CN103467689A - B-grade high-flame-retardancy heat-insulating plant-oil-based polyurethane material as well as preparation method and application thereof - Google Patents
B-grade high-flame-retardancy heat-insulating plant-oil-based polyurethane material as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN103467689A CN103467689A CN201310371374XA CN201310371374A CN103467689A CN 103467689 A CN103467689 A CN 103467689A CN 201310371374X A CN201310371374X A CN 201310371374XA CN 201310371374 A CN201310371374 A CN 201310371374A CN 103467689 A CN103467689 A CN 103467689A
- Authority
- CN
- China
- Prior art keywords
- vegetable oil
- based polyurethane
- flame
- retardant
- highly effective
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to the technical field of flame-retardant polyurethane materials, in particular to a B-grade high-flame-retardancy heat-insulating plant-oil-based polyurethane material as well as a preparation method and application thereof. The composite polyether of the heat-insulating plant-oil-based polyurethane material comprises the following components in percentage by weight: 50-88% of recycled plant oil-based polyether polyol containing an Si, P and N intrinsic structure, 0-16% of universal hard-foam polyether polyol or polyester polyol, 0-10% of nitrogenous flame retardant, 10-30% of physical foaming agent, 1.0-2.0% of catalyst, 0.5-2.5% of foam stabilizer and 0.5-2% of water. The heat-insulating plant-oil-based polyurethane material can serve as an external heat-insulating material for building an exterior wall and can also be applicable to the fields of refrigeration industry, hot water pipes, solar water heaters, grain depots and the like. Through the adoption of the scheme, the heat-insulating plant-oil-based polyurethane material is obtained. The heat-insulating plant-oil-based polyurethane material has the advantages that the hydroxyl value is 400-500 mgKOH/g, the viscosity is 1500-3500 mPas/25 DEG C, the flame retardancy is high, no halogen exists, the cost-performance ratio is high, and the flame retardancy can meet the B-grade technical requirement comprehensively after being tested by Szechwan fire department, Ministry of Public Security.
Description
Technical field
The present invention relates to polyurethane flame-proof material technology field, be specifically related to a kind of B level highly effective flame-retardant vegetable oil based polyurethane lagging material and preparation method thereof and purposes.
Background technology
Polyurethane heat insulation material has that thermal conductivity is low, good heat insulating, mechanics, waterproof, the excellent property characteristics such as durable, has again the advantages such as product form is various, easy construction, is a kind of organic insulation material of high comprehensive performance.In fields such as refrigeration (refrigerator, refrigerator-freezer, freight container), building, hot water pipeline, solar water heater, grain depots, be used widely thus.But without flame-retardant modified polyurethane heat insulation material, be a kind of combustible matl, the burning grade is only inflammable D level (standard GB/T 8624-2006 " material of construction and goods classification system for fire performance " is divided into material by combustionproperty: A1 level, A2 level, B level, C level, D level, E level, 7 grades of F level).
The polyurethane heat insulation material flame-retarded technology mainly contains two kinds at present: a kind of is to add fire retardant, and fire retardant commonly used is the fire retardants such as phosphoric acid ester, halogenated phosphate, aluminium hydroxide, hydrowax, ammonium polyphosphate and expanded graphite.The additive flame combustion technology has following shortcoming: (1) Material Physics mechanical property descends, and (2) flame retardant effect extends in time and reduces, and (3) are added the solid flame retardant manufacture and are restricted.Spraying and sheet material continuous production processes are difficult to realize.Another kind is the structure-type flame-retarded technology, is about to ignition-proof element and brings in the polyether glycol molecular structure.The principal item of existing market supply has containing P, N and halogen (Cl and Br) flame retardant polyether polyol, and makes thus structure-type flame retardant polyurethane lagging material.There is following shortcoming in this kind of polyurethane heat insulation material: (1) flame retardant effect is poor.The polyether glycol flame retardant effect of existing market supply is generally all poor, reaches the fire-retardant requirement of B level and need add two kinds of flame retarding polyethers.(2) price is high.The flame retardant polyether polyol price of existing market supply is all higher, and especially the flame retarding polyether price of transnational company's supply is higher.(3) halogen-containing.Reach the fire-retardant requirement of B level, generally need to adopt containing the Br flame retardant polyether polyol, contain HBr in combustion gas thus, bring the major defect that toxicity is large, smog is large.
For above-mentioned reasons, the general price of polyurethane heat insulation material that reaches difficult combustion B level is all higher, and this has affected polyurethane heat insulation material applying in building field to a great extent.
As everyone knows, China has been the maximum construction market in the whole world, but building energy consumption is large, accounts for whole society's energy consumption 30%.Building energy conservation has become the state basic policy that country adheres to for a long time.Country is in the urgent need to insulation and the flame retardant properties excellent lagging material of holding concurrently.Polyurethane material is the lagging material of high comprehensive performance, and in American-European building heat preservation, utility ratio reaches more than 50%, and in China at present still less than 10%.Its one of the main reasons is that construction market lacks insulation and the double excellent high-quality lagging material of flame retardant properties.
Summary of the invention
The present invention is in order to solve the problems of the technologies described above the shortcoming of middle existence, and a kind of Halogen, cost performance is good, flame retardant properties reaches the technical requirements of B level comprehensively vegetable oil based polyurethane lagging material and preparation method thereof and purposes are provided.
The technical scheme solved the problems of the technologies described above is as follows:
A kind of combined polyether of B level highly effective flame-retardant vegetable oil based polyurethane lagging material comprises the component of following weight percentage ratio:
Further, describedly reclaim vegetable oil-based polyether polyol containing Si, P, N intrinsic junction configuration and made by following steps:
(1) take vegetables oil as raw material, by purifying, epoxidation, hydroxylating, make vegetable oil-based polyether polyol;
(2) after being reacted under the effect of olefin oxide, γ ?glycidoxy Trimethoxy silane γ ?(. epoxy the third oxygen) propyl trimethoxy silicane (GPTMS) and phosphoric acid obtains Si, P and N hydridization polyvalent alcohol;
(3) Si, the P that vegetable oil-based polyether polyol step (1) obtained makes with step (2) and N hydridization polyvalent alcohol react with olefin oxide can make containing Si, P, N intrinsic junction configuration and reclaim vegetable oil-based polyether polyol under the effect of catalyzer.
Further, described pneumatogen is any one or a few mixture of HCFC-141b, HFC-245, pentamethylene.
The mixture of any one or a few of triethylene diamine solution (A-33), pentamethyl-triethylene diamine (PC-5) and the dimethylcyclohexylamine (PC-8) that further, described catalyzer is 33%.
A kind of preparation method of B level highly effective flame-retardant vegetable oil based polyurethane lagging material, it is according to mass ratio, to be that 1:1～1:1.5 makes by the combined polyether of above-mentioned B level highly effective flame-retardant vegetable oil based polyurethane lagging material and isocyanic ester, and this technique comprises the foaming of (comprising bare board, aluminium sheet, color steel, stone material and inorganic plate etc.) of spraying, cast and various sheet material.
A kind of B level highly effective flame-retardant vegetable oil based polyurethane lagging material as above can be used for the external wall heat insulating material for external, the B level polyurethane heat insulation material that its cost performance is better than supplying in the market.
A kind of B level highly effective flame-retardant vegetable oil based polyurethane lagging material as above also can be used for the fields such as refrigeration industry (refrigerator, refrigerator-freezer, freight container), hot-water line, solar water heater, grain depot.
A kind of B level highly effective flame-retardant vegetable oil based polyurethane lagging material as above also can be made into C level polyurethane heat insulation material.
A kind of B level highly effective flame-retardant vegetable oil based polyurethane lagging material as above and inorganic heat insulation material are compound, can make and not fire A level polyurethane composite thermal insulation material.
Adopted such scheme, a kind of B level highly effective flame-retardant vegetable oil based polyurethane lagging material that the refiltered oil of take is made as base and preparation method thereof and purposes.The final index of this lagging material: hydroxyl value is 400-500mgKOH/g, and viscosity is 1500-3500mPas/25 ℃, and flame retardant properties is good, Halogen, and cost performance is good, through Ministry of Public Security's Sichuan fire house, detects, and flame retardant properties reaches the technical requirements of B level comprehensively.
Embodiment
Below in conjunction with embodiment, the present invention is further detailed explanation.
Embodiment 1:
1, the 900g sewer oil reclaims vegetables oil (zero pour≤30 ℃, this example is 26 ℃) add in the 2L glass reactor, add 100g formic acid (30%), be warming up to 60 ℃, drip 600g hydrogen peroxide (30%), within two hours, drip off, be warming up to 80 ℃ after dripping off, insulation 2h, add 30% aqueous sodium carbonate 60g, pH is controlled at 5-7, standing, remove lower clear liquid, add 200g water, be warming up to 80 ℃, insulation 2h, vacuum hydro-extraction to moisture is less than 0.1%, now tests hydroxyl value >=165mgKOH/g, test value is 168.65mgKOH/g, and this is Q-1.
2, γ-glycidoxy Trimethoxy silane γ-(. epoxy the third oxygen) propyl trimethoxy silicane (GPTMS) and phosphoric acid (85%) add in there-necked flask according to weight ratio 82:18, be warming up to 120 ℃ of condensations, vacuum hydro-extraction 3h, sampling detecting acid number≤0.5mgKOH/g, sampling 1000g pours in autoclave, vacuum displacement three times, be warming up to 130 ℃, add 50g oxyethane, aging 1h, vacuum 1h, obtain Si, P and N hydridization polyvalent alcohol Z-1, viscosity 1240mPas/25 ℃, range of viscosities is 1100-1600mPas/25 ℃, actual test: viscosity 1240mPas/25 ℃.
3,400gQ-1 and 400gZ-1 are dropped in autoclave, add the 20gKOH aqueous solution (45.54%), twice of vacuum displacement, dehydration heats up, 120 ℃ of bulging nitrogen dehydration 4h, testing moisture≤0.05%, close vacuum, start to drip propylene oxide 2400g, dropping temperature is 115-125 ℃, dropwises rear insulation 1h, vacuum outgas 1h during 120 ℃ of temperature, obtain highly effective flame-retardant vegetable oil-based polyether polyol MA-4040-1, sampling and testing hydroxyl value: 446.98mgKOH/g, viscosity: 2600mPas/25 ℃.
4, by the above-mentioned highly effective flame-retardant vegetable oil-based polyether polyol of 60.5g MA-4040-1, the general rigid-foam polyether polyol of 10g or polyester polyol, 10g is containing nitrogen combustion inhibitor, 14gHCFC-141b, 2g A-33,2.5g foam stabilizer and 1g water join in reactor, control rotating speed at 400rpm, stirring at normal temperature 1.5h, blowing obtains a kind of combined polyether of B level highly effective flame-retardant vegetable oil based polyurethane lagging material.
5, getting 1 part of combined polyether that above-mentioned steps 4 obtains carries out spraying coating process with 1.4 parts of isocyanic ester by the low pressure spraying machine and can obtain polyurethane heat insulation material.
Embodiment 2:
1, (zero pour is at 16 ℃ to 30 ℃ for 900g recovery vegetables oil, this example is 22 ℃) add in the 2L glass reactor, add 100g formic acid (30%), be warming up to 60 ℃, drip 650g hydrogen peroxide (30%), within two hours, drip off, be warming up to 80 ℃ after dripping off, insulation 2h, add 30% aqueous sodium carbonate 60g, pH is controlled at 5-7, standing, removes lower clear liquid, add 200g water, be warming up to 80 ℃, insulation 2h, vacuum hydro-extraction, moisture is less than 0.1%, test hydroxyl value 140-190mgKOH/g, test value is 175mgKOH/g, this is Q-2.
2, GPTMS and phosphoric acid (85%) add in there-necked flask according to weight ratio 80:20, be warming up to 120 ℃ of condensations, vacuum hydro-extraction 3h, sampling detecting acid number≤0.5mgKOH/g, sampling 1000g pours in autoclave, vacuum displacement three times, be warming up to 130 ℃, adds 50g oxyethane, aging 1h, vacuum 1h, obtain Si, P and N hydridization polyvalent alcohol Z-2, viscosity 1300mPas/25 ℃.
3,400gQ-2 and 800gZ-2 are dropped in autoclave, add the 20gKOH aqueous solution (45.54%), twice of vacuum displacement, dehydration heats up, 130 ℃ of bulging nitrogen dehydration 4h, testing moisture≤0.05%, close vacuum, start to drip the mixture 1800g of propylene oxide and oxyethane, dropping temperature is 115-125 ℃, after dropwising, insulation 1h, vacuum outgas 1h during 120 ℃ of temperature, sampling and testing hydroxyl value: 452.74mgKOH/g, viscosity: 2720mPas/25 ℃, obtain highly effective flame-retardant vegetable oil-based polyether polyol MA-4040-2.
4, by the above-mentioned highly effective flame-retardant vegetable oil-based polyether polyol of 75g MA-4040-2, the general rigid-foam polyether polyol of 5g or polyester polyol, 5g is containing nitrogen combustion inhibitor, 5g pentamethylene, 5g HFC-245,1g PC-5,1g PC-8,1.8g foam stabilizer and 1.2g water join in reactor, control rotating speed at 400rpm, stirring at normal temperature 1.5h, blowing obtains a kind of combined polyether of B level highly effective flame-retardant vegetable oil based polyurethane lagging material.
5, get the foaming that 1.5 parts of 1 part of combined polyether that above-mentioned steps 4 obtains and isocyanic ester carry out two-sided aluminium sheet on panel production line continuously and can obtain polyurethane heat insulation material.
Embodiment 3:
1,900g plam oil (zero pour≤30 ℃, this example is 28 ℃) add in the 2L glass reactor, add 100g formic acid (30%), be warming up to 60 ℃, drip 580g hydrogen peroxide (30%), within two hours, drip off, be warming up to 80 ℃ after dripping off, insulation 2h, add 30% aqueous sodium carbonate 60g, pH is controlled at 5-7, standing, removes lower clear liquid, add 200g water, be warming up to 80 ℃, insulation 2h, vacuum hydro-extraction, moisture is less than 0.1%, test hydroxyl value 140-190mgKOH/g, test value is 152.43mgKOH/g, this is Q-3.
2, GPTMS and phosphoric acid (85%) add in there-necked flask according to weight ratio 71:29, be warming up to 120 ℃ of condensations, vacuum hydro-extraction 3h, sampling detecting acid number≤0.5mgKOH/g, sampling 1000g pours in autoclave, vacuum displacement three times, be warming up to 130 ℃, adds the mixture of 50g propylene oxide and propylene oxide, aging 1h, vacuum 1h, obtain Si, P and N hydridization polyvalent alcohol Z-3, viscosity 1500mPas/25 ℃.
3,400gQ-3 and 400gZ-3 are dropped in autoclave, add the 20gKOH aqueous solution (45.54%), twice of vacuum displacement, heat up and dewater, 125 ℃ of bulging nitrogen dehydration 4h, testing moisture≤0.05%, close vacuum, start to drip oxyethane 4800g, dropping temperature is the 115-125 degree, dropwises rear insulation 1h, vacuum outgas 1h during 120 ℃ of temperature, obtain highly effective flame-retardant vegetable oil-based polyether polyol MA-4040-3, test result is: 442mgKOH/g, viscosity: 2345mPas/25 ℃.
4, by the above-mentioned highly effective flame-retardant vegetable oil-based polyether polyol of 59g MA-4040-3, the general rigid-foam polyether polyol of 16g or polyester polyol, 10g HFC-245,10gHCFC-141b, 1g A-33,0.5g PC-5,2.5g foam stabilizer and 1g water join in reactor, control rotating speed at 400rpm, stirring at normal temperature 1.5h, blowing obtains a kind of combined polyether of B level highly effective flame-retardant vegetable oil based polyurethane lagging material.
5, get the foaming that 1 part of 1 part of combined polyether that above-mentioned steps 4 obtains and isocyanic ester carry out two-sided stone material on panel production line continuously and can obtain polyurethane heat insulation material.
Following MA-4110 is common rigid-foam polyether polyol, without flame retardant effect.
One, below, be by the foaming result of above-mentioned highly effective flame-retardant vegetable oil-based polyether polyol:
| 1 | 2 | 3 | 4 | |
| MA-4110 | 100 | |||
| MA-4040-1 | 90 | |||
| MA-4040-2 | 90 | |||
| MA-4040-3 | 90 | |||
| Containing nitrogen combustion inhibitor | 10 | 10 | 10 | |
| Catalyzer | 1.5 | 1.5 | 1.5 | 1.5 |
| Silicone oil | 2.0 | 2.0 | 2.0 | 2.0 |
| Whipping agent | 15 | 15 | 15 | 15 |
| Water | 1.3 | 1.3 | 1.3 | 1.3 |
| The MDI index | 1.4 | 1.4 | 1.4 | 1.4 |
Two, quantitative measurement result:
Claims (7)
1. the combined polyether of a B level highly effective flame-retardant vegetable oil based polyurethane lagging material comprises the component of following weight percentage ratio:
2. the combined polyether of a kind of B level highly effective flame-retardant vegetable oil based polyurethane lagging material according to claim 1, is characterized in that, describedly reclaims vegetable oil-based polyether polyol containing Si, P, N intrinsic junction configuration and made by following steps:
(1) take vegetables oil as raw material, by purifying, epoxidation, hydroxylating, make vegetable oil-based polyether polyol;
(2) after being reacted under the effect of olefin oxide, γ ?glycidoxy Trimethoxy silane γ ?(. epoxy the third oxygen) propyl trimethoxy silicane (GPTMS) and phosphoric acid obtains Si, P and N hydridization polyvalent alcohol;
(3) Si, the P that vegetable oil-based polyether polyol step (1) obtained makes with step (2) and N hydridization polyvalent alcohol react with olefin oxide can make containing Si, P, N intrinsic junction configuration and reclaim vegetable oil-based polyether polyol under the effect of catalyzer.
3. the combined polyether of a kind of B level highly effective flame-retardant vegetable oil based polyurethane lagging material according to claim 1, is characterized in that, described pneumatogen is any one or a few mixture of HCFC-141b, HFC-245, pentamethylene.
4. the combined polyether of a kind of B level highly effective flame-retardant vegetable oil based polyurethane lagging material according to claim 1, it is characterized in that the mixture of any one or a few of the triethylene diamine solution (A-33) that described catalyzer is 33%, pentamethyl-triethylene diamine (PC-5) and dimethylcyclohexylamine (PC-8).
5. the preparation method of a B level highly effective flame-retardant vegetable oil based polyurethane lagging material, its combined polyether by the described B level of any one in claim 1～5 highly effective flame-retardant vegetable oil based polyurethane lagging material and isocyanic ester are that 1:1～1:1.5 makes according to mass ratio.
6. a B level highly effective flame-retardant vegetable oil based polyurethane lagging material as claimed in claim 5 can be used for the external wall heat insulating material for external.
7. a B level highly effective flame-retardant vegetable oil based polyurethane lagging material as claimed in claim 5 also can be used for the fields such as refrigeration industry, hot-water line, solar water heater, grain depot.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310371374XA CN103467689A (en) | 2013-08-22 | 2013-08-22 | B-grade high-flame-retardancy heat-insulating plant-oil-based polyurethane material as well as preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310371374XA CN103467689A (en) | 2013-08-22 | 2013-08-22 | B-grade high-flame-retardancy heat-insulating plant-oil-based polyurethane material as well as preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103467689A true CN103467689A (en) | 2013-12-25 |
Family
ID=49792747
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310371374XA Pending CN103467689A (en) | 2013-08-22 | 2013-08-22 | B-grade high-flame-retardancy heat-insulating plant-oil-based polyurethane material as well as preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103467689A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104844777A (en) * | 2015-04-22 | 2015-08-19 | 湖北大学 | Preparation method of soybean oil-based flame-retardant hard polyurethane foam |
| CN107266659A (en) * | 2017-08-16 | 2017-10-20 | 闫艳 | Fermenter is hard bubbled synthetic material and preparation method thereof with flexible polyurethane |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3686254A (en) * | 1969-12-24 | 1972-08-22 | Union Carbide Corp | Siloxane-polyoxyalkylene block copolymers |
| CN101033285A (en) * | 2007-02-14 | 2007-09-12 | 南京红宝丽股份有限公司 | Soft polyurethane foam plastic prepared by rape oil |
| CN101555319A (en) * | 2009-05-07 | 2009-10-14 | 中国科学院广州化学研究所 | Hybrid organic silicon-phosphorus type epoxy modifying agent used for copper clad laminate of printed circuit board, preparation method and application thereof |
-
2013
- 2013-08-22 CN CN201310371374XA patent/CN103467689A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3686254A (en) * | 1969-12-24 | 1972-08-22 | Union Carbide Corp | Siloxane-polyoxyalkylene block copolymers |
| CN101033285A (en) * | 2007-02-14 | 2007-09-12 | 南京红宝丽股份有限公司 | Soft polyurethane foam plastic prepared by rape oil |
| CN101555319A (en) * | 2009-05-07 | 2009-10-14 | 中国科学院广州化学研究所 | Hybrid organic silicon-phosphorus type epoxy modifying agent used for copper clad laminate of printed circuit board, preparation method and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104844777A (en) * | 2015-04-22 | 2015-08-19 | 湖北大学 | Preparation method of soybean oil-based flame-retardant hard polyurethane foam |
| CN107266659A (en) * | 2017-08-16 | 2017-10-20 | 闫艳 | Fermenter is hard bubbled synthetic material and preparation method thereof with flexible polyurethane |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102030977B (en) | Conjugate polyether, polyurethane raw material composition, polyurethane foams and applications thereof | |
| CN103804711B (en) | A kind of low heat conductivity polyurethane hard bubble foam and manufacture method and application taking pentamethylene as main body | |
| CN104017154B (en) | Electric water heater combined polyether, urethane and feedstock composition and preparation method thereof | |
| CN102585148A (en) | Composition for preparing highly fire-resistant polyisocyanurate foam | |
| CN103435769B (en) | Solar water heater water tank inorganic fire foaming thermal-insulating | |
| CN104497251A (en) | Combined polyether, polyisocyanurate foam and preparation method thereof | |
| CN103333308B (en) | Solar water heater water tank perlite foaming thermal-insulating | |
| CN101542214A (en) | Thermal insulation foam | |
| CN102229697A (en) | Solar polyurethane thermal insulation material | |
| CN103709727A (en) | PIR (polyisocyanurate) high-flame-retardancy heat-insulating material for deep refrigeration and preparation method thereof | |
| CN104130368A (en) | Flame-retardant polyurethane cast rigid foamed plastic sheet | |
| CN103923290A (en) | Polyurethane foam two-component raw material suitable for low-temperature environment and construction method thereof | |
| CN103342792A (en) | Polyurethane rigid foam organic fireproof heat preservation material for solar water tank | |
| CN103467689A (en) | B-grade high-flame-retardancy heat-insulating plant-oil-based polyurethane material as well as preparation method and application thereof | |
| CN103739809A (en) | Polyurethane thermal-insulation material and preparation method thereof | |
| CN103333310B (en) | Solar water heater water tank organic fire prevention foaming composition | |
| CN110845697A (en) | Polyurethane flame-retardant foam material | |
| CN106432672A (en) | All-water-blown rigid polyurethane foam material and production method thereof | |
| CN115093553B (en) | Tetrabromobisphenol A polyether ester polyol, preparation method thereof, polyurethane rigid foam and preparation method thereof | |
| CN103739808A (en) | Polyurethane thermal-insulation material and preparation method thereof | |
| KR102133321B1 (en) | Low carbon eco-friendly foaming agent composition | |
| CN102757545A (en) | Heat-preserving, flame-retardant, water-proof and corrosion-resistant functional gel material and preparation method thereof | |
| CN103319679A (en) | Polyurethane rigid foam inorganic fireproof thermal-insulation material for solar water tank | |
| CN107236445A (en) | A kind of fireproof coating and its application method for integrated house profile material | |
| CN100546801C (en) | A kind of production method of solar energy thermal insulation material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| AD01 | Patent right deemed abandoned |
Effective date of abandoning: 20160511 |
|
| C20 | Patent right or utility model deemed to be abandoned or is abandoned |