CN1179167A - Insulating foam plastic and its manufacturing method - Google Patents
Insulating foam plastic and its manufacturing method Download PDFInfo
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- CN1179167A CN1179167A CN 96192772 CN96192772A CN1179167A CN 1179167 A CN1179167 A CN 1179167A CN 96192772 CN96192772 CN 96192772 CN 96192772 A CN96192772 A CN 96192772A CN 1179167 A CN1179167 A CN 1179167A
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- coating
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- resol
- abscess
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Abstract
The present invention relates to insulating foams and to a process for producing the foams. Preferably, the foams are made from phenol formaldehyde resins. The blowing agents for making the foams include a film-forming coating material which coats the interior surfaces of the foam cells. The coated foams have better thermal conductivity .
Description
Technical field
The present invention relates to synthetic insulating foam plastic based on polymeric material.These porous plastics can be made by thermoplastic resin such as polystyrene or polyethylene, perhaps can be made by the more basic organic molecule that generates the thermosetting polymer porous plastics such as phenol and formaldehyde or isocyanic ester and polyvalent alcohol.The present invention mainly also relates to the preparation method of these closed-cell foamed plasticss.
Prior art
Found that the synthetic insulating foam plastic has various application in modern society.One of application of these porous plastics maximums is at building field, as the thermal insulation material of wall, roof, vault etc.The more special application of these porous plastics comprises refrigerating apparatus, pipeline, conduit, automobile, aerospace and shipping industry.
Although the application of insulating foam plastic constantly enlarges and output constantly increases, its thermal insulating properties in nearest 10 years, particularly long-term insulation character are not improved, and also cause some disadvantageous effects owing to change over environment for use close friend's whipping agent.But, will save a large amount of energy in the improvement of the thermal insulating properties aspect of these porous plastics, particularly low-density kind, reduce the consumption expense of fossil oil, simultaneously because the minimizing of the greenhouse gases of combustion of fossil fuel generation has improved environment.
Summary of the invention
We have now found that a kind of production has the method for the insulating foam plastic that improves thermal conduction.This method is used the whipping agent that contains film forming coatings.Coating mixes or is dissolved in the whipping agent.In foaming process, form closed pore, each abscess has internal surface.In foaming process, coating also is coated on the internal surface of each abscess continuously.Because this one-tenth film coating is discharged the formation barrier to air admission and adiabatic gas.Coating and hole wall are equivalent to the multilayered barrier film.
With inorganic, organic, oligomeric or polymeric, and synthetic or the natural liquid or solid coating that obtains mixes with whipping agent or is dissolved in whipping agent, and whipping agent is used to the foam structure that foams subsequently.Foam structure is by inorganic, organic or polymeric material generation, and they are insoluble to coating or at coating very limited solvability are arranged.In foaming process, when foam structure such as window and support formation, coating deposits from the gas phase of whipping agent, and forms rete on the foam structure surface.The whipping agent that uses in the present invention can be various CFCs, HCFCs, HFCs, inorganic gas such as CO
2, N
2, alkane or any other are used to make cellular material expansible reagent.The laminate structure that forms in this method has lower gas permeability than known plastic foam material, therefore stops the loss of air admission and whipping agent and reduces the thermal-insulating value (T.I.V.) loss.Our method improvement the thermal properties of cellular material (particularly aging thermal properties).This method also can be improved the mechanical properties of cellular material under certain density.The present invention has the processing of the porous plastics that improves non-CFC foaming under high-solvency and/or the lower boiling occasion at non-CFC whipping agent.
Implement best mode of the present invention
Our method may further comprise the steps:
(a) provide foaming composition;
(b) whipping agent;
(c) tensio-active agent; And
(d) catalyzer;
Mix said composition so that begin foaming and generate the resol porous plastics; And to make porous plastics be solidified into density be 0.5-3.0 pound/cubic feet (8.009-48.055 kilogram/rice
3).
This method makes us that very full-bodied resol foaming can be arranged, and makes porous plastics curing obtain very low-density porous plastics.
Composition foaming by following thermosetting material and thermoplastic material makes porous plastics: as polyethylene, polypropylene, polyester, urethane, two chlorotrifluoroethylenes, fluorinated ethylene propylene, poly(vinylidene fluoride), polymethylmethacrylate, resol and silicone and polycarbonate resin.Preferably, foaming composition is made by resol.More preferably, composition is that not have free formaldehyde, water content basically be that 4-8% and 40 ℃ of viscosity are 5000 centipoises (5 handkerchief second) to the resol of 40000 centipoises (40 handkerchief second).
The internal surface that each abscess limits in the porous plastics is aggregated the continuous covering of thing symphysis.Being suitable for the example that the present invention applies the polymkeric substance of porous plastics abscess is polyvinyl alcohol, polyacrylic acid, Polyvinylpyrolidone (PVP) and polyoxyethylene glycol.We have found that polymethacrylate is a particularly suitable.Also can obtain good result with mineral oil and vegetables oil.
Whipping agent can be selected from many HCFCs or HFCs.The object lesson of these whipping agents comprises 1-chloro-1,1-C2H4F2 C2H4F2 (142b), Dichloromonofluoromethane (22), 2-chloro-1,1,1,2-Tetrafluoroethane (124), 1,1-C2H4F2 C2H4F2 (152a), pentafluoride ethane (125) and 1,1,1,2 ,-Tetrafluoroethane, dichloro one fluoroethane (141b) etc.
Whipping agent also can comprise perfluoro alkane, and wherein perfluoro alkane is the 1-5% (weight) of whipping agent gross weight.Preferred perfluoro alkane is represented with following formula:
CnHxFy
In the formula, n is an integer among the 4-20, x be 0 or 2-10 in an integer, x+y=2n+2.The concrete example of perfluoro alkane comprises R-4112, Tetradecafluorohexane, ten hexafluoro heptane.
Preferably, perfluoro alkane is the 1-3% (weight) of whipping agent total amount, more preferably 1-2% (weight).Also can use the alkane that resembles butane, pentane or pentamethylene.
The tensio-active agent that is generally used for phenolic foamed plastics production is being generally non-ionic type in nature.Be extensive use of siliceous tensio-active agent, as the silicon ethylene oxide/propylene oxide multipolymer of organoalkoxysilane, poly-silyl/phosphonic acid ester, polydimethylsiloxane and polyoxyalkylene base co-polymer.The example of the suitable siliceous tensio-active agent of commodity is Dow Corning Trademarks DC-190 and DC-193 and Union Carbide Trademarks L-530, L-5310 and L-5410.Other nonionic surface active agent that are fit to comprise Pluronic (trade mark of BASF Wynadotte) nonionic surface active agent, particularly high-molecular weight F-127, F-108 and F-98 polyethylene oxide-poly(propylene oxide).
Surfactant concentrations can change in the 2-10% scope of prescription gross weight.For resol described here, preferred concentration is 2-5%.To contain the sufficient amount whipping agent to obtain the closed-cell foamed plastics of good adiabatic numerical value in order producing, need carefully to select the character of resin and tensio-active agent.
Used catalyzer is generally acids.In some cases, porous plastics can only make without catalyzer with heating.But in practice, in order to finish the curing of porous plastics, catalyzer is essential.
Many organic and inorganic acid catalysts are known, and open in prior art.The example of mineral acid comprises hydrochloric acid, sulfuric acid, nitric acid and various phosphoric acid.The organic acid example comprises aromatic sulfuric acid, as Phenylsulfonic acid, toluenesulphonic acids, xylene monosulfonic acid, phenol sulfonic acid and naphthene sulfonic acid; Latent acid catalyst as the phenolic ester of carboxylic acid, comprises trifluoroacetic acid phenyl ester and toxilic acid hydrogen phenyl ester; And the various SO that contain
2Compound, as the sulfide of α, β-undersaturated ketone and aldehydes and various diolefine; Monobasic and polycarboxylic acid are as the organic acid of acetate, formic acid, propionic acid, oxalic acid, toxilic acid and strong replacement, as trichoroacetic acid(TCA).The mixture of toluenesulphonic acids is normally preferred.Acid catalyst is sold with trade(brand)name Ultra TX (Witco Chemical Company), and dimethylbenzene-toluenesulphonic acids is particularly preferred.
The density of thick fusible phenolic foamed plastics is 0.5-3.0 pound/cubic feet (8.009-48.055 kilogram/rice
3).The density of fusible phenolic foamed plastics is preferably 0.7-1.8 pound/cubic feet (11.213-28.833 kilogram/rice
3).Under 40 ℃, the viscosity of resol is preferably 5000-40000 centipoise (5-40 handkerchief second).Preferably, under 40 ℃, the viscosity of resol is 8000-20000 centipoise (8-20 handkerchief second).
The basic step that is prepared porous plastics by resol is as follows:
(a) preparation resol;
(b) add any properties-correcting agent;
(c) in and resin;
(d) stripping goes out moisture content, as uses the coupling vacuum stripping device;
(e) add tensio-active agent;
(f) add whipping agent and coating;
(g) add acid catalyst, make mixture make porous plastics; And
(h) porous plastics is solidified.
The resol that makes with the initial mol ratio of phenol commonly used and formaldehyde prepares porous plastics; Under existing conditions, mol ratio is 1: 1 to 1: 4.5, preferred 1: 1.5 to 1: 2.5.The material of high molar ratio is to be substantially free of the resin of phenol and available formaldehyde coreagent or scavenging agent to handle, with the basis of the resin that reduces initial high free formaldehyde content.
Resin is through concentrating, to reduce the free water content of resin.The viscosity of resin that is used to prepare the typical viscosities of fusible phenolic foamed plastics is 5000 to 40000 centipoises (5-40 handkerchief seconds), and free water content is 4～8%.But, according to the present invention, prepare by high viscosity resins in the process of phenolic foamed plastics, under 40 ℃, the viscosity of used resin is preferably 8000 to 20000 centipoises (8-20 handkerchief second).
The after fixing step that we also can adopt following substep to heat up:
Descended 0～70 minute at 75-85 ℃, subsequently
90-95 ℃ 20-105 minute, subsequently
At 100-105 ℃ of following 60-170 minute.
Embodiment 1
The preparation of resol
The formaldehyde that the resol that uses in the production of these porous plastics uses: phenol (F/P) mol ratio is 2.3: 1, the formaldehyde of use 52% and 99% phenol.Be reflected under the alkaline condition that uses 50% causticity liquation, under heating up, carry out.When the Ostwald of resin viscosity reaches 62 centistokes(cst)s (6210
-6Rice
2When/second) (measuring down), reactant is cooled off, and neutralize with the 50% aromatic sulfonic acid aqueous solution at 25 ℃.Urea adds as formaldehyde scavenger, and content is 77% (mole) of removing residue formaldehyde.By thin-film evaporator, make water content drop to 4-8% resin from about 30%.The Oxyranyle nonionic surface active agent Pluronic F-127 (BASF) that adds molten state then, its amount is 3.5% (weight) of resin, is mixed in the resin, forms uniform mixture.The final viscosity of resin is 9000-12000 centipoise (9-12 handkerchief second) (measuring down at 40 ℃).
Embodiment 2
The preparation of resol porous plastics
By the method that resol and tensio-active agent and whipping agent and acid catalyst mix being prepared the resol porous plastics with the short rotor/stator continuous mixing device that stops of high-shear.Whipping agent is being sent into before the high-shear mixer with 200 pounds/inch
2Nitrogen under (30 kPas) is saturated.Kicker is the blend of the mixture of Resorcinol, Diethylene Glycol and xylene monosulfonic acid and toluenesulphonic acids.(referring to US4883824 and 4945077).Resol, whipping agent and catalyzer add mixing tank in following ratio with the flow metering equipment continuous measurement that is fit to:
Resin/tensio-active agent 100
HCFC?141b 8.63
Catalyzer
111.8
Foamable mixture (resin/tensio-active agent, whipping agent, catalyzer) is discharged from mixing tank by even spacer tube and nozzle, forms successive spray foam bead on the die face that moves.Form the porous plastics parallel lines like this, they are bonded together as spray foam foaming thing, make continuous sheet material.Foam plastics slab by about 80 ℃ travelling belt stove, is made the solidified slab with constant speed then.Slab further solidifies through following steps:
75 ℃ following 25 minutes, subsequently,
85 ℃ following 25 minutes, subsequently,
90 ℃ following 50 minutes, subsequently,
95 ℃ following 25 minutes, subsequently,
100 ℃ following 25 minutes, subsequently
Following 50 minutes at 105 ℃.
The mixture of 1 xylene monosulfonic acid and toluenesulphonic acids
Embodiment 3
Reactive blowing agent additive-standard foam plastics
We have prepared and have contained 52.25 parts of resol (formaldehyde: the phenol ratio is 2.3: 1, free-water 6.5%, viscosity 12000 centipoises (12 handkerchief second)).It and 2.75 parts of Harfoam PI (HuntsmanChemical Company) and Pluronie F-127 (BASF) etc. the blend in advance of mixed thing.
17 parts of HCFC141b (Atochem) are blended in cup in the above-mentioned material.Under vigorous stirring, 5 parts of catalyzer of being made up of the blend of the mixture of Resorcinol, Diethylene Glycol and xylene monosulfonic acid and toluenesulphonic acids are added rapidly.At this moment, blend composition is entered in 8 airtight inch * 8 inch * 2 inch (203 millimeters * 203 millimeters * 51 millimeters) mould.With the mould sealing, and under 80 ℃, placed 20 minutes.
The porous plastics that take out to generate from hot-die, and at room temperature storing 5 days, at this moment, the discovery thermal conductivity is 0.262 BTU * inch hour
-1Foot
-2°F
-1(0.038 watt of/meter K), its density is 1.5 pounds/foot
3(24 kilograms/meter
3).This porous plastics has very thick structure, and average cell size is 280 microns.
Embodiment 4
1% polymethylmethacrylate (PMMA) in the whipping agent
Under 28 ℃, in encloses container, 1 part of polymethylmethacrylate (average MW is 120000Aldrich) is dissolved among 99 parts of HCFC141b (Atochem) (a).
Make porous plastics by embodiment 3, different whipping agents that is to use 11 parts of preparations and additive (a).
The porous plastics that generates has thin foam structure, and thermal conductivity is 0.144BTU * inch hour
-1Foot
-2°F
-1(0.021 watt of/meter K), its density is 1.5 pounds/foot
3Or 24 kilograms/meter
3SEM spectrum shows that material has multilayer on cell wall and support.
Embodiment 5
5-10%PMMA in whipping agent
Under 28 ℃, in encloses container, 10 parts of PMMA (average MW is 120000Aldrich) are dissolved among 90 parts of HCFC141b (Atochem) (b).
Press embodiment 3 preparation porous plastics, the different whipping agents that is to use 11 parts of preparations and additive agent mixtures (b).
The porous plastics that generates has thin foam structure, and thermal conductivity is 0.138BTU * inch hour
-1Foot
-2°F
-1(0.020 watt of/meter K), its density is 1.5 pounds/foot
3Or 24 kilograms/meter
3SEM spectrum shows that material has multilayer on cell wall and support.Average cell size is 150 microns.
Embodiment 6
5% oil and 1%Rexol65/10
5 parts of sunflower oil (food grade) and 1 part of surfactant R ex01 65/10 (Huntsman Chemical Company) are dissolved among 94 parts of Freon 113 (dupont) (c).
We use surfactant blend and 14 parts of whipping agents (c) blend of resol and the 1.9 parts of embodiment 3 of 36.1 parts of embodiment 1, use the catalyst blends of 4.5 parts of embodiment 3 to prepare porous plastics.
The porous plastics that generates has thin foam structure, and oily gloss is arranged, and thermal conductivity is 0.129 BTU * inch hour
-1Foot
-2°F
-1(0.019 watt of/meter K), its density is 1.5 pounds/foot
3Or 24 kilograms/meter
3SEM spectrum shows that drop and wetting areas are arranged on cell wall and support.
Claims (20)
1. method for preparing insulating foam plastic, this method may further comprise the steps:
A., foaming composition is provided;
B. whipping agent, wherein whipping agent contains film for additive; And
C. said composition is mixed so that cause foaming, generate the insulating foam plastic of the abscess that coating is arranged, each abscess has internal surface, and coating applies the internal surface of abscess continuously; And
D. making porous plastics be solidified into density is 0.5-3.0 pound/foot
3(8.009-48.055 kilogram/rice
3), the thermal conductivity of porous plastics that the abscess through applying is wherein arranged is less than 0.200BTU * inch hour
-1Foot
-2°F
-1(0.029 watt of/meter K).
2. according to the process of claim 1 wherein that foam composition made by thermoplastic composition or heat cured composition.
3. according to the process of claim 1 wherein that foam composition made by resol.
4. according to the method for claim 1, wherein a kind of like this resol of foam composition is made, it is substantially free of free formaldehyde, its water content is 4-8%, viscosity under 40 ℃ is 5000 to 40000 centipoises (5-40 handkerchief seconds), and wherein the foam composition of Sheng Chenging is a closed pore resol porous plastics.
According to the process of claim 1 wherein cell wall with become film coating to constitute the multilayered barrier film.
6. according to the process of claim 1 wherein that cell wall and pore membrane coating barrier air enter the inside of discharging closed pore with adiabatic gas.
7. according to the process of claim 1 wherein that coating is polymkeric substance.
8. according to the process of claim 1 wherein that coating is the mixture of tensio-active agent and mineral oil or vegetables oil.
9. according to the process of claim 1 wherein that coating is polyvinyl alcohol, polyacrylic acid, Polyvinylpyrolidone (PVP) or polyoxyethylene glycol.
10. according to the process of claim 1 wherein that coating is polymethylmethacrylate.
11. insulating foam plastic that obtains by following component:
A. foaming composition;
B. whipping agent, wherein whipping agent contains film forming coating; And this insulation foams has the abscess through applying, and each abscess has internal surface, and film forming coating applies the internal surface of closed pore continuously, and density is 0.5-3.0 pound/foot
3(8.009-48.055 kilogram/rice
3), the thermal conductivity of resol porous plastics that the abscess through applying is wherein arranged is less than 0.200BTU * inch hour
-1Foot
-2°F
-1(0.029 watt of/meter K).
12. according to the porous plastics of claim 11, wherein foam composition is thermoplastic compounds or thermoset composition.
13. according to the porous plastics of claim 11, wherein porous plastics is a resol.
14. porous plastics according to claim 11, wherein foam composition is a kind of like this fusile resol, it is substantially free of free formaldehyde, its water content is 4-8%, viscosity under 40 ℃ is 5000-40000 centipoise (5-40 handkerchief second), and wherein the foam composition of Sheng Chenging is the fusile phenolic foamed plastics of closed pore.
15. according to the porous plastics of claim 11, wherein cell wall with become film coating to constitute the multilayered barrier film.
16. according to the porous plastics of claim 11, wherein cell wall and film forming coating barrier air enter the inside of discharging closed pore with adiabatic gas.
17. according to the porous plastics of claim 11, wherein coating is polymkeric substance.
18. according to the porous plastics of claim 11, wherein coating is the mixture of tensio-active agent and mineral oil or vegetables oil.
19. according to the porous plastics of claim 11, wherein coating is polyvinyl alcohol, polyacrylic acid, Polyvinylpyrolidone (PVP) or polyoxyethylene glycol.
20. according to the porous plastics of claim 11, wherein coating is polymethylmethacrylate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96192772 CN1179167A (en) | 1995-03-24 | 1996-01-19 | Insulating foam plastic and its manufacturing method |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/410,607 | 1995-03-24 | ||
| CN 96192772 CN1179167A (en) | 1995-03-24 | 1996-01-19 | Insulating foam plastic and its manufacturing method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1179167A true CN1179167A (en) | 1998-04-15 |
Family
ID=5128463
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 96192772 Pending CN1179167A (en) | 1995-03-24 | 1996-01-19 | Insulating foam plastic and its manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1179167A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102193083A (en) * | 2010-02-09 | 2011-09-21 | 富士重工业株式会社 | System and method for measuring damage length |
| CN114736400A (en) * | 2022-05-20 | 2022-07-12 | 武汉理工大学 | A kind of ceramizable phenolic aerogel and preparation method thereof |
-
1996
- 1996-01-19 CN CN 96192772 patent/CN1179167A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102193083A (en) * | 2010-02-09 | 2011-09-21 | 富士重工业株式会社 | System and method for measuring damage length |
| CN102193083B (en) * | 2010-02-09 | 2014-10-01 | 富士重工业株式会社 | Damage length measurement system and damage length measurement method |
| CN114736400A (en) * | 2022-05-20 | 2022-07-12 | 武汉理工大学 | A kind of ceramizable phenolic aerogel and preparation method thereof |
| CN114736400B (en) * | 2022-05-20 | 2024-02-02 | 武汉理工大学 | Ceramizable phenolic aerogel and preparation method thereof |
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