CN103289307A - Preparation method of high energy-saving type modified environment-friendly phenolic fireproof insulation board - Google Patents

Preparation method of high energy-saving type modified environment-friendly phenolic fireproof insulation board Download PDF

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CN103289307A
CN103289307A CN2012100470510A CN201210047051A CN103289307A CN 103289307 A CN103289307 A CN 103289307A CN 2012100470510 A CN2012100470510 A CN 2012100470510A CN 201210047051 A CN201210047051 A CN 201210047051A CN 103289307 A CN103289307 A CN 103289307A
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resol
agent
preparation
high energy
waste
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刘兵
唐晓君
吕晟楠
张春衡
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YINGKOU SOUNRUN NEW MATERIAL ENGINEERING TECHNOLOGY Co Ltd
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YINGKOU SOUNRUN NEW MATERIAL ENGINEERING TECHNOLOGY Co Ltd
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Abstract

The invention provides a preparation method of a high energy-saving type modified environment-friendly phenolic fireproof insulation board. The method comprises the following steps of: mixing and evenly stirring leftover and waste materials of the phenolic resin fireproof insulation board, waste rubber powder, expandable phenolic resin, modifying agents, a surface active agent and a foaming agent; then, adding a composite curing agent into the mixture, stirring the mixture and the agent, and pouring the obtained mixture into a mould to obtain the phenolic resin fireproof insulation board. By adopting the double modifying agents, the method can alleviate environment pollution caused by the waste rubber and the leftover and waste materials of the phenolic resin fireproof insulation board, reduce energy consumed by the preparation of the phenolic resin fireproof insulation board, improve the strength and the toughness of the phenolic insulation board, reduce the brittleness of the phenolic insulation board and lower the industrial cost, is beneficial to improving economic benefits, and meets the construction demand of a building outer wall (specifically an outer wall insulation system).

Description

A kind of preparation method of high energy-saving type modified environment-friendly phenolic fireproof insulating plate
Technical field
The invention belongs to building material technical field, be specifically related to a kind of preparation method of high energy-saving type modified environment-friendly phenolic fireproof insulating plate.
Background technology
Owing to inflammable, shortcomings such as toxic smoke big, water absorbing properties difference, there is potential safety hazard as extruded sheet, styrofoam etc. in present employed building thermal insulation material.Phenol formaldehyde foam since have raw material be easy to get, cheap, product performance are good, difficult fire, put out certainly, hang down characteristics such as smog, water-proof breathable properties are good, can better application in exterior wall heat-preserving system, therefore be subjected to the attention of domestic and international building thermal insulation material industry day by day.But a shortcoming of prior art phenol formaldehyde foam be crisp, tensile strength is not high; a kind of as in the macromolecular material of phenol formaldehyde foam simultaneously, to the consumption of the energy, the pollution of environment also is very serious; especially along with the more and more mass-producing of production of phenol formaldehyde foam warming plate, industrialization.Corresponding a large amount of corners and the waste and old material of having occurred in process of production, according to statistics, after 20 years only China millions of building wastes that exist with resol fireproof heated board form that stand just will appear.How reasonably reaching the purpose of energy-conserving and environment-protective these corners of recycling and waste and old material the time, is a great problem again of far-reaching significance.In addition, along with the develop rapidly of China's automobile industry, utilizing again of waste rubber also becomes the problem of discussing warmly in the present energy-conserving and environment-protective project.The greenhouse gases life-span cycle analysis that the Malcolm Pimie company of Environmental Projects Inc. of technological precedence does the PolyDyne rubber powder is pointed out, per 10 pounds (1 pound=0.454kg) rubber powder of recycling is applied in the synthetic polymer, just is equivalent to prevent that 10 pounds of carbonic acid gas from entering atmosphere.Simultaneously, be equivalent to reduce 1 gal (1 gal=3.785L) crude oil consumption.And China has become the first producing country of world's tire, and the output of waste tire also ranks first in the world, and year discarded amount is above 300,000,000.So utilize phenol formaldehyde foam warming plate corner, waste and old material and waste rubber two big industry polymeric scraps, turn waste into wealth, reduce by two less contamination, preparing a kind of energy saving and environment friendly modified phenolic resins fireproof heated board becomes the most significant large project of New Times energy-conserving and environment-protective.
Summary of the invention
The objective of the invention is to overcome above-mentioned the deficiencies in the prior art and limitation, a kind of preparation method of high energy-saving type modified environment-friendly phenolic fireproof insulating plate is provided, this method is filler with resol fireproof heated board scrap stock or waste and old material, the method of waste rubber powder and the dual properties-correcting agent of ethylene glycol, waste rubber and resol fireproof heated board corner have been reduced, waste and old material is to the pollution of environment, preparation resol fireproof heated board is to the consumption of the energy, intensity and the toughness of phenolic aldehyde heat preserving plate have also been improved, reduced the fragility of phenolic aldehyde heat preserving plate, reduced industrial cost, be conducive to increase economic efficiency, satisfy the needs of skin construction (exterior wall heat-preserving system) simultaneously.
The invention provides a kind of preparation method of high energy-saving type modified environment-friendly phenolic fireproof insulating plate, with resol fireproof heated board corner, waste and old material, the waste rubber powder, expandable phenolic resin, properties-correcting agent, tensio-active agent, whipping agent mixes, and after stirring, adds composite curing agent again, pour mould after the stirring into, get the resol fireproof heated board.
The preparation method of high energy-saving type modified environment-friendly phenolic fireproof insulating plate provided by the invention, described resol fireproof heated board corner, waste and old material, the waste rubber powder, can send out resol, properties-correcting agent, tensio-active agent, whipping agent, the mass fraction of these 7 kinds of material add-ons of composite curing agent is respectively: resol fireproof heated board corner, waste and old material 10-30 part, and waste rubber powder 10-20 part can be sent out 100 parts in resol, properties-correcting agent 6-15 part, tensio-active agent 3-8 part, whipping agent 3-8 part, composite curing agent 14-22 part.
The resol sent out preparation method among the present invention is as follows: by phenol/formaldehyde is added by 1mol: 1.8mol agitator is housed, in the four-hole boiling flask of thermometer and reflux condensing tube, starts agitator and use heating in water bath.When question response liquid is 40 ℃, the NaOH aqueous solution with 20% is regulated between the pH value to 8, continue to be heated to 60 ℃ and kept one hour, heat up again and control and stopping heating behind the reaction 120min between 80 ℃~90 ℃, with cooling bath mixture is cooled under 70 ℃ rapidly, with acid for adjusting pH value to 6.8~7.2, decompression dehydration namely obtains expandable resol.
The preparation method of high energy-saving type modified environment-friendly phenolic fireproof insulating plate provided by the invention sneaks into resol fireproof heated board corner, waste and old material in the described resol raw material.Described waste rubber powder source waste tire, its particle size range is 44-105 μ m.Described properties-correcting agent is ethylene glycol.Described tensio-active agent is silicone oil H230.Described whipping agent is Skellysolve A.Described composite curing agent is the combination of xylene monosulfonic acid, sulfuric acid, boric acid, and wherein solvent is water, ethanol combination.
All components among the present invention all at home market make after buying or buying.
The mechanism of waste rubber powder modified phenolic resins among the present invention: 1. rubber toughened resol belongs to physics blending modification, but because elastomerics has active end group (as carboxyl, hydroxyl etc.) and two key usually, can with resole in the methylol grafting or the block copolymerization that take place in various degree react.This grafting or block copolymerization are reflected in the phenolic aldehyde stiff molecule structure and have introduced the snappiness segment, have fundamentally changed the stiff molecule structure that can send out resol, thereby have improved the toughness of phenol formaldehyde foam (goods), have reduced fragility.2. the rubber-like elastomeric segments generally can be separated out from matrix in resin solidification and foaming process, forms the island two phase structure physically.Thereby improve ultimate compression strength and the flexural strength of goods.
Ultimate title of the present invention is called " phenol formaldehyde foam " in the art.
Each component of the present invention effect in the present invention is respectively: can send out resol crosslinking reaction can take place at a certain temperature, form the needed crosslinking structure of phenol formaldehyde foam; Tensio-active agent plays a part to send out resol in foaming system and whipping agent mixes, and makes abscess regular, and evenly, minimizing is broken; Whipping agent can make phenol formaldehyde foam produce microvoid structure; Solidifying agent still can not sent out the crosslinked initiator of resol, and can also promote the whipping agent foaming because of the heat release of initiation reaction.
Preparation method of the present invention evenly stirs.
The present invention is owing to adopt technique scheme, waste rubber and resol fireproof heated board corner, waste and old material environmental pollution have not only been reduced, preparation resol fireproof heated board is to the consumption of the energy, intensity and the toughness of phenolic aldehyde heat preserving plate have also been improved, reduced its fragility, reduced industrial cost, be conducive to improve economic the effect, benefit satisfies the needs of skin construction (exterior wall heat-preserving system) simultaneously.
Embodiment
Following examples will give further instruction to the present invention, but not thereby limiting the invention.
Embodiment 1
Claim 10 parts in resol corner, waste and old material by quality, 10 parts in waste rubber powder, 100 parts of expandable phenolic resins, 6 parts of ethylene glycol (properties-correcting agent), 3 parts of H230 (tensio-active agent), 3 parts of Skellysolve As (whipping agent) mix, after stirring, add 14 parts of xylene monosulfonic acids again: sulfuric acid: boric acid is pressed 6: 2: 2 mixed solutions (solidifying agent) of mass ratio, and wherein solvent is 5: 1 water: ethanol, pour mould after the stirring into, get the resol fireproof heated board.Specific performance sees Table 1.
Embodiment 2
Claim 20 parts in resol corner, waste and old material by quality, 15 parts in waste rubber powder, 100 parts of expandable phenolic resins, 8 parts of ethylene glycol (properties-correcting agent), 4 parts of H230 (tensio-active agent), 4 parts of Skellysolve As (whipping agent) mix, after stirring, add 16 parts of xylene monosulfonic acids again: sulfuric acid: boric acid is pressed 6: 2: 2 mixed solutions (solidifying agent) of mass ratio, and wherein solvent is 5: 1 water: ethanol, pour mould after the stirring into, get the resol fireproof heated board.Specific performance sees Table 1.
Embodiment 3
Claim 20 parts in resol corner, waste and old material by quality, 20 parts in waste rubber powder, 100 parts of expandable phenolic resins, 10 parts of ethylene glycol (properties-correcting agent), 6 parts of H230 (tensio-active agent), 6 parts of Skellysolve As (whipping agent) mix, after stirring, add 16 parts of xylene monosulfonic acids again: sulfuric acid: boric acid is pressed 6: 2: 2 mixed solutions (solidifying agent) of mass ratio, and wherein solvent is 5: 1 water: ethanol, pour mould after the stirring into, get the resol fireproof heated board.Specific performance sees Table 1.
Embodiment 4
Claim 30 parts in resol corner, waste and old material by quality, 20 parts in waste rubber powder, 100 parts of expandable phenolic resins, 15 parts of ethylene glycol (properties-correcting agent), 8 parts of H230 (tensio-active agent), 8 parts of Skellysolve As (whipping agent) mix, after stirring, add 22 parts of xylene monosulfonic acids again: sulfuric acid: boric acid is pressed 6: 2: 2 mixed solutions (solidifying agent) of mass ratio, and wherein solvent is 5: 1 water: ethanol, pour mould after the stirring into, get the resol fireproof heated board.Specific performance sees Table 1.
Comparative example 1 does not add ethylene glycol (properties-correcting agent)
Claim 10 parts in resol corner, waste and old material by quality, 10 parts in waste rubber powder, 100 parts of expandable phenolic resins, 3 parts of H230 (tensio-active agent), 3 parts of Skellysolve As (whipping agent) mix, after stirring, add 14 parts of xylene monosulfonic acids again: sulfuric acid: boric acid is pressed 6: 2: 2 mixed solutions (solidifying agent) of mass ratio, wherein solvent is 5: 1 water: ethanol, pour mould after the stirring into, and get the resol fireproof heated board.Specific performance sees Table 1.
Comparative example 2 has changed the kind of solidifying agent
Claim 20 parts in resol corner, waste and old material by quality, 15 parts in waste rubber powder, 100 parts of expandable phenolic resins, 8 parts of ethylene glycol (properties-correcting agent), 4 parts of H230 (tensio-active agent), 4 parts of Skellysolve As (whipping agent) mix, after stirring, add 16 parts of xylene monosulfonic acids (solidifying agent) again, wherein solvent is 5: 1 water: ethanol, pour mould after the stirring into, get the resol fireproof heated board.Specific performance sees Table 1.
Comparative example 3 has changed the kind of tensio-active agent
Claim 20 parts in resol corner, waste and old material by quality, 20 parts in waste rubber powder, 100 parts of expandable phenolic resins, 10 parts of ethylene glycol (properties-correcting agent), 6 parts of H202 (tensio-active agent), 6 parts of Skellysolve As (whipping agent) mix, after stirring, add 16 parts of xylene monosulfonic acids again: sulfuric acid: boric acid is pressed 6: 2: 2 mixed solutions (solidifying agent) of mass ratio, and wherein solvent is 5: 1 water: ethanol, pour mould after the stirring into, get the resol fireproof heated board.Specific performance sees Table 1.
Comparative example 4 does not add properties-correcting agent waste rubber powder
Claim 30 parts in resol corner, waste and old material by quality, 100 parts of expandable phenolic resins, 15 parts of ethylene glycol (properties-correcting agent), 8 parts of H230 (tensio-active agent), 8 parts of Skellysolve As (whipping agent) mix, after stirring, add 22 parts of xylene monosulfonic acids again: sulfuric acid: boric acid is pressed 6: 2: 2 mixed solutions (solidifying agent) of mass ratio, wherein solvent is 5: 1 water: ethanol, pour mould after the stirring into, and get the resol fireproof heated board.Specific performance sees Table 1.
Table 1 is that the performance of embodiment and comparative example compares
Figure BDA0000138851970000071
Embodiment 1, embodiment 2, embodiment 3 all reaches national standard (seeing Table 2) with every performance of embodiment 4, and with industry in common resol fireproof heated board compare excellent performance.
In the comparative example 1, do not add ethylene glycol (properties-correcting agent), the result shows that each performance all has decline, some standard not up to standard, and outward appearance has warpage, and fold is arranged.In the comparative example 2, changed the kind of solidifying agent, each performance all has decline, and the outward appearance unfairness, and is unclean, and broken hole is arranged, and cracking is arranged.Comparative example 3 has changed the kind of tensio-active agent, and each performance all has decline, and outward appearance has fold, and broken hole is arranged, and cracking is arranged.Comparative example 4 does not add properties-correcting agent waste rubber powder, and each performance all has decline, and some standard, especially compressive strength not up to standard and flexural strength suppression ratio are bigger, and the outward appearance unfairness, and warpage is arranged, and fold is arranged, and broken hole is arranged.
The standard index of each performance of table 2
Figure BDA0000138851970000081

Claims (8)

1. the preparation method of a high energy-saving type modified environment-friendly phenolic fireproof insulating plate, it is characterized in that: with resol fireproof heated board corner, waste and old material, the waste rubber powder can be sent out resol, properties-correcting agent, tensio-active agent, whipping agent mixes, and after stirring, adds composite curing agent again, pour mould after the stirring into, get the resol fireproof heated board.
2. according to the preparation method of the described high energy-saving type modified environment-friendly of claim 1 phenolic fireproof insulating plate, it is characterized in that: described resol fireproof heated board corner, waste and old material, the waste rubber powder, can send out resol, properties-correcting agent, tensio-active agent, whipping agent, the mass fraction of these 7 kinds of material add-ons of composite curing agent is respectively: resol fireproof heated board corner, waste and old material 10-30 part, and waste rubber powder 10-20 part can be sent out 100 parts in resol, properties-correcting agent 6-15 part, tensio-active agent 3-8 part, whipping agent 3-8 part, composite curing agent 14-22 part.
3. according to the preparation method of the described high energy-saving type modified environment-friendly of claim 1 phenolic fireproof insulating plate, it is characterized in that: described to send out the resol preparation method as follows: by phenol/formaldehyde is added by 1mol: 1.8mol agitator is housed, in the four-hole boiling flask of thermometer and reflux condensing tube, start agitator and use heating in water bath, when question response liquid is 40 ℃, the NaOH aqueous solution with 20% is regulated between the pH value to 8, continue to be heated to 60 ℃ and kept one hour, heat up again and control and stopping heating behind the reaction 120min between 80 ℃~90 ℃, with cooling bath mixture is cooled under 70 ℃ rapidly, with acid for adjusting pH value to 6.8~7.2, decompression dehydration namely obtains sending out resol.
4. according to the preparation method of the described high energy-saving type modified environment-friendly of claim 1 phenolic fireproof insulating plate, it is characterized in that: described waste rubber powder source waste tire, its particle size range is 44-105 μ m.
5. according to the preparation method of the described high energy-saving type modified environment-friendly of claim 1 phenolic fireproof insulating plate, it is characterized in that: described properties-correcting agent is ethylene glycol.
6. according to the preparation method of the described high energy-saving type modified environment-friendly of claim 1 phenolic fireproof insulating plate, it is characterized in that: described tensio-active agent is silicone oil H230.
7. according to the preparation method of the described high energy-saving type modified environment-friendly of claim 1 phenolic fireproof insulating plate, it is characterized in that: described whipping agent is Skellysolve A.
8. according to the preparation method of the described high energy-saving type modified environment-friendly of claim 1 phenolic fireproof insulating plate, it is characterized in that: described composite curing agent is the combination of xylene monosulfonic acid, sulfuric acid, boric acid, and wherein solvent is water, ethanol combination.
CN2012100470510A 2012-02-28 2012-02-28 Preparation method of high energy-saving type modified environment-friendly phenolic fireproof insulation board Pending CN103289307A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105174822A (en) * 2015-08-18 2015-12-23 苏州赛斯德工程设备有限公司 Preparation method for self-insulation material used for exterior wall of building
CN106746898A (en) * 2016-12-12 2017-05-31 天津红光京建科技有限公司 A kind of novel heat insulation plate and its production method
CN108314465A (en) * 2016-04-19 2018-07-24 王维娜 A kind of energy-conserving thermal insulation board of high fire-retardance and preparation method thereof
CN109233539A (en) * 2018-10-17 2019-01-18 合肥隆扬环保科技有限公司 A kind of preparation method of external wall special-purpose thermal insulation coating
CN109280326A (en) * 2018-09-14 2019-01-29 营口象圆新材料工程技术有限公司 A kind of phenolic board and preparation method thereof that rock wool is modified

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CN101633225A (en) * 2009-08-07 2010-01-27 天津大学 Method for preparing composite board by waste thermosetting foamed plastics
CN101735552A (en) * 2010-01-07 2010-06-16 上海雅达特种涂料有限公司 Material for manufacturing modified phenolic fireproof insulating plate

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CN101735552A (en) * 2010-01-07 2010-06-16 上海雅达特种涂料有限公司 Material for manufacturing modified phenolic fireproof insulating plate

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105174822A (en) * 2015-08-18 2015-12-23 苏州赛斯德工程设备有限公司 Preparation method for self-insulation material used for exterior wall of building
CN108314465A (en) * 2016-04-19 2018-07-24 王维娜 A kind of energy-conserving thermal insulation board of high fire-retardance and preparation method thereof
CN108314465B (en) * 2016-04-19 2020-07-10 山东基舜节能建材有限公司 High-flame-retardance energy-saving insulation board and preparation method thereof
CN106746898A (en) * 2016-12-12 2017-05-31 天津红光京建科技有限公司 A kind of novel heat insulation plate and its production method
CN109280326A (en) * 2018-09-14 2019-01-29 营口象圆新材料工程技术有限公司 A kind of phenolic board and preparation method thereof that rock wool is modified
CN109233539A (en) * 2018-10-17 2019-01-18 合肥隆扬环保科技有限公司 A kind of preparation method of external wall special-purpose thermal insulation coating

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Application publication date: 20130911