CN102838719B - High hydrophobic organic silicon-polyurethane insulation compound material and preparation method thereof - Google Patents
High hydrophobic organic silicon-polyurethane insulation compound material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high hydrophobic organic silicon-polyurethane insulation compound material and a preparation method of the high hydrophobic organic silicon-polyurethane insulation compound material. The preparation method comprises the steps as follows: introducing hydroxyl-terminated and amino-terminated polysiloxane and a silane coupling agent containing hydroxyl and amino into a main chain or a side chain of polyurethane molecules, and compounding with a hollow microsphere. The compound material is formed by compounding the hollow microsphere with organic silicon-polyurethane with hydrophobic organic silicon chain segments in the main chain or the side chain of the molecules, and can be used for insulation protection of 300-5000m deep marine oil pipelines.
Description
Technical field
The present invention relates to piping insulation field, especially submarine oil, natural gas line field of thermal insulation, more particularly, relate to a kind of high hydrophobic organic silicon modified polyurethane heat-preserving complex material and preparation method thereof.
Background technology
Along with Energy resources demand is further expanded, the exploitation of oil and gas turns to shoaling water, seabed by land, and (500～1500m), super deep-sea (1500～3000m) expansion to deep-sea gradually, and pelagic realm has higher hydrostaticpressure (reaching 30.0MPa) and lower outside temperature (4 ℃/3000m).The generation of the hydrate causing due to low temperature for fear of oil and gas and wax etc. and blocking pipe need to carry out heat insulating processing to pipeline.At present, the heat preservation technology of pipeline is mainly wet type thermal insulation, and having low thermal conductivity is the important indicator of material heat-insulating property, and the water-intake rate of matrices of composite material under High Temperature High Pressure is the key factor that affects lagging material thermal conductivity.In lagging material, compound polyurethane material has the main flow material that the advantages such as shaping cycle is short, mechanical property is high, good heat resistance become field of heat insulating materials.But common compound polyurethane material matrix has the polar group of high level, as-N-H ,-COO-,-COC-,-NH-CO-NH-etc. cause it to have higher water-intake rate, material thermal conductivity increased, thereby affect the heat-insulating property of material.For complicated, the harsh seabed underwater environment of condition, the long-term water-fast heat-insulating property of polyurethane material has much room for improvement.
In recent years, the appearance along with the green high temperature resistant hydrophobic material of organosilicon, extensively receives people's concern, is constantly applied to the hydrophobic heat resist modification aspect of waterproof paint, high temperature resistant device and other macromolecular materials.Patent about silicane-modified polyurethane is actually rare, and wherein, patent US 2006/0270818A1 has invented in polymer molecular chain the polyurethane material containing polysiloxane chain structure; Patent US 2003/0109623A1 by different mass ratio silicone elastomer and polyurethane termoplastic elastomer be mixed to get the polyurethane elastomer containing silicone elastomer; Patent US2008/0125503A1 has prepared hard polyaminoester or polyisocyanurate foam by adding silicane suds-stabilizing agent in the situation that ammonia ester and catalyst for trimerization exist; Patent US 2009/0118455A1 has synthesized the polyurethane-urea elastomer with biologically stable by end amino silicones; Patent US 2011/0201712A1 adopts branching organopolysiloxane to synthesize flame retardant polyurethane foam material by single stage method.But have no report in the silane-modified document at home and abroad for submerged pipeline urethane composite foam lagging material.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of high hydrophobic organosilicon-polyurethane heat-insulation matrix material and preparation method are provided, can on the basis that keeps original material excellent mechanical properties, improve its thermotolerance, reduce water-intake rate, can be applicable to the insulation protection of high undersea hydrostatic pressures high humidity environment, for example the heat-insulation and heat-preservation of submerged pipeline equipment.
Object of the present invention is achieved by following technical proposals:
High hydrophobic organosilicon-polyurethane heat-insulation matrix material and preparation method, adopt super-hydrophobic silane to come modified polyurethane compound to realize, and adopts following feed composition to be prepared according to following step:
After the 3rd component is added and mixed in the first component, then second component is added in said mixture and mixed, and react under preset temp, to obtain target product.
Preparation technology's concrete conditions in the establishment of a specific crime of material is, after the material short mix of three components is even, pour into and be preheating to 50～200 ℃, preferably in the mould of 50～100 ℃, solidify 30～180min, preferably 30～60min demoulding, goods are placed under room temperature (20-25 ℃) and carry out slaking, and (density is 500～900kg/m to have reached final performance
3, compressive property > 40MPa, thermal conductivity <0.13w m
-1k
-1, weight water-intake rate <3%), make a kind of heat-preserving complex material with high hydrophobicity.Wherein the curing time is the time (meeting the required time of above performance) that reactant reaction arrives certain mechanical strength completely, and adopting in 1 week is Best Times, for example 20-170h.
In described the first component, in mass parts, polysiloxane accounts for 5～50 parts; Polyether glycol accounts for 10～50 parts, preferably 30～45 parts; Chainextender accounts for 0～30, preferably 0.5～20 part; Catalyzer accounts for 0.001～4 part, preferably 0.02～2 part; Silane coupling agent accounts for 0.5～5 part, preferably 1～5 part.
In technical scheme of the present invention, adopt polysiloxane to carry out modified polyurethane, described polysiloxane is response type polysiloxane, be preferably terminal hydroxy group or end amino, realization carrys out modified polyurethane base resin by one or more in hydroxy-terminated polysiloxane, response type silane polymer such as end amino silicones etc., make to comprise siloxanes segment in its molecular chain main chain or side chain, wherein hydroxy-terminated polysiloxane number-average molecular weight is 100～6000, preferably 200～3000, viscosity 1～10000mPas, preferably 5～1000mPas; End amino silicones number-average molecular weight is 100～6000, preferably 200～2000, and viscosity 50～10000mpas, preferably 50～2000mPas; While using two kinds of polysiloxane, can select separately equal consumption, structure is as follows simultaneously:
R
1～6for identical or different groups, R
7,8for participating in hydroxyl, the amino of reaction, preferred hydroxyl; The preferred terminal hydroxy group linear polysiloxane of described polysiloxane, i.e. hydroxy silicon oil, i.e. R
1～4for methyl, R
5,6for propyl group, butyl, amyl group, hexyl, ethyl propoxy-, propoxy-, butoxy, phenyl etc.
In described the first component, described polyether glycol is wherein a kind of of following three kinds of polyvalent alcohols: PTMG (PTMEG), number-average molecular weight 250～3000, preferably 250～1000; Polypropylene glycol (PPG), number-average molecular weight 100～3000, preferably 100～1500; Polyoxyethylene glycol (PEG), number-average molecular weight 100～3000, preferably 100～1000.
In described the first component, described silane coupling agent is intended to improve the bonding force between resin matrix and tiny balloon interface, reduce the hole between matrix resin and filler, reduced the infiltration of water molecules, thereby reduced the water-intake rate of material, can select one or more in KH550, KH602, KH792, its trade mark and structural formula are as follows:
γ-aminopropyl triethoxysilane (KH550):
N-(β-aminoethyl)-γ-aminopropyl methyl dimethoxysilane (KH602):
γ-aminoethyl aminopropyl trimethoxysilane (KH792):
In described the first component, described catalyzer comprises tertiary amines, N for example, N-dimethyl benzylamine, triethylamine, 2, 4, 6-(dimethylamino methyl) phenol, N, N-dimethylcyclohexylamine, N, N, N ', N '-Tetramethyl Ethylene Diamine, N-methylmorpholine, quinoline, pyridine etc., quaternary ammonium salt is TMR-2 for example, organometallic compound is dibutyl tin laurate for example, stannous octoate, n-Butyl Lithium, di-n-butyltin dilaurate, capric acid bismuth, capric acid zinc, acetylacetonate nickel, methyl ethyl diketone zirconium, metal complex is such as one or more composite catalysts such as zinc chloride/Trimethylamine 99 complex compounds.The preferred catalyzer of novel environment friendly wherein, wherein, preferably organo-bismuth/zinc environmental protection catalyst such as capric acid bismuth, capric acid zinc and boths' is catalyst compounded, during composite use, the consumption of Zn is Bi 1～10 times.
Described chainextender comprises 1,4-butyleneglycol (BDO), ethylene glycol, propylene glycol, glycol ether, glycerol, TriMethylolPropane(TMP), 1,4-cyclohexanediol, Hydrogenated Bisphenol A, 1,6-hexylene glycol, diethanolamine, trolamine, methyldiethanolamine, diethyl toluene diamine, 3, wherein one or more such as 5-dimethythiotoluene diamine, preferred BDO (BDO), ethylene glycol, propylene glycol, glycol ether, glycerol a kind of wherein.
Described the second component is that isocyanic ester comprises aliphatics, alicyclic, aromatic diisocyanate, polymeric polyisocyanate, isocyanic ester performed polymer, preferably MDI.Wherein, the MDI modification MDI that preferably liquefies, in liquefaction modification MDI containing the modified structures such as uretonimine, biuret, allophanate, isocyanuric acid ester, carbodiimide and carbamate, wherein preferred urethane-modified MDI.Its NCO mass content is 10～30%, preferably 10～28%.Above-mentioned isocyanic ester can carry out commercial, also can be prepared as follows voluntarily: in urethane-modified MDI, according to mass parts meter, polyol component accounts for 5～50 parts, preferably 5～25 parts, 4,4 '-MDI content accounts for 20～80 parts, preferably 30～70 parts, 2,4 '-MDI accounts for 0～60 part, preferably 0～40 part.Modification polyvalent alcohol is PTMEG or PPG, and PTMEG number-average molecular weight is 100～3000, preferably 100～1000; PPG number-average molecular weight is 100～4000, preferably 100～2000.
The mass ratio of described the first component and second component is (1 ~ 3): 1.
Described the 3rd component is tiny balloon, and its consumption is 1%～50% of whole matrix material total mass, preferably 10～30%, and the particle size range of microballoon is 0.1 ~ 700 μ m, preferably 1 ~ 200 micron.Tiny balloon comprises polymer hollow microsphere, ceramic hollow microballoon or glass tiny balloon, includes rare gas element, and density is lower than 0.25g/cc, and the quality packing ratio of tiny balloon is 1%～50%, preferably 10～30%.
Technical solution of the present invention is by introducing terminal hydroxy group, end amino silicones and hydroxyl, amino silane coupling agent in polyurethane molecular main chain or side chain, and itself and tiny balloon is compound, obtain the hydrophobic organosilicon/polyurethane heat-insulation matrix material of a kind of novel height.Described compound polyurethane material is that the urethane of property and dissimilar tiny balloon are composited, and its density is 500～900kg/m
3, compressive property > 40MPa, thermal conductivity <0.13w m
-1k
-1, weight water-intake rate <3%, presents higher hydrophobicity, and its water contact angle becomes 120～175 ° from original 80～90 °; Under material at high temperature high pressure, the water-intake rate of (90 ℃/20MPa) is by original more than 5% reducing to below 2%.Matrix material of the present invention is in molecular backbone chain or side chain, to contain the polysiloxane-polyurethane of hydrophobicity organosilicon segment and the matrix material of tiny balloon, can be used for the marine oil piping insulation protection of 300 ~ 5000m depth of water.
Embodiment
Below in conjunction with specific embodiment, further illustrate technical scheme of the present invention.The explanation of the reagent to using in example below:
Hydroxy-terminated polysiloxane, QLS-203, viscosity≤30mm
2/ s, hydroxy radical content>=8.5%; QLS-203-D, viscosity 38～45mm
2/ s, hydroxy radical content 3.6～4.5%; Wuhan Yi Huacheng development in science and technology company limited;
Polyether glycol PPG-2000, PPG-1000, Shandong blue star east major company;
BDO, glycol ether, dry 4h at 60 ℃, vacuum, Shanghai Ling Feng Chemical Co., Ltd.;
BiCAT, the leading chemical company of the U.S.;
NCO-A, represents modification MDI, and Suprasec 2412, and NCO% is 26.1%; Hensel steps Shanghai urethane company limited;
NCO-B, represents modification MDI, and Suprasec 5005, and NCO% is 30.8%; Hensel steps Shanghai urethane company limited;
Silane coupling agent, KH550, KH602, KH792;
Hollow glass micro-ball K-46, ceramic hollow microballoon G200, Minnesota Mining and Manufacturing Company's product;
Below analytical procedure used be properties of sample method therefor in test invention example.
Contact angle adopts video optics contact angle measurement DSA30Kruss angle gauge formula contact angle instrument to test.Adopt deionized water, water droplet is dripped after film surface (length and width 120 * 120mm, thickness 2mm) l min and tested, each sample is got at a distance of 3 points of spacing 5mm and is measured, and totally 6 readings, get arithmetical av.
Water-intake rate test under high pressure-temperature: the weight water-intake rate in 90 ℃/20MPa deionized water, sample is the high 80mm of cylindrical sample, diameter 30mm adopts after water suction balance the ratio (percentage ratio) of the of poor quality and primary sample quality before and after water suction.
Comparative example:
In the reactor with vacuum and heating unit, by PPG-2000(100g) vacuum-drying 1.5h at 95 ℃, then cool to 50 ~ 60 ℃, by dried BDO(30.4g), silane resin acceptor kh-550 (9.2g) and catalyst B iCAT(0.19g) add, after mixing A component; Subsequently by hollow glass micro-ball K-46(60g) add, after being uniformly mixed, obtain Preblend.
Controlling temperature of charge is 30 ℃, adds 155g modification MDI NCO-A, rapid stirring evenly after, pour into mould temperature and be in the mould of 70 ℃, solidify the demoulding after 1h, sample was placed under dry room temperature condition after 1 week, carried out performance test.The water contact angle result demonstration of sample, the contact angle of urethane/tiny balloon matrix material is 75 °.Water-intake rate test result demonstration under High Temperature High Pressure, the water-intake rate of this material is 5.3%.
Embodiment 1:
In the reactor with vacuum and heating unit, by linear polysiloxane QLS-20340g, PPG-2000(60g) mix and vacuum-drying 1.5h at 95 ℃, then cool to 50 ~ 60 ℃, by dried BDO(29g), silane resin acceptor kh-550 (9.2g) and catalyst B iCAT(0.18g) add, after mixing A component; Subsequently by hollow glass micro-ball K-46(60g) add, after being uniformly mixed, obtain Preblend.
Controlling temperature of charge is 30 ℃, adds 157g modification MDI NCO-A, rapid stirring evenly after, pour into mould temperature and be in the mould of 70 ℃, solidify the 1h demoulding, sample was placed under dry room temperature condition after 1 week, carried out performance test.The water contact angle result demonstration of sample, the contact angle of polysiloxane-polyurethane/tiny balloon matrix material is 135 °; The demonstration of high temperature high voltage resistant water-intake rate test result, its water-intake rate is 1.8%.
Embodiment 2:
In the reactor with vacuum and heating unit, linear polysiloxane QLS-203-D 60g, PPG-1000 (40g) are mixed and vacuum-drying 1.5h at 95 ℃, then cool to 50 ~ 60 ℃, by dried glycol ether (48.1g), silane resin acceptor kh-550 (9.7g) and catalyst B iCAT(0.13g) add, after mixing, obtain A component; Subsequently by hollow glass micro-ball K-46(70g) add, after being uniformly mixed, obtain Preblend.
Controlling temperature of charge is 30 ℃, adds 171g modification MDI NCO-A, rapid stirring evenly after, pour into mould temperature and be in the mould of 70 ℃, solidify the 1h demoulding, sample was placed under dry room temperature condition after 1 week, carried out performance test.The water contact angle result demonstration of sample, the contact angle of polysiloxane-polyurethane/tiny balloon matrix material is 141 °; The demonstration of high temperature high voltage resistant water-intake rate test result, its water-intake rate is 0.9%.
Embodiment 3:
In the reactor with vacuum and heating unit, by linear polysiloxane QLS-20360g, PPG-2000(40g) mix and vacuum-drying 1.5h at 95 ℃, then cool to 50 ~ 60 ℃, by dried glycol ether (42g), silane coupling agent KH-602(10.7g) and catalyst B iCAT(0.21g) add, A component after mixing, obtained; Subsequently by ceramic hollow microballoon G200(70g) add, after being uniformly mixed, obtain Preblend.
Controlling temperature of charge is 30 ℃, adds 191.3g modification MDI NCO-A, rapid stirring evenly after, pour into mould temperature and be in the mould of 70 ℃, solidify the 1h demoulding, sample was placed under dry room temperature condition after 1 week, carried out performance test.The water contact angle result demonstration of sample, the contact angle of polysiloxane-polyurethane/tiny balloon matrix material is 124 °; The demonstration of high temperature high voltage resistant water-intake rate test result, its water-intake rate is 1.1%.
Embodiment 4:
In the reactor with vacuum and heating unit, linear polysiloxane QLS-203-D 30g, PPG-1000 (70g) are mixed and vacuum-drying 1.5h at 95 ℃, then cool to 50 ~ 60 ℃, by dried BDO(45.9g), silane coupling agent KH-792(10.7g) and catalyst B iCAT(0.21g) add, after mixing A component; Subsequently by ceramic hollow microballoon G200(70g) add, after being uniformly mixed, obtain Preblend.
Controlling temperature of charge is 30 ℃, adds 181.3g modification MDINCO-B, rapid stirring evenly after, pour into mould temperature and be in the mould of 70 ℃, solidify the 1h demoulding, sample was placed under dry room temperature condition after 1 week, carried out performance test.The water contact angle result demonstration of sample, the contact angle of polysiloxane-polyurethane/tiny balloon matrix material is 132 °; The demonstration of high temperature high voltage resistant water-intake rate test result, its water-intake rate is 1.4%.
Embodiment 5:
In the reactor with vacuum and heating unit, by linear polysiloxane QLS-20365g, PPG-1000(35g) mix and vacuum-drying 1.5h at 95 ℃, then cool to 50 ~ 60 ℃, by dried glycol ether (30g), silane coupling agent KH-792(8.4g) and catalyst B iCAT(0.13g) add, A component after mixing, obtained; Subsequently by ceramic hollow microballoon G200(55g) add, after being uniformly mixed, obtain Preblend.
Controlling temperature of charge is 30 ℃, adds 120g modification MDI NCO-B, rapid stirring evenly after, pour into mould temperature and be in the mould of 70 ℃, solidify the 1h demoulding, sample was placed under dry room temperature condition after 1 week, carried out performance test.The water contact angle result demonstration of sample, the contact angle of polysiloxane-polyurethane/tiny balloon matrix material is 128 °; The demonstration of high temperature high voltage resistant water-intake rate test result, its water-intake rate is 1.3%.
In the above example, comparative example is without organic-silicon-modified urethane tiny balloon matrix material, embodiment 1～5 is organic silicon modified polyurethane tiny balloon matrix material, by the water-intake rate test result under water contact angle and High Temperature High Pressure, can be found out, contact angle scope containing the compound polyurethane material of organosilicon segment is 120～145 °, is all greater than not containing 70 ~ 90 ° of the water contact angles of organosilyl urethane tiny balloon matrix material; In the water-intake rate test result contrast under High Temperature High Pressure, can find out, containing the water-intake rate of the compound polyurethane material of organosilicon segment, lower than 2%, all be less than not the water-intake rate 5.3% containing organosilyl urethane tiny balloon matrix material.Result shows that the prepared polysiloxane-polyurethane/tiny balloon of the present invention matrix material has higher hydrophobicity and lower water-intake rate.
By above-mentioned test, show, the low water-absorbent composite material of the present invention can be served 300 meters of oceans and is incubated to 5000m petroleum pipe line protection under water, and its comprehensive hydrophobic heat-insulating property is better than prior art.
Above the present invention has been done to exemplary description; should be noted that; in the situation that not departing from core of the present invention, the replacement that is equal to that any simple distortion, modification or other those skilled in the art can not spend creative work all falls into protection scope of the present invention.
Claims (16)
1. high hydrophobic organosilicon-polyurethane heat-insulation matrix material, is characterized in that, adopt super-hydrophobic silane to come modified polyurethane compound to realize, density is 500～900kg/m
3, compressive property > 40MPa, thermal conductivity <0.13wm
-1k
-1, weight water-intake rate <3%, water contact angle is 120～175 °, adopts following feed composition to be prepared according to following step:
After the 3rd component is added and mixed in the first component, then second component is added in said mixture and mixed, and react under preset temp, to obtain target product;
In described the first component, in mass parts, polysiloxane accounts for 5～50 parts; Polyether glycol accounts for 10～50 parts; Chainextender accounts for 0～30; Catalyzer accounts for 0.001～4 part; Silane coupling agent accounts for 0.5～5 part;
Described polysiloxane is response type polysiloxane; Described polyether glycol is wherein a kind of of following three kinds of polyvalent alcohols: PTMG, number-average molecular weight 250～3000; Polypropylene glycol, number-average molecular weight 100～3000; Polyoxyethylene glycol, number-average molecular weight 100～3000; Described silane coupling agent is selected one or more in KH550, KH602, KH792; Described catalyzer comprises one or more composite catalysts in tertiary amines, quaternary ammonium salt, organometallic compound; Described chainextender comprises 1,4-butyleneglycol, ethylene glycol, propylene glycol, glycol ether, glycerol, TriMethylolPropane(TMP), 1,4-cyclohexanediol, Hydrogenated Bisphenol A, 1,6-hexylene glycol, diethanolamine, trolamine, methyldiethanolamine, diethyl toluene diamine, 3, one or more in 5-dimethythiotoluene diamine;
Described second component is isocyanic ester, comprises aliphatics, alicyclic and aromatic diisocyanate, polymeric polyisocyanate, isocyanic ester performed polymer; The mass ratio of described the first component and second component is (1～3): 1;
Described the 3rd component is tiny balloon, its consumption is 1%～50% of whole matrix material total mass, microspherulite diameter is 0.1～700 μ m, described tiny balloon comprises polymer hollow microsphere, ceramic hollow microballoon or glass tiny balloon, include rare gas element, density is lower than 0.25g/cc, and the quality packing ratio of tiny balloon is 1%～50%;
Preparation technology's concrete conditions in the establishment of a specific crime of material is: after the material short mix of three components is even, pour into curing 30～180min demoulding in the mould that is preheating to 50～200 ℃, goods are placed in and under room temperature, carry out slaking, reached final performance, wherein the curing time is the time that reactant reaction arrives mechanical strength completely.
2. the hydrophobic organosilicon-polyurethane heat-insulation matrix material of height according to claim 1, is characterized in that, in described the first component, in mass parts, polysiloxane accounts for 5～50 parts; Polyether glycol accounts for 30～45 parts; Chainextender accounts for 0.5～20 part; Catalyzer accounts for 0.02～2 part; Silane coupling agent accounts for 1～5 part;
In described the first component, to be terminal hydroxy group or end amino silicones carry out modified polyurethane base resin to realize by one or more in hydroxy-terminated polysiloxane, end amino silicones to described polysiloxane, make to comprise siloxanes segment in its molecular chain main chain or side chain, wherein hydroxy-terminated polysiloxane number-average molecular weight is 100～6000, viscosity 1～10000mPas; End amino silicones number-average molecular weight is 100～6000, viscosity 50～10000mPas; While using two kinds of polysiloxane, select separately equal consumption simultaneously;
Described polyether glycol is wherein a kind of of following three kinds of polyvalent alcohols: PTMG, number-average molecular weight 250～1000; Polypropylene glycol, number-average molecular weight 100～1500; Polyoxyethylene glycol, number-average molecular weight 100～1000;
Described catalyzer comprises N, N-dimethyl benzylamine, triethylamine, N, N-dimethylcyclohexylamine, N, N, N', N'-Tetramethyl Ethylene Diamine, N-methylmorpholine, quinoline, pyridine, TMR-2, dibutyl tin laurate, stannous octoate, n-Butyl Lithium, capric acid bismuth, capric acid zinc, acetylacetonate nickel, one or more composite catalysts in methyl ethyl diketone zirconium, zinc chloride/Trimethylamine 99 complex compound;
The preferred BDO of described chainextender, ethylene glycol, propylene glycol, glycol ether, glycerol a kind of.
3. the hydrophobic organosilicon-polyurethane heat-insulation matrix material of height according to claim 2, is characterized in that, described hydroxy-terminated polysiloxane number-average molecular weight preferably 200～3000, and viscosity is 5～1000mPas preferably; End amino silicones number-average molecular weight preferably 200～2000, viscosity is 50～2000mPas preferably; While using two kinds of polysiloxane, select separately equal consumption simultaneously; The preferred capric acid bismuth of described catalyzer, capric acid zinc and boths' is catalyst compounded, during composite use, the consumption of Zn is Bi 1～10 times.
4. the hydrophobic organosilicon-polyurethane heat-insulation matrix material of height according to claim 1, it is characterized in that, described second component is liquefaction modification MDI, in liquefaction modification MDI, contains uretonimine, biuret, allophanate, isocyanuric acid ester, carbodiimide and carbamate.
5. the hydrophobic organosilicon-polyurethane heat-insulation matrix material of height according to claim 4, is characterized in that, the preferred urethane-modified MDI of described second component, and NCO mass content is 10～30%.
6. the hydrophobic organosilicon-polyurethane heat-insulation matrix material of height according to claim 5, is characterized in that, described NCO mass content preferably 10～28%.
7. the hydrophobic organosilicon-polyurethane heat-insulation matrix material of height according to claim 1, is characterized in that, described the 3rd component tiny balloon consumption is 10～30% of whole matrix material total mass, and the particle size range of microballoon is 1～200 micron.
8. the hydrophobic organosilicon-polyurethane heat-insulation matrix material of height according to claim 1, it is characterized in that, preparation technology's concrete conditions in the establishment of a specific crime of material is: after the material short mix of three components is even, pour into curing 30～60min demoulding in the mould that is preheating to 50～100 ℃, goods are placed at 20-25 ℃ of room temperatures and carry out slaking, reached final performance, wherein the curing time is 20-170h.
9. the preparation method of high hydrophobic organosilicon-polyurethane heat-insulation matrix material, adopt super-hydrophobic silane to come modified polyurethane compound to realize, it is characterized in that, after the 3rd component is added and is mixed in the first component, then second component is added in said mixture and mixed, and react under preset temp, to obtain target product;
In described the first component, in mass parts, polysiloxane accounts for 5～50 parts; Polyether glycol accounts for 10～50 parts; Chainextender accounts for 0～30; Catalyzer accounts for 0.001～4 part; Silane coupling agent accounts for 0.5～5 part;
Described polysiloxane is response type polysiloxane; Described polyether glycol is wherein a kind of of following three kinds of polyvalent alcohols: PTMG, number-average molecular weight 250～3000; Polypropylene glycol, number-average molecular weight 100～3000; Polyoxyethylene glycol, number-average molecular weight 100～3000; Described silane coupling agent is selected one or more in KH550, KH602, KH792; Described catalyzer comprises one or more composite catalysts in tertiary amines, quaternary ammonium salt, organometallic compound; Described chainextender comprises 1,4-butyleneglycol, ethylene glycol, propylene glycol, glycol ether, glycerol, TriMethylolPropane(TMP), 1,4-cyclohexanediol, Hydrogenated Bisphenol A, 1,6-hexylene glycol, diethanolamine, trolamine, methyldiethanolamine, diethyl toluene diamine, 3, one or more in 5-dimethythiotoluene diamine;
Described second component is isocyanic ester, comprises aliphatics, alicyclic and aromatic diisocyanate, polymeric polyisocyanate, isocyanic ester performed polymer; The mass ratio of described the first component and second component is (1～3): 1;
Described the 3rd component is tiny balloon, its consumption is 1%～50% of whole matrix material total mass, microspherulite diameter is 0.1～700 μ m, described tiny balloon comprises polymer hollow microsphere, ceramic hollow microballoon or glass tiny balloon, include rare gas element, density is lower than 0.25g/cc, and the quality packing ratio of tiny balloon is 1%～50%;
Preparation technology's concrete conditions in the establishment of a specific crime of material is: after the material short mix of three components is even, pour into curing 30～180min demoulding in the mould that is preheating to 50～200 ℃, goods are placed in and under room temperature, carry out slaking, reached final performance, wherein the curing time is the time that reactant reaction arrives mechanical strength completely.
10. the preparation method of the hydrophobic organosilicon-polyurethane heat-insulation matrix material of height according to claim 9, is characterized in that, in described the first component, in mass parts, polysiloxane accounts for 5～50 parts; Polyether glycol accounts for 30～45 parts; Chainextender accounts for 0.5～20 part; Catalyzer accounts for 0.02～2 part; Silane coupling agent accounts for 1～5 part;
In described the first component, to be terminal hydroxy group or end amino silicones carry out modified polyurethane base resin to realize by one or more of hydroxy-terminated polysiloxane, end amino silicones to described polysiloxane, make to comprise siloxanes segment in its molecular chain main chain or side chain, wherein hydroxy-terminated polysiloxane number-average molecular weight is 100～6000, viscosity 1～10000mPas; End amino silicones number-average molecular weight is 100～6000, viscosity 50～10000mPas; While using two kinds of polysiloxane, select separately equal consumption simultaneously;
Described polyether glycol is wherein a kind of of following three kinds of polyvalent alcohols: PTMG, number-average molecular weight 250～1000; Polypropylene glycol, number-average molecular weight 100～1500; Polyoxyethylene glycol, number-average molecular weight 100～1000;
Described catalyzer comprises N, N-dimethyl benzylamine, triethylamine, N, N-dimethylcyclohexylamine, N, N, N', N'-Tetramethyl Ethylene Diamine, N-methylmorpholine, quinoline, pyridine, TMR-2, dibutyl tin laurate, stannous octoate, n-Butyl Lithium, capric acid bismuth, capric acid zinc, acetylacetonate nickel, one or more composite catalysts in methyl ethyl diketone zirconium, zinc chloride/Trimethylamine 99 complex compound;
The preferred BDO of described chainextender, ethylene glycol, propylene glycol, glycol ether, glycerol a kind of.
The preparation method of organosilicon-polyurethane heat-insulation matrix material that 11. height according to claim 10 are hydrophobic, is characterized in that, described hydroxy-terminated polysiloxane number-average molecular weight preferably 200～3000, and viscosity is 5～1000mPas preferably; End amino silicones number-average molecular weight preferably 200～2000, viscosity is 50～2000mPas preferably; While using two kinds of polysiloxane, select separately equal consumption simultaneously; The preferred capric acid bismuth of described catalyzer, capric acid zinc and boths' is catalyst compounded, during composite use, the consumption of Zn is Bi 1～10 times.
The preparation method of organosilicon-polyurethane heat-insulation matrix material that 12. height according to claim 9 are hydrophobic, it is characterized in that, described second component is liquefaction modification MDI, in liquefaction modification MDI, contains uretonimine, biuret, allophanate, isocyanuric acid ester, carbodiimide and carbamate.
The preparation method of organosilicon-polyurethane heat-insulation matrix material that 13. height according to claim 12 are hydrophobic, is characterized in that, the preferred urethane-modified MDI of described second component, and NCO mass content is 10～30%.
The preparation method of organosilicon-polyurethane heat-insulation matrix material that 14. height according to claim 13 are hydrophobic, is characterized in that, described NCO mass content preferably 10～28%.
The preparation method of organosilicon-polyurethane heat-insulation matrix material that 15. height according to claim 9 are hydrophobic, it is characterized in that, described the 3rd component tiny balloon consumption is 10～30% of whole matrix material total mass, and the particle size range of microballoon is 1～200 micron.
The preparation method of organosilicon-polyurethane heat-insulation matrix material that 16. height according to claim 9 are hydrophobic, it is characterized in that, preparation technology's concrete conditions in the establishment of a specific crime of material is: after the material short mix of three components is even, pour into curing 30～60min demoulding in the mould that is preheating to 50～100 ℃, goods are placed in and at 20-25 ℃, carry out slaking, reached final performance, wherein the curing time is 20-170h.
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