CN106046317B - A kind of polyurethane combined material and its polyurethane heat insulation material of preparation - Google Patents
A kind of polyurethane combined material and its polyurethane heat insulation material of preparation Download PDFInfo
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- CN106046317B CN106046317B CN201610340924.5A CN201610340924A CN106046317B CN 106046317 B CN106046317 B CN 106046317B CN 201610340924 A CN201610340924 A CN 201610340924A CN 106046317 B CN106046317 B CN 106046317B
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- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
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- C08G18/72—Polyisocyanates or polyisothiocyanates
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- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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Abstract
The present invention provides a kind of polyurethane combined material and its polyurethane heat insulation material of preparation.The combination material includes polyol component and isocyanate component, and the isocyanate component includes polyisocyanates and modified isocyanate.The combination material has preferable mobility, prepared thermal insulation material has extremely low thermal conductivity factor, suitable for the various fields more demanding to heat insulation effect, especially it is had excellent performance in low-temperature deep environment, with splendid low-temperature flexibility and dimensional stability, the pipe insulation material particularly useful for making conveying deep cooling medium.
Description
Technical field
The invention belongs to polyurethane field, further to polyurethane foamed material, further relate to it is a kind of have compared with
Good mobility, low thermal conductivity, low temperature resistant polyurethane pipe insulation material.
Background technology
Hard polyurethane foam is mostly hole-closing structure, has that insulation effect is good, light-weight, specific strength is big, easy for construction etc. excellent
Characteristic, while also there is sound insulation, shockproof, electrical isolation, heat-resisting, cold-resistant, solvent resistant, it is widely used in the case of refrigerator, refrigerator-freezer
The heat-insulating materials such as body heat insulation layer, freezer, refrigerator car, building, storage tank and pipe insulation material, on a small quantity for nonadiabatic occasion,
Such as imitation wood material, packaging material.
Insulating tube is the abbreviation of insulated piping, is mainly used for the conveying of liquid, gas and other media, oil, chemical industry,
The adiabatic heat-insulation engineering of the pipelines such as central heating, central air-conditioning, municipal administration.With the development of the city, to urban heat supplying it is universal with
And thermal requirements are gradually increased, hard polyurethane foam insulating tube will preferably be developed.Hard polyurethane foam insulating tube can be
Long-term operation at 120 DEG C, thermal conductivity factor is relatively low, and heat insulation effect is good, and water absorption rate, percent opening is low, can preferably keep the temperature and waterproof,
Greatly reduce the whole heat consumption of heat preservation and heat supply pipeline.
Document《Application of the polyurethane foam plastics in utilidor》(Wei Chunliu, engineering plastics application, 2003 02
Phase, volume 31, p34) elaborate raw material, reaction principle and the performance of polyurethane foam plastics, describe polyurethane foam plastics
Preparation process, construction method in pipe insulation construction and points for attention in the construction process, and illustrate one step foaming
The major advantage of the method for forming describes the pipeline that certain factory's living area steam heating changes in hot water heating engineering and uses polyurethane plastics
Make heat insulation effect during thermal insulation material.
Patent CN102391775A discloses a kind of high temperature resistant polyurethane pipeline combination material, the polyurethane thermal pipe of the invention
Road expects there is good heat-resisting quantity with combination, will not lose its mechanical property under 120 DEG C or more high temperature, nothing under 200 DEG C of high temperature
Carbonization.
Patent CN203404562U discloses a kind of polyurethane foam plastics utilidor, has the poly- second of low temperature resistant cracking resistance
The polyurethane foam plastics utilidor of alkene outer protection tube has good low temperature resistance, insulating tube under -40 DEG C or so environment
Cracking rate within 5%, cost is suitable with current conventional products cost, meets the construction requirement under low-temperature cold environment.
But with the exhaustion of traditional energy and energy-saving and environment-friendly requirement, the storage and conveying of the novel environment friendly energy are increasingly
More, the cryogenic liquids such as LPG, LNG propose higher requirement to the cold insulation performance and cryogenic environment performance of conveyance conduit.
Traditional polyurethane pipe insulation material can not meet the rigors of the application field.
Patent CN1221433 discloses a kind of by polyalcohol and polyisocyanates and foaming agent and the life of optional blowing promotor
The method for producing hard polyurethane foams with low heat conductivity improves foam thermal conductivity by using extraordinary polyalcohol.It is but extraordinary polynary
The use of alcohol reduces the foam toughness under bubble mobility and low temperature.
Patent CN103709355A be related to a kind of modified polyurethane spraying combination material for ultralow temperature LNG storage tank cold insulation and
Preparation method.The dimensional stability under foam low temperature is improved by using specialty polyesters.But to the thermal conductivity factor of foam system
Do not improve, and domestic technique is mostly traditional pouring type, the combination material viscosity is larger, and mobility is poor.
Although studies have reported that being added in white material system using special polyether or specialty polyesters, foam low temperature can be improved
Dimensional stability, but the polyalcohol of high hydroxyl value can further reduce the mobility of combination material, in view of domestic main pouring type
Utilidor is very high to the requirement of the combination stream property moved, and above-mentioned adjustment mode can seriously affect the Density Distribution of pipe insulating layer, into
One step influences the homogeneity and heat insulation effect of foam.
The practical thermal conductivity factor of conventional urethane pipe insulation material is 0.03W/mK or so, and the resistance to pressure difference ability of abscess is weaker,
Low-Temperature Size stability is poor, is easily generated under cryogenic environment and shrinks even crack, can not ensure the long-term heat preservation effect of pipeline,
And there are larger security risks.The thermal requirements for deep cooling medium cannot have been met.
Invention content
The present invention provides a kind of polyurethane combined material, which has preferable mobility, prepared thermal insulation material tool
There is extremely low thermal conductivity factor, had excellent performance in low-temperature deep environment, there is splendid low-temperature flexibility and dimensional stability, be applicable in
In the pipeline for preparing conveying deep cooling medium.
The present invention also provides a kind of method using the combination material production polyurethane heat insulation material and its poly- ammonia of preparation
Ester thermal insulation material.
For solution more than technical problem, the technical solution adopted by the present invention is as follows：
A kind of polyurethane combined material, including component A and B component, component A includes polyol component, and B component is isocyanates
Component, the B component are included following component, are calculated on the basis of B component gross weight：
55~80wt% of polyisocyanates, preferably 60~75wt%；
20~45wt% of modified polyisocyanate, preferably 25~40wt%.
Polyisocyanates of the present invention includes following component, is calculated on the basis of the gross weight of polyisocyanates：
Poly methylene poly phenyl poly isocyanate (abbreviation PM) 60~80wt%, preferably 65~75wt%；
Toluene di-isocyanate(TDI) (abbreviation TDI) 13~35wt%, preferably 15~25wt%；
Hexamethylene diisocyanate (abbreviation HDI) 3~25wt%, preferably 5~15wt%.
Modified polyisocyanate of the present invention includes following component, is counted on the basis of the gross weight of modified polyisocyanate
It calculates：
NCO content is 22~26wt%, and viscosity is the modification polymethylene polyphenyl polyisocyanic acid of 30000~60000cp
Ester (referred to as modified PM) 70~90wt%, preferably 75~85wt%；
NCO content is 30~35wt%, the modified toluene diisocyanate (referred to as modified TDI) that viscosity is 200~400cp
3~25wt%, preferably 5~15wt%；
NCO content is 27~31wt%, and the modified diphenylmethane diisocyanate that viscosity is 500~1000cp is (referred to as
Modified MDI) 3~25wt%, preferably 5~15wt%.
The NCO content of PM of the present invention is 30.5~32wt%, and viscosity is 150~250cp, degree of functionality for 2.5~
3.0, it is preferred that the example of suitable PM includes but not limited to PM200, DOW chemistry of Wanhua Chemical Group Co., Ltd.
The PAPI 27 of company, Cosmonate M-200 of Mitsui force field Chemical Co., Ltd., Japanese polyurethane industry strain formula meeting
Millionate MR-200 of society, the 44V20 of Bayer companies, BASF AG M20s and Huntsman companies 5005 in
It is one or more, the PM200 of more preferable Wanhua Chemical Group Co., Ltd..
TDI of the present invention includes 2,4-TDI and/or 2,6-TDI；Preferably comprise 50~90wt% 2,4-TDI and
The TDI mixtures of 2, the 6-TDI of 10~50wt%, the example of suitable TDI include but not limited to the Mondur of Bayer companies
The Suprasec TDI 80/20 of TD-80, Huntsman company, the Cosmonate T- of Mitsui force field Chemical Co., Ltd.
80th, it is one or more in the Voranate T-80 of the Lupranate T-80 and DOW chemical companies of BASF AG；It is preferred that
The Lupranate T-80 of BASF AG.
The example of HDI of the present invention includes but not limited to Desmodur T of Bayer companies, Mitsui force field
Learn the Takenate 700 of Co., Ltd., Rhodia companies HDI and Degussa companies Vestanat HDI in one kind or
It is a variety of；It is preferred that the Desmodur T of Bayer companies.
The modifying agent that modified PM of the present invention, modified TDI and modified MDI are used is small molecular alcohol, high functionality gathers
It is one or more in ethoxylated polyhydric alcohol and polyester polyol.
MDI of the present invention includes one or more in 4,4 '-MDI, 2,4 '-MDI and 2,2 '-MDI.Suitably
The example of MDI includes but not limited to MDI100, MDI50, Bayer company of Wanhua Chemical Group Co., Ltd.
Desmodur 44MC, Lupranate MS of BASF AG, Mitsui force field Chemical Co., Ltd. Cosmonate PH and
It is one or more in the Suprasec 1004 of Huntsman companies, preferred Wanhua Chemical Group Co., Ltd.
MDI100 and/or MDI50.
Small molecular alcohol in modifying agent of the present invention is that degree of functionality is 2~6, and molecular weight is 80~300 polyalcohol.
The example of suitable small molecular alcohol includes but not limited to butanediol, pentanediol, hexylene glycol, diglycol, a contracting dipropyl two
It is one or more in alcohol, tripropylene glycol, 1,2,6- hexanetriols, triethylene-glycol, pentaerythrite and sorbierite.
High functionality polyether polyol in modifying agent of the present invention is polyhydroxy-alcohol and ethylene oxide and/or epoxy
Propane is polymerized, number-average molecular weight be 200~1000, hydroxyl value be 300~600mgKOH/g, degree of functionality be 3~8 it is polynary
Alcohol, the example of the polyhydroxy-alcohol is including but not limited to sucrose, sorbierite, xylitol, pentaerythrite, glycerine and trihydroxy methyl
It is one or more in propane.The example of suitable high functionality polyether polyol includes but not limited to ten thousand China chemical (Ningbo) and holds
Prestige polyurethane Co., Ltd 6245, A29-1, the N-635, N-635SA of Jiangsu Zhongshang Chemical Co., Ltd., Tianjin third oil
It is one or more in the SY-6560 in chemical plant and the GR-635S of Shanghai Gaoqiao petrochemical corporation (complex)；It is preferred that ten thousand China's chemistry are (peaceful
Wave) Rong Wei polyurethane Co., Ltd 6245.
Polyester polyol in modifying agent of the present invention is aromatic carboxylic acid, aromatic carboxylic acid acid anhydride, terephthalic acid (TPA)
The reaction product between one or more and diglycol (DEG) and/or glycerine in Arrcostab.Suitable aromatic series
The example of carboxylic acid (acid anhydride) includes but not limited to phthalic acid, phthalic anhydride, M-phthalic acid, terephthalic acid (TPA), inclined benzene
It is one or more in three acid anhydrides；The carbon atom number of terephthaldehyde's acid alkyl ester is 10~16.Suitable terephthaldehyde
The example of acid alkyl ester is including but not limited to dimethyl terephthalate (DMT), diethyl terephthalate, dibutyl terephthalate
Deng.The example of suitable polyester polyol includes but not limited to the PS-3152 of Nanjing Nanjing Si Taipan Chemical Co., Ltd.s (with neighbour
Phthalate anhydride is formed with DEG polycondensations, hydroxyl value 315mgKOH/g, average functionality 2), PS-2002 is (with phthalic acid
Acid anhydride is formed with DEG polycondensations, hydroxyl value 200mgKOH/g, average functionality 2), the CF- of Jiangsu Fu Sheng new materials Co., Ltd
6245 (using dimethyl terephthalate (DMT), DEG, adipic acid as raw material, carry out transesterification, polycondensation etc. and react, hydroxyl value is
250mgKOH/g, average functionality 2) and CF-6200 (formed using dimethyl terephthalate (DMT), DEG as raw material polycondensation, hydroxyl value is
200mgKOH/g, average functionality 2) in one or more, the preferably PS- of Nanjing Nanjing Si Taipan Chemical Co., Ltd.s
3152。
Modified PM of the present invention is by PM of the present invention and small molecular alcohol, high functionality polyether polyol and polyester
One or more 2~3h that reacted at 30~100 DEG C in polyalcohol are obtained, 15~30wt% of NCO content, preferably 20~
25wt%.It is preferred that diglycol, dipropylene glycol, tripropylene glycol, ten thousand China chemical (Ningbo) appearance prestige polyurethane have
The 6245 of limit company, the reaction product of the one or more and PM in the PS-3152 of Nanjing Nanjing Si Taipan Chemical Co., Ltd.s；
More preferable diglycol, dipropylene glycol, tripropylene glycol, Wanhua Chemical (Ningbo) Rongwei Polyurethane Co., Ltd.
6245, one or more in the PS-3152 of Nanjing Nanjing Si Taipan Chemical Co., Ltd.s have with ten thousand magnificent chemical groups shares
The reaction product of the PM200 of limit company.
Modified TDI of the present invention is by TDI of the present invention and small molecular alcohol, high functionality polyether polyol and gathers
One or more 2~3h that reacted at 30~100 DEG C in ester polyol are obtained, 20~40wt% of NCO content, preferably 25~
35wt%.It is preferred that diglycol, dipropylene glycol, Nanjing Nanjing Si Taipan Chemical Co., Ltd.s PS-2002 and ten thousand
One or more reaction products with TDI in the 6245 of magnificent chemistry (Ningbo) Rong Wei polyurethane Co., Ltd；A more preferable contracting
Diethylene glycol, dipropylene glycol, Nanjing Nanjing Si Taipan Chemical Co., Ltd.s PS-2002 and Wan Hua chemistry (Ningbo) Rong Wei
The reaction product of the Lupranate T-80 of one or more and BASF AG in the 6245 of polyurethane Co., Ltd.
Modified MDI of the present invention is by MDI of the present invention and small molecular alcohol, high functionality polyether polyol and gathers
One or more 2~3h that reacted at 30~100 DEG C in ester polyol are obtained, 15~35wt% of NCO content, preferably 20~
30wt%.It is preferred that MDI and butanediol, pentanediol, hexylene glycol, diglycol, dipropylene glycol, tripropylene glycol,
1,2,6- hexanetriols, the 6245 of Wanhua Chemical (Ningbo) Rongwei Polyurethane Co., Ltd. and the limited public affairs of Nanjing Nanjing Si Taipan chemistry
One or more reaction products in the PS-3152 of department；The MDI100 of more preferable Wanhua Chemical Group Co., Ltd. and/
Or MDI50 and butanediol, pentanediol, hexylene glycol, diglycol, dipropylene glycol, tripropylene glycol, 1,2,6- oneself
Triol, the 6245 of Wanhua Chemical (Ningbo) Rongwei Polyurethane Co., Ltd. and Nanjing Nanjing Si Taipan Chemical Co., Ltd.s PS-
One or more reaction products in 3152.
The polyol component of component A of the present invention includes small molecule polyol, polyether polyol, polyester polyol, gathers
Carbonate diol, polymer polyatomic alcohol, grease or combination.
The degree of functionality of the small molecule polyol of component A of the present invention is 2~6, and molecular weight is 50~500.It can be used for
The example of the small molecule polyol of the present invention includes but not limited to：Ethylene glycol, diglycol, diethylene glycol, triethylene glycol, four
Glycol, 1,2- propylene glycol, 1,3- propylene glycol, 1,4- butanediols, 3- methyl-1s, 5- pentanediols, 1,5- pentanediols, 1,6- oneself two
Positive penta triol of alcohol, 1,10- decanediols, glycerine, 1,2,4- butantriols, 1,2,5-, positive penta triols of 1,3,5-, 1,2,6- just oneself three
The positive hexanetriol of alcohol, 1,2,5-, the positive hexanetriols of 1,3,6-, tri hydroxy methyl butane, trimethylolpropane or two (trimethylolpropanes),
Trimethylolethane, pentaerythrite, dipentaerythritol and sorbierite or combination.In some preferred embodiments of the invention,
Small molecule polyol is selected from：Glycerine, diglycol, ethylene glycol, propylene glycol, trimethylolpropane, diethylene glycol (DEG), pentaerythrite
Or combination.
The degree of functionality of the polyether polyol of component A of the present invention is 2~6, preferably 2~4, number-average molecular weight 100
~8000, preferably 300~5000.The polyether polyol can be prepared by known technical process, for example, being deposited in catalyst
Under, reacted and be made with initiator by alkylene oxide.The catalyst is preferably but not limited to alkaline hydrated oxide, alkalinity
Alkoxide, Antimony pentachloride, boron fluoride close ether or their mixture.The alkylene oxide is preferably but not limited to tetrahydrochysene furan
It mutters, ethylene oxide, propylene oxide, 1,2- epoxy butanes, 2,3- epoxy butanes, styrene oxide or their mixture, especially
Optimization ethylene oxide and/or propylene oxide.The initiator is preferably but not limited to polyol or polyamines base chemical combination
Object, the polyol are preferably but not limited to water, ethylene glycol, 1,2-PD, 1,3-PD, diethylene glycol (DEG), three hydroxyl first
Base propane, glycerine, bisphenol-A, bisphenol S or their mixture, the polyamines based compound, are preferably but not limited to ethylenediamine, third
Diamines, butanediamine, hexamethylene diamine, diethylenetriamines, toluenediamine or their mixture.
The polyester polyol of component A of the present invention, by one in dicarboxylic acids, dicarboxylic acid anhydride, dicarboxylic esters
Kind or a variety of be made with polyol reaction.The degree of functionality 2~3 of the polyester polyol, preferably 2, number-average molecular weight 200~
1000, preferably 400~800.The dicarboxylic acids is preferably but not limited to the aliphatic carboxylic acid containing 2~12 carbon atoms, in fact
Example including but not limited to succinic acid, malonic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, decanedioic acid, dodecyl carboxylic acid,
Maleic acid, fumaric acid, phthalic acid, isophathalic acid, terephthalic acids or their mixture.The binary carboxylic
Acid anhydrides is preferably but not limited to phthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride or their mixture.The dicarboxylic esters
It is preferably but not limited to dimethyl terephthalate (DMT), diethyl terephthalate, dibutyl terephthalate, adipate ester, pungent two
Acid esters, dimethyl sebacate, dodecanedioic acid dibutyl ester, tridecandioic acid dimethyl ester or their mixture.It is described with two
The polyalcohol of one or more reactions in first carboxylic acid, dicarboxylic acid anhydride, dicarboxylic esters, is preferably but not limited to ethylene glycol, two
Glycol (DEG), 1,2- propylene glycol, 1,3- propylene glycol, dipropylene glycol, 1,3- methyl propanediols, 1,4- butanediols, 1,5- penta 2
Alcohol, 1,6-HD, neopentyl glycol, 1,10- decanediols, glycerine, trimethylolpropane or their mixture.Described
Polyester polyol further includes the polyester polyol prepared by lactone.The polyester polyol prepared by lactone, it is preferably but unlimited
In 6-caprolactone.
The polycarbonate glycol of component A of the present invention, can be by dihydric alcohol and dialkyl carbonic ester or diaryl carbon
Acid esters or phosgene reaction are made, and number-average molecular weight is 100~1500, preferably 200~1000.The dihydric alcohol, preferably but not
It is limited to 1,2- propylene glycol, 1,3- propylene glycol, 1,4- butanediols, 1,5- pentanediols, 1,6-HD, diethylene glycol (DEG), metaformaldehyde two
Alcohol or their mixture.The dialkyl carbonic ester or diaryl carbonate, are preferably but not limited to diphenyl carbonate.
The grease of component A of the present invention includes animal oil and/or vegetable oil and/or their derivative, the oil
The preferred castor oil of fat, soybean oil, safflower oil, linseed oil, corn oil, sunflower oil, olive oil, Semen Brassicae Campestris oil, sesame oil, cottonseed
Oil, palm oil, rapeseed oil, tung oil, high oleic safflower oil, high oleic acid soybean oil, high oleic acid peanut oil, high oleic sunflower oil,
High oleic acid Semen Brassicae Campestris oil, high erucic acid rape seed oil and the derivative of one or more or above-mentioned animal oil in fish oil and/or vegetable oil
Object, the derivative include one or more in partial hydrogenation product, epoxidation product.
Preferably, the polyol component of component A of the present invention include following component, using the gross weight of polyol component as
Benchmark：
Degree of functionality is 2~3, and number-average molecular weight is 4000~7000, and preferably degree of functionality is 3, number-average molecular weight for 4500~
6000 1 20~60wt% of polyether polyol, preferably 30~50wt%；
Degree of functionality is that 3~5 number-average molecular weights are 200~700, and preferably degree of functionality is 4, and number-average molecular weight is 300~500
2 10~40wt% of polyether polyol, preferably 15~30wt%；
Degree of functionality is 2, and number-average molecular weight is 200~1000, and preferably degree of functionality is 2, and number-average molecular weight is 300~700
10~40wt% of polyester polyol, preferably 15~30wt%；
Degree of functionality is 2~4, and number-average molecular weight is 500~1500, and preferably degree of functionality is 3, number-average molecular weight for 700~
1300 10~40wt% of grease, preferably 15~35wt%.
The initiator of polyether polyol 1 of the present invention is ethylene glycol, propylene glycol, diglycol, a contracting dipropyl
Glycol, triethylene-glycol, glycerine, trimethylolpropane, triethanolamine, diethanol amine and one kind in 1,2,6- hexanetriols or
A variety of, polymerized unit is propylene oxide and/or ethylene oxide, and preferably initiator is glycerine, and polymerized unit is propylene oxide and ring
Oxidative ethane, the example of suitable polyether polyol 1 include but not limited to the TEP-330N of three petrochemical industry of Tianjin, Shanghai Gaoqiao company
GEP-330N etc..
The initiator of polyether polyol 2 of the present invention is ethylenediamine, dipropylene glycol, triethylene-glycol, sweet
Oil, trimethylolpropane, triethanolamine, diethanol amine, ortho-toluene diamine, p-phenylenediamine, sucrose, sorbierite, xylitol and season
One or more in penta tetrol, polymerized unit is propylene oxide and/or ethylene oxide, and preferably initiator is ortho-toluene diamine,
Polymerized unit is propylene oxide and ethylene oxide, and the example of suitable polyether polyol 2 includes but not limited to ten thousand China's chemistry (rather
Wave) Rong Wei polyurethane Co., Ltd R4036, R2438A etc..
The polyester polyol of component A of the present invention is preferably aromatic binary carboxylic acid, aromatic carboxylic acid acid anhydride, aliphatic
The one or more and DEG of dicarboxylic acids and carboxylate reacts the polyester polyol prepared.
The present invention prepares the preferred phthalic acid of the aromatic carboxylic acid of the polyester polyol in component A；The fragrance
The preferred phthalic anhydride of race's carboxylic acid anhydrides；The preferred adipic acid of aliphatic carboxylic acid, the preferred terephthalic acid (TPA) two of carboxylate
Methyl esters.
The suitable example of polyester polyol of component A of the present invention includes but not limited to Nanjing Nanjing Si Taipan chemistry
Co., Ltd production polyester polyol PS-3152 (formed with phthalic anhydride and DEG polycondensations, hydroxyl value 315mgKOH/g,
Average functionality be 2), Nanjing Nanjing Si Taipan Chemical Co., Ltd.s production polyester polyol PS-2002 (with phthalic acid
Acid anhydride is formed with DEG polycondensations, hydroxyl value 200mgKOH/g, average functionality 2), Jiangsu Fu Sheng new materials Co., Ltd production
Polyester polyol CF-6245 (using dimethyl terephthalate (DMT), DEG, adipic acid as raw material, carry out transesterification, the reaction such as polycondensation and
Into hydroxyl value 250mgKOH/g, average functionality 2), Jiangsu Fu Sheng new materials Co., Ltd production polyester polyol CF-
6200 (being formed using dimethyl terephthalate (DMT), DEG as raw material polycondensation, hydroxyl value 200mgKOH/g, average functionality 2), Jining
The polyester polyol HKP-2022 of hundred river Chemical Co., Ltd.s production (is formed, hydroxyl value is using adipic acid, DEG as raw material polycondensation
220mgKOH/g, average functionality 2) etc..
The grease of component A of the present invention, preferred plant grease are made of peroxide treatment, suitable to plant
The example of physical property grease include but not limited to Semen setariae oil, peanut oil, olive oil, camellia oil, palm oil, sunflower oil, soybean oil,
Sesame oil, linseed oil, corn oil, walnut oil etc., preferably soybean oil and/or linseed oil.
Preferably, water, catalyst, foaming agent, foam stabiliser, plasticising can also be included in component A of the present invention
Agent etc..
It is furthermore preferred that component A of the present invention includes following components, calculated on the basis of the gross weight of component A：
The weight ratio of component A and B component of the present invention is 1：1.3~1.6, preferably 1：1.4~1.5.
Catalyst of the present invention includes one or more in tertiary amine catalyst and organometallic catalysts.
The applicable tertiary amine catalyst of the present invention includes pentamethyl-diethylenetriamine, N- methylimidazoles, 1,2- dimethyl miaows
Azoles, N, N- dimethyl cyclohexyl amines, triethylene diamine, N-methylmorpholine, N-ethylmorpholine, N- cyclohexyl morpholines, triethylamine, three fourths
Amine, 1,4- lupetazins, N, N- dimethyl benzylamines, two (dimethylaminoethyl) ethers, N, N, N ', N '-tetramethylethylenediamine, N,
N, N ', N '-tetramethyl butane diamine, N, N, N ', N '-tetramethyl diamino-dicyclohexyl methane, triethanolamine, triisopropanolamine,
It is one or more in N methyldiethanol amine, N- ethyldiethanolamines and dimethylethanolamine；It is preferred that pentamethyl divinyl three
Amine, N- methylimidazoles, N, N- dimethyl cyclohexyl amines, triethylene diamine, N-methylmorpholine, triethylamine, 1,4- lupetazins, N,
It is one or more in N- dimethyl benzylamines and double dimethylamino ethyl ethers.
The applicable organometallic catalysts of the present invention, such as organic potassium compound, organo-tin compound, such as organic carboxyl acid
Tin (II) salt, such as oxalic acid tin (II), two tin octoates (II), two (ethyl) caproic acid tin (II) and tin dilaurate tin (II) and
Dialkyl tin (IV) salt of organic carboxyl acid, such as dibutyltin diacetate, dibutyl tin laurate, dibutyitin maleate and two
Acetic acid dioctyl tin.Very applicable other compounds are dialkyl tin (IV) sulfhydryl compounds, such as (IV) two sulphur of dilauryl tin
Alkoxide and general formula R2Sn(SR′-O-CO-R″)2Or R2Sn(SR′-CO-OR″)2Compound, R is at least 8 carbon in formula
The alkyl of atom, R ' are the alkyl of at least 2 carbon atoms, and R " is the alkyl of at least 4 carbon atoms.
The example of this kind of catalyst is such as the catalyst disclosed in DD-A-218668：(the 2- ethyl hexyls of dioctyl tin-two
Sour thioglycol ester), dioctyl tin-two (lauric acid thioglycol ester), (thiol acid group closes acetic acid 2- to dioctyl tin-two
Ethylhexyl), dioctyl tin-two (thiol acid group close hexyl acetate) and (the thiol acid group conjunction acetic acid bay of dioctyl tin-two
Ester).Other very applicable catalyst are the general formula (R as disclosed in DD-A-2555353Sn)2O、R2SnS、(R3Sn)2S、R2Sn、
(SR′)2Or RSn (SR ')3The organo-tin compound for having tin-oxygen or tin-sulfide linkage, in formula R and R ' for have 4~8 carbon atoms (
In the case of R) and 4~12 carbon atoms (in the case of R '), it is to have 1 that R ', which is alternatively-R " COO R " or-R " COOR, wherein R ",
The alkyl of~6 carbon atoms, R are the alkylidene for having 4~12 carbon atoms.The example that can be mentioned that is：Two (tributyl tins) aoxidize
Object, dibutyl tin sulfide, dioctyl tin sulfide, two (tributyl tin) sulfide, dibutyl tin-(thio Glycolic acid 2- second
The own ester of base), dioctyl tin-two (thio Glycolic acid 2- ethylhexyls), tin octylate-three (thio Glycolic acid 2- ethylhexyls), two
Tin octylate-two (2 ethyl hexanoic acid thioglycol ester) and dibutyl tin-two (lauric acid thioglycol ester).
The example of suitable organic potassium compound includes but not limited to isooctyl acid potassium, potassium acetate, potassium oleate etc..
The example of suitable organometallic catalysts can also be other organo-metallic compounds, such as butyl titanate
Deng.
Organo-metallic compound can be used alone as catalyst or be used in the form of carbon monoxide-olefin polymeric.
Organometallic catalysts of the present invention preferably include isooctyl acid potassium, potassium acetate, dibutyl tin laurate,
It is one or more in butyl titanate, stannous octoate and potassium oleate.
The possible selection of foaming agent of the present invention includes liquid CO2, cycloalkane, particularly including pentamethylene, hexamethylene
Alkane and its mixture；Other cycloalkane for including most 4 carbon atoms；Dialkyl ether, ring alkylene ether, fluoroalkane and its mixed
Close object.The specific example of alkane is, for example, the pentane of propane, normal butane, iso-butane, pentane and isopentane and technical grade
Mixture；Cycloalkane, for example, cyclobutane；Dialkyl ether, for example, dimethyl ether, methyl ethyl ether, methyl butyl ether and diethyl ether；
Ring alkylene ether, for example, furans；(think that it is decomposed in troposphere, it is therefore currently assumed that it will not destroy ozone with fluoroalkane
Layer), for example, fluoroform, difluoromethane, 1,1- Difluoroethanes, 1,1-, bis- chloro- 1- fluoroethanes, chlorodifluoroethane, tetrafluoro second
Alkane, 1,1,1,3,3- pentafluoropropanes, heptafluoro-propane, 1,1,1,2- tetrafluoros butane, 1,1,1,3,3-pentafluorobutane.
Preferably, foaming agent of the present invention is 1,1-, bis- chloro- 1- fluoroethanes (HCFC-141B), 1,1,1,3,3- five
Fluoro-propane (HFC-245fa), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), 1,1- Difluoroethanes, chlorodifluoroethane and
One or both of 1,1,1,2- tetrafluoros butane (HFC-134a) is a variety of.
Foam stabiliser of the present invention is to promote to form the substance of regular foam structure during formation of foam, can
To use arbitrary foam stabiliser well known in the art, the preferably such as siloxane-oxyalkylene of the foam stabiliser containing polysiloxanes is total to
Polymers and fatty alcohol, oxo alcohol, fatty amine, alkylphenol, dialkyl group phenol, alkylated cresol, alkyl-resorcin, tea
The alkoxylate production of phenol, alkyl tea phenol, theamin, aniline, alkyl benzene amine, toluidines, bisphenol-A, alkylated bisphenols A or polyvinyl alcohol
The contracting of object and formaldehyde and alkylphenol, formaldehyde and dialkyl group phenol, formaldehyde and alkylated cresol, formaldehyde and alkyl-resorcin
It closes one or more in the alkoxylated polymerization product of product.The example of currently preferred foam stabiliser includes but not limited to moral
The silicone oil AK8803 of U.S. generation wound, silicone oil B8533 of Degussa etc..
Plasticizer of the present invention can use the arbitrary plasticizer in this field, preferably include phthalic acid diformazan
Ester, diethyl phthalate, diisobutyl phthalate, BBP(Butyl Benzyl Phthalate, dihexyl phthalate, adjacent benzene
Dioctyl phthalate dinonyl, diisooctyl phthalate, phthalic acid two (hendecane) ester, phthalic acid two (tridecane)
Ester, dibutyl phthalate, dioctyl phthalate, dimethyl adipate, diisopropyl adipate, two fourth of adipic acid
Ester, di-n-hexyl adipate, dioctyl adipate, decanedioic acid diethyl fat, decanedioic acid diisopropyl fat, azelaic acid dibutyl ester, benzene first
Sour diol ester, dioctyl sebacate, triphenyl phosphate, tricresyl phosphate, diphenyl 2 ethylhexyl phosphate, phosphate diphenyl isodecyl ester,
It is one or more in triethyl phosphate, trioctyl phosphate, tributyl phosphate and dioctyl terephthalate.
A kind of method for preparing polyurethane heat insulation material, includes the following steps：Proportionally,
(1) polyol component, foam stabiliser, water, foaming agent, catalyst, plasticizer and other auxiliary agents are uniformly mixed,
Obtained component A expects component in vain；
(2) modified PM, modified TDI, modified MDI, PM, TDI and HDI are uniformly mixed, the black material B component of combination is made；
(3) step (1)~component A and B component made from (2) is cast in pipe mould and be prepared.
Pouring technology of the present invention can use arbitrary already known processes well known in the art, it is preferable to use Crouse's agate
Luxuriant and rich with fragrance high pressure casting machine is controlled by pouring technology known to operating personnel, such as component A and B component temperature at 22~26 DEG C, cast
It is made and forms in polyurethane mould or polyurethane tube middle pipe.
In the present invention, the use of the submissiveer polyether polyol 1 of strand and grease significantly increases cross-linked network chain
The flexibility of section so that foam is not susceptible to brittle fracture under cryogenic environment.The addition of polyether polyol 2 and polyester polyol
Cause abscess more uniform and smooth, the heat-proof quality of foam and Low-Temperature Size stability can be improved.
The addition of TDI significantly decreases the bond angle between two strands of crosslinking points so that and cross-linked network is finer and close,
So as to finer and smoother foam structure so that foam has splendid Low-Temperature Size stability and heat insulation.HDI is more flexible
Strand improve the tensile strength of converging network, reduce the brittleness of material under low temperature environment, it is safe to use to improve foam
Stability.
The modifying agent that modified PM, modified TDI and modified MDI are used is small molecular alcohol, high functionality polyether polyol and gathers
One or more in ester polyol, this substantially improves the length of rigid chain segment, more regular rigid chain segment is mutual
The rigid cross-linked areas of microfacies is piled into, substantially increase the intensity of foam and does not influence the flexibility of integral material, hard section
Enrichment significantly improves the crosslink density of polymer network, further abscess is made to attenuate, so as to improve the thermal insulation of foamed material
Can, improve foam Low-Temperature Size stability.
The present invention also provides a kind of polyurethane heat insulation materials.The density of the material>60kg/m3, compressive strength>
700KPa, tensile strength>800KPa, thermal conductivity factor is less than 0.017w/m ﹒ k at 25 DEG C, thermal conductivity factor base after 300 Frozen-thawed cycleds
This is constant, less than 0.017w/m ﹒ k, water absorption rate<0.5%, rate of closed hole>98%, abscess average-size<0.05mm, -163 DEG C of decentralizations
It puts more than 96h and does not shrink and do not crack, deformation ratio<0.1%, it foams in the plastic film tube of diameter 5cm, flow coefficient (flowing
Length/foam quality) it is 0.822~0.843, at least improve 5~8% compared with conventional formulation.
The present invention provides a kind of polyurethane combined material, which has preferable mobility, prepared thermal insulation material tool
There is extremely low thermal conductivity factor, suitable for the various fields more demanding to heat insulation effect, the performance especially in low-temperature deep environment
It is excellent, there is splendid low-temperature flexibility and dimensional stability, the pipe insulation material particularly useful for making conveying deep cooling medium.
Specific embodiment
The following examples will be further described method provided by the present invention, but the present invention is not limited to listed
The embodiment gone out should also include other any well known changes in interest field of the presently claimed invention.
Grease：Epoxidized soybean oil, the epoxy linseed oil of Aladdin company
Water：Distilled water
Foam stabiliser：The silicone oil AK8803, the silicone oil B8533 of Degussa of dolantin generation wound
Catalyst：Pentamethyl-diethylenetriamine (trade mark PC5), N, N- dimethyl cyclohexyl amines (trade mark PC8), potassium acetate
(trade mark LCM-1)
Foaming agent：HCFC-141B, HFC-245fa, HFC-365mfc, HFC-134a
Plasticizer：Dioctyl phthalate (DOP)
Examples 1 to 10
The preparation of polyurethane heat insulation material, includes the following steps：According to the dosage of table 1, the dosage of each substance is in table 1
Mass parts,
(1) PM200 is added in reaction kettle, is warming up to 70 DEG C, tripropylene glycol is added dropwise, react 1h, control NCO contains
It measures as 28wt%, is added dropwise the 6245 of Wanhua Chemical (Ningbo) Rongwei Polyurethane Co., Ltd., react 1h, control NCO content is
24wt% obtains modified PM200；
(2) Lupranate T-80 are added in reaction kettle, are warming up to 70 DEG C, PS-2002 (this Thailand of Nanjing Nanjing is added dropwise
Pan Chemical Co., Ltd.), 1h is reacted, control NCO content is 43wt%, and dipropylene glycol is added dropwise, and reacts 1h, and control NCO contains
It measures as 34wt%, obtains modified Lupranate T-80A；
(3) Lupranate T-80 are added in reaction kettle, are warming up to 70 DEG C, ten thousand magnificent chemistry (Ningbo) Rong Weiju are added dropwise
1h is reacted in the 6245 of urethane Co., Ltd, and control NCO content is 43wt%, and diglycol is added dropwise, reacts 1h, controls NCO
Content is 33wt%, obtains modified Lupranate T-80B；
(4) Lupranate T-80 are added in reaction kettle, are warming up to 70 DEG C, diglycol is added dropwise, instead
1h is answered, control NCO content is 35wt%, obtains modified Lupranate T-80C；
(5) MDI100 is added in reaction kettle, is warming up to 70 DEG C, CF-6200 is added dropwise, and (Jiangsu richness contains the limited public affairs of new material
Department), 1h is reacted, control NCO content is 32wt%, is added dropwise the 6245 of Wanhua Chemical (Ningbo) Rongwei Polyurethane Co., Ltd., instead
1h is answered, control NCO content is 31wt%, and tripropylene glycol is added dropwise, and reacts 1h, and control NCO content is 29wt%, is modified
MDI100；
(6) MDI50 is added in reaction kettle, is warming up to 70 DEG C, it is limited that ten thousand China chemical (Ningbo) appearance prestige polyurethane are added dropwise
1h is reacted in the 6245 of company, and control NCO content is 30wt%, obtains modified MDI50；
(7) by polyether polyol 1, polyether polyol 2, polyester polyol, grease, foam stabiliser, water, foaming agent, urge
Agent, plasticizer are uniformly mixed, and component A is made and expects component in vain；
(8) modified PM, modified TDI, modified MDI, PM, TDI and HDI are uniformly mixed, B component isocyanates group is made
Point；
(9) by temperature it is respectively 25 DEG C of component A and B component, respectively by Crouse's agate phenanthrene high pressure casting machine, is cast in
It is prepared in pipe mould.
1 composition of raw materials of table
Comparative example 1~4
Comparative example 1~4 prepares polyurethane heat insulation material according to the preparation method of embodiment, according to the dosage of table 2, in table 2
The dosage of each substance is mass parts.
2 composition of raw materials of table
Performance test
The foamed material of preparation is tested for the property, testing standard is as follows, and test result is shown in Table 3.
Testing standard：
It at 25 DEG C of flow coefficient, foams in the plastic film tube of diameter 5cm, the numerical value of length of flow/foam quality is made
For flow coefficient.
3 Examples 1 to 10 of table, 1~4 properties of product test result of comparative example
The product of above example has preferable mobility, and 5~8% are improved compared with conventional formulation flow coefficient；Heat conduction system
Number is extremely low, has fabulous heat-proof quality；It does not crack under low-temperature deep environment, excellent dimensional stability.It is very suitable for preparing
The deep cooling medium conveyance conduit thermal insulation material of traditional pouring technology.The formula combined in comparative example using modified isocyanate is above-mentioned
Performance is also obviously improved compared with the prior art.
Although above for explanation, the present invention is described in detail, it should be appreciated that these are retouched in detail
It writes and is merely to illustrate that, without departing from the spirit and scope of the present invention, those skilled in the art can carry out it
Modification, the present invention are limited only by the appended claims.
Claims (17)
1. a kind of polyurethane combined material, including component A and B component, component A includes polyol component, and B component is isocyanates group
Point, which is characterized in that the B component includes following component, is calculated on the basis of B component gross weight：
55~80wt% of polyisocyanates；
20~45wt% of modified polyisocyanate；
The polyisocyanates includes following component, is calculated on the basis of the gross weight of polyisocyanates：
60~80wt% of poly methylene poly phenyl poly isocyanate；
13~35wt% of toluene di-isocyanate(TDI)；
3~25wt% of hexamethylene diisocyanate；
The modified polyisocyanate includes following component, is calculated on the basis of the gross weight of modified polyisocyanate：
NCO content is 22~26wt%, and viscosity is the modification poly methylene poly phenyl poly isocyanate of 30000~60000cp
70~90wt%；
NCO content is 30~35wt%, and viscosity is 3~25wt% of modified toluene diisocyanate of 200~400cp；
NCO content is 27~31wt%, and viscosity is 3~25wt% of modified diphenylmethane diisocyanate of 500~1000cp；
The modification poly methylene poly phenyl poly isocyanate, modified toluene diisocyanate and modified diphenylmethane two are different
The modifying agent that cyanate uses is one or more in small molecular alcohol, high functionality polyether polyol and polyester polyol；Institute
It is 2~6 that state small molecular alcohol, which be degree of functionality, and molecular weight is 80~300 polyalcohol；The high functionality polyether polyol is polyhydroxy
Base alcohol is formed with ethylene oxide and/or Polymerization of Propylene Oxide, and number-average molecular weight is 200~1000, hydroxyl value for 300~
600mgKOH/g, degree of functionality are 3~8 polyalcohol；The polyester polyol for modifying agent is aromatic carboxylic acid, aromatic series
One or more reaction productions between diglycol and/or glycerine in carboxylic acid anhydrides and terephthaldehyde's acid alkyl ester
Object；
The polyol component of the component A includes following component, is calculated on the basis of the gross weight of polyol component：
2. combination material according to claim 1, which is characterized in that the B component includes following component, with B component gross weight
On the basis of calculate：
60~75wt% of polyisocyanates；
25~40wt% of modified polyisocyanate；
The polyisocyanates includes following component, is calculated on the basis of the gross weight of polyisocyanates：
65~75wt% of poly methylene poly phenyl poly isocyanate；
15~25wt% of toluene di-isocyanate(TDI)；
5~15wt% of hexamethylene diisocyanate；
The modified polyisocyanate includes following component, is calculated on the basis of the gross weight of modified polyisocyanate：
NCO content is 22~26wt%, and viscosity is the modification poly methylene poly phenyl poly isocyanate of 30000~60000cp
75~85wt%；
NCO content is 30~35wt%, and viscosity is 5~15wt% of modified toluene diisocyanate of 200~400cp；
NCO content is 27~31wt%, and viscosity is 5~15wt% of modified diphenylmethane diisocyanate of 500~1000cp.
3. it is according to claim 1 combination material, which is characterized in that the small molecular alcohol be selected from butanediol, pentanediol, oneself two
Alcohol, diglycol, dipropylene glycol, tripropylene glycol, 1,2,6- hexanetriols, triethylene-glycol, pentaerythrite
With it is one or more in sorbierite；
Polyhydroxy-alcohol in the high functionality polyether polyol be selected from sucrose, sorbierite, xylitol, pentaerythrite, glycerine and
It is one or more in trimethylolpropane；
Aromatic carboxylic acid, aromatic carboxylic acid acid anhydride in the polyester polyol for modifying agent are selected from phthalic acid, adjacent benzene
It is one or more in dicarboxylic acid anhydride, M-phthalic acid, terephthalic acid (TPA) and trimellitic anhydride；
The carbon atom number of terephthaldehyde's acid alkyl ester is 10~16.
4. combination material according to claim 1, which is characterized in that the high functionality polyether polyol is selected from ten thousand China's chemistry
(Ningbo) Rong Wei polyurethane Co., Ltd 6245, A29-1, the N-635, N-635SA of Jiangsu Zhongshang Chemical Co., Ltd., Tianjin
It is one or more in the SY-6560 of third petrochemical plant and the GR-635S of Shanghai Gaoqiao petrochemical corporation (complex)；
Terephthaldehyde's acid alkyl ester is selected from dimethyl terephthalate (DMT), diethyl terephthalate and terephthalic acid (TPA) two
It is one or more in butyl ester.
5. combination material according to claim 1, which is characterized in that the polyester polyol for modifying agent is selected from Nanjing
PS-3152, PS-2002 of Nanjing Si Taipan Chemical Co., Ltd.s, the CF-6245 and CF- of Jiangsu Fu Sheng new materials Co., Ltd
It is one or more in 6200.
6. combination material according to claim 1, which is characterized in that the modification poly methylene poly phenyl poly isocyanate
For diglycol, dipropylene glycol, tripropylene glycol, Wanhua Chemical (Ningbo) Rongwei Polyurethane Co., Ltd.
6245th, the one or more and polymethylene polyphenyl polyisocyanate cyanogen in the PS-3152 of Nanjing Nanjing Si Taipan Chemical Co., Ltd.s
The reaction product of acid esters；
The modified toluene diisocyanate is diglycol, dipropylene glycol, Nanjing Nanjing Si Taipan chemistry have
One or more and toluene two in the PS-2002 of limit company and the 6245 of Wanhua Chemical (Ningbo) Rongwei Polyurethane Co., Ltd.
The reaction product of isocyanates；
The modified diphenylmethane diisocyanate is methyl diphenylene diisocyanate and butanediol, pentanediol, oneself two
Alcohol, diglycol, dipropylene glycol, tripropylene glycol, 1,2,6- hexanetriols, the ten thousand magnificent chemistry poly- ammonia of (Ningbo) Rong Wei
One or more reaction productions in the 6245 of the ester Co., Ltd and PS-3152 of Nanjing Nanjing Si Taipan Chemical Co., Ltd.s
Object.
7. combination material according to claim 1, which is characterized in that the modification poly methylene poly phenyl poly isocyanate
For diglycol, dipropylene glycol, tripropylene glycol, Wanhua Chemical (Ningbo) Rongwei Polyurethane Co., Ltd.
6245 and Nanjing Nanjing Si Taipan Chemical Co., Ltd.s PS-3152 in it is one or more limited with ten thousand magnificent chemical groups shares
The reaction product of the PM200 of company；
The modified toluene diisocyanate is diglycol, dipropylene glycol, Nanjing Nanjing Si Taipan chemistry have
One or more and BASF in the PS-2002 of limit company and the 6245 of Wanhua Chemical (Ningbo) Rongwei Polyurethane Co., Ltd. is public
The reaction product of the Lupranate T-80 of department；
The modified diphenylmethane diisocyanate for Wanhua Chemical Group Co., Ltd. MDI100 and/or
MDI50 and butanediol, pentanediol, hexylene glycol, diglycol, dipropylene glycol, tripropylene glycol, 1,2,6- oneself three
Alcohol, the 6245 of Wanhua Chemical (Ningbo) Rongwei Polyurethane Co., Ltd. and Nanjing Nanjing Si Taipan Chemical Co., Ltd.s PS-
One or more reaction products in 3152.
8. it is according to claim 1 combination material, which is characterized in that the polyol component of the component A include below into
Point, it is calculated on the basis of the gross weight of polyol component：
9. combination material according to claim 1, which is characterized in that the initiator of the polyether polyol 1 is ethylene glycol, third
Glycol, diglycol, dipropylene glycol, triethylene-glycol, glycerine, trimethylolpropane, triethanolamine, diethanol
Amine and 1, one or more in 2,6- hexanetriols, polymerized unit is propylene oxide and/or ethylene oxide；
The initiator of the polyether polyol 2 is ethylenediamine, dipropylene glycol, triethylene-glycol, glycerine, trihydroxy methyl
One in propane, triethanolamine, diethanol amine, ortho-toluene diamine, p-phenylenediamine, sucrose, sorbierite, xylitol and pentaerythrite
Kind is a variety of, and polymerized unit is propylene oxide and/or ethylene oxide；
Polyester polyol in the component A is aromatic binary carboxylic acid, aromatic carboxylic acid acid anhydride, aliphatic dicarboxylic acid and carboxylic
The one or more and diglycol of acid esters reacts preparation；
The grease is made for vegetative grease of peroxide treatment；The vegetative grease is selected from Semen setariae oil, flower
In oil generation, olive oil, camellia oil, palm oil, sunflower oil, soybean oil, sesame oil, linseed oil, corn oil and walnut oil
It is one or more.
10. combination material according to claim 1, which is characterized in that the initiator of the polyether polyol 1 is glycerine, is gathered
It is propylene oxide and ethylene oxide to close unit；
The initiator of the polyether polyol 2 is ortho-toluene diamine, and polymerized unit is propylene oxide and ethylene oxide；
Polyester polyol in the component A is phthalic acid, phthalic anhydride, adipic acid and terephthalic acid (TPA) diformazan
One or more and diglycol in ester reacts preparation.
11. combination material according to claim 1, which is characterized in that the polyether polyol 1 is the TEP- of three petrochemical industry of Tianjin
The 330N and/or GEP-330N of Shanghai Gaoqiao company；
The polyether polyol 2 is the R4036 and/or R2438A of Wanhua Chemical (Ningbo) Rongwei Polyurethane Co., Ltd.；
Polyester polyol in the component A is the polyester polyol PS- of Nanjing Nanjing Si Taipan Chemical Co., Ltd.s production
3152nd, the polyester polyol PS-2002 of Nanjing Nanjing Si Taipan Chemical Co., Ltd.s production, Jiangsu Fu Sheng new materials Co., Ltd
Polyester polyol CF-6245, the polyester polyol CF-6200 of Jiangsu Fu Sheng new materials Co., Ltd production and Jining hundred of production
It is one or more in the polyester polyol HKP-2022 of river Chemical Co., Ltd. production.
12. combination material according to claim 1, which is characterized in that the component A includes following components, with the total of component A
It is calculated on the basis of weight：
13. combination material according to claim 1, which is characterized in that the component A includes following components, with the total of component A
It is calculated on the basis of weight：
14. combination material according to claim 1, which is characterized in that the weight ratio of the component A and B component is 1：1.3~
1.6。
15. combination material according to claim 1, which is characterized in that the weight ratio of the component A and B component is 1：1.4~
1.5。
16. a kind of method that polyurethane heat insulation material is prepared according to any one of the claim 1-15 combination material, including following
Step：Proportionally,
(1) polyol component, foam stabiliser, water, foaming agent, catalyst, plasticizer are uniformly mixed, component A is made；
(2) polyisocyanates and modified polyisocyanate are uniformly mixed, B component is made；
(3) step (1)~component A and B component made from (2) is cast in pipe mould and be prepared.
17. polyurethane heat insulation material prepared by a kind of method according to claim 11, which is characterized in that the material
Density>60kg/m3, compressive strength>700KPa, tensile strength>800KPa, thermal conductivity factor is less than 0.017w/m ﹒ k at 25 DEG C, and 300
Thermal conductivity factor is less than 0.017w/m ﹒ k, water absorption rate after secondary Frozen-thawed cycled<0.5%, rate of closed hole>98%, abscess average-size<
0.05mm places more than 96h at -163 DEG C and does not shrink and do not crack, deformation ratio<0.1%, it is sent out in the plastic film tube of diameter 5cm
Bubble, flow coefficient are 0.822~0.843.
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| EP3574033B1 (en) * | 2017-01-25 | 2020-12-30 | Basf Se | Cold flexible polyurethane formulation |
| CN107177028B (en) * | 2017-06-13 | 2020-08-04 | 合肥华凌股份有限公司 | Combined polyether, polyurethane foam and preparation method and application thereof |
| KR101985105B1 (en) * | 2017-11-10 | 2019-05-31 | 서울시립대학교 산학협력단 | Polyurethane composition, acoustic absorbent comprising the same and manufacturing method polyurethane foam |
| CN109929086B (en) * | 2017-12-19 | 2021-06-29 | 万华化学（北京）有限公司 | Polyurethane composition and thermosetting polyurethane composite material prepared from same |
| CN108864507A (en) * | 2018-07-10 | 2018-11-23 | 安徽省星年华电器有限公司 | A kind of polyurethane seal strip for refrigerator door production technology |
| CN109535378B (en) * | 2018-12-11 | 2021-04-20 | 万华化学集团股份有限公司 | Polyurethane cavity filling foam with high aperture ratio |
| CN109575856B (en) * | 2018-12-19 | 2021-01-19 | 南京红宝丽聚氨酯有限公司 | Polyurethane-pressure-sensitive adhesive composite single-component adhesion promoter |
| CN110452356A (en) * | 2019-07-09 | 2019-11-15 | 广东德美精细化工集团股份有限公司 | A kind of oligomer inhibitor of environment-friendly high-efficiency and preparation method thereof |
| CN111040427A (en) * | 2019-12-31 | 2020-04-21 | 百事基材料（青岛）股份有限公司 | Preparation method of plant extract modified PU (polyurethane) pipe |
| CN112900510B (en) * | 2020-12-09 | 2022-04-15 | 湖北工业大学 | Underground building concrete repairing method under high water pressure and corrosion conditions |
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| JPS60110717A (en) * | 1983-11-21 | 1985-06-17 | Nichias Corp | Production of polyurethane foam |
| US5332860A (en) * | 1993-06-29 | 1994-07-26 | The Dow Chemical Company | Polyols useful for preparing polyurethane foams having improved retention of insulative properties, polyurethane foams prepared therewith and methods for the preparation thereof |
| EP1123341B1 (en) * | 1998-09-10 | 2005-04-27 | Dow Global Technologies Inc. | Polyols useful for preparing water blown rigid polyurethane foam |
| JP2002128850A (en) * | 2000-10-23 | 2002-05-09 | Nippon Polyurethane Ind Co Ltd | Polyisocyanate composition for hard polyurethane foam and method of manufacturing hard polyurethane foam using the same |
| US20060084709A1 (en) * | 2004-10-14 | 2006-04-20 | Bayer Materialscience Llc | High-temperature rigid polyurethane spray foam for pipe insulation |
| WO2013024108A1 (en) * | 2011-08-16 | 2013-02-21 | Bayer Intellectual Property Gmbh | Method for producing a polyurethane/polyisocyanurate rigid foam |
| BR112014004471A2 (en) * | 2011-08-26 | 2017-03-28 | Bayer Ip Gmbh | stable emulsions and their use in the production of isocyanate-based foams |
| PL2870188T3 (en) * | 2012-07-04 | 2017-03-31 | Basf Se | Production of foams having improved properties |
| WO2014019103A1 (en) * | 2012-07-31 | 2014-02-06 | Bayer Materialscience Ag | Method for the production of polyurethane foam using emulsified blowing agent |
| CN105199071B (en) * | 2015-09-16 | 2018-06-12 | 万华化学（广东）有限公司 | A kind of polyurethane combined material, its prepare the method for compound polyurethane material and the purposes of obtained product |
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