CN105713401B - It is a kind of full water foamed bitumen polyurethane hard foamed and preparation method thereof - Google Patents
It is a kind of full water foamed bitumen polyurethane hard foamed and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of full water foamed bitumen polyurethane hard foamed and preparation method thereof, preparation methods are as follows: (1) asphalt is added in reaction kettle, castor oil is gradually added into after heating and melting, obtain pitch castor oil mixed liquor；(2) polyether polyol, plasticizer are added in the mixed liquor of step (1)；(3) water, curing catalysts etc. are added in the mixture of step (2)；(4) polyisocyanates is added in the mixture of step (3) preparation and carries out foamed solidification molding.The present invention dissolves pitch using castor oil, prepares colas without using organic solvent, and use ODP value is zero water as foaming agent, preparation it is bitumen polyurethane hard foamed have many advantages, such as moisture-proof corrosion resistant, crushing resistance by force, good stability of the dimension.
Description
Technical field
The invention belongs to polyurethane fields, and in particular to a kind of full water foamed bitumen polyurethane hard foamed and its preparation side
Method.
Background technique
Hard polyurethane foam is a kind of heat-insulating material of function admirable, has excellent physical mechanical property and chemically-resistant
Performance is widely used in the various fields such as refrigerator, refrigerator, automobile, building and pipe insulation cold insulation.But since chlorofluorocarbons is sent out
Infusion has a destruction to atmospheric ozone layer, and international convention has produced it and using being made that stringent limitation and regulation.
Full water foamed technology using water as chemical foaming agent instead of traditional fluorochlorohydrocarbon class physical blowing agent, in the system of hard polyurethane foam
During standby, occur to chemically react CO generated using water and isocyanates2Foam, be a kind of ODP value be zero it is new
Type ring protects foaming technique.
Full water foamed system is compared with freon foaming system, and larger, dimensional stability that there are viscosity, cementability are poor etc.
Disadvantage.In order to solve this problem, the companies such as BASF, Bayer by adjusting pfpe molecule structure, develop the poly- of low viscosity
Ether and full water polyethers with good fluidity have good dimensional stability, viscous with the polyurethane foam plastics that this is prepared
Connecing property and lower thermal coefficient.But currently, the water-blown polyurethane rigid foam of several major companies combines material both at home and abroad
It is applied to pipeline at home, density is all larger than 45kg/m3, some density is 55~80kg/m3Deng.When with full water foamed preparation
When low-density polyurethane foam, since water is larger, it will cause foam embrittlement, intensity, dimensional stability and thermal insulation and be deteriorated, and
Rough coat, it is easy to fall off, it is difficult to form fine and close smooth epidermis.
Bitumen polyurethane hard foamed plastics be in conventional polyurethanes foamed plastics component blend part asphalt modification and
The new varieties generated, not only have the heat-insulating property of conventional polyurethanes rigid foam, but also have both the anti-of pitch
The performances such as burn into is anti-aging, resistance to infiltration.
CN1341685A discloses a kind of bitumen polyurethane hard foamed plastics, it is by combination material A and polyisocyanates B
By a certain percentage through chemical blowing, it is made using casting or spraying process.The combination material A is more by coal coke asphalt liquid, polyethers
First alcohol, fire retardant, foam stabiliser, crosslinking agent, catalyst, foaming agent are made through being mixed, and the foaming agent used is HCFC-
141b.The asphalt polyurethane rigid foam of the invention has the corrosion resistance to steel and resists the slacking of atmosphere.
CN1696167 discloses a kind of production method of poly aminoester foamed plastics of carbobitumen, it is moulded in common polyurethane foam
It blends a small amount of tar asphalt in material component and is formed, using alkanes foaming agent such as HCFC-141b, pentamethylene, methylene chloride
In any one.But the halohydrocarbon foaming agents such as HCFC-141b, methylene chloride are volatile at normal temperature, though meeting density
It can make product that there is good epidermis and preferable feel in the case where it is required that, but not meet environmental requirement.In addition, pentamethylene is sent out
Infusion is inflammable and explosive, belongs to dangerous material, and the high requirements on the equipment.
Summary of the invention
In view of the deficiencies in the prior art, the present invention provides a kind of full water foamed bitumen polyurethane hard foamed and its preparations
Method.It is zero water as foaming agent that the present invention, which uses ODP value, preparation it is bitumen polyurethane hard foamed have moisture-proof corrosion resistant,
The advantages that crushing resistance is strong, good stability of the dimension.
Of the invention is full water foamed bitumen polyurethane hard foamed, and formula is as follows, in terms of mass parts:
60~140 parts of asphalt, preferably 60~100 parts
80 parts of polyether polyol
35~50 parts of castor oil
2~8 parts of water, preferably 2~6 parts
2~10 parts of plasticizer, preferably 3~6 parts
0~5 part of curing catalysts, preferably 1~3 part
3~20 parts of organic foam stabilizer, preferably 5~15 parts
0~70 part of fire retardant, preferably 20~30 parts
90~140 parts of polyisocyanates, preferably 100~130 parts.
The full water foamed bitumen polyurethane hard foamed preparation method of the present invention, comprising the following steps:
(1) heating and melting in reaction kettle is added in asphalt and stirred, be warming up to 200 DEG C or more 0.5~2h of heat preservation, so
After be gradually added into castor oil, stirred evenly at 150~170 DEG C, obtain pitch castor oil mixed liquor；
(2) polyether polyol, plasticizer are added in the mixed liquor of step (1) preparation, are stirred at 60~80 DEG C equal
It is even；
(3) water, curing catalysts, organic foam stabilizer and fire retardant are added to the mixture of step (2) preparation
In, at 35~55 DEG C, preferably stirred evenly at 35~50 DEG C；
(4) polyisocyanates is added in the mixture of step (3) preparation, quickly after mixing evenly, is poured into mold
Foamed solidification molding, can be obtained full water foamed bitumen polyurethane hard foamed.
In the present invention, the composition of asphalt is closely bound up with the mechanical strength of final froth pulp, therefore use is 25
Needle penetration is 5~25mm at DEG C, and the asphalt that softening point (ring and ball method) is 40~60 DEG C, preferably needle penetration are 8~18mm's
Asphalt (Asphalt Penetration refers to that at 25 DEG C, standard needle 100g is pierced into the depth of bitumen samples in 5s), Ke Yibao
The mechanical strength of card final products meets the requirements.The softening point of asphalt is 40~60 DEG C, can be at a certain temperature
Adequately and uniformly it is dissolved in castor oil and polyether polyol.Pitch is added in polyether polyol, when usage amount is less, no
Big influence can be generated to polyurethane foam process；But when usage amount is larger, especially because full water foamed system lacks greatly
The dilution and dissolution of the low viscosity foaming agent of amount, can be such that reaction mixture viscosity increases, and pitch is compatible with polyether polyol
Property it is poor, be easy be precipitated.Therefore, it is necessary to improve reaction temperature to be sufficiently mixed each reactant, but temperature improves to a certain extent
Expansion rate can be made to accelerate, and be difficult to control.Therefore, the present invention first dissolves pitch using castor oil at high temperature, by
There is typical unsaturated fatty acid triglyceride structure in castor oil, it can be with phenolic group, alcoholic extract hydroxyl group, amido and imido grpup in pitch
Equal active hydrogen compounds are reacted, and promote dissolution of the pitch in castor oil, therefore castor oil and pitch mixed liquor should be kept the temperature
For a period of time, guarantee that the chemical reaction between pitch and castor oil is complete.Then the pure and mild plasticizer of polyether polyols, castor oil is added
It is affinity to pitch, by reducing the surface tension of pitch, make to be not easy to be blended in originally pitch in polyether polyol more
It is easy to be dispersed in polyether polyol, improves the storage stability of mixture.Meet the asphalt of above-mentioned requirements with
The mixture that castor oil mixed liquor and polyether polyol are prepared after mixing with plasticizer is close with polyisocyanates viscosity, is easy to send out
Soak type.
In the present invention, the degree of functionality of castor oil is 2.2~3.5, and hydroxyl value is 120~300mgKOH/g, preferably 150~
200mgKOH/g, molecular weight are 900~1000.It can be added in castor oil in glycerol, diethylene glycol (DEG), triethylene glycol or sucrose a kind of
Or it is several compounded, be preferably added to glycerol, additional amount accounts for the 10%~30% of castor-oil plant oil quality, preferably 10%~15%.Glycerol,
The addition of diethylene glycol (DEG), triethylene glycol or sucrose facilitates castor oil dissolution pitch, while can also be used as crosslinking agent improvement foams
Brittleness.
In the present invention, it is 3~6, preferably 3~4 that polyether polyol, which selects degree of functionality, and average molecular weight is 200~1200,
Preferably 300~900, viscosity is 500~1800mPas, the preferably polyether polyol of 500~1200mPas.Degree of functionality
Quantity helps speed up foam generating rate more and improves the degree of cross linking of asphalt base foam, can also reduce the use of polyalcohol
Amount.
In the present invention, plasticizer uses dioctyl phthalate, diisooctyl phthalate, the positive fourth of phthalic acid two
Ester, phthalic acid diisobutyl ester, octadecadienoic acid methyl esters, diisooctyl phthalate, triphenyl phosphate, three monooctyl esters,
One or more of two isodecyl Arrcostab of diisononyl adipate and adipic acid.It is preferable to use dioctyl phthalates, can not only be used for
Emulsifier also can be used as viscosity reductant.
In the present invention, foaming agent use water, water number be adjustable density foam, water is more, final foams
Density is lower, but reaction system viscosity increases, and therefore, should adjust foaming agent according to final products density requirements and system viscosity
Dosage.Common use for hard bubble of polyurethane water soluble polyether siloxanes can be used in organic foam stabilizer, main to play emulsification foam
Material, stable foam and the effect for adjusting abscess, facilitate the formation of bubble, control the size and uniformity of abscess.
In the present invention, it is not necessary that the catalyst for promoting polyurethane foam is added, but a certain amount of solidification being added is needed to urge
Agent, such as DABCO DC-2, POLYCAT SA-1, benzhydryl vulcabond, for accelerating consolidating after formation of foam
Change process.Because the castor oil reactivity being added is high, and reaction temperature is high, and reaction speed is very fast, such as adds amines catalysis
Agent and organo-metallic catalyst such as triethanolamine, triethylene diamine, stannous octoate etc. can keep expansion rate too fast and uncontrollable.
And a certain amount of curing catalysts are added can regulate and control expansion rate well, avoid expansion rate too fast and uncontrollable.
In the present invention, liquid additive flame retardant is can be used in fire retardant, such as trichloroethyl phosphate, three chloropropyl phosphoric acid
Ester, methyl-phosphoric acid dimethyl ester etc., can also be used corpuscular type fire retardant such as microcapsule red phosphorus etc., and fire retardant can use above-mentioned fire-retardant
One or more of agent compounding.
In the present invention, the polyisocyanates used is toluene di-isocyanate(TDI) (TDI), diphenylmethyl phenylene diisocyanate
(MDI), one of polymethylene multi-phenenyl isocyanate (PAPI), isophorone diisocyanate (IPDI) or a variety of.It is excellent
It is selected as polymethylene multi-phenenyl isocyanate (PAPI).
The full water foamed preparation of the present invention it is bitumen polyurethane hard foamed, good stability of the dimension, high mechanical strength, waterproof are anti-
It is rotten functional, it can be not only used for external wall and roof water-proof heat preservation, it can also be used to which the corrosion-resistant thermal insulation of pipeline, especially oil field are defeated
Corrosion-resistant thermal insulation on oil pipeline.
Compared with prior art, advantages of the present invention is as follows:
1, asphalt is dissolved using castor oil, prepares colas, environmental protection and economy without using organic solvent；Castor-oil plant
Oil is affinity to pitch, reduces the surface tension of pitch, can make the pitch for being not easy to be blended in polyether polyol originally
It is easier to be dispersed in polyether polyol, mixture excellent storage stability, precipitation phenomenon of flocculating will not occur.
2, using full water foamed technology, since the boiling point of water is 100 DEG C, unlike alkane foaming agent is lower than 50 DEG C in boiling point,
Vaporization volatilization quickly at high temperature, therefore reaction temperature can be improved to 35-55 DEG C, the viscosity of reaction system is further decreased,
Reinforce the mobility of logistics.Especially larger amount of water can be added in the present invention, prepare the asphalt polyurethane hard bubble of low-density
Foam, the smooth densification of foam epidermis effectively increase the corrosion resistance of foam and reduce the water imbibition of foam, solve conventional low
Density water-blown polyurethane rigid foam rough coat, caducous problem.
3, polyether polyol is added in pitch castor oil mixed liquor together with plasticizer, pitch, castor-oil plant can be improved
The viscosity of oil, polyether polyol system, it is close with polyisocyanates viscosity, facilitate foamable reaction.
4, castor oil is the polyol of a kind of high activity, low molecular weight, and alternative part polyether polyol participates in
The foamable reaction of polyurethane foam.Meanwhile the hydroxyl average functionality of castor oil is 2.7 or so, can be promoted in foaming process
Chain extension-crosslinking reaction, forms the higher polyurethane high molecule network of crosslink density.With the polyurethane foam of this combination material preparation
Good stability of the dimension improves the easily crisp problem with resilience difference of conventional pitch polyurethane foam, and the rigid foam generated
Caking property is good.
Specific embodiment
Below with reference to embodiment, the present invention will be further described.Number of the present invention is mass fraction.
In the present invention, the polyether polyol uses degree of functionality 3~4, average molecular weight 600~800, viscosity 800
The polyether polyol of~1000mPas.Castor oil is 2.5~3.0 using degree of functionality, and hydroxyl value is 180~200mgKOH/g, point
The castor oil that son amount is 900~1000.
Embodiment 1
(1) be 8mm by needle penetration, 48 DEG C of softening point of 80 parts of asphalt are added in reaction kettle, and heating is allowed to melt
And stir, it is warming up to 200 DEG C of heat preservation about 1h and then after mixing by 35 parts of castor oil and 3.5 parts of glycerol is added gradually to melt
In the asphalt of change, in 160 DEG C of strong stirring 1h, pitch castor oil mixed liquor is obtained；
(2) 80 parts of polyether polyol, 3 parts of plasticizer dioctyl phthalates are added in the mixed liquor of step (1) preparation,
Continue to stir 2h at 60 DEG C, obtains uniform mixture；
(3) then by 6 parts of water, 3 parts of POLYCAT SA-1,12 parts of organic foam stabilizers, 30 parts of trichloroethyl phosphoric acid
Ester is added in the mixture of step (2) preparation, is stirred evenly at 38 DEG C；
(4) injection-molding foam after addition 115 parts of PAPI, high-speed stirred about 40s in the mixture prepared in step (3), Gu
Bitumen polyurethane hard foamed A can be obtained after chemical conversion type.
Embodiment 2
(1) be 12mm by needle penetration, 56 DEG C of softening point of 100 parts of asphalt are added in reaction kettle, and heating is allowed to melt
Change and stir, is warming up to 200 DEG C of heat preservation about 1h and then after mixing by 50 parts of castor oil and 4 parts of glycerol is added gradually to melt
In the asphalt of change, in 160 DEG C of strong stirring 1h, pitch castor oil mixed liquor is obtained；
(2) 80 parts of polyether polyol, 5 parts of plasticizer dioctyl phthalates are added in the mixed liquor of step (1) preparation,
Continue to stir 2h at 70 DEG C；
(3) then by 4.5 parts of water, 1 part of DABCO DC-2,8 parts of organic foam stabilizers, 25 parts of trichloroethyl phosphoric acid
Ester is added in the mixture of step (2) preparation, is stirred evenly at 45 DEG C；
(4) injection-molding foam after addition 130 parts of PAPI, high-speed stirred about 40s in the mixture prepared in step (3), Gu
Bitumen polyurethane hard foamed B can be obtained after chemical conversion type.
Embodiment 3
(1) be 18mm by needle penetration, 41 DEG C of softening point of 60 parts of asphalt are added in reaction kettle, and heating is allowed to melt
And stir, 200 DEG C of heat preservation about 1h are warming up to, then 40 parts of castor oil are added gradually in the asphalt melted, at 160 DEG C
Strong stirring 1h obtains pitch castor oil mixed liquor；
(2) 80 parts of polyether polyol, 6 parts of plasticizer dioctyl phthalates are added in the mixed liquor of step (1) preparation,
Continue to stir 2h at 80 DEG C；
(3) then by 2.5 parts of water, 1 part of DABCO DC-2,8 parts of organic foam stabilizers, 20 parts of trichlorine propyl phosphates
It is added in the mixture of step (2) preparation, is stirred evenly at 42 DEG C.
(4) injection-molding foam after addition 110 parts of PAPI, high-speed stirred about 40s in the mixture prepared in step (3), Gu
Bitumen polyurethane hard foamed C can be obtained after chemical conversion type.
Comparative example 1
Using material and process conditions same as Example 1, the difference is that foaming agent does not use water, but by 25
Part HCFC-141b, 3 parts of POLYCAT SA-1,12 parts of organic foam stabilizers, 30 parts of trichloroethyl phosphates are added to mixing
It is stirred evenly in kettle.Since boiling point is only 32 DEG C to HCFC-141b under normal pressure, 28 are all made of with blowing temperature so being mixed
℃.Subsequent step can be prepared by bitumen polyurethane hard foamed plastics D after curing molding with embodiment 1.
Comparative example 2
Using material and process conditions same as Example 3, the difference is that castor oil is not used, but by 40 parts
Organic solvent is added in the asphalt of 60 parts of thawings, in 160 DEG C of strong stirring 1h.Organic solvent uses dimethylbenzene.It is subsequent
Step can be prepared by bitumen polyurethane hard foamed E after curing molding with embodiment 3.
Comparative example 3
Using material and process conditions same as Example 3, the difference is that 60 parts of castor oil are added to 60 parts
In the asphalt of thawing, in 160 DEG C of strong stirring 1h.It is poly- to can be prepared by pitch with embodiment 3 for subsequent step after curing molding
Urethane rigid foam F.
Comparative example 4
Using material same as Example 3, the difference is that using preparation method described in CN1341685A, successively
In the material investment reaction kettle of metering, bitumen polyurethane hard foamed G can be prepared by after curing molding.
Comparative example 5
Using material and process conditions same as Example 3, the difference is that 15 parts of castor oil are added to 60 parts
In the asphalt of thawing, in 160 DEG C of strong stirring 1h.It can be prepared by bitumen polyurethane hard foamed H after curing molding.
Above-described embodiment and the bitumen polyurethane hard foamed performance indicator of comparative example preparation are as shown in table 1.
The bitumen polyurethane hard foamed performance indicator of table 1
From table 1 it follows that with full water foamed bitumen polyurethane hard foamed better performances prepared by the present invention, completely
Meet national correlated quality requirement.Polyurethane properties prepared by comparative example 1 are up to standard, but its density is much higher than embodiment 1
Density；The easy embrittlement of foams prepared after dissolving pitch with organic solvent in comparative example 2, it is poor with matrix adhesiveness；Compare
Because the amount that castor oil is added is larger in example 3, the water absorption rate and dimensional stability of preparation are all accordingly reduced, and foams easily shrink change
Shape；Foam density obviously increases in comparative example 4, and foams are more crisp, poor with base bonding property；Castor oil is added in comparative example 5
Amount it is less, pitch is easier to be precipitated, and prepare foams it is more crisp.
Claims (10)
1. a kind of full water foamed bitumen polyurethane hard foamed preparation method, it is characterised in that the following steps are included:
(1) asphalt is added in reaction kettle and heating and melting and is stirred, be warming up to 200 DEG C or more 0.5~2h of heat preservation, then by
Castor oil is gradually added, is stirred evenly at 150~170 DEG C, obtains pitch castor oil mixed liquor；
(2) polyether polyol, plasticizer are added in the mixed liquor of step (1) preparation, are stirred evenly at 60~80 DEG C；
(3) water, curing catalysts, organic foam stabilizer and fire retardant are added in the mixture of step (2) preparation,
It is stirred evenly at 35~55 DEG C of temperature；
(4) polyisocyanates is added in the mixture of step (3) preparation, quickly after mixing evenly, pours into mold and foam
Curing molding can be prepared by bitumen polyurethane hard foamed；
Wherein full water foamed bitumen polyurethane hard foamed formula is as follows, in terms of mass parts:
60~100 parts of asphalt, 80 parts of polyether polyol, 35~50 parts of castor oil, 2~6 parts of water, 3~6 parts of plasticizer, Gu
Change 1~3 part of catalyst, 5~15 parts of organic foam stabilizer, 20~30 parts of fire retardant, 100~130 parts of polyisocyanates.
2. according to the method for claim 1, it is characterised in that: asphalt is that needle penetration is 50~250 1/ at 25 DEG C
10mm, the asphalt that softening point is 40~60 DEG C.
3. according to the method for claim 1, it is characterised in that: the degree of functionality of castor oil be 2.2~3.5, hydroxyl value be 120~
300mgKOH/g, molecular weight are 900~1000.
4. according to the method for claim 1, it is characterised in that: the hydroxyl value of castor oil is 150~300mgKOH/g.
5. according to method described in claim 3 or 4, it is characterised in that: glycerol, diethylene glycol (DEG), triethylene glycol are added in castor oil
Or one or more are compounded in sucrose, additional amount accounts for the 10%~30% of castor-oil plant oil quality.
6. according to the method for claim 5, it is characterised in that: glycerol is added in castor oil, additional amount accounts for castor-oil plant oil
The 10%~15% of amount.
7. according to the method for claim 1, it is characterised in that: it is 3~6 that polyether polyol, which selects degree of functionality, mean molecule
Amount is 200~1200, and viscosity is the polyether polyol of 500~1800mPas.
8. according to the method for claim 1, it is characterised in that: plasticizer uses dioctyl phthalate, phthalic acid two
Different monooctyl ester, n-butyl phthalate, phthalic acid diisobutyl ester, octadecadienoic acid methyl esters, two isodecyl of phthalic acid
One or more of ester, triphenyl phosphate, two isodecyl Arrcostab of three monooctyl esters, hexanedioic acid dinonyl and adipic acid；Solidification is urged
Agent is using one or more of DABCO DC-2, POLYCAT SA-1 and benzhydryl vulcabond；Fire retardant uses
One or more of trichloroethyl phosphate, trichlorine propyl phosphate, methyl-phosphoric acid dimethyl ester and microcapsule red phosphorus.
9. according to the method for claim 1, it is characterised in that: polyisocyanates is toluene di-isocyanate(TDI) (TDI), hexichol
Dicyclohexylmethane diisocyanate (MDI), polymethylene multi-phenenyl isocyanate (PAPI) and isophorone diisocyanate (IPDI)
One or more of.
10. it is described in accordance with the claim 1 it is full water foamed it is bitumen polyurethane hard foamed external wall and roof water-proof heat preservation,
The application of corrosion-resistant thermal insulation on the corrosion-resistant thermal insulation and oilfield oil pipeline of pipeline.
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| CN109485899A (en) * | 2018-09-25 | 2019-03-19 | 青岛世林新海绵有限公司 | Halogen-free flameproof foam and preparation method thereof |
| EP4008737A1 (en) * | 2020-12-02 | 2022-06-08 | Logstor A/S | An insulated pipe with an increased compressive strength and axial shear strength |
| CN113845640B (en) * | 2021-11-16 | 2023-03-03 | 万华化学集团股份有限公司 | Polyether polyol for polyurethane foam plastic and preparation method and application thereof |
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| US4225678A (en) * | 1979-07-19 | 1980-09-30 | George F. Thagard, Jr. | Foamed polyurethane materials with a bitumen and a hydroxy fatty oil |
| EP0787069B1 (en) * | 1994-10-20 | 2002-03-06 | Thagard, George F. III | Asphaltic foam |
| CN1191304C (en) * | 2001-09-30 | 2005-03-02 | 青岛金北洋工程有限公司 | Bitumen polyurethane hard foamed plastics and preparation method thereof |
| CN1202172C (en) * | 2003-08-07 | 2005-05-18 | 张树华 | Waterproof and heat holding hard polyether ester with asphalf mixed for building and its prepn process |
| 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 |
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