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CN108727551A - A kind of hard polyurethane foams and the preparation method and application thereof - Google Patents

A kind of hard polyurethane foams and the preparation method and application thereof Download PDF

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Publication number
CN108727551A
CN108727551A CN201710291572.3A CN201710291572A CN108727551A CN 108727551 A CN108727551 A CN 108727551A CN 201710291572 A CN201710291572 A CN 201710291572A CN 108727551 A CN108727551 A CN 108727551A
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CN
China
Prior art keywords
polyether polyol
polyurethane foams
hard polyurethane
component
isocyanate
Prior art date
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Pending
Application number
CN201710291572.3A
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Chinese (zh)
Inventor
汪先木
高建伍
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Deutschland AG
Original Assignee
Bayer MaterialScience AG
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Filing date
Publication date
Application filed by Bayer MaterialScience AG filed Critical Bayer MaterialScience AG
Priority to CN201710291572.3A priority Critical patent/CN108727551A/en
Priority to PCT/EP2018/059932 priority patent/WO2018192990A1/en
Publication of CN108727551A publication Critical patent/CN108727551A/en
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • C08G18/4841—Polyethers containing oxyethylene units and other oxyalkylene units containing oxyethylene end groups
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
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    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
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    • 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
    • C08J9/12—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 physical blowing agent
    • C08J9/14—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 physical blowing agent organic
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    • 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
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    • C08J9/14—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 physical blowing agent organic
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    • 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
    • C08J9/12—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 physical blowing agent
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    • C08J9/143—Halogen containing compounds
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    • C08J9/12—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 physical blowing agent
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    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/022—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments premixing or pre-blending a part of the components of a foamable composition, e.g. premixing the polyol with the blowing agent, surfactant and catalyst and only adding the isocyanate at the time of foaming
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    • C08J2203/00—Foams characterized by the expanding agent
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    • C08J2205/00—Foams characterised by their properties
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  • Chemical & Material Sciences (AREA)
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  • Polymers & Plastics (AREA)
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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Emergency Medicine (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The present invention relates to a kind of hard polyurethane foams, by following A) polyether polyol premix component and B) isocyanate component is obtained by the reaction：A) polyether polyol premix component, it includes：A1 the hydroxyl value of) one or more of polyether polyol, the polyether polyol is 200-600mgKOH/g, degree of functionality 2-7；A2) one or more of foaming agents, it includes alkenyl halides；A3) one or more of foam stabilisers；A4) one or more of catalyst；B) isocyanate component, the isocyanate component include one or more of organic multiple isocyanates.Electric insulation device prepared by hard polyurethane foams using the present invention has higher breakdown voltage；Zero odp and low GWP, VOC free discharge, meet environmental requirement；Lightweight, transport and installation risk are small；It is anti-aging to degrade.

Description

A kind of hard polyurethane foams and the preparation method and application thereof
Technical field
The invention belongs to polyurethane fields.In particular it relates to a kind of hard polyurethane foams and its preparation side Method and application.
Background technology
Insulator as high voltage power transmission can be made of glass, ceramics or polymer composites.Ceramic insulation Son is made of clay, quartz soil or bauxite, has the advantages that high mechanical strength, but surface vulnerable to pollution and generating is leaked electricity etc. Potential risk.Glass is also easy to produce moisture condensation, and irregular heavy sheet glass difficulty of processing is big.Since the later stage sixties 19th century, one A little insulator manufacturers stop production glass insulator, use ceramics manufacture insulator instead.
Recently, some Utilities Electric Co.s begin to use polymer composites to produce the insulators of some models.These insulation Son is made of hollow glass steel central post and outer silicone insulator.Different insulative material is filled in hollow glass steel central post Material is to meet different transmission of electricity requirements.Polymer composites insulator has remarkable hydrophobic performance, and cost economy is light-weight, The potential dangers such as flash burn and cracking can be completely eliminated.Cast polyurethane expanded material just becomes polymer in hollow glass steel A kind of technical solution of composite material insulator.
Patent CA1051191 is disclosed using SF6, CFC and other low-boiling foaming agent HFC manufacture foamed polymer material For electric insulation.The use of these low-boiling foaming agents needs special foaming machine to coordinate foaming, actual production process Middle poor operability, repeatability are low.Although sulfur hexafluoride itself is nontoxic to human body, harmless, it is a kind of greenhouse effects gas Body, monomolecular greenhouse effects are 2.2 ten thousand times of carbon dioxide, it is《The Kyoto Protocol》In be prohibited discharge 6 kinds of temperature One of room gas.Foaming agent CFC is big to Atmospheric Ozone Layer Depletion power, and chamber effect potential value is high, quilt《Montreal Protocol》 It is classified as obsolete product.Blowing agent H FC is also high because of chamber effect potential value, and《Montreal Protocol》In be classified as superseded production Product.Although pentamethylene and water can be used as foaming agent to be applied to polyurethane foam cannot meet electricity since its breakdown potential is forced down Gas insulator requirement.
Therefore, it is necessary to develop a kind of material that meeting electric insulator requirement and can readily produce.
Invention content
Meeting electric insulator requirement technical problem to be solved by the invention is to provide a kind of and can be easy The material of ground production.
The technical problems to be solved by the invention are addressed by the following technical programs：
According to an aspect of the present invention, a kind of hard polyurethane foams are provided, by following A) polyether polyol premix Material component and B) isocyanate component is obtained by the reaction：
A) polyether polyol premix component, it includes：
A1 the hydroxyl value of) one or more of polyether polyol, the polyether polyol is 200-600mgKOH/g, degree of functionality For 2-7；
A2) one or more of foaming agents, it includes alkenyl halides；
A3) one or more of foam stabilisers；
A4) one or more of catalyst；
B) isocyanate component, the isocyanate component include one or more of organic multiple isocyanates.
According to another aspect of the present invention, a kind of method preparing above-mentioned hard polyurethane foams is provided comprising with Lower step：
I) it is mixed and stirred for following component and optional other ingredients uniformly, to obtain A) polyether polyol premix group Point,
A1 the hydroxyl value of) one or more of polyether polyol, the polyether polyol is 200-600mgKOH/g, degree of functionality For 2-7；
A2) one or more of foaming agents, it includes alkenyl halides；
A3) one or more of foam stabilisers；
A4) one or more of catalyst；
Other ingredients are selected from antioxidant, antistatic agent and pigment；
Ii) by following B) isocyanate component and A) polyether polyol premix component is mixed to get reaction mixture：
B) isocyanate component, it includes one or more of organic multiple isocyanates；With
Iii) make reaction mixture reaction to obtain hard polyurethane foams.
According to another aspect of the present invention, application of the above-mentioned hard polyurethane foams in electric insulation device is provided.
Further aspect according to the present invention provides a kind of electric insulation device, and it includes above-mentioned hard polyurethane foams.
The greenhouse effects of alkenyl halide used in use of the present invention are low and do not destroyed to atmospheric ozone layer.The present invention uses The electrical insulating property of polyurethane foam prepared by halogenated olefin blowing agents is good, can be used for preparing electric insulation device.
Specific implementation mode
The specific implementation mode for implementing the present invention is described below.
According to an aspect of the present invention, a kind of hard polyurethane foams are provided, by following A) polyether polyol premix Material component and B) isocyanate component is obtained by the reaction：
A) polyether polyol premix component, it includes：
A1 the hydroxyl value of) one or more of polyether polyol, the polyether polyol is 200-600mgKOH/g, degree of functionality For 2-7；
A2) one or more of foaming agents, it includes alkenyl halides；
A3) one or more of foam stabilisers；
A4) one or more of catalyst；
B) isocyanate component, the isocyanate component include one or more of organic multiple isocyanates.
The polyether polyol is common polyether polyol in prepared by hard polyurethane foams, such as can be by ethylene oxide And/or propylene oxide reacts obtained polyether polyol with initiator, the initiator be selected from aliphatic amine, aromatic amine or With 2 to 16, the polyol such as glycerine, pentaerythrite and carbohydrate such as sorb of usual 3 to 8 hydroxyls Alcohol, glucose, sucrose etc..
The aliphatic amine can be aliphatic mono or diamine with 2-4 carbon atom.It, can as aliphatic amine Include ethylenediamine, triethanolamine and diethylenetriamine etc. with the example referred to.
The aromatic amine can be aromatic monoamines or diamine with 6-13 carbon atom.As aromatic amine, It can be mentioned that example have aniline, toluenediamine and methylene dianiline (MDA) etc..
It is preferred that the hydroxyl value of polyether polyol is 300-500mgKOH/g, degree of functionality 3-5.
As used in this application, unless otherwise specified, the degree of functionality of polyether polyol, hydroxyl value each mean average functionality and Average hydroxyl value.
Polyether polyol is particularly preferably obtained using amine (such as toluenediamine) as initiator and using sorbierite as starting The combination of agent polyether polyol, to obtain excellent foam structure and reduce foam anisotropy.
Amount of the polyether polyol in the polyether polyol premix component is about 40-80wt.%, preferably 50- 70wt.%, more preferable 55-65wt.%, the total weight relative to the polyether polyol premix component.
The alkenyl halide refers to the alkene being optionally substituted by halogen, the C preferably replaced by fluorine and/chlorine2-C6Alkene, more preferably quilt The C of fluorine and the substitution of/chlorine2-C4Alkene.As the example of alkenyl halide, it can be mentioned that hexafluorobutene (CF3CH=CHCF3), trifluoro One chloropropene (CF3CH=CHCl), fluorine dichloropropane (CH3CCl2F), pentafluoropropane (CF3CH2CHF2), 3-pentafluorobutane (CF3CH2CF2CH3), tetrafluoropropene (CHF=CHCF3).It is preferable to use hexafluorobutenes as foaming agent, so that electric insulation device The breakdown voltage of part is higher.
Amount of the foaming agent in the polyether polyol premix component is about 1-30wt.%, preferably 5- 25wt.%, more preferable 10-20wt.%, the total weight relative to the polyether polyol premix component.
The foam stabiliser is the substance for stablizing reaction mixture during foam reactant, preferably type siloxane table Face activating agent.
As the example of foam stabiliser, it can be mentioned that include：L-5130, L-5180, L- from Momentive 5340, L-5440, L-6100, L-6900, L-6915, L6920, L-6980, L-6988 and L-6863；From Air Products DC-193, DC-197, DC-5582 and DC-5598；B-8462 from Evonic, B-8524, B-8534, B-8544, B- 8474 and B-8476；AK8805, AK8830, AK8863 and AK8871 of Mei Side.
The amount of the foam stabiliser is about 0.1-5wt.%, the total weight based on all formation of foam ingredients.
In the specification of the present application, all formation of foam ingredients include the polyether polyol premix component and described different Isocyanate component.
It is preferred that the total weight based on all formation of foam ingredients, the amount of foam stabiliser is 1-3wt.%, to be had The foams of stable bubble hole structure, gained foam cell uniformity, rate of closed hole is high, and water absorption rate is low.
The catalyst can be common amines catalyst or non-amines catalyst in prepared by hard polyurethane foams.Amine Class catalyst is the amino-containing compound with catalytic activity of packet.Non- amines catalyst is not comprising amino there is catalysis to live The compound of property.
The example of amines catalyst for use in the present invention includes N, N, N ', N ", N "-pentamethyldiethylenetriamine；N, N- Dicyclohexylmethylamine；N,N-Dimethylaniline；N, N- ethyl diisopropyl amine；N, N- dimethylcyclohexylam,ne；N, N- diformazan Base isopropylamine；N- methyl-N-isopropyl benzyl amine；N- methyl-N- cyclopenta benzyl amine；N- isopropyl-N- sec-butyls- Trifluoroethyl amine；N, N- diethyl-(α-phenylethyl) amine, N, tri- n-propyl amine of N, N-, dicyclohexylamine or combinations thereof.It can use In the example of non-amines catalyst of the present invention include organic tin compound, such as：Tin acetate (II), tin octoate (II), second Base caproic acid tin, tin laurate, Dibutyltin oxide, dibutyl tin dichloride, dibutyl tin acetate, dibutyl maleic acid tin, Dioctyl oxalic acid tin or their mixture.
The amount of the catalyst is about 0.1-5wt.%, preferably 0.3-3wt.%, based on the total of all formation of foam ingredients Weight.
As needed, the polyether polyol premix component can also include optional other ingredients, such as but unlimited In：The auxiliary agents such as antioxidant, antistatic agent and pigment.
Common antioxidant during the antioxidant can be prepared for hard polyurethane foams, such as 2,6- di-t-butyl -4- first Base phenol (BHT), four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters (1010), bis- (2,4- bis- tertiary fourths Base phenol) pentaerythritol diphosphites (626), in an amount of from 0.1-10wt.%, the gross weight based on all formation of foam ingredients Amount.
The antistatic agent can be common antistatic agent in prepared by hard polyurethane foams, such as octadecyldimethyl Ethoxy quaternary ammonium nitrate, quaternary cationics and alkylsulfonate etc. are based on institute in an amount of from 0-10wt.% There is the total weight of formation of foam ingredient.
Common pigment during the pigment can be prepared for hard polyurethane foams, such as PV FAST Brown RL, Reactint Balck X95AB, Reactint Yellow X15 are based on all formation of foam ingredients in an amount of from 0-10wt.% Total weight.
The type and amount of optional other ingredients should be not negatively affect the performance of gained hard polyurethane foams Subject to.
The organic multiple isocyanate is common organic multiple isocyanate in prepared by hard polyurethane foams.It is described organic Polyisocyanates is preferably selected from 4,4 '-methyl diphenylene diisocyanates, 2,4 '-methyl diphenylene diisocyanates, 2,2 '-two Methylenebis phenyl isocyanate, 2,4- toluene di-isocyanate(TDI)s, 2,6- toluene di-isocyanate(TDI)s, polyphenyl polymethylene polyisocyanate cyanogen Acid esters, 1,6- hexa-methylenes-diisocyanate, 1- isocyanate groups -3,5,5- trimethyls -1,3- isocyanatometyl-hexamethylene, 2,4- hexahydrotoluenes-diisocyanate, 2,6- hexahydrotoluenes-diisocyanate, 4,4 "-dicyclohexyl methyl hydride diisocyanate, 2,2- hexamethylene dicyclohexyl methyl hydride diisocyanates and 2,4 "-dicyclohexyl methyl hydride diisocyanate and corresponding isomers are mixed Close object.
Those skilled in the art are easy to determine organic polyisocyanic acid according to the type of the polyether polyol and amount The amount of ester, herein without repeating.
According to another aspect of the present invention, a kind of method preparing above-mentioned hard polyurethane foams is provided comprising with Lower step：
I) it is mixed and stirred for following component and optional other ingredients uniformly, to obtain A) polyether polyol premix group Point,
A1 the hydroxyl value of) one or more of polyether polyol, the polyether polyol is 200-600mgKOH/g, degree of functionality For 2-7；
A2) one or more of foaming agents, it includes alkenyl halides；
A3) one or more of foam stabilisers；
A4) one or more of catalyst；
Other ingredients are selected from antioxidant, antistatic agent and pigment；
Ii) by following B) isocyanate component and A) polyether polyol premix component is mixed to get reaction mixture：
B) isocyanate component, it includes one or more of organic multiple isocyanates；With
Iii) make reaction mixture reaction to obtain hard polyurethane foams.
The type of above each ingredient and measure with above in relation to identical described in hard polyurethane foams.
Prepare the technique of hard polyurethane foams and equipment be to those skilled in the art it is well known, herein not into Row repeats.It can be foamed using common foaming machine.
The hard polyurethane foams prepared using alkenyl halide such as hexafluorobutene foaming agent, foam density 50- 200kg/m3, intensity is high, and up to 0.4MPa, rate of closed hole is more than 90%, and breakdown voltage is more than 3kv/mm, is suitable as being electrically insulated Son.
According to another aspect of the present invention, application of the above-mentioned hard polyurethane foams in electric insulation device is provided.
The electric insulation device includes electric(al) insulator, insulated wire cable, insulated switch, insulated tension pole, insulator crossarm With insulation spacer etc..
Electric insulation device prepared by hard polyurethane foams using the present invention has higher breakdown voltage；Zero odp With low GWP, VOC free discharge meets environmental requirement；Lightweight, transport and installation risk are small；It is anti-aging to degrade.
Further aspect according to the present invention provides a kind of electric insulation device, and it includes above-mentioned hard polyurethane foams.
The electric insulation device includes electric(al) insulator, insulated wire cable, insulated switch, insulated tension pole, insulator crossarm With insulation spacer etc..
Electric insulator includes fiberglass reinforced hollow tube, housing and cluster parachute, and wherein fiberglass reinforced hollow tube cavity filling is poly- Urethane foam, to form polymer composite insulator.
Unless otherwise defined, all technical and scientific terms used herein have those skilled in the art of the invention Normally understood identical meaning.When the definition of term in this specification and the normally understood meaning of those skilled in the art of the invention When justice is contradictory, it is subject to definition described herein.
The present invention is illustrated by the following examples, it should be understood that the scope of the present invention is not implemented by these The restriction of example.
Embodiment
Used test method explanation in embodiment：
Foam density：It is measured according to standard GB/T6343.
Rate of closed hole：It is measured according to GB/T 10799.
Foamy body：It is measured according to GB/T 8813.
Foam breakdown voltage：It is tested according to standard IEC 62231.
Raw materials used explanation in embodiment
Polyalcohol A：Using the polyether polyol that sorbierite is prepared as initiator, hydroxyl value is 430mg KOH/g, and degree of functionality is 4.2, it is purchased from Jurong Ningwu new material Co., Ltd.
Polyalcohol B：Using the polyether polyol that toluenediamine is prepared as initiator, hydroxyl value is 330mg KOH/g, and degree of functionality is 4.0, purchased from Cohan wound polymer Co., Ltd.
Polyalcohol C：Using the polyether polyol that glycerine is prepared as initiator, hydroxyl value is 235mg KOH/g, and degree of functionality is 3.0, it is purchased from Nanjing Jin Pu Chemical Co., Ltd.s.
Silicon class surfactant：AK8860 is purchased from Jiangsu Maysta Chemical Co., Ltd..
Amines catalyst：Polycat 8 is purchased from air chemical industry (China) Co., Ltd.
Antioxidant：2,6- di-tert-butyl-4-methy phenols (BHT) are purchased from Lang Sheng Chemical Co., Ltd.s.
Embodiment 1-21
Using described in table 1 raw material and its amount prepare hard polyurethane foams, wherein embodiment 5-6,12-13 and 19- 20 belong to the embodiment of the present invention, and embodiment 1-4,7-11,14-18 and 21 are not belonging to the embodiment of the present invention.By polyether polyol, hair Infusion, foam stabiliser, catalyst, antioxidant are mixed and stirred for uniformly, obtaining mixture A) polyether polyol premix component, By A) polyether polyol premix component is added in the component A material work tank in foaming machine, and wherein foaming machine includes component A material Work tank and B component material work tank, A carry material pump and B carries material pump, A proportioning pumps and B proportioning pumps, A expects pipes and B expects pipes, loading chamber Body, wherein A put forward material pump, A proportioning pumps and A expects pipes and are sequentially connected, and B puies forward material pump, B proportioning pumps and B expects pipes and is sequentially connected, and A expects pipes It is connect with charging cavity with B expects pipes.By B) polyisocyanate component is added to the B component material work tank in high pressure foaming machine In.Material pump is carried by the A in component A material work tank in high pressure foaming machine by A) polyether polyol premix component is transported to A ratios In example pump, by the supercharging of A proportioning pumps by A) polyether polyol premix component is transported to high pressure foaming machine hybrid gun by A expects pipes Head；Material pump is carried by the B in B component material work tank in high pressure foaming machine by B) isocyanate component is transported in B proportioning pumps, leads to The supercharging of B proportioning pumps is crossed by B) isocyanate component is transported to high pressure foaming machine by B expects pipes and mixes pipette tips, and component A exists with B component After high-pressure foam machine gun head impingement mix, injects in fiberglass reinforced hollow tube cavity and carry out foaming, wherein A proportioning pumps and B The temperature of proportioning pump, A expects pipes and B expects pipes is set as 20~30 DEG C.
Table 1 is raw materials used and gained performance
As shown in table 1, using CF3CH=CHCl and CF3CH=CHCF3The rigid polyurethane foam prepared as foaming agent The breakdown voltage of foam is apparently higher than using water, CH3CCl2F、C5H10、CF3CH2CF2CH3Or CF3CH2CHF2As foaming agent system The breakdown voltage of standby hard polyurethane foams.
Table 2 is raw materials used and gained performance
As shown in table 2, using CF3CH=CHCl and CF3CH=CHCF3The rigid polyurethane foam prepared as foaming agent The breakdown voltage of foam is apparently higher than using water, CH3CCl2F、C5H10、CF3CH2CF2CH3Or CF3CH2CHF2As foaming agent system The breakdown voltage of standby hard polyurethane foams.
Table 3 is raw materials used and gained performance
As shown in table 3, using CF3CH=CHCl and CF3CH=CHCF3The rigid polyurethane foam prepared as foaming agent The breakdown voltage of foam is apparently higher than using water, CH3CCl2F、C5H10、CF3CH2CF2CH3Or CF3CH2CHF2As foaming agent system The breakdown voltage of standby hard polyurethane foams.
Although the present invention is described in detail above with respect to the object of the invention, it will be appreciated that, this detailed description is Illustratively, other than the content that can be defined by the claims, without departing from spirit and scope of the present invention, Those skilled in the art can carry out various changes.

Claims (10)

1. a kind of hard polyurethane foams, which is characterized in that it is by following A) polyether polyol premix component and B) isocyanic acid Ester component reaction obtains：
A) polyether polyol premix component, it includes：
A1 the hydroxyl value of) one or more of polyether polyol, the polyether polyol is 200-600mgKOH/g, degree of functionality 2- 7；
A2) one or more of foaming agents, it includes alkenyl halides；
A3) one or more of foam stabilisers；
A4) one or more of catalyst；
B) isocyanate component, the isocyanate component include one or more of organic multiple isocyanates.
2. hard polyurethane foams according to claim 1, which is characterized in that the polyether polyol is by ethylene oxide And/or propylene oxide reacts obtained polyether polyol with initiator, the initiator is selected from the fat with 2-4 carbon atom Fat race monoamine or diamine, the aromatic monoamines with 6-13 carbon atom or diamine or with 2 to 16 hydroxyls Polyol.
3. hard polyurethane foams according to claim 1 or 2, which is characterized in that the alkenyl halide be selected from by fluorine and/ The C of chlorine substitution2-C6Alkene.
4. hard polyurethane foams according to claim 1 or 2, which is characterized in that the polyether polyol premix group Divide also includes other ingredients selected from the following：Antioxidant, antistatic agent and pigment.
5. hard polyurethane foams according to claim 1 or 2, which is characterized in that the organic multiple isocyanate is selected from 4,4 '-methyl diphenylene diisocyanates, 2,4 '-methyl diphenylene diisocyanates, 2,2 '-diphenylmethane diisocyanates Ester, 2,4- toluene di-isocyanate(TDI)s, 2,6- toluene di-isocyanate(TDI)s, polyphenyl polymethylene polyisocyanates, 1,6-, six methylenes Base-diisocyanate, 1- isocyanate groups -3,5,5- trimethyls -1,3- isocyanatometyl-hexamethylene, 2,4- hexahydrotoluenes-two Isocyanates, 2,6- hexahydrotoluenes-diisocyanate, 4,4 "-dicyclohexyl methyl hydride diisocyanate, 2,2- hexamethylene dicyclohexyls Methane diisocyanate and 2,4 "-dicyclohexyl methyl hydride diisocyanate and corresponding isomer mixtures.
6. a kind of method preparing the hard polyurethane foams described in any one of claim 1-5, which is characterized in that it includes Following steps：
I) it is mixed and stirred for following component and optional other ingredients uniformly, to obtain A) polyether polyol premix component,
A1 the hydroxyl value of) one or more of polyether polyol, the polyether polyol is 200-600mgKOH/g, degree of functionality 2- 7；
A2) one or more of foaming agents, it includes alkenyl halides；
A3) one or more of foam stabilisers；
A4) one or more of catalyst；
Other ingredients are selected from antioxidant, antistatic agent and pigment；
Ii) by following B) isocyanate component and A) polyether polyol premix component is mixed to get reaction mixture：
B) isocyanate component, it includes one or more of organic multiple isocyanates；With
Iii) make reaction mixture reaction to obtain hard polyurethane foams.
7. purposes of the hard polyurethane foams in preparing electric insulation device described in any one of claim 1-5.
8. purposes according to claim 7, which is characterized in that the electric insulation device is selected from electric(al) insulator, insulated electro Line cable, insulated switch, insulated tension pole, insulator crossarm and insulation spacer.
9. a kind of electric insulation device, which is characterized in that it includes the rigid polyurethane foams described in any one of claim 1-5 Foam.
10. electric insulation device according to claim 9, which is characterized in that it is selected from electric(al) insulator, insulated electric conductor electricity Cable, insulated switch, insulated tension pole, insulator crossarm and insulation spacer.
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