CN1834152A - 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 PDFInfo
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- CN1834152A CN1834152A CN 200610024902 CN200610024902A CN1834152A CN 1834152 A CN1834152 A CN 1834152A CN 200610024902 CN200610024902 CN 200610024902 CN 200610024902 A CN200610024902 A CN 200610024902A CN 1834152 A CN1834152 A CN 1834152A
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Abstract
This invention relates to a method to produce phenolic foam heat preserving materials by ordinary-temperature foaming, is which phenol formaldehyde is adopted as raw materials and anhydrous polyethylene oxide sorbitan mono-oleate, aluminium hydroxide, pentane and composite acid curing agent are added. It has the characteristics that auxiliary agents and reinforcing modifiers can be also added in the raw materials; the ingredients added into the phenol formaldehyde raw materials have proportions as follows: 4~8 shares of polyethylene oxide sorbitan mono-oleate, 0.1~20 shares of auxiliary agents, 0.5~25 shares of reinforcing modifiers, 0~80 shares of aluminium hydroxide, 6~20 shares of pentane and 8~20 shares of composite acid curing agent, counting in 100 mass shares of phenol formaldehyde. In this invention, ordinar-temperature preparation of phenolic foam heat preserving materials above 0 deg. C can be realized. The phenolic foam heat preserving materials prepared have excellent properties; they help save energy and can be applied in spot construction, and therefore, they are promising materials.
Description
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 (4)
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.
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 auxiliary agent is chosen a kind of in aluminium powder, zinc powder, aluminum chloride, iron(ic) chloride, flyash or Vanadium Pentoxide in FLAKES.
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 plasticized modifier is chosen a kind of in ethylene glycol, polyoxyethylene glycol, active polyether, paracril or polyvinyl chloride.
4. 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.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2006100249024A CN100341929C (en) | 2006-03-21 | 2006-03-21 | Method of preparing phenolic foam insulation material via foaming at normal temp |
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| CNB2006100249024A CN100341929C (en) | 2006-03-21 | 2006-03-21 | Method of preparing phenolic foam insulation material via foaming at normal temp |
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| CN1834152A true CN1834152A (en) | 2006-09-20 |
| CN100341929C CN100341929C (en) | 2007-10-10 |
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Cited By (9)
| 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 |
| CN103450630A (en) * | 2013-08-09 | 2013-12-18 | 江苏德明新材料有限公司 | Preparation method of environment-friendly phenol aldehyde-inorganic composite heat insulating material |
| CN103952055A (en) * | 2014-04-23 | 2014-07-30 | 苏州羽帆新材料科技有限公司 | Antifreeze and insulated coating and preparation method thereof |
| CN104194254A (en) * | 2014-08-28 | 2014-12-10 | 苏志刚 | Curing agent for phenol formaldehyde foamed resins and synthesis 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 |
| CN106433016A (en) * | 2016-08-30 | 2017-02-22 | 江苏德明新材料有限公司 | Modified reinforced heat insulation and sound insulation phenolic foam plate and production method thereof |
| 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 |
Family Cites Families (1)
| 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 |
-
2006
- 2006-03-21 CN CNB2006100249024A patent/CN100341929C/en not_active Expired - Fee Related
Cited By (12)
| 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 |
| CN103450630A (en) * | 2013-08-09 | 2013-12-18 | 江苏德明新材料有限公司 | Preparation method of environment-friendly phenol aldehyde-inorganic composite heat insulating material |
| 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 |
| CN103952055A (en) * | 2014-04-23 | 2014-07-30 | 苏州羽帆新材料科技有限公司 | Antifreeze and insulated coating and preparation method thereof |
| CN104194254A (en) * | 2014-08-28 | 2014-12-10 | 苏志刚 | Curing agent for phenol formaldehyde foamed resins and synthesis 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 |
| CN106433016A (en) * | 2016-08-30 | 2017-02-22 | 江苏德明新材料有限公司 | Modified reinforced heat insulation and sound insulation phenolic foam plate and production 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 |
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| CN100341929C (en) | 2007-10-10 |
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Owner name: SHANGHAI SHENGXING RESIN COATING CO., LTD.; APPLI Free format text: FORMER OWNER: SHANGHAI SHENGXING RESIN COATING CO., LTD. Effective date: 20061103 |
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Effective date of registration: 20061103 Address after: 200124 Shanghai City Sanxin Pudong New Area Sanlin Town Road No. 888 Applicant after: Shanghai Shengxing Resin & Paint Co., Ltd. Co-applicant after: Shanghai Institute of Technology Address before: 200124 Shanghai City Sanxin Pudong New Area Sanlin Town Road No. 888 Applicant before: Shanghai Shengxing Resin & Paint Co., Ltd. |
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