CN1341685A - Bitumen polyurethane hard foamed plastics and preparation method thereof - Google Patents
Bitumen polyurethane hard foamed plastics and preparation method thereof Download PDFInfo
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- CN1341685A CN1341685A CN 01127528 CN01127528A CN1341685A CN 1341685 A CN1341685 A CN 1341685A CN 01127528 CN01127528 CN 01127528 CN 01127528 A CN01127528 A CN 01127528A CN 1341685 A CN1341685 A CN 1341685A
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- propylene oxide
- oxide polyethers
- foamed plastics
- hard foamed
- polyurethane hard
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Abstract
The present invention discloses a kind of hard asphalt polyurethane foamed plastics. It is made up by using composite material A and polyisocyanate B according to a certain proportion through the processes of chemically foaming and pouring or spraying. The described composite material A is made up by using coal-tar pitch liquor, polyether polyol, fire-retardant, foam stabilizing agent, crosslinking agent, catalyst and foaming agent through the processes of mixing and stirring. Said invented foamed plastics can make steel material possess corrosion-resisting property and anti-weathering action, and is specially applicable to heat insulation for field gathering line and oil transmission pipe and city underground heat supply pipeline, industrial heat insulation, building heat insulation, water-proofing and noise insulation.
Description
Technical field
The present invention relates to be used in the polyurethane industrial that industry is adiabatic, construction industry insulation cold insulation sound insulation and noise reduction and the packed and transported hard foam material of usefulness already, it be continue polyester-polyurethane hard bubble, a novel thermal insulation material after polyether-polyurethane hard bubbles, poly-isocyanurate hard bubbles.
Prior art
The annual meeting in 1989 of U.S. association of plastics industry, article in the proceedings " Anovelasphalt-blended polyurethane foam " report blending bituminous polyurethane semi-rigid foam plastics, being used for the sealing of automotive industry sound insulation vibration damping and water proof, is a kind of elastomer foam material.
European patent 226459 reports make latex foam with asphalt modification styrene-butadiene rubber(SBR), and be sprayed at carpet and be used for the tuft bonding by lining, be a kind of microcellular elastomeric foams.
The polyurethane rigid foam plastic of present industrial thermal insulation and the waterproof thermal-insulated a large amount of uses of construction industry, be hydroxyl value components such as the polyether glycol of 350-650mgKOH/g, fluorine-containing whipping agent, catalyzer, suds-stabilizing agent, phosphoric acid ester polyethers, fire retardant normally, make combination material A (practise and claim white material) by a certain percentage, poly isocyanate is as B component (practise and claim black material), in site of deployment two liquid component being mixed the foaming of generation chemical reaction, is polyurethane rigid foam plastic after the moulding.
The combination material of selling at present on the market has polyether polyol combination material and polyester polyol combination material.Because of the polyester polyol combination expects that price is higher, though people try hard to the alcoholysate preparation polyester type combination material of ethylene glycol terephthalate recovery article or residue, to reduce cost, foaming effect is unsatisfactory, the one, abscess is big, and is inhomogeneous: the 2nd, and foam is crisp.The polyether polyol combination that remains of mass selling is in the market expected.These two kinds are made up the corrosive nature of expecting all to exist to steel tubing.Flame retarded polyurethane-foam plastics particularly, usually in prescription, need to add the polyether glycol of phosphorous acid esters, because of phosphoric acid ester polyethers instability, be easy to hydrolysis, generate acidic substance, corrosion steel tubing, it is more serious especially to bury the corrosion of ground heating pipeline and oil field gathering and transportation gas pipeline, and the maintenance cost of pipeline system is improved greatly.
Summary of the invention
The objective of the invention is to overcome the corrosion default of urethane foam, and reduce manufacturing cost steel.The asphalt polyurethane porous plastics not only has the heat-insulating property of the insulation cold insulation of polyurethane rigid foam plastic, and steel had antiseptic property, the coal tar pitch low price, rigid urethane foam with its preparation has more watertightness, to the cohesiveness of base material and resist atmospheric weathering, and waterproof, sound absorption, sound insulation and noise reduction performance.
The present invention is realized by following technical scheme: at first prepare coal coke asphalt liquid, cooperate polyether glycol, whipping agent and other auxiliary agent to be mixed with combination material A with coal coke asphalt liquid again, combination material A and poly isocyanate B adopt cast or spraying coating process to make bitumen polyurethane hard foamed plastics by a certain percentage through chemical foaming.
Wherein consisting of of A expected in combination:
The component mass fraction
70% coal coke asphalt liquid 100
Polyether glycol 100-200
Linking agent 10-30
Suds-stabilizing agent 4-6
Fire retardant 0-60
Catalyzer 3-12
Water 0-4.5
HCFC-141b whipping agent 40-90
Compound and best proportioning that aforesaid combination material A is adopted are as follows:
70% above-mentioned coal coke asphalt liquid, can adopt low temperature, middle temperature and high temperature coal tar pitch, but preferably adopt the bottom paint special asphalt of 40-60 ℃ of softening temperature (ring and ball method), combination material A with its preparation is not stratified in storage process, it is low not have flocculation, no skinning, viscosity, close with poly isocyanate viscosity, be suitable for the foaming machine foaming, and antiseptic property is good.
Contain condensed ring and heterogeneous ring compound in the coal tar pitch, its chemical constitution is based on fragrance and naphthenic hydrocarbon, and straight-chain paraffin is auxilliary, and reactive hydrogen content is that its composition of 0.8-1% has phenolic group, alcoholic extract hydroxyl group, active hydrogen compoundss such as amido and imido grpup.With the process of isocyanate reaction under the normal temperature isocyanic ester earlier with amido, imido grpup and alcoholic extract hydroxyl group reaction, rising along with temperature in the foaming process, isocyanic ester and phenolic group reaction form the part of foams skeleton, and amido and imido grpup play katalysis in this reaction.
Above-mentioned polyether glycol can adopt the cyclopolymer that rises by multi-group alcohol or polyfunctional group amine and propylene oxide, comprises glycerine-propylene oxide polyethers, TriMethylolPropane(TMP)-propylene oxide polyethers, tetramethylolmethane-propylene oxide polyethers, sorbyl alcohol-propylene oxide polyethers, N.F,USP MANNITOL-propylene oxide polyethers, sucrose-glycerine-propylene oxide polyethers, sucrose-amine-propylene oxide polyethers, quadrol-propylene oxide polyethers, diethylenetriamine-propylene oxide polyethers, hydramine-propylene oxide polyethers, tolylene diamine-propylene oxide polyethers, aniline formaldehyde oligopolymer-propylene oxide polyethers.
The present invention preferably adopts one or more of sucrose-glycerine-propylene oxide polyethers, sucrose-amine-propylene oxide polyethers, quadrol-propylene oxide polyethers, tolylene diamine-propylene oxide polyethers composite.Its optimum amount is the 120-160 mass parts.Adopt sucrose be polyethers and nitrogenous be the asphalt polyurethane porous plastics shrinking percentage that makes of polyether glycol at the bottom of, fragility is little.Substitute the phosphoric acid ester polyethers with nitrogen-containing polyether and can avoid the phosphoric acid ester polyethers to produce acidic substance, increase its Corrosion Protection because of hydrolysis.
Above-mentioned linking agent can adopt that following one or more are composite: glycerine, TriMethylolPropane(TMP), trolamine, diethanolamine, Viscotrol C, sucrose, two amido ditans.Best employing sucrose and the composite use of trolamine, optimum amount is the 12-25 mass parts.
Make fragility and the shrink defects that linking agent can improve foams with sucrose, it also is a kind of katalysis demulcent catalyzer that trolamine had both played crosslinked action.
Above-mentioned whipping agent can adopt the environment-friendly type whipping agent that does not damage the ozone layer, for example, and water (carbonic acid gas), pentane and HCFC-141b whipping agent.Because of pentane foaming agent inflammable, strict to foaming machine, and pentane foaming agent is not suitable for spray coating foaming, the asphalt polyurethane porous plastics of using for building materials industry, preferably adopt HCFC-141b and water (carbonic acid gas) composite foamable agent, can suitably regulate the consumption of whipping agent according to the requirement of density foam.
Above-mentioned fire retardant can adopt liquid additive flame retardant, for example trichloroethyl phosphate (TCEP), trichlorine propyl phosphate (TCPP), tribromo propyl phosphate, methyl-phosphoric acid dimethyl ester (DMMP).Fire retardant preferably both or three is composite.Fire retardant can influence foam performance, and consumption is unsuitable excessive, preferably selects the 25-50 mass parts for use.
Above-mentioned catalyzer can adopt tertiary amine and organo-metallic catalyst, because catalyzer has " synergistic effect ", preferably tertiary amine and the composite use of organo-metallic catalyst in the prescription.
Tertiary amine catalyst can adopt triethylene diamine, dimethylcyclohexylamine, dimethylethanolamine, three (dimethylamino) phenol (DMP-30), two (dimethylamino ethyl ethers) etc.; Organo-metallic catalyst can adopt dibutyl tin laurate, toxilic acid dibutyl tin, mercaptan dibutyl tin, potassium oleate, Potassium ethanoate.Because dibutyl tin laurate is easy to hydrolysis, in moisture, as to contain tertiary amine catalyst combination material formula, easily lost efficacy.Preferably adopt the tertiary amine and the toxilic acid dibutyl tin of facile hydrolysis not, or tertiary amine and mercaptan dibutyl tin are catalyst compounded.Catalyst levels is looked combination material type, as: mould material, spray material and envrionment temperature are regulated catalyst levels.
Above-mentioned suds-stabilizing agent adopts the silicon foams stablizer, in the asphalt polyurethane foam formulation, mainly plays nucleation emulsifying effect and even bubble effect.Can adopt the use for hard bubble of polyurethane water soluble polyether siloxanes of selling on the market, as, trade names JSY-2000, CGY-1, JFS-818 etc.They are multipolymers of polydimethylsiloxane and oxyethane and propylene oxide.Optimum amount 2-4 mass parts.
Combination material A and poly isocyanate make bitumen polyurethane hard foamed plastics through chemical foaming, the poly isocyanate that is adopted can be thick diphenylmethanediisocyanate (thick MD1) and many phenyl polymethine polyisocyanates (PAP1), trade names have: PM-100, PM-200, PM-300, MR100, MR200, M20S, 5005, U20LMD1 etc., isocyanate index is 105-110.
The compound method of 70% coal coke asphalt liquid that is adopted in the prescription: coal tar pitch is broken into piece drops in the still, heating makes it fusing and starts stirring, be warming up to 180-200 ℃, softening temperature is per hour surveyed in insulation, be terminal point in 57 ± 3 ℃ of scopes to reaching, be cooled to 110-120 ℃, add solvent in batches, stir, be cooled to 50-80 ℃ of filtration, non-volatile part of content 70 ± 2%
The blending process of combination material A: successively the coal coke asphalt liquid of metering, polyether glycol, fire retardant, suds-stabilizing agent, linking agent, catalyzer, whipping agent are dropped in the still, middling speed stirs under the room temperature, filters and packages.
The preparation method of bitumen polyurethane hard foamed plastics: adopt spraying or pouring foaming machine to make the combination material A and the poly isocyanate B of 100 mass parts through chemical foaming.
According to the porous plastics applicable cases, select spraying, the cast foaming machine of the different model of selling on the market for use.
The present invention has Corrosion Protection and the good coal tar pitch of anti-water permeability owing to having adopted, suitable polyether glycol, suds-stabilizing agent, the environment-friendly type whipping agent, the mutual synergy of the composite catalyst of facile hydrolysis and fire retardant not, obtained a kind of not only thermal insulation but also can be to the etch-proof bitumen polyurethane hard foamed plastics of steel, because the synergy of each component, make asphalt polyurethane combination material viscosity lower, close with poly isocyanate viscosity, be applicable to various common foaming machines, do not need common foaming machine is improved, and combination material A is not stratified in storage process, do not flocculate, skinning not, room temperature storage can reach 6 months, and the asphalt polyurethane porous plastics that makes does not shrink, and is not crisp.Bitumen polyurethane hard foamed plastics of the present invention can be resisted atmospheric weathering, do not discharge acidic substance be more suitable in oil field gathering and transportation oil pipe and concentrated supply of heating in the city bury outside ground heat distribution pipeline insulation antiseptic and the basin thermal insulation and buildings thermal insulation, waterproof, dry material falls in sound insulation.
Specific embodiment
Embodiments of the invention further specifically understand asphalt polyurethane hard bubble The feasibility of foam plastics and reliability, however the present invention is not limited to following embodiment In. In detail open to the present invention below in conjunction with embodiment.
Table 1 is the formulation Example of bitumen polyurethane hard foamed plastics. Wherein four Combination material A and isocyanate index that individual embodiment all gets 100 mass parts are 105 Poly isocyanate (PAP1) reaction make.
Table 2 is performance indications of bitumen polyurethane hard foamed plastics
Table 1
Table 2
Claims (10)
1. bitumen polyurethane hard foamed plastics is characterized in that: it, is adopted and pours into a mould or spraying coating process makes by a certain percentage through chemical foaming by combination material A and poly isocyanate B.
Wherein consisting of of A expected in combination:
The component mass fraction
70% coal coke asphalt liquid 100
Polyether glycol 100-200
Linking agent 10-30
Suds-stabilizing agent 4-6
Fire retardant 0-60
Catalyzer 3-12
Water 0-4.5
HCFC-141b whipping agent 40-90 wherein poly isocyanate B is selected from thick diphenylmethanediisocyanate (thick MD1) and many phenyl polymethine polyisocyanates (PAP1), and isocyanate index is 105-110.
2. according to the bitumen polyurethane hard foamed plastics of claim 1, it is characterized in that: described 70% coal coke asphalt liquid, preferably adopt the bottom paint special asphalt of 40-60 ℃ of softening temperature (ring and ball method).
3. according to the bitumen polyurethane hard foamed plastics of claim 1, it is characterized in that: described polyether glycol is selected from the cyclopolymer that rises of multi-group alcohol or polyfunctional group amine and propylene oxide, comprises glycerine-propylene oxide polyethers, TriMethylolPropane(TMP)-propylene oxide polyethers, tetramethylolmethane-propylene oxide polyethers, sorbyl alcohol-propylene oxide polyethers, N.F,USP MANNITOL-propylene oxide polyethers, sucrose-glycerine-propylene oxide polyethers, sucrose-amine-propylene oxide polyethers, quadrol-propylene oxide polyethers, diethylenetriamine-propylene oxide polyethers, hydramine-propylene oxide polyethers, tolylene diamine-propylene oxide polyethers, aniline formaldehyde oligopolymer-propylene oxide polyethers.Its optimum amount is the 120-160 mass parts.
4. according to the bitumen polyurethane hard foamed plastics of claim 3, it is characterized in that: described polyether glycol is best to adopt one or more of sucrose-glycerine-propylene oxide polyethers, sucrose-amine-propylene oxide polyethers, quadrol-propylene oxide polyethers, tolylene diamine-propylene oxide polyethers composite.
5. according to the bitumen polyurethane hard foamed plastics of claim 1, it is characterized in that: described linking agent is selected from that following one or more are composite: glycerine, TriMethylolPropane(TMP), trolamine, diethanolamine, Viscotrol C, sucrose, two amido ditans etc., its optimum amount is 12-25 part.
6. according to the bitumen polyurethane hard foamed plastics of claim 5, it is characterized in that: described linking agent best employing sucrose and the composite use of trolamine.
7. according to the bitumen polyurethane hard foamed plastics of claim 1, it is characterized in that: described fire retardant adopts liquid additive flame retardant, can be selected from following one or more: trichloroethyl phosphate (TCEP), trichlorine propyl phosphate (TCPP), tribromo propyl phosphate, methyl-phosphoric acid dimethyl ester (DMMP), its optimum amount 25-50 mass parts.
8. according to the bitumen polyurethane hard foamed plastics of claim 1, it is characterized in that: described catalyzer is selected from tertiary amine and the composite use of organo-metallic catalyst, and tertiary amine catalyst comprises triethylene diamine, dimethylcyclohexylamine, dimethylethanolamine, three (dimethylamino) phenol (DMP-30), two (dimethylamino ethyl ethers); Organo-metallic catalyst comprises dibutyl tin laurate, toxilic acid dibutyl tin, mercaptan dibutyl tin, potassium oleate, Potassium ethanoate.
9. bitumen polyurethane hard foamed plastics according to Claim 8, it is characterized in that: described catalyzer the best is selected tertiary amine and toxilic acid dibutyl tin for use, or tertiary amine and mercaptan dibutyl tin are catalyst compounded.
10. according to the bitumen polyurethane hard foamed plastics of claim 1, it is characterized in that: the blending process of described combination material A: successively 70% coal coke asphalt liquid of metering, polyether glycol, fire retardant, suds-stabilizing agent, linking agent, catalyzer, whipping agent are dropped in the still, middling speed stirs under the room temperature, filters and packages.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011275286A CN1191304C (en) | 2001-09-30 | 2001-09-30 | Bitumen polyurethane hard foamed plastics and preparation method thereof |
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| CNB011275286A CN1191304C (en) | 2001-09-30 | 2001-09-30 | Bitumen polyurethane hard foamed plastics and preparation method thereof |
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| CN1191304C CN1191304C (en) | 2005-03-02 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1303123C (en) * | 2003-08-29 | 2007-03-07 | 青岛金北洋工程材料有限公司 | Composite catalyst for improving size stability and its asphalt polyurethane hard foam body |
| CN100523084C (en) * | 2007-04-20 | 2009-08-05 | 常熟佳发化学有限责任公司 | Polyurethane resin combination and preparation method and using method thereof |
| CN101805559A (en) * | 2010-04-07 | 2010-08-18 | 杭州东科建筑节能材料有限公司 | Polyurethane paint |
| CN102093531B (en) * | 2009-12-11 | 2012-12-19 | 财团法人工业技术研究院 | Fireproof polyurethane foamed material and preparation method thereof |
| CN105273601A (en) * | 2014-07-24 | 2016-01-27 | 佛山市顺德区合胜化工实业有限公司 | High-strength polyurethane waterproof coating material and preparation method thereof |
| CN105647166A (en) * | 2014-12-05 | 2016-06-08 | 中国石油化工股份有限公司 | Phase change energy storage asphalt polyurethane rigid foam and preparation method thereof |
| CN105713401A (en) * | 2014-12-05 | 2016-06-29 | 中国石油化工股份有限公司 | All-water-blown asphalt-polyurethane hard foam and preparation method thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1323095C (en) * | 2005-05-17 | 2007-06-27 | 孟鋆辉 | Poly aminoester foamed plastics of carbobitumen |
| CN100363578C (en) * | 2006-03-23 | 2008-01-23 | 青岛金北洋工程材料有限公司 | Polyurethane rigid foam material for external thermal insulation system of external wall |
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2001
- 2001-09-30 CN CNB011275286A patent/CN1191304C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1303123C (en) * | 2003-08-29 | 2007-03-07 | 青岛金北洋工程材料有限公司 | Composite catalyst for improving size stability and its asphalt polyurethane hard foam body |
| CN100523084C (en) * | 2007-04-20 | 2009-08-05 | 常熟佳发化学有限责任公司 | Polyurethane resin combination and preparation method and using method thereof |
| CN102093531B (en) * | 2009-12-11 | 2012-12-19 | 财团法人工业技术研究院 | Fireproof polyurethane foamed material and preparation method thereof |
| CN101805559A (en) * | 2010-04-07 | 2010-08-18 | 杭州东科建筑节能材料有限公司 | Polyurethane paint |
| CN105273601A (en) * | 2014-07-24 | 2016-01-27 | 佛山市顺德区合胜化工实业有限公司 | High-strength polyurethane waterproof coating material and preparation method thereof |
| CN105647166A (en) * | 2014-12-05 | 2016-06-08 | 中国石油化工股份有限公司 | Phase change energy storage asphalt polyurethane rigid foam and preparation method thereof |
| CN105713401A (en) * | 2014-12-05 | 2016-06-29 | 中国石油化工股份有限公司 | All-water-blown asphalt-polyurethane hard foam and preparation method thereof |
| CN105647166B (en) * | 2014-12-05 | 2018-10-12 | 中国石油化工股份有限公司 | A kind of phase change energy-storage type is bitumen polyurethane hard foamed and preparation method thereof |
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| CN1191304C (en) | 2005-03-02 |
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Owner name: QINGDAO JINBEIYANG ENGINEERING MATERIALS CO., LTD Free format text: FORMER OWNER: QINGDAO JINBEIYANG ENGINEERING CO. LTD. Effective date: 20050819 |
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