid, xylene monosulfonic acid and acetic acid, and described mineral acid is any one or a few combination in sulfuric acid, phosphoric acid and hydrochloric acid.
7. a kind of flame retardant type phenolic foam board according to claim 1 or 2 or 3 or 4 or 5 or 6, it is characterized in that: described alkalescent phenol resin is prepared as follows: by phenol, formaldehyde, react containing amino organic compound with containing phosphorus base organic compound under the effect of basic catalyst, obtain alkalescent phenol resin.
8. the preparation method of a flame retardant type phenolic foam board as claimed in claim 1, it is characterized in that: by the parts by weight of component each described in claim 1, alkalescent phenol resin, fire retardant, whipping agent, water, solidifying agent, stablizer are mixed, obtain phenol resin foam system;
Above-mentioned phenol resin foam system is once carried out foamable, curing molding and post curing treatment and obtains phenolic foam board, the temperature of described foamable is 40 DEG C ~ 80 DEG C, and humidity is 40% ~ 90%, and the time is 2 ~ 4 hours.
CN201410654772.7A 2014-11-17 2014-11-17 A kind of flame retardant type phenolic foam board Active CN104327452B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107955325A (en) * 2017-12-02 2018-04-24 范运昌 A kind of processing method for reducing phenolic foam board thermal conductivity factor
CN109293971A (en) * 2018-10-10 2019-02-01 中国科学院化学研究所 The safe preparation method of phenolic aldehyde tiny balloon

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102838770A (en) * 2012-09-10 2012-12-26 山东圣泉化工股份有限公司 Preparation method of phenolic foam boards
CN103073740A (en) * 2013-01-29 2013-05-01 山东圣泉化工股份有限公司 Preparation method of phenolic foamed plastic
CN103613904A (en) * 2013-11-27 2014-03-05 山东圣泉化工股份有限公司 Low-density low-acidicity phenol formaldehyde foam board and preparation technique thereof

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
CN102838770A (en) * 2012-09-10 2012-12-26 山东圣泉化工股份有限公司 Preparation method of phenolic foam boards
CN103073740A (en) * 2013-01-29 2013-05-01 山东圣泉化工股份有限公司 Preparation method of phenolic foamed plastic
CN103613904A (en) * 2013-11-27 2014-03-05 山东圣泉化工股份有限公司 Low-density low-acidicity phenol formaldehyde foam board and preparation technique thereof

Non-Patent Citations (1)

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Title
杨金平等: "水在酚醛泡沫泡体结构中的作用", 《2006年绝热隔音材料轻质建筑板材新技术新产品论文集》, 1 November 2011 (2011-11-01), pages 101 - 102 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107955325A (en) * 2017-12-02 2018-04-24 范运昌 A kind of processing method for reducing phenolic foam board thermal conductivity factor
CN109293971A (en) * 2018-10-10 2019-02-01 中国科学院化学研究所 The safe preparation method of phenolic aldehyde tiny balloon
CN109293971B (en) * 2018-10-10 2020-12-15 中国科学院化学研究所 Safe preparation method of phenolic aldehyde hollow microspheres

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