CN104327452B - A kind of flame retardant type phenolic foam board - Google Patents
A kind of flame retardant type phenolic foam board Download PDFInfo
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- CN104327452B CN104327452B CN201410654772.7A CN201410654772A CN104327452B CN 104327452 B CN104327452 B CN 104327452B CN 201410654772 A CN201410654772 A CN 201410654772A CN 104327452 B CN104327452 B CN 104327452B
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Abstract
The present invention relates to a kind of flame retardant type phenolic foam board, its preparation process is as follows: is mixed by the curing agent of the alkalescent phenol resin of 50 ~ 70 weight portions, the fire retardant of 7 ~ 30 weight portions, the foaming agent of 5 ~ 15 weight portions, the water of 15 ~ 30 weight portions and 10 ~ 30 weight portions, obtains phenol resin foam system；Above-mentioned phenol resin foam system once carrying out foamable, curing molding and rear solidification process 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.The present invention is to the modification carried out the when of Foaming of phenolic resin, on the premise of not reducing its mechanical property, improves fire resistance, and improves the Cost Problems of its large-scale production.
Description
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 phenolic resin and fire retardant mixed foaming.
Background technology
Under the influence of global financial crisis, can Chinese national economy keep continual and steady high speed development, and energy problem has become a prominent contradiction.There are at present maximum construction market, existing building area 40,000,000,000 square metres in China, 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 the 27% of whole society's energy consumption.If not taking conservation measures, will there is 50% whole nation energy resource consumption 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 the most relatively low, the bulk thermal conductivity constants of exterior wall and window is 3 ~ 4 times of equal developed country, and the power consumption of exterior wall unit construction area to exceed 4 ~ 5 times, and China's construction unit area total amount of heat is that the close developed country of weather conditions exceeds 2 ~ 5 times.The potential being indicated above China's building energy conservation is very big, according to the overall goal of Ministry of Construction's building energy conservation: realizing energy-conservation 50% to national cities and towns new building in 2010, existing building reducing energy consumption big city is completed 25%, 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.It is indicated above building energy conservation and becomes the key factor affecting China's energy sustainable development strategic decision, the unshakable state basic policy that Ye Shi China is lasting.
In nearly 30 years building trades of China and industry manufacturing development course, insulation material experienced by tradition inorganic material and two stages of organic synthesis material, is made that tremendous contribution for China's building energy conservation, but above-mentioned wall heat insulation material all exists shortcoming.Inorganic heat insulation material process of manufacture energy consumption Long-Time Service heat insulation effect huge, round-the-clock instability, complicated construction technique, especially materials'use process and environment and human body are harmful to post processing, to such an extent as to be prohibited from using in some occasion even some country；The excellent heat insulation effect that traditional styrofoam, polyurethane foam board have, it is widely used in the wall heat insulation material market that China is current, but do not possess safe fire protecting performance, especially producing poison gas during burning, the use of this type of material is limited in minimum application 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 phenolic resin with 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 fire resistance, and conservation, reduce production cost.
A kind of flame retardant type phenolic foam board, including following raw material, by weight ratio: alkalescent phenol resin 50 ~ 70 parts；Fire retardant 7 ~ 30 parts；Foaming agent 5 ~ 15 parts；15 ~ 30 parts of water；10 ~ 30 parts of curing agent；Stabilizer 3 ~ 10 parts；
Preferably, described stabilizer is polyvinyl alcohol, PVP, any one or a few combination of polyethylene glycol.
Preferably, also including high activity modified dose of 3 ~ 20 weight portions, described high activity modified dose is any one or a few the combination in polyurethane, base polyurethane prepolymer for use as, epoxy resin and modified epoxy.
Preferably, any one or a few the combination during described fire retardant is tetrabromobisphenol A, eight bromo ether, deca-BDE, TDE.
Preferably, any one or a few the combination during described foaming agent is pentane, isohexane, n-hexane, pentamethylene and petroleum ether.
Preferably, described curing agent is made up of organic acid and inorganic acid, and described organic acid is one or more in P-TOLUENE SULFO ACID 99, phenolsulfonic acid, xylene monosulfonic acid and acetic acid, and described inorganic 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, organic compound containing amino and reacts containing phosphorus base organic compound under the effect of base catalyst, obtains alkalescent phenol resin.
A kind of preparation method of flame retardant type phenolic foam board, by the alkalescent phenol resin of 50 ~ 70 weight portions, the fire retardant of 7 ~ 30 weight portions, the foaming agent of 5 ~ 15 weight portions, the water of 15 ~ 30 weight portions and the curing agent of 10 ~ 30 weight portions, stabilizer part mixing of 3 ~ 10 weight portions, obtains phenol resin foam system；
Above-mentioned phenol resin foam system once carrying out foamable, curing molding and rear solidification process 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 effects 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 fire resistance of phenolic foam board, controls temperature, at 40 DEG C ~ 80 DEG C, can greatly reduce energy consumption during batch production.Simultaneously as the addition of fire retardant, increase the pore size of original Foaming of phenolic resin plate so that it is density is reduced, but more improves than original phenolic resin foamed board in terms of fire resistance.Therefore, the present invention, on the premise of not reducing phenolic foam board mechanical property, improves its fire resistance, the most also reduces density, reduces cost.Experiment shows, phenolic foam board prepared by the method using the present invention to provide, compression strength>0.15 MPa, hot strength>0.1 MPa, thermal conductivity factor<0.025 W/m K.Keep preferable flame retardant rating is B1 level (difficult combustion level) simultaneously.
Detailed description of the invention
The preparation method of a kind of flame retardant type phenolic foam board, comprises the following steps:
The curing agent of the alkalescent phenol resin of 50 ~ 70 weight portions, the fire retardant of 7 ~ 30 weight portions, the foaming agent of 5 ~ 15 weight portions, the water of 15 ~ 30 weight portions and 10 ~ 30 weight portions is mixed, it it is 50 DEG C ~ 90 DEG C in temperature, humidity is foamable in the environment of 40% ~ 90%, curing molding, obtains phenolic foam board.
Preferably, the present invention is first by fire retardant, phenolic resin, stabilizer mixing, then, after high-speed stirred is uniform, adds foaming agent and mix, adding water, curing agent, pouring into after mixing in mould, foamed solidification is molded, and reaction temperature is preferably 40 DEG C ~ 80 DEG C, more preferably 50 DEG C ~ 70 DEG C, most preferably 60 DEG C ~ 70 DEG C.
Phenolic resin used in the present invention is preferably alkalescent phenol resin, described alkalescent phenol resin is a kind of low water absorption phenol-formaldehyde resin modified, preparation method is: by phenol, formaldehyde, organic compound containing amino and organic phosphorus compound mixing, react under conditions of base catalyst, obtain alkalescent phenol resin.Described alkalescent phenol resin consumption is preferably 50 ~ 70 weight portions, more preferably 60 ~ 70 weight portions.
Fire retardant used in the present invention is preferably one or more in tetrabromobisphenol A, eight bromo ether, deca-BDE, TDE.Used amount of flame-retardant agent is preferably 7 ~ 30 weight portions, more preferably 7 ~ 20 weight portions, most preferably 12 ~ 20 weight portions.
Foaming agent is the important component producing phenol formaldehyde foam, is the material making phenol formaldehyde foam produce microcellular structure, and the present invention selects physical blowing agent to exist, physical blowing agent is in participating in foaming process, there is not chemical change in itself, simply by the change of physical state, produces a large amount of gas.Foaming agent used in the present invention is preferably one or more in low boiling alkane, more preferably pentane, isopentane, n-hexane, pentamethylene, petroleum ether.Described foaming agent consumption is preferably 5 ~ 15 weight portions, more preferably 10 ~ 15 weight portions.
Phenolic foam board needs to absorb heat during foamed solidification, and cure cycle is longer, is usually added into sour as curing agent, and curing agent effect is to promote exothermic reaction, accelerates foamed solidification.Inorganic acid price is low, but owing to purity is high, curing rate is too fast, the inorganic acid that curing agent is PH=2 that therefore present invention selects.Inorganic acid is preferably sulfuric acid, phosphoric acid and hydrochloric acid, more preferably sulfuric acid.
In order to make reaction be smoothed out, the present invention is also added into stabilizer.Stabilizer polyvinyl alcohol, PVP, polyethylene glycol its one or compounding.
Also can add high activity modified dose of 3 ~ 20 weight portions in phenol resin foam system, described high activity modified dose is preferably 5 ~ 15 weight portions, more preferably 5 ~ 10 weight portions.High activity modified dose can crosslink reaction with the hydroxyl in phenolic resin, increase the stress within phenolic resin, increase its intensity.Described high activity modified dose of one or more being preferably in urethane, base polyurethane prepolymer for use as, epoxy resin and modified epoxy, more preferably base polyurethane prepolymer for use as.
The present invention is by phenolic resin, fire retardant, stabilizer, high activity modified dose of mixing, then, after high-speed stirred is uniform, adds foaming agent and mix, adding curing agent, then pouring into after being mixed by mixture in mould, the condition of curing molding is that reaction temperature controls to be 40 DEG C ~ 80 DEG C
In order to further illustrate the present invention, the phenolic foam board provided the present invention below in conjunction with case study on implementation is described in detail.
Embodiment 1:
Calculating by weight, each gram is a, weighs each constitutive material:
Expandable alkalescent phenol resin 70 parts, without fire retardant, pentane 12 parts, 20 parts of water, 20 parts of the sulfuric acid of PH=2, polyethylene glycol 3 parts, polyurethane prepolymer 5 parts.
In a mold, carry out the foamed solidification duration in temperature 70 C, the insulating box 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:
Calculating by weight, each gram is a, weighs each constitutive material:
Expandable alkalescent phenol resin 63 parts, tetrabromobisphenol A 7 parts, pentane 12 parts, 20 parts of water, 20 parts of the sulfuric acid of PH=2, polyethylene glycol 3 parts, polyurethane prepolymer 5 parts.
In a mold, carry out the foamed solidification duration in temperature 70 C, the insulating box 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 modified with fire retardant.
Embodiment 3:
Calculating by weight, each gram is a, weighs each constitutive material:
Expandable alkalescent phenol resin 56 parts, tetrabromobisphenol A 14 parts, pentane 12 parts, 20 parts of water, 20 parts of the sulfuric acid of PH=2, polyethylene glycol 3 parts, polyurethane prepolymer 5 parts.
In a mold, carry out the foamed solidification duration in temperature 70 C, the insulating box 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 modified with fire retardant.
Embodiment 4:
Calculating by weight, each gram is a, weighs each constitutive material:
Expandable alkalescent phenol resin 49 parts, tetrabromobisphenol A 21 parts, pentane 12 parts, 20 parts of water, 20 parts of the sulfuric acid of PH=2, polyethylene glycol 3 parts, polyurethane prepolymer 5 parts.
In a mold, carry out the foamed solidification duration in temperature 70 C, the insulating box 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 modified with fire retardant.
Embodiment 5:
Calculating by weight, each gram is a, weighs each constitutive material:
Expandable alkalescent phenol resin 42 parts, tetrabromobisphenol A 28 parts, pentane 12 parts, 20 parts of water, 20 parts of the sulfuric acid of PH=2, polyethylene glycol 3 parts, polyurethane prepolymer 5 parts.
In a mold, carry out the foamed solidification duration in temperature 70 C, the insulating box 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 modified with fire retardant.
Testing affiliated phenolic foam board, result sees 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, the phenolic foam board that the present invention provides carries out foaming according to different flame retardant addition, solidify and prepare, its density first presents growth trend along with the increase of the addition of fire retardant, downward trend is presented more than 30%, its compressive strength reduces along with the increase of fire retardant, but remaining to reach requirement, the change of its hot strength is little.The limited oxygen index of phenolic foam board increases along with the increase of fire retardant, and its flame retardant rating has reached B1.As can be seen here, phenol formaldehyde foam adds fire retardant to be greatly improved its fire resistance, more can reduce cost on the premise of not reducing its mechanical property.
The explanation of above example is only intended to help and understands the inventive method and core concept thereof.It should be pointed out that, for those skilled in the art, under the premise without departing from the principles of the invention, it is also possible to the present invention is carried out some improvement and modification, these improve and modification also falls in the claims in the present invention protection domain.
Claims (1)
1. a flame retardant type phenolic foam board, including following raw material, by weight ratio: expandable alkalescent phenol resin 63 parts, tetrabromobisphenol A 7 parts, pentane 12 parts, 20 parts of water, 20 parts of the sulfuric acid of pH=2, polyethylene glycol 3 parts, polyurethane prepolymer 5 parts；
In a mold, carry out the foamed solidification duration in temperature 70 C, the insulating box 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 modified with fire retardant.
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| CN201410654772.7A CN104327452B (en) | 2014-11-17 | 2014-11-17 | A kind of flame retardant type phenolic foam board |
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| CN201410654772.7A CN104327452B (en) | 2014-11-17 | 2014-11-17 | A kind of flame retardant type phenolic foam board |
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| CN104327452B true CN104327452B (en) | 2016-06-29 |
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| CN107955325A (en) * | 2017-12-02 | 2018-04-24 | 范运昌 | A kind of processing method for reducing phenolic foam board thermal conductivity factor |
| 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 |
Citations (3)
| 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 |
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Patent Citations (3)
| 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)
| Title |
|---|
| 水在酚醛泡沫泡体结构中的作用;杨金平等;《2006年绝热隔音材料轻质建筑板材新技术新产品论文集》;20111101;第101-102页 * |
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