CN100341929C - Method of preparing phenolic foam insulation material via foaming at normal temp - Google Patents

Method of preparing phenolic foam insulation material via foaming at normal temp Download PDF

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Publication number
CN100341929C
CN100341929C CNB2006100249024A CN200610024902A CN100341929C CN 100341929 C CN100341929 C CN 100341929C CN B2006100249024 A CNB2006100249024 A CN B2006100249024A CN 200610024902 A CN200610024902 A CN 200610024902A CN 100341929 C CN100341929 C CN 100341929C
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China
Prior art keywords
parts
foaming
weight
raw
phenolic foam
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Expired - Fee Related
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CNB2006100249024A
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CN1834152A (en
Inventor
黄剑清
王琪生
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Shanghai Shengxing Resin & Paint Co., Ltd.
Shanghai Institute of Technology
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Shanghai Shengxing Resin & Paint Co Ltd
Shanghai Institute of Technology
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Publication of CN100341929C publication Critical patent/CN100341929C/en
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Abstract

The present invention relates to a method for preparing a phenolic foam heat insulating material by foaming at normal temperature. Phenolic resin (A) is adopted as a raw material, and 4 to 8 parts by weight of dehydrated sorbitol oleate polyoxyethylene ether, 0 to 80 parts by weight of aluminum hydroxide, 6 to 20 parts by weight of pentane and 8 to 20 parts by weight of mixed acid solidifying agent are added into the raw material. The present invention is characterized in that 0.1 to 20 parts by weight of auxiliary agent which can react with acid, and 0.5 to 25 parts by weight of toughening modifying agent are also added to the raw material, and the proportion of the added components in the phenolic resin (A) raw material is measured by 100 parts by weight of phenolic resin (A). The present invention prepares the phenolic foam heat-insulating material by foaming at normal temperature. The phenolic foam heat-insulating material prepared by the method of the present invention has the advantages of excellent performance and energy source saving. The phenolic foam heat-insulating material can be applied to site operation, and has a wide application prospect.

Description

A kind of method of preparing phenolic foam insulation material via foaming at normal temp
One, technical field:
The present invention relates to a kind of method of preparing phenolic foam insulation material via foaming at normal temp, be intended to resole not carried out under the situation of modification, realize the preparing phenolic foam insulation material via foaming at normal temp more than 0 ℃.
Two, background technology:
Phenol formaldehyde foam is because thermal conductivity is low by (0.018~0.032W/mk), compare traditional lagging material such as mineral wool, rock wool, glass wool etc. (0.034~0.043W/mk), its energy-saving heat preserving performance improves nearly one times, suitable with urethane (PU) foam, be better than polystyrene (PS) foam, the energy-saving heat preserving performance occupy first of all lagging materials, it has characteristics such as the unexistent difficult combustion of organic insulation materials such as PU, PS, low cigarette, low toxicity again simultaneously, so phenolic aldehyde foam thermal insulation material is greatly developed since the nineties.At first they are subjected to the attention of the state militaries such as Great Britain and America, be applied to space flight and aviation, defence and military field, be applied to the place of fire protection requirement strictnesses such as civilian aircraft, boats and ships, station, oil well afterwards again, and progressively pushed fields such as covil construction, factory building, warehouse, hospital, school, exhibition center, Sports facilities, movable dwellings to.
The preparation phenolic aldehyde foam thermal insulation material uses resole to be main raw material usually, and its component known and that generally use is: resole, tensio-active agent (as tween-80), filler (as aluminium hydroxide), whipping agent (as pentane), solidifying agent (various mineral acids or organic acid).Because of the resole foamed solidification need absorb heat, usually manufacturing condition: 60~100 ℃ of controlled temperature, set time 30~120min, need to consume a large amount of heat energy thus.On the other hand because the resole foaming needs heating and long set time; therefore phenolic aldehyde foam thermal insulation material must be used the die casting foaming in advance in factory; this makes phenolic aldehyde foam thermal insulation material can't use in some occasion; as complexity or small space, various valve elbow, large-scale spherical tank, roof etc., then can't molding or the molding cost too high.In the case, people begin to develop the foaming at normal temp technology that is applicable to the cast-in-site foaming.
The resole reactive behavior of existing foaming usefulness is poor, can only be activated under higher temperature, and the polycondensation crosslinking reaction takes place.Therefore at present people's research focus on resole is carried out modification, improve the reactive behavior of resole with the method that increases methylol group content in the resin, thereby realize foaming at normal temp.But also produced new problem thus: the 1. active raising of resin, greatly reduce package stability, generally can only deposit for 1~2 week.2. resin branching is serious, has increased the fragility of product, has reduced the usability of product.3. resin viscosity is too high, makes the production operation difficulty, and the foam hole size differs, and influences attractive in appearance and thermal conductivity.Someone attempts adding aluminium hydroxide, pentane, nitration mixture solidifying agent and produces phenolic aldehyde foam thermal insulation material, but fall flat goes for well behaved product, is still waiting perfect.
So the preparing phenolic foam insulation material via foaming at normal temp technology is the problem that remains further research and solve.
Three, summary of the invention:
The object of the present invention is to provide a kind of need not that resole is carried out modification, can be in the production technology that realizes foaming at normal temp more than 0 ℃.Its meaning: 1. avoided the problem that occurs because of the modification resole; 2. production technique is simple, easy to operate; 3. expanded the use face of phenolic aldehyde foam thermal insulation material; 4. excellent product performance.
The present invention is achieved in that a kind of method of preparing phenolic foam insulation material via foaming at normal temp, adopting resole is that raw material adds sorbitan monooleate Soxylat A 25-7, aluminium hydroxide, pentane and nitration mixture solidifying agent, it is characterized in that: also add in the raw material can with the auxiliary agent and the plasticized modifier of acid-respons; The component proportioning that adds each material in the resole raw material is counted with 100 weight part resoles: 4~8 parts of sorbitan monooleate Soxylat A 25-7s, 0.1~20 part of auxiliary agent, 0.5~25 part of plasticized modifier, 0~80 part in aluminium hydroxide, 6~20 parts of pentanes, 8~20 parts in nitration mixture solidifying agent.Described auxiliary agent is chosen a kind of in aluminium powder, zinc powder, aluminum chloride, iron(ic) chloride, flyash or Vanadium Pentoxide in FLAKES.Described plasticized modifier is chosen a kind of in ethylene glycol, polyoxyethylene glycol, active polyether, paracril or polyvinyl chloride.Described nitration mixture solidifying agent is that weight part is the mixture of 20 parts of sulfuric acid, 25 parts of phosphoric acid, 15 parts of tosic acid and 40 parts of water.
The present invention has chosen the auxiliary agent that can carry out deferred reaction with the nitration mixture solidifying agent and produce more heat transfer.Experiment shows, makes auxiliary agent as direct employing alkali, acid-base neutralisation then, and speed of response is too fast, causing foaming and solidifying to carry out synchronously, and therefore selecting proper auxiliary agent for use is key of the present invention.
The present invention carries out deferred reaction by adding 0.10~20% aluminium powder, zinc powder, aluminum chloride, iron(ic) chloride, flyash, Vanadium Pentoxide in FLAKES etc. with the nitration mixture solidifying agent, foaming institute heat requirement is provided, realize foaming and curing synchronously, thereby make preparing phenolic foam insulation material via foaming at normal temp become possibility.
Simultaneously because the state of cure of foaming at normal temp is thorough inadequately, and As time goes on, the polycondensation crosslinking reaction still can slowly be carried out, cause it to become fragile gradually and cracking phenomena occurs, this is the problem that foaming at normal temp faces.If in system, introduce the macromole of band active group, utilize the hydroxyl of its active group and resol to react, thereby play the toughening modifying effect, as:
1. the hydroxyl of the hydroxyl of polyoxyethylene glycol and resol forms hydrogen bond:
2. the hydroxyl dehydration reaction of the hydroxyl of polyoxyethylene glycol and resol:
3. in the active polyether-hydroxyl reaction of NCO and resol:
The present invention by add 0.5~25% plasticized modifier as: ethylene glycol, polyoxyethylene glycol, active polyether, paracril, polyvinyl chloride etc. have overcome foaming at normal temp phenolic aldehyde foam thermal insulation material defective easy to crack.
Four, embodiment:
Component proportioning of the present invention is counted with 100 weight part resoles:
4~8 parts of sorbitan monooleate Soxylat A 25-7s (tween-80),
0.1~20 part of auxiliary agent,
0.5~25 part of plasticized modifier,
0~80 part in aluminium hydroxide,
6~20 parts of pentanes,
8~20 parts in nitration mixture solidifying agent.
Described auxiliary agent is a kind of in aluminium powder, zinc powder, aluminum chloride, iron(ic) chloride, flyash or the Vanadium Pentoxide in FLAKES etc.
Described plasticized modifier is a kind of in ethylene glycol, polyoxyethylene glycol, active polyether, paracril or the polyvinyl chloride etc.
Described nitration mixture solidifying agent is formed and weight part is the mixture of 20 parts of sulfuric acid and 25 parts of phosphoric acid and 15 parts of tosic acid and 40 parts of water.
Above-mentioned component is added mixing kettle successively, and high-speed stirring 15~60 seconds is poured in the mould, closed die, and in foamed solidification more than 0 ℃ 0.5~3 hour, the demoulding.According to mold shape, send the material of respective shapes; According to mold thickness, send the material of respective thickness; According to mould volume size, add corresponding compound, send the material of corresponding density.Also compound can be injected complexity or small space foaming at normal temp, play the effect of filling and being incubated; Or utilize spraying equipment with compound directly spray to equably need insulation such as places such as roof, metope, large-size spherical tank surfaces, the normal temperature natural foaming forms thermal insulation layer.
Main performance index:
Apparent density (kg/m 3) 30~120,
Thermal conductivity (w/mk) 0.020~0.041,
The difficult combustion of combustionproperty B1 level,
Smoke density (%)≤5,
Oxygen index (%) 〉=45,
Compressive strength (Mpa) 〉=0.10,
Dimensional stability (%)≤2,
Use temperature (℃)-190~+ 150.
The invention will be further described with three embodiment below.
Embodiment 1:
With 4500g resole, 180g sorbitan monooleate Soxylat A 25-7, trade name tween-80,40g aluminium powder, 1000g aluminium hydroxide, 200g active polyether, 540g pentane and 675g nitration mixture solidifying agent add mixing kettle successively, high-speed stirring 15 seconds, also equal fast equal portions are poured 100 pairs of 0.06m into 3Template die or pipe die in, closed die solidified 3 hours in 0 ℃ of following foaming at normal temp, the demoulding, density be 100kg/m 3About phenolic aldehyde foam thermal insulation material.
Embodiment 2:
20kg resole, 1kg tween-80,4kg flyash, 2kg paracril, 2.5kg pentane and 2.5kg nitration mixture solidifying agent are added mixing kettle successively, and high-speed stirring 40 seconds is poured 1.5m into 3Opening box in, solidified 4 hours in 10 ℃ of following normal temperature natural foamings, density be 30kg/m 3About phenolic aldehyde foam thermal insulation material, cut into the material of all size shape as required.
Embodiment 3:
10kg resole, 0.8kg tween-80,0.5kg iron(ic) chloride, 5kg aluminium hydroxide, 1.5kg polyoxyethylene glycol, 2kg pentane and 2kg nitration mixture solidifying agent are added mixing kettle successively, high-speed stirring 60 seconds directly sprays to 70m with spraying equipment equably with compound 2On the roof, solidify, form the thick thermal insulation layer of 3~5cm in 20 ℃ of following normal temperature natural foamings.

Claims (3)

1. the method for a preparing phenolic foam insulation material via foaming at normal temp, adopting resole is that raw material adds sorbitan monooleate Soxylat A 25-7, aluminium hydroxide, pentane and nitration mixture solidifying agent, it is characterized in that: also add in the raw material can with the auxiliary agent and the plasticized modifier of acid-respons;
The component proportioning that adds each material in the resole raw material is counted with 100 weight part resoles:
4~8 parts of sorbitan monooleate Soxylat A 25-7s,
0.1~20 part of auxiliary agent,
0.5~25 part of plasticized modifier,
0~80 part in aluminium hydroxide,
6~20 parts of pentanes,
8~20 parts in nitration mixture solidifying agent;
Described auxiliary agent is chosen a kind of in aluminium powder, zinc powder, aluminum chloride, iron(ic) chloride, flyash or Vanadium Pentoxide in FLAKES.
2. the method for a kind of preparing phenolic foam insulation material via foaming at normal temp according to claim 1, it is characterized in that: described plasticized modifier is chosen a kind of in ethylene glycol, polyoxyethylene glycol, active polyether, paracril or polyvinyl chloride.
3. the method for a kind of preparing phenolic foam insulation material via foaming at normal temp according to claim 1, it is characterized in that: described nitration mixture solidifying agent is that weight part is the mixture of 20 parts of sulfuric acid, 25 parts of phosphoric acid, 15 parts of tosic acid and 40 parts of water.
CNB2006100249024A 2006-03-21 2006-03-21 Method of preparing phenolic foam insulation material via foaming at normal temp Expired - Fee Related CN100341929C (en)

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CN100341929C true CN100341929C (en) 2007-10-10

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Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102268172A (en) * 2010-08-25 2011-12-07 田瑞军 Rigid spray phenolic foam
CN102775724A (en) * 2012-06-13 2012-11-14 南京航空航天大学 Honeycomb-reinforced phenolic foam material and preparation method thereof
CN103450630B (en) * 2013-08-09 2016-05-25 江苏德明新材料有限公司 A kind of preparation method of environment-friendly type phenolic aldehyde-inorganic composite heat-insulating material
CN103952055B (en) * 2014-04-23 2017-02-22 东莞市德莱得涂料有限公司 Antifreeze and insulated coating and preparation method thereof
CN104194254B (en) * 2014-08-28 2016-02-24 苏志刚 Phenolic foam resin solidifying agent and synthetic method thereof
CN106009493A (en) * 2016-08-01 2016-10-12 合肥广能新材料科技有限公司 Phenolic foam external wall thermal insulation material and preparation method thereof
CN106433016B (en) * 2016-08-30 2020-08-14 南通中保节能科技有限公司 Preparation method of modified enhanced heat-preservation sound-insulation phenolic foam board
CN106883550A (en) * 2017-02-22 2017-06-23 广西芮芽科技有限公司 The preparation method of phenolic foam material
CN106928645A (en) * 2017-02-22 2017-07-07 广西芮芽科技有限公司 The preparation method of the phenolic foam material with heat insulating ability high

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1609128A (en) * 2003-10-25 2005-04-27 江伟 Foamed phenolic material and its prepn process

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1609128A (en) * 2003-10-25 2005-04-27 江伟 Foamed phenolic material and its prepn process

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