CN106046317A - Polyurethane composite material and polyurethane heat-preserving material prepared therefrom - Google Patents

Polyurethane composite material and polyurethane heat-preserving material prepared therefrom Download PDF

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CN106046317A
CN106046317A CN201610340924.5A CN201610340924A CN106046317A CN 106046317 A CN106046317 A CN 106046317A CN 201610340924 A CN201610340924 A CN 201610340924A CN 106046317 A CN106046317 A CN 106046317A
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component
nanjing
acid
polyurethane
chemical
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CN106046317B (en
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庞德政
齐旺顺
于深
顾永江
华卫琦
丁建生
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Wanhua Chemical Guangdong Co Ltd
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Wanhua Chemical Group Co Ltd
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/80—Masked polyisocyanates
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
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    • C08J2203/184—Binary blends of expanding agents of chemical foaming agent and physical blowing agent, e.g. azodicarbonamide and fluorocarbon

Abstract

The invention provides a polyurethane composite material and a polyurethane heat-preserving material prepared therefrom. The polyurethane composite material comprises a polyol component and an isocyanate component, wherein the isocyanate component comprises polyisocyanate and modified isocyanate. The composite material has excellent fluidity; and the heat-preserving material prepared from the composite material has low thermal conductivity, is applicable to a variety of fields with high requirements on heat-preserving effects, has excellent performances especially in a low-temperature and cryogenic environment, has excellent low-temperature toughness and dimensional stability, and is especially applicable to preparation of a heat-preserving material of a pipeline used for transporting cryogenic mediums.

Description

A kind of polyurethane combined material and the polyurethane heat insulation material of preparation thereof
Technical field
The invention belongs to polyurethane field, further to polyurethane foamed material, further relate to one and have relatively Good mobility, low thermal conductivity, low temperature resistant polyurethane pipe insulation material.
Background technology
Hard polyurethane foam mostly is hole-closing structure, have that insulation effect is good, lightweight, specific strength big, easy construction etc. excellent Characteristic, the most also has the feature such as sound insulation, shockproof, electric insulation, heat-resisting, cold-resistant, solvent resistant, is widely used in the case of refrigerator, refrigerator-freezer The adiabators such as body heat insulation layer, freezer, refrigerator car, building, storage tank and pipe insulation material, a small amount of for nonadiabatic occasion, Such as imitation wood material, packaging material etc..
Insulating tube is the abbreviation of insulated piping, is mainly used in 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.Along with the development in city, urban heat supplying is popularized with And the gradually stepping up of thermal requirements, hard polyurethane foam insulating tube will preferably be developed.Hard polyurethane foam insulating tube can be Long-term operation at 120 DEG C, heat conductivity is relatively low, high insulating effect, water absorption rate, and percent opening is low, it is possible to preferably insulation is with waterproof, Greatly reduce the overall heat consumption of heat preservation and heat supply pipeline.
Document " polyurethane foam plastics application in utilidor " (Wei Chunliu, engineering plastics application, 2003 02 Phase, volume 31, p34) elaborate the raw material of polyurethane foam plastics, reaction principle and performance, describe polyurethane foam plastics Preparation technology, construction method and the points for attention in work progress in pipe insulation is constructed, and illustrate one step foaming The major advantage of the method for forming, describes the pipeline employing polyurethane plastics that certain factory's living area steam heating changes in hot water heating engineering Make heat insulation effect during insulation material.
Patent CN102391775A discloses a kind of high temperature resistant polyurethane pipeline premixed systems, the polyurethane thermal pipe of this invention Road premixed systems, has good heat-resisting quantity, will not lose its mechanical property, nothing under 200 DEG C of high temperature under 120 DEG C of high temperature above 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 the outer pillar of alkene has good low-temperature resistance performance, insulating tube under about-40 DEG C environment Cracking rate within 5%, cost and current conventional products cost are suitable, meet the construction requirement under low-temperature cold environment.
But along with exhaustion and the requirement of energy-conserving and environment-protective of traditional energy, the storage of the novel environment friendly energy and conveying are increasingly Many, the cryogenic liquid such as such as LPG, LNG, cold insulation performance and cryogenic environment performance to conveyance conduit are had higher requirement. Traditional polyurethane pipe insulation material can not meet the rigors of this application.
Patent CN1221433 discloses a kind of raw with foaming agent and optional blowing promotor by polyhydric alcohol and polyisocyanates The method producing hard polyurethane foams with low heat conductivity, by using extraordinary polyhydric alcohol to improve foam thermal conductivity.But it is extraordinary polynary The use of alcohol, reduces the foam toughness under bubble mobility and low temperature.
Patent CN103709355A relate to a kind of modified polyurethane for ultralow temperature LNG storage tank cold insulation spray premixed systems and Its preparation method.By using specialty polyesters to improve the dimensional stability under foam low temperature.But the heat conductivity to foam system Not improving, and domestic technique mostly is tradition pouring type, this premixed systems viscosity is relatively big, and mobility is poor.
Although studies have reported that use special polyether or specialty polyesters join in white material system, foam low temperature can be improved Dimensional stability, but the polyhydric alcohol of high hydroxyl value can reduce the mobility of premixed systems further, in view of domestic main pouring type Premixed systems mobility is required the highest by utilidor, and above-mentioned adjustment mode can have a strong impact on the Density Distribution of pipe insulating layer, enters One step affects homogeneity and the heat insulation effect of foam.
The actual heat conductivity of conventional urethane pipe insulation material is about 0.03W/mK, and abscess resistance to pressure reduction ability is more weak, Low-Temperature Size less stable, easily produces under cryogenic environment and shrinks even crack, it is impossible to ensure the long-term heat preservation effect of pipeline, And there is bigger security risk.Can not meet the thermal requirements for deep cooling medium.
Summary of the invention
The present invention provides a kind of polyurethane combined material, and this premixed systems has preferable mobility, prepared insulation material tool There is extremely low heat conductivity, excellent performance in low-temperature deep environment, there is splendid low-temperature flexibility and dimensional stability, be suitable for Pipeline in preparation conveying deep cooling medium.
The present invention also provides for a kind of method using described premixed systems to produce polyurethane heat insulation material and the poly-ammonia of preparation thereof Ester insulation material.
For solving above technical problem, the technical solution used in 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, described B component includes following component, calculates on the basis of B component gross weight:
Polyisocyanates 55～80wt%, preferably 60～75wt%；
Modified polyisocyanate 20～45wt%, preferably 25～40wt%.
Polyisocyanates of the present invention includes following component, calculates on the basis of the gross weight of polyisocyanates:
Poly methylene poly phenyl poly isocyanate (being called for short PM) 60～80wt%, preferably 65～75wt%；
Toluene di-isocyanate(TDI) (being called for short TDI) 13～35wt%, preferably 15～25wt%；
Hexamethylene diisocyanate (being called for short HDI) 3～25wt%, preferably 5～15wt%.
Modified polyisocyanate of the present invention includes following component, counts on the basis of the gross weight of modified polyisocyanate Calculate:
NCO content is 22～26wt%, and viscosity is the modified polymethylene polyphenyl polyisocyanic acid of 30000～60000cp Ester (being called for short modified PM) 70～90wt%, preferably 75～85wt%；
NCO content is 30～35wt%, and viscosity is the modified toluene diisocyanate (being called for short modified TDI) of 200～400cp 3～25wt%, preferably 5～15wt%；
NCO content is 27～31wt%, and viscosity is the modified diphenylmethane diisocyanate (abbreviation of 500～1000cp 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 be 2.5～ 3.0, it is preferred that the suitably example of PM includes but not limited to PM200, DOW chemistry of Wanhua Chemical Group Co., Ltd. The PAPI 27 of company, the Cosmonate M-200 of Mitsui Wu Tian KCC, Japanese polyurethane industry strain formula meeting The 44V20 of Millionate MR-200, Bayer company of society, BASF AG M20s and Huntsman company 5005 in One or more, the more preferably PM200 of Wanhua Chemical Group Co., Ltd..
TDI of the present invention comprises 2,4-TDI and/or 2,6-TDI；Preferably comprise 50～90wt% 2,4-TDI and The 2 of 10～50wt%, the TDI mixture of 6-TDI, the example of suitable TDI includes but not limited to the Mondur of Bayer company The Suprasec TDI 80/20 of TD-80, Huntsman company, the Cosmonate T-of Mitsui Wu Tian KCC 80, one or more in the Lupranate T-80 of BASF AG and the Voranate T-80 of DOW chemical company；Preferably The Lupranate T-80 of BASF AG.
The example of HDI of the present invention includes but not limited to the Desmodur T of Bayer company, Mitsui force field Learn the Takenate 700 of Co., Ltd., Rhodia company HDI and Degussa company Vestanat HDI in one or Multiple；The Desmodur T of preferably Bayer company.
The modifying agent that modified PM of the present invention, modified TDI and modified MDI use is that small molecular alcohol, high functionality gather One or more in ethoxylated polyhydric alcohol and PEPA.
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, the Lupranate MS of BASF AG, the Cosmonate PH of Mitsui Wu Tian KCC and One or more in the Suprasec 1004 of Huntsman company, preferably Wanhua Chemical Group Co., Ltd. MDI100 and/or MDI50.
Small molecular alcohol in modifying agent of the present invention be degree of functionality be 2～6, molecular weight is the polyhydric alcohol of 80～300. The suitably example of small molecular alcohol includes but not limited to butanediol, pentanediol, hexanediol, diglycol, a contracting dipropyl two In alcohol, tripropylene glycol, 1,2,6-hexanetriol, triethylene-glycol, tetramethylolmethane and sorbitol one or more.
High functionality polyether polyol in modifying agent of the present invention is polyhydroxy-alcohol and oxirane and/or epoxy Propane is polymerized, and number-average molecular weight is 200～1000, and hydroxyl value is 300～600mgKOH/g, degree of functionality be 3～8 polynary Alcohol, the example of described polyhydroxy-alcohol is including but not limited to sucrose, sorbitol, xylitol, tetramethylolmethane, glycerol and trihydroxy methyl One or more in propane.The suitably example of high functionality polyether polyol includes but not limited to that ten thousand China's chemistry (Ningbo) hold The 6245 of prestige polyurethane company limited, A29-1, the N-635 of Jiangsu Zhongshang Chemical Co., Ltd., N-635SA, Tianjin the 3rd oil One or more in the SY-6560 in chemical plant and the GR-635S of Shanghai Gaoqiao petrochemical corporation (complex)；Preferably ten thousand China's chemistry are (peaceful Ripple) Rong Wei polyurethane company limited 6245.
PEPA in modifying agent of the present invention is aromatic carboxylic acid, aromatic carboxylic acid acid anhydride, p-phthalic acid The product between one or more and diglycol (DEG) and/or glycerol in Arrcostab.Suitably aromatic series The example of carboxylic acid (acid anhydride) includes but not limited to phthalic acid, phthalic anhydride, M-phthalic acid, p-phthalic acid, inclined benzene One or more in three anhydride；The carbon number of described terephthaldehyde's acid alkyl ester is 10～16.Suitably terephthaldehyde The example of acid alkyl ester is including but not limited to dimethyl terephthalate (DMT), diethyl terephthalate, dibutyl terephthalate Deng.The suitably example of PEPA includes but not limited to that the PS-3152 of Nanjing, Nanjing Si Taipan Chemical Co., Ltd. is (with neighbour Phthalate anhydride forms with DEG polycondensation, and hydroxyl value is 315mgKOH/g, average functionality is 2), PS-2002 is (with phthalic acid Acid anhydride forms with DEG polycondensation, and hydroxyl value is 200mgKOH/g, average functionality is 2), the CF-of Jiangsu Fu Sheng new material company limited 6245 (with dimethyl terephthalate (DMT), DEG, adipic acid as raw material, carry out ester exchange, polycondensation etc. reaction form, hydroxyl value is 250mgKOH/g, average functionality 2) and CF-6200 (forming with dimethyl terephthalate (DMT), DEG for raw material polycondensation, hydroxyl value is 200mgKOH/g, average functionality 2) in one or more, the PS-of preferably Nanjing, Nanjing Si Taipan Chemical Co., Ltd. 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 in polyhydric alcohol react at 30～100 DEG C 2～3h acquisition, NCO content 15～30wt%, preferably 20～ 25wt%.Preferably diglycol, dipropylene glycol, tripropylene glycol, ten thousand China's chemistry (Ningbo) appearance prestige polyurethane have The 6245 of limit company, one or more in the PS-3152 of Nanjing, Nanjing Si Taipan Chemical Co., Ltd. and the product of PM； More preferably 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. have with ten thousand China's chemical groups shares The 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 in ester polyol react at 30～100 DEG C 2～3h acquisition, NCO content 20～40wt%, preferably 25～ 35wt%.Preferably diglycol, dipropylene glycol, the PS-2002 and ten thousand of Nanjing, Nanjing Si Taipan Chemical Co., Ltd. One or more in the 6245 of chemical (Ningbo) Rong Wei polyurethane company limited of China and the product of TDI；More preferably one contracting Diethylene glycol, dipropylene glycol, PS-2002 and Wan Hua chemistry (Ningbo) Rong Wei of Nanjing, Nanjing Si Taipan Chemical Co., Ltd. The product of the Lupranate T-80 of one or more in the 6245 of polyurethane company limited and BASF AG.
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 in ester polyol react at 30～100 DEG C 2～3h acquisition, NCO content 15～35wt%, preferably 20～ 30wt%.Preferably MDI and butanediol, pentanediol, hexanediol, diglycol, dipropylene glycol, tripropylene glycol, 1,2,6-hexanetriol, the 6245 of Wanhua Chemical (Ningbo) Rongwei Polyurethane Co., Ltd. and Nanjing, Nanjing Si Taipan limited public affairs of chemistry The product of one or more in the PS-3152 of department；The more preferably MDI100 of Wanhua Chemical Group Co., Ltd. and/ Or MDI50 and butanediol, pentanediol, hexanediol, diglycol, dipropylene glycol, tripropylene glycol, 1,2,6-oneself Triol, the 6245 of Wanhua Chemical (Ningbo) Rongwei Polyurethane Co., Ltd. and the PS-of Nanjing, Nanjing Si Taipan Chemical Co., Ltd. The product of one or more in 3152.
The polyol component of component A of the present invention includes small molecule polyol, polyether polyol, PEPA, gathers Carbonate diol, polymer polyatomic alcohol, oils and fats or a combination thereof.
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.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, 2,2'-ethylenedioxybis(ethanol)., four Glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 3-methyl isophthalic acid, 5-pentanediol, 1,5-pentanediol, 1,6-oneself two Positive penta triol of alcohol, 1,10-decanediol, glycerol, 1,2,4-butantriol, 1,2,5-, positive penta triol of 1,3,5-, 1,2,6-just oneself three The positive hexanetriol of alcohol, 1,2,5-, the positive hexanetriol of 1,3,6-, tri hydroxy methyl butane, trimethylolpropane or two (trimethylolpropanes), Trimethylolethane, tetramethylolmethane, dipentaerythritol and sorbitol or a combination thereof.In some preferred embodiments of the present invention, Small molecule polyol is selected from: glycerol, diglycol, ethylene glycol, propylene glycol, trimethylolpropane, diethylene glycol, tetramethylolmethane Or a combination thereof.
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.Described polyether polyol can be prepared by known technical process, such as, deposits at catalyst Under, alkylene oxide and initiator react and prepare.Described catalyst, is preferably but not limited to alkaline hydrated oxide, alkalescence Alkoxide, Antimony pentachloride, boron fluoride close ether or their mixture.Described alkylene oxide, is preferably but not limited to tetrahydrochysene furan Mutter, oxirane, expoxy propane, 1,2-epoxy butane, 2,3-epoxy butane, styrene oxide or their mixture, especially Optimization ethylene oxide and/or expoxy propane.Described initiator, is preferably but not limited to polyol or many amidos chemical combination Thing, described polyol, it is preferably but not limited to water, ethylene glycol, 1,2-PD, 1,3-PD, diethylene glycol, three hydroxyl first Base propane, glycerol, bisphenol-A, bisphenol S or their mixture, described many amine compounds, be preferably but not limited to ethylenediamine, third Diamidogen, butanediamine, hexamethylene diamine, diethylenetriamines, toluenediamine or their mixture.
The PEPA of component A of the present invention, by dicarboxylic acids, dicarboxylic acid anhydride, dicarboxylic esters Plant or multiple prepared with polyol reaction.The degree of functionality 2～3, preferably 2 of described PEPA, number-average molecular weight 200～ 1000, preferably 400～800.Described 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, 1,3-propanedicarboxylic 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.Described binary carboxylic Anhydride is preferably but not limited to phthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride or their mixture.Described dicarboxylic esters Be 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.Described with two Unit carboxylic acid, dicarboxylic acid anhydride, dicarboxylic esters in one or more reaction polyhydric alcohol, be preferably but not limited to ethylene glycol, two Glycol (DEG), 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,3-methyl propanediol, 1,4-butanediol, 1,5-penta 2 Alcohol, 1,6-HD, neopentyl glycol, 1,10-decanediol, glycerol, trimethylolpropane or their mixture.Described PEPA, also includes the PEPA prepared by lactone.The described PEPA prepared by lactone, preferably but does not limits In 6-caprolactone.
The PCDL of component A of the present invention, can be by dihydroxylic alcohols and dialkyl carbonic ester or diaryl carbon Acid esters or phosgene reaction prepare, and number-average molecular weight is 100～1500, preferably 200～1000.Described dihydroxylic alcohols, preferably but not It is limited to 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-HD, diethylene glycol, metaformaldehyde two Alcohol or their mixture.Described dialkyl carbonic ester or diaryl carbonate, be preferably but not limited to diphenyl carbonate.
The oils and fats of component A of the present invention includes animal oil and/or vegetable oil and/or their derivant, described oil The preferred Oleum Ricini of fat, soybean oil, safflower oil, Semen Lini oil, Semen Maydis oil, sunflower oil, olive oil, Semen Brassicae Campestris oil, Oleum sesami, Semen Gossypii Oil, Petiolus Trachycarpi oil, rapeseed oil, Oleum Verniciae fordii, high oleic safflower oil, high gas oil ratio soybean oil, high gas oil ratio Oleum Arachidis hypogaeae semen, high oleic sunflower oil, One or more or above-mentioned animal oil in high gas oil ratio Semen Brassicae Campestris oil, high erucic acid rape seed oil and fish oil and/or vegetable oil derivative Thing, described derivant includes one or more in partial hydrogenation product, epoxidation product.
Preferably, the polyol component of component A of the present invention includes following component, with the gross weight of polyol component is 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 be 4500～ The polyether polyol 1 20～60wt% of 6000, preferably 30～50wt%；
Degree of functionality be 3～5 number-average molecular weights be 200～700, preferably degree of functionality is 4, and number-average molecular weight is 300～500 Polyether polyol 2 10～40wt%, 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 PEPA 10～40wt%, 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 be 700～ The oils and fats 10～40wt% of 1300, preferably 15～35wt%.
The initiator of polyether polyol 1 of the present invention is ethylene glycol, propylene glycol, diglycol, a contracting dipropyl One in glycol, triethylene-glycol, glycerol, trimethylolpropane, triethanolamine, diethanolamine and 1,2,6-hexanetriol or Multiple, polymerized unit be expoxy propane and/or oxirane, preferably initiator be glycerol, polymerized unit is expoxy propane and ring Oxidative ethane, the example of suitable polyether polyol 1 includes but not limited to the TEP-330N of Tianjin three petrochemical industry, 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, diethanolamine, ortho-toluene diamine, p-phenylenediamine, sucrose, sorbitol, xylitol and season One or more in penta tetrol, polymerized unit be expoxy propane and/or oxirane, preferably initiator be ortho-toluene diamine, Polymerized unit is expoxy propane and oxirane, and the example of suitable polyether polyol 2 includes but not limited to that ten thousand China's chemistry are (peaceful Ripple) R4036, R2438A etc. of Rong Wei polyurethane company limited.
The PEPA of component A of the present invention is preferably aromatic binary carboxylic acid, aromatic carboxylic acid acid anhydride, aliphatic One or more of dicarboxylic acids and carboxylate and DEG react the PEPA of preparation.
The present invention prepares the preferred phthalic acid of described aromatic carboxylic acid of the PEPA in component A；Described fragrance The preferred phthalic anhydride of race's carboxylic acid anhydrides；The preferred adipic acid of described aliphatic carboxylic acid, the preferred p-phthalic acid of described carboxylate two Methyl ester.
The suitable example of PEPA of component A of the present invention includes but not limited to Nanjing, Nanjing Si Taipan chemistry Company limited produce PEPA PS-3152 (form with DEG polycondensation with phthalic anhydride, hydroxyl value be 315mgKOH/g, Average functionality is 2), Nanjing, Nanjing Si Taipan Chemical Co., Ltd. produce PEPA PS-2002 (with phthalic acid Acid anhydride forms with DEG polycondensation, and hydroxyl value is 200mgKOH/g, average functionality is 2), Jiangsu Fu Sheng new material company limited produce PEPA CF-6245 (with dimethyl terephthalate (DMT), DEG, adipic acid as raw material, carry out ester exchange, polycondensation etc. reaction and Become, hydroxyl value is 250mgKOH/g, average functionality 2), Jiangsu Fu Sheng new material company limited produce PEPA CF- 6200 (form for raw material polycondensation with dimethyl terephthalate (DMT), DEG, hydroxyl value is 200mgKOH/g, average functionality 2), Jining (forming with adipic acid, DEG for raw material polycondensation, hydroxyl value is the PEPA HKP-2022 that hundred river Chemical Co., Ltd.s produce 220mgKOH/g, average functionality 2) etc..
The oils and fats of component A of the present invention, preferred plant oils and fats uses peroxide treatment to make, suitably plants The example of physical property oils and fats include but not limited to Semen setariae oil, Oleum Arachidis hypogaeae semen, olive oil, Camellia oil, Petiolus Trachycarpi oil, Oleum Helianthi, soybean oil, Oleum sesami, Semen Lini oil, Semen Maydis oil, walnut oil etc., preferably soybean oil and/or Semen Lini oil.
Preferably, component A of the present invention can also include water, catalyst, foaming agent, foam stabiliser, plasticising Agent etc..
It is furthermore preferred that component A of the present invention includes following components, calculate on the basis of the gross weight of component A:
Component A of the present invention is 1:1.3～1.6 with the weight ratio of B component, preferably 1:1.4～1.5.
Catalyst of the present invention includes one or more in tertiary amine catalyst and organometallic catalysts.
The tertiary amine catalyst that the present invention is suitable for includes pentamethyl-diethylenetriamine, N-Methylimidazole., 1,2-dimethyl miaow Azoles, N, N-dimethyl cyclohexyl amine, triethylene diamine, N-methylmorpholine, N-ethylmorpholine, N-cyclohexyl morpholine, triethylamine, three fourths Amine, 1,4-lupetazin, N, N-dimethyl benzylamine, two (dimethylaminoethyl) ether, N, N, N ', N '-tetramethylethylenediamine, N, N, N ', N '-tetramethyl butane diamine, N, N, N ', N '-tetramethyl diamino-dicyclohexyl methane, triethanolamine, triisopropanolamine, One or more in N methyldiethanol amine, N-ethyldiethanolamine and dimethylethanolamine；Preferably pentamethyl divinyl three Amine, N-Methylimidazole., N, N-dimethyl cyclohexyl amine, triethylene diamine, N-methylmorpholine, triethylamine, 1,4-lupetazin, N, One or more in N-dimethyl benzylamine and double dimethylamino ethyl ether.
The organometallic catalysts that the present invention is suitable for, such as organic potassium compound, organo-tin compound, such as organic carboxyl acid Stannum (II) salt, such as oxalic acid stannum (II), two tin octoates (II), two (ethyl) caproic acid stannum (II) and tin dilaurate stannum (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.Other the most applicable compound is dialkyl tin (IV) sulfhydryl compound, such as dilauryl stannum (IV) two sulfur Alkoxide, and general formula R2Sn(SR′-O-CO-R″)2Or R2Sn(SR′-CO-OR″)2Compound, in formula, R is at least 8 carbon The alkyl of atom, R ' is the alkyl of at least 2 carbon atoms, R " is the alkyl of at least 4 carbon atoms.
The example of this kind of catalyst such as the catalyst disclosed in DD-A-218668 is: dioctyl tin-two (2-ethyl hexyl Acid THIOGLYCOL ester), dioctyl tin-two (lauric acid THIOGLYCOL ester), (thiol acid group closes acetic acid 2-for dioctyl tin-two Ethyl hexyl ester), dioctyl tin-two (thiol acid group closes Exceed 600) and dioctyl tin-two (thiol acid group conjunction acetic acid Laurel Ester).Other the most applicable catalyst are the formula (R as disclosed in DD-A-2555353Sn)2O、R2SnS、(R3Sn)2S、R2Sn、 (SR′)2Or RSn (SR ')3Have stannum-oxygen or the organo-tin compound of stannum-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 '), R ' is alternatively-R " COO R " or-R, and " COOR, wherein R are " for having 1 ～the alkyl of 6 carbon atoms, R is the alkylidene having 4～12 carbon atoms.The example that can be mentioned that is: two (tributyl tin) aoxidizes Thing, dibutyl tin sulfide, dioctyl tin sulfide, two (tributyl tin) sulfide, dibutyl tin-(sulfur is for glycolic acid 2-second The own ester of base), dioctyl tin-two (sulfur is for glycolic acid 2-Octyl Nitrite), tin octylate-three (sulfur is for glycolic acid 2-Octyl Nitrite), two Tin octylate-two (2 ethyl hexanoic acid THIOGLYCOL ester) and dibutyl tin-two (lauric acid THIOGLYCOL ester).
The suitably example of organic potassium compound includes but not limited to isooctyl acid potassium, potassium acetate, potassium oleate etc..
The suitably example of organometallic catalysts can also is that other organo-metallic compound, such as butyl titanate Deng.
Organo-metallic compound can be used alone as catalyst or use with the form of carbon monoxide-olefin polymeric.
Organometallic catalysts of the present invention preferably include isooctyl acid potassium, potassium acetate, dibutyl tin laurate, 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, it is particularly including Pentamethylene., hexamethylene Alkane and mixture thereof；Other comprises the cycloalkane of most 4 carbon atoms；Dialkyl ether, ring alkylene ether, fluoroalkane and mixed Compound.The instantiation of alkane is, such as, and propane, normal butane, iso-butane, pentane and isopentane and the pentane of technical grade Mixture；Cycloalkane, such as, Tetramethylene.；Dialkyl ether, such as, dimethyl ether, methyl ethyl ether, methyl butyl ether and diethyl ether； Ring alkylene ether, such as, furan；(think that it decomposes in troposphere, it is therefore currently assumed that it will not destroy ozone with fluoroalkane Layer), such as, fluoroform, difluoromethane, 1,1-Difluoroethane, 1,1-bis-chloro-1-fluoroethane, chlorodifluoroethane, tetrafluoro second Alkane, 1,1,1,3,3-pentafluoropropane, heptafluoro-propane, 1,1,1,2-tetrafluoro butane, HFC-365.
Preferably, foaming agent of the present invention is 1,1-bis-chloro-1-fluoroethane (HCFC-141B), 1,1,1,3,3-five Fluoro-propane (HFC-245fa), HFC-365 (HFC-365mfc), 1,1-Difluoroethane, chlorodifluoroethane and One or two or more in 1,1,1,2-tetrafluoro butane (HFC-134a).
Foam stabiliser of the present invention is the material promoting to be formed regular foam structure during formation of foam, can To use any foam stabiliser well known in the art, preferably the foam stabiliser such as siloxane-oxyalkylene containing polysiloxanes is altogether Polymers, and fatty alcohol, oxo alcohol, fatty amine, alkylphenol, dialkyl group phenol, alkylated cresol, alkyl-resorcin, tea The alkoxylate of phenol, alkyl tea phenol, theamin, aniline, alkyl benzene amine, toluidines, bisphenol-A, alkylated bisphenols A or polyvinyl alcohol is produced Thing, and formaldehyde and alkylphenol, formaldehyde and the contracting of dialkyl group phenol, formaldehyde and alkylated cresol, formaldehyde and alkyl-resorcin Close one or more in the alkoxylated polymerization product of product.The example of currently preferred foam stabiliser includes but not limited to moral Silicone oil AK8803, the silicone oil B8533 etc. of Degussa of U.S. generation wound.
Plasticizer of the present invention can use the arbitrary plasticizer in this area, preferably includes phthalic acid diformazan Ester, diethyl phthalate, diisobutyl phthalate, BBP(Butyl Benzyl Phthalate, dihexylphthalate, 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, adipic acid two fourth Ester, di-n-hexyl adipate, dioctyl adipate, decanedioic acid diethyl fat, decanedioic acid diisopropyl fat, Azelaic Acid dibutyl ester, benzene first Acid diol ester, dioctyl sebacate, triphenyl phosphate, tricresyl phosphate, diphenyl 2 ethylhexyl phosphate, phosphate diphenyl isodecyl ester, One or more in triethyl phosphate, trioctyl phosphate, tributyl phosphate and DOTP.
A kind of method preparing polyurethane heat insulation material, comprises the following steps: proportionally,
(1) by polyol component, foam stabiliser, water, foaming agent, catalyst, plasticizer and other auxiliary agent mix homogeneously, Prepared component A expects component in vain；
(2) by modification PM, modified TDI, modified MDI, PM, TDI and HDI mix homogeneously, prepare and combine black material B component；
(3) component A and B component step (1)～(2) prepared is cast in pipe mould and is prepared from.
Pouring technology of the present invention can use any already known processes well known in the art, and Crouse agate is preferably used Luxuriant and rich with fragrance high pressure casting machine controls at 22～26 DEG C by the pouring technology known to operator, such as component A and B component temperature, cast Polyurethane mould or polyurethane tube-in-tube prepare and forms.
In the present invention, polyether polyol 1 that strand is submissiveer and the use of oils and fats, significantly increase cross-linked network chain The pliability of section so that foam is not susceptible to brittle fracture under cryogenic environment.Polyether polyol 2 and the addition of PEPA Make abscess more uniform and smooth, heat-proof quality and the Low-Temperature Size stability of foam can be improved.
The addition of TDI significantly decreases the bond angle between two strands of crosslinking points so that cross-linked network is finer and close, Thus finer and smoother foam structure so that foam has splendid Low-Temperature Size stability and effect of heat insulation.HDI is the most flexible Strand improve the hot strength of converging network, reduce the fragility of material under low temperature environment, improve foam and use safety Stability.
The modifying agent that modified PM, modified TDI and modified MDI use 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, and the most regular rigid chain segment is mutual It is piled into the rigidity cross-linked areas of microfacies, substantially increases the intensity of foam and do not affect the pliability of integral material, hard section Enrichment significantly improves the crosslink density of polymer network, makes abscess attenuate further, thus improves the thermal insulation of foamed materials Can, improve foam Low-Temperature Size stability.
The present invention also provides for a kind of polyurethane heat insulation material.The density of described material > 60kg/m3, compressive strength > 700KPa, hot strength > 800KPa, at 25 DEG C, heat conductivity is less than 0.017w/m k, heat conductivity base after 300 freeze-thaw cycle This is constant, and less than 0.017w/m k,<0.5%, rate of closed hole>98%,<0.05mm transfers for-163 DEG C abscess average-size water absorption rate Put more than 96h not shrink and do not ftracture, and deformation ratio < 0.1%, foam in the plastic film tube of diameter 5cm, flow coefficient (flowing Length/foam quality) it is 0.822～0.843, relatively conventional formulation at least improves 5～8%.
The present invention provides a kind of polyurethane combined material, and this premixed systems has preferable mobility, prepared insulation material tool There is extremely low heat conductivity, it is adaptable to heat insulation effect is required higher various fields, especially performance in low-temperature deep environment Excellence, has splendid low-temperature flexibility and dimensional stability, is particularly useful for making the pipe insulation material of conveying deep cooling medium.
Detailed description of the invention
Method provided by the present invention will be further described by the following examples, but the invention is not restricted to listed The embodiment gone out, also should be included in other any known change in interest field of the presently claimed invention.
Oils and fats: the epoxy soybean oil of Aladdin company, epoxy Semen Lini oil
Water: distilled water
Foam stabiliser: the silicone oil AK8803, the silicone oil B8533 of Degussa of dolantin generation wound
Catalyst: pentamethyl-diethylenetriamine (trade mark is PC5), N, N-dimethyl cyclohexyl amine (trade mark is PC8), potassium acetate (trade mark is LCM-1)
Foaming agent: HCFC-141B, HFC-245fa, HFC-365mfc, HFC-134a
Plasticizer: dioctyl phthalate (DOP)
Embodiment 1～10
The preparation of polyurethane heat insulation material, comprises the following steps: according to the consumption of table 1, in table 1, the consumption of each material is Mass parts,
(1) PM200 is joined in reactor, be warming up to 70 DEG C, drip tripropylene glycol, react 1h, control NCO and contain Amount is 28wt%, and 1h is reacted in the 6245 of dropping Wanhua Chemical (Ningbo) Rongwei Polyurethane Co., Ltd., controls NCO content and is 24wt%, obtains modified PM200；
(2) Lupranate T-80 is joined in reactor, be warming up to 70 DEG C, dropping PS-2002 (this Thailand of Nanjing, Nanjing Pan Chemical Co., Ltd.), react 1h, control NCO content is 43wt%, drips dipropylene glycol, reacts 1h, controls NCO and contains Amount is 34wt%, obtains modified Lupranate T-80A；
(3) Lupranate T-80 is joined in reactor, be warming up to 70 DEG C, dropping ten thousand China chemistry (Ningbo) Rong Weiju The 6245 of urethane company limited, react 1h, and control NCO content is 43wt%, drip diglycol, react 1h, control NCO Content is 33wt%, obtains modified Lupranate T-80B；
(4) Lupranate T-80 is joined in reactor, be warming up to 70 DEG C, drip diglycol, instead
Answering 1h, control NCO content is 35wt%, obtains modified Lupranate T-80C；
(5) joining in reactor by MDI100, be warming up to 70 DEG C, (Jiangsu richness contains the limited public affairs of new material to dropping CF-6200 Department), react 1h, control NCO content is 32wt%, the 6245 of dropping Wanhua Chemical (Ningbo) Rongwei Polyurethane Co., Ltd., instead Answering 1h, control NCO content is 31wt%, drips tripropylene glycol, reacts 1h, and control NCO content is 29wt%, obtains modification MDI100；
(6) joining in reactor by MDI50, be warming up to 70 DEG C, it is limited that dropping ten thousand China's chemistry (Ningbo) holds prestige polyurethane The 6245 of company, react 1h, and control NCO content is 30wt%, obtain modified MDI50；
(7) by polyether polyol 1, polyether polyol 2, PEPA, oils and fats, foam stabiliser, water, foaming agent, urge Agent, plasticizer mix homogeneously, prepared component A expects component in vain；
(8) by modification PM, modified TDI, modified MDI, PM, TDI and HDI mix homogeneously, B component isocyanates group is prepared Point；
(9) temperature is respectively component A and the B component of 25 DEG C, respectively by Crouse's agate phenanthrene high pressure casting machine, is cast in Pipe mould is prepared from.
Table 1 composition of raw materials
Comparative example 1～4
Comparative example 1～4 prepares polyurethane heat insulation material according to the preparation method of embodiment, according to the consumption of table 2, in table 2 The consumption of each material is mass parts.
Table 2 composition of raw materials
Performance test
The foamed materials of preparation is carried out performance test, and testing standard is as follows, and test result is shown in Table 3.
Testing standard:
At flow coefficient 25 DEG C, foaming in the plastic film tube of diameter 5cm, the numerical value of length of flow/foam quality is made For flow coefficient.
Table 3 embodiment 1～10, comparative example 1～4 properties of product test result
The product of above example has preferably mobility, and relatively conventional formulation flow coefficient improves 5～8%；Heat conduction system Number is extremely low, has fabulous heat-proof quality；Do not ftracture under low-temperature deep environment, excellent dimensional stability.It is very suitable for preparation The deep cooling medium conveyance conduit insulation material of tradition pouring technology.The formula using modified isocyanate combination in comparative example is above-mentioned Performance relatively prior art is also obviously improved.
Although the most for explanation, the present invention being described in detail, it should be appreciated that these are retouched in detail Writing and be merely to illustrate that, in the case of without departing from the spirit and scope of the present invention, it can be carried out by those skilled in the art Amendment, the present invention is limited only by the appended claims.

Claims (10)

1. a polyurethane combined material, including component A and B component, component A includes polyol component, and B component is isocyanates group Point, it is characterised in that described B component includes following component, calculates on the basis of B component gross weight:
Polyisocyanates 55～80wt%, preferably 60～75wt%；
Modified polyisocyanate 20～45wt%, preferably 25～40wt%；
Described polyisocyanates includes following component, calculates on the basis of the gross weight of polyisocyanates:
Poly methylene poly phenyl poly isocyanate 60～80wt%, preferably 65～75wt%；
Toluene di-isocyanate(TDI) 13～35wt%, preferably 15～25wt%；
Hexamethylene diisocyanate 3～25wt%, preferably 5～15wt%；
Described modified polyisocyanate includes following component, calculates: NCO content is on the basis of the gross weight of modified polyisocyanate 22～26wt%, viscosity is the modified poly methylene poly phenyl poly isocyanate 70～90wt% of 30000～60000cp, preferably 75～85wt%；
NCO content is 30～35wt%, and viscosity is the modified toluene diisocyanate 3～25wt%, preferably 5 of 200～400cp ～15wt%；
NCO content is 27～31wt%, and viscosity is the modified diphenylmethane diisocyanate 3～25wt% of 500～1000cp, Preferably 5～15wt%.
Premixed systems the most according to claim 1, it is characterised in that described modified polymethylene polyphenyl polyisocyanic acid The modifying agent that ester, modified toluene diisocyanate and modified diphenylmethane diisocyanate use is small molecular alcohol, Gao Guanneng One or more in degree polyether polyol and PEPA.
Premixed systems the most according to claim 2, it is characterised in that described small molecular alcohol be degree of functionality be 2～6, molecular weight It it is the polyhydric alcohol of 80～300；Preferably butanediol, pentanediol, hexanediol, diglycol, dipropylene glycol, two contractings 3 third In glycol, 1,2,6-hexanetriol, triethylene-glycol, tetramethylolmethane and sorbitol one or more；
Described high functionality polyether polyol is that polyhydroxy-alcohol forms with oxirane and/or Polymerization of Propylene Oxide, the equal molecule of number Amount is 200～1000, and hydroxyl value is 300～600mgKOH/g, and degree of functionality is the polyhydric alcohol of 3～8, the preferred sugarcane of described polyhydroxy-alcohol One or more in sugar, sorbitol, xylitol, tetramethylolmethane, glycerol and trimethylolpropane；Described high functionality polyethers is many Unit the 6245 of the preferred Wanhua Chemical (Ningbo) Rongwei Polyurethane Co., Ltd. of alcohol, A29-1, the N-of Jiangsu Zhongshang Chemical Co., Ltd. 635, in the GR-635S of N-635SA, the SY-6560 of Tianjin the 3rd petrochemical plant and Shanghai Gaoqiao petrochemical corporation (complex) Plant or multiple, more preferably the 6245 of Wanhua Chemical (Ningbo) Rongwei Polyurethane Co., Ltd.；
Described PEPA be in aromatic carboxylic acid, aromatic carboxylic acid acid anhydride and terephthaldehyde's acid alkyl ester one or more with Product between diglycol and/or glycerol；Described aromatic carboxylic acid, aromatic carboxylic acid acid anhydride preferably are selected from adjacent benzene two One or more in formic acid, phthalic anhydride, M-phthalic acid, p-phthalic acid and trimellitic anhydride；Described to benzene The carbon number of dioctyl phthalate Arrcostab is 10～16, preferably dimethyl terephthalate (DMT), diethyl terephthalate and to benzene two One or more in formic acid dibutyl ester；The PS-of described PEPA preferred Nanjing Nanjing Si Taipan Chemical Co., Ltd. 3152, one or more in CF-6245 and CF-6200 of PS-2002, Jiangsu Fu Sheng new material company limited, more preferably south The PS-3152 of Nanjing, capital Si Taipan Chemical Co., Ltd..
4. according to the premixed systems described in any one of claim 1-3, it is characterised in that described modified polymethylene polyphenyl is many It is limited that isocyanates is diglycol, dipropylene glycol, tripropylene glycol, ten thousand China's chemistry (Ningbo) hold prestige polyurethane The 6245 of company, one or more in the PS-3152 of Nanjing, Nanjing Si Taipan Chemical Co., Ltd. and many phenyl polyisocyanic acid The product of ester；Preferably diglycol, dipropylene glycol, tripropylene glycol, ten thousand China chemistry (Ningbo) Rong Weiju One or more in the 6245 of urethane company limited and the PS-3152 of Nanjing, Nanjing Si Taipan Chemical Co., Ltd. and ten thousand Chinaization Learn the product of the PM200 of Group Plc；
Described modified toluene diisocyanate is that diglycol, dipropylene glycol, Nanjing, Nanjing Si Taipan chemistry have One or more in the PS-2002 of limit company and the 6245 of Wanhua Chemical (Ningbo) Rongwei Polyurethane Co., Ltd. and toluene two The product of isocyanates；Preferably diglycol, dipropylene glycol, Nanjing, Nanjing Si Taipan Chemical Co., Ltd. One or more in the 6245 of PS-2002 and Wanhua Chemical (Ningbo) Rongwei Polyurethane Co., Ltd. and BASF AG The product of Lupranate T-80；
Described modified diphenylmethane diisocyanate be methyl diphenylene diisocyanate with butanediol, pentanediol, oneself two Alcohol, diglycol, dipropylene glycol, tripropylene glycol, 1,2,6-hexanetriol, ten thousand China's chemistry poly-ammonia of (Ningbo) Rong Wei The reaction of one or more in the 6245 of ester company limited and the PS-3152 of Nanjing, Nanjing Si Taipan Chemical Co., Ltd. is produced Thing；Preferably MDI100 and/or MDI50 of Wanhua Chemical Group Co., Ltd. and butanediol, pentanediol, hexanediol, a contracting Diethylene glycol, dipropylene glycol, tripropylene glycol, 1,2,6-hexanetriol, ten thousand China's chemistry (Ningbo) appearance prestige polyurethane are limited The product of one or more in the 6245 of company and the PS-3152 of Nanjing, Nanjing Si Taipan Chemical Co., Ltd..
5. according to the premixed systems described in any one of claim 1-4, it is characterised in that the polyol component of described component A includes One or many in small molecule polyol, polyether polyol, PEPA, PCDL, polymer polyatomic alcohol, oils and fats Kind；Preferably, the polyol component of described component A includes following component, calculates on the basis of the gross weight of polyol component:
Degree of functionality is 2～3, and number-average molecular weight is 4000～7000, and preferably degree of functionality is 3, and number-average molecular weight is 4500～6000 Polyether polyol 1 20～60wt%, preferably 30～50wt%；
Degree of functionality be 3～5 number-average molecular weights be 200～700, preferably degree of functionality is 4, and number-average molecular weight is the polyethers of 300～500 Polyhydric alcohol 2 10～40wt%, 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 the polyester of 300～700 Polyhydric alcohol 10～40wt%, preferably 15～30wt%；
Degree of functionality is 2～4, and number-average molecular weight is 500～1500, and preferably degree of functionality is 3, and number-average molecular weight is 700～1300 Oils and fats 10～40wt%, preferably 15～35wt%.
Premixed systems the most according to claim 5, it is characterised in that the initiator of described polyether polyol 1 be ethylene glycol, third Glycol, diglycol, dipropylene glycol, triethylene-glycol, glycerol, trimethylolpropane, triethanolamine, diethanol Amine and 1, one or more in 2,6-hexanetriols, polymerized unit is expoxy propane and/or oxirane；Preferably initiator is sweet Oil, polymerized unit is expoxy propane and oxirane；The more preferably TEP-330N of Tianjin three petrochemical industry and/or Shanghai Gaoqiao company GEP-330N；
The initiator of described polyether polyol 2 is ethylenediamine, dipropylene glycol, triethylene-glycol, glycerol, trihydroxy methyl In propane, triethanolamine, diethanolamine, ortho-toluene diamine, p-phenylenediamine, sucrose, sorbitol, xylitol and tetramethylolmethane one Planting or multiple, polymerized unit is expoxy propane and/or oxirane；Preferably initiator is ortho-toluene diamine, and polymerized unit is ring Ethylene Oxide and oxirane；More preferably R4036 and/or R2438A of Wanhua Chemical (Ningbo) Rongwei Polyurethane Co., Ltd.；
Described PEPA is aromatic binary carboxylic acid, aromatic carboxylic acid acid anhydride, aliphatic dicarboxylic acid and the one of carboxylate Kind or multiple react preparation with diglycol；Preferably phthalic acid, phthalic anhydride, adipic acid and p-phthalic acid One or more in dimethyl ester and diglycol react preparation；More preferably Nanjing, Nanjing Si Taipan Chemical Co., Ltd. is raw The PEPA PS-3152 of product, the PEPA PS-2002 of Nanjing, Nanjing Si Taipan Chemical Co., Ltd. production, Jiangsu The polyester that PEPA CF-6245 that Fu Sheng new material company limited produces, Jiangsu Fu Sheng new material company limited produce is many One or more in the PEPA HKP-2022 that unit alcohol CF-6200 and Jining Bai Chuan Chemical Co., Ltd. produce；
Described oils and fats is that vegetative grease uses peroxide treatment to make；Described vegetative grease is selected from Semen setariae oil, flower In oil generation, olive oil, Camellia oil, Petiolus Trachycarpi oil, Oleum Helianthi, soybean oil, Oleum sesami, Semen Lini oil, Semen Maydis oil and walnut oil One or more, preferably soybean oil and/or Semen Lini oil.
7. according to the premixed systems described in any one of claim 1-6, it is characterised in that described component A includes following components, with A Calculate on the basis of the gross weight of component:
8. according to the premixed systems described in any one of claim 1-7, it is characterised in that described component A with the weight ratio of B component is 1:1.3～1.6, preferably 1:1.4～1.5.
9. the method preparing polyurethane heat insulation material according to premixed systems described in any one of claim 1-8, including following step It is rapid: proportionally,
(1) by polyol component, foam stabiliser, water, foaming agent, catalyst, plasticizer mix homogeneously, component A is prepared；
(2) by polyisocyanates and modified polyisocyanate mix homogeneously, B component is prepared；
(3) component A and B component step (1)～(2) prepared is cast in pipe mould and is prepared from.
10. the polyurethane heat insulation material that prepared by a method according to claim 9, it is characterised in that described material Density > 60kg/m3, compressive strength > 700KPa, hot strength > 800KPa, at 25 DEG C heat conductivity be less than 0.017w/m k, 300 After secondary freeze-thaw cycle, heat conductivity is basically unchanged, and less than 0.017w/m k,<0.5%, rate of closed hole>98%, abscess is average for water absorption rate Size < 0.05mm, at-163 DEG C, placement more than 96h does not shrink and does not ftracture, deformation ratio < 0.1%, at the plastic sheeting of diameter 5cm Foaming in pipe, flow coefficient is 0.822～0.843.
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CN110234674A (en) * 2017-01-25 2019-09-13 巴斯夫欧洲公司 Cold soft polyurethane formulation
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KR20190053437A (en) * 2017-11-10 2019-05-20 서울시립대학교 산학협력단 Polyurethane composition, acoustic absorbent comprising the same and manufacturing method polyurethane foam
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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
CN109535378A (en) * 2018-12-11 2019-03-29 万华化学集团股份有限公司 A kind of high opening rate polyurethane cavity filled and process
CN109575856A (en) * 2018-12-19 2019-04-05 南京红宝丽聚氨酯有限公司 A kind of compound one-component adhesion promoter of polyurethane-pressure sensitive adhesive
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
CN112900510A (en) * 2020-12-09 2021-06-04 湖北工业大学 Underground building concrete repairing method under high water pressure and corrosion conditions
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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