CN114516954A - Polyether polyol and polyurethane foam - Google Patents

Polyether polyol and polyurethane foam Download PDF

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Publication number
CN114516954A
CN114516954A CN202210146062.8A CN202210146062A CN114516954A CN 114516954 A CN114516954 A CN 114516954A CN 202210146062 A CN202210146062 A CN 202210146062A CN 114516954 A CN114516954 A CN 114516954A
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polyether polyol
formula
reaction
unsubstituted
epoxy
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CN114516954B (en
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邢益辉
吴一鸣
张蒙蒙
芮辉辉
赵德喜
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Nanjing Hongbaoli Polyurethane Co ltd
Hongbaoli Group Co ltd
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Nanjing Hongbaoli Polyurethane Co ltd
Hongbaoli Group Co ltd
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Abstract

The invention discloses polyether polyol, which contains an alicyclic group, wherein the alicyclic group has a structure shown in a formula (I):

Description

Polyether polyol and polyurethane foam
Technical Field
The invention belongs to the technical field of chemistry, and particularly relates to polyether polyol and polyurethane foam.
Background
The rigid polyurethane foam material has a key effect on energy conservation and consumption reduction of household appliances such as refrigerators and freezers as a heat insulation material with excellent performance, and can efficiently obstruct heat transfer, thereby being beneficial to reducing energy consumption of the household appliances and reducing carbon emission. In order to achieve the above effects for a long time, it is usually required that the rigid polyurethane foam has good stability, and firstly, the stability to environmental change is stable, that is, the rigid polyurethane foam can still keep a small deformation rate under a low-temperature or damp-heat environment, so as to avoid affecting the appearance of the product due to foam deformation; and secondly, the stability after demoulding is realized, namely the complex cavity is filled, and the change rate of the thickness of the polyurethane foam filled in the complex cavity after demoulding is small so as to avoid deformation and rejection of the product.
The prior art generally adopts a mode of increasing the core density to improve the stability of rigid polyurethane foam, but the method has the following problems: firstly, the higher core density represents higher material injection amount, which not only increases the cost of raw materials, but also is not beneficial to the saving of petrochemical resources; secondly, higher core densities often require longer demould times, which means longer times for the production of a unit of domestic electrical appliance product, which is detrimental to increasing production efficiency and reducing carbon emissions.
Therefore, in order to promote resource conservation and green development in the polyurethane field, there is a need to solve the low density (i.e., bulk density of molded polyurethane foam < 31 kg/m)3Core density of less than 27kg/m3) The problem of difficult compatibility with high stability.
Disclosure of Invention
The invention aims to solve the problem that the low density and the high stability of the hard polyurethane foam material are difficult to be considered at the same time, and the following technical scheme is adopted specifically:
firstly, the invention provides polyether polyol, which contains alicyclic group, wherein the structure of the alicyclic group is shown as formula (I):
Figure BDA0003508314450000011
wherein n is any natural number from 2 to 6, and m is 1 or 2. The alicyclic ring formed by carbon atoms in the formula (I) can be a quaternary carbon ring, a quinary carbon ring, a hexabasic carbon ring, a heptabasic carbon ring or an octabasic carbon ring, 1-2 hydrogen atoms of the alicyclic ring can be replaced by inert groups, each alicyclic structure is connected into a polyether polyol molecular chain through a pair of adjacent carbon atoms, one carbon atom is connected with an oxygen atom, and the other carbon atom is connected with an oxygen atom or a nitrogen atom. Further, n is any natural number of 3-5, so that the convenience of obtaining raw materials is improved.
When 1 to 2 hydrogen atoms of the alicyclic group are substituted with an inert group, an alicyclic group of the following structure may be formed:
Figure BDA0003508314450000021
Figure BDA0003508314450000022
and the like, but not limited to the above structure, R 'may be substituted for any hydrogen atom on the alicyclic ring, wherein R' is an inert group, and m is 1 or 2, the inert group being a group satisfying the following conditions at the same time: (1) unreactive with alkylene oxides under the conditions of the preparation of the polyether polyols of the present invention, and (2) unreactive with isocyanate groups. The optional inert group comprises an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alicyclic group, an ether group, a tertiary amino group and the like, and in order to take the raw material availability into consideration, the inert group is preferably a C1-C4 alkyl group, the number of the inert groups is preferably 1-2, the C1-C4 alkyl groups comprise methyl, ethyl, propyl, isopropyl, butyl, n-butyl and isobutyl, and the most preferred inert group is methyl or ethyl.
Further, the alicyclic group in the present invention is introduced by the alkylene oxide and/or the initiator.
The first embodiment: the alicyclic group is introduced by alkylene oxide, namely the alkylene oxide containing the alicyclic structure and an initiator are subjected to ring-opening polymerization reaction, so that polyether polyol containing the structure of the formula (I) and/or polyether polyol containing the structure that hydrogen on the alicyclic ring of the formula (I) is replaced by an inert group are obtained. Preferably, the alkylene oxide comprises at least one of unsubstituted epoxycycloalkane and C1-C4 alkyl-substituted epoxycycloalkane, and the unsubstituted epoxycycloalkane is at least one of 1, 2-epoxycyclobutane, 1, 2-epoxycyclopentane, 1, 2-epoxycyclohexane, 1, 2-epoxycycloheptane or 1, 2-epoxycyclooctane. C1-C4 alkyl-substituted epoxycycloalkanes, i.e. said unsubstituted epoxycycloalkanes in which one or several hydrogen atoms are replaced by C1-C4 alkyl groups, e.g. unsubstituted epoxycycloalkanes in which one or two hydrogen atoms are replaced by methyl, ethyl, propyl, isopropyl, butyl, n-butyl or isobutyl groups, preferably C1-C4 alkyl-substituted epoxycycloalkanes are 1, 2-epoxy-1-methyl-cyclobutane, 1, 2-epoxy-3-methyl-cyclobutane, 1, 2-epoxy-1-methyl-cyclopentane, 1, 2-epoxy-3-methyl-cyclopentane, 1, 2-epoxy-4-methyl-cyclopentane, 1, 2-epoxy-1-ethyl-cyclopentane, 1, 2-epoxy-3-ethyl-cyclopentane, n-butyl, 1, 2-epoxy-3-methyl-cyclopentane, n-methyl-cyclopentane, n-butyl-ethyl-methyl-cyclopentane, n-o-methyl-cyclopentane, n-butyl-o-methyl-o-n-o-butyl-n-o-n-o-n-o-n-butyl-o-n-o-n-o-n-o-n-o-n-lane, 1, 2-epoxy-4-ethyl-cyclopentane, 1, 2-epoxy-1-propyl-cyclopentane, 1, 2-epoxy-3-propyl-cyclopentane, 1, 2-epoxy-1-isopropyl-cyclopentane, 1, 2-epoxy-3-isopropyl-cyclopentane, 1, 2-epoxy-4-isopropyl-cyclopentane, 1, 2-epoxy-1-butyl-cyclopentane, 1, 2-epoxy-4-butyl-cyclopentane, 1, 2-epoxy-1-n-butyl-cyclopentane, 1, 2-epoxy-4-n-butyl-cyclopentane, 3- (2-methylpropyl) -7-oxabicyclo [4.1.0] heptane, heptane, 3-but-2-yl-7-oxabicyclo [4.1.0] heptane, 1-but-2-yl-7-oxabicyclo [4.1.0] heptane, 2, 4-dimethyl-7-oxabicyclo [4.1.0] heptane, 1- (isobutyl) -1, 2-epoxycyclohexane, 4-methyl-1, 2-epoxycyclohexane, 1, 2-epoxy-3-methyl-cyclohexane, 1, 2-epoxy-1-ethyl-cyclohexane, 1, 2-epoxy-3-ethyl-cyclohexane, 1, 2-epoxy-4-isopropyl-cyclohexane, 1-butyl-2-yl-7-oxabicyclo [4.1.0] heptane, 1-but-2-yl-7-oxabicyclo [4.1.0] heptane, 1- (isobutyl) -1, 2-epoxy-1, 2-methyl-1, 2-epoxycyclohexane, 1, 2-epoxy-3-isopropyl-cyclohexane, 1, 2-epoxy-1-isopropyl-cyclohexane, 1, 2-epoxy-3-n-butyl-cyclohexane, 1-methyl-1, 2-epoxycycloheptane or 5-methyl-1, 2-epoxycyclooctane and isomers of the above compounds. The preferable unsubstituted epoxycycloalkane or C1-C4 alkyl-substituted epoxycycloalkane can be alkoxylated with an initiator under mild conditions, has the characteristic of simple process, and is convenient for industrial implementation.
In order to obtain polyether polyol products with moderate viscosity, the alkylene oxide adopted by the invention also comprises C2-C3 alkylene oxide, and the C2-C3 alkylene oxide is at least one of ethylene oxide and propylene oxide. Preferably, the alkylene oxide consists of propylene oxide and unsubstituted epoxycycloalkane, or consists of propylene oxide and methyl-substituted epoxycycloalkane, or consists of propylene oxide, ethylene oxide and unsubstituted epoxycycloalkane, or consists of propylene oxide, ethylene oxide and methyl-substituted epoxycycloalkane.
In the preparation of the polyether polyol of the present invention using the above-mentioned materials, a mode of mixing all the components in the alkylene oxide together to form a mixture or a mode of using each component in the alkylene oxide individually in order may be selected, and among them, preferred are: firstly, the initiator is alkoxylated with unsubstituted epoxycycloalkane and/or C1-C4 alkyl substituted epoxycycloalkane in the oxyalkyleneAnd then carrying out ring-opening polymerization reaction with C2-C3 alkylene oxide in the alkylene oxide to obtain a polyether crude product, and refining to obtain the polyether polyol. Wherein the ratio of the total mole number of the unsubstituted epoxy cycloalkane and the C1-C4 alkyl substituted epoxy cycloalkane to the total mole number of the initiator is (1-2): 1. The initiator is an active hydrogen-containing compound, and can be a polyol or polyamino compound known in the art, the polyol is preferably, but not limited to, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylolpropane, sorbitol, sucrose, glycerol, xylitol, pentaerythritol, and the like, and the initiator having a functionality of 3. ltoreq. less than 8, such as trimethylolpropane, sorbitol, glycerol, xylitol, and the like, is preferably used to obtain a catalyst containing
Figure BDA0003508314450000031
The polyether polyol with the structure of the formula (I-1) or the polyether polyol with the structure that hydrogen on an alicyclic ring of the formula (I-1) is substituted by an inert group, wherein n is any natural number of 2-6, and m is 1 or 2, so that the fluidity and the crosslinking density are both considered. The polyamino compound is preferably, but not limited to, alkyldiamine, alkanolamine, aromatic diamine, etc., preferably ethylenediamine, phenylenediamine, propylenediamine, etc., to obtain a polyamino compound containing
Figure BDA0003508314450000032
Polyether polyol with a structure shown in a formula (I-2) or polyether polyol with a structure shown in a formula (I-2) in which hydrogen on an alicyclic ring is substituted by an inert group, wherein n is any natural number of 2-6, and m is 1 or 2.
The second embodiment: the alicyclic group is introduced by an initiator, namely the initiator containing the alicyclic structure and alkylene oxide are subjected to ring-opening polymerization reaction, so that polyether polyol containing the structure of the formula (I) and/or polyether polyol containing the structure that hydrogen on the alicyclic ring of the formula (I) is replaced by an inert group are obtained. Preferably, the initiator comprises at least one of unsubstituted cycloalkanols and C1-C4 alkyl-substituted cycloalkanols. The structure of the unsubstituted cycloalkanol compound is shown as a formula (II) or a formula (III), wherein the formula (II) is as follows:
Figure BDA0003508314450000033
wherein x is any natural number of 2-6, R 1Is H or R2Is C2-C4 hydroxyalkyl or C2-C4 aminoalkyl, or R1And R2Are all C2-C4 hydroxyalkyl, the formula (III) is
Figure BDA0003508314450000041
Wherein y is any natural number of 2-6, R3Is C2-C4 alkylene, R4Is hydrogen or C2-C3 hydroxyalkyl, R5Is hydrogen or C2-C3 hydroxyalkyl, R6Is C2-C3 hydroxyalkyl. It has been unexpectedly found that when the initiator contains the unsubstituted cycloalkanol compound or the C1-C4 alkyl-substituted cycloalkanol compound with the above structure, the dimensional stability of the low-density rigid polyurethane foam under low temperature and damp-heat conditions can be improved, and the deformation rate of the rigid polyurethane foam after demolding can be further reduced, so that the dimensional stability after demolding can be improved.
The structural formula of the hydroxyalkyl group in the present invention is preferably formula (IV): -CzH2z-OH, the structural formula of aminoalkyl is preferably of formula (V): -CzH2z—NH2The alkylene group preferably has the formula: -CzH2zWherein z is any natural number from 2 to 4. In order to obtain polyether polyols having both a higher functionality and a lower viscosity, more preferably formula (IV) is: -CH2—CH2-OH formula (IV-1) or-CH2—CH2—CH2-OH formula (IV-2) or-CH (CH)3)—CH2-OH formula (IV-3) or-CH2—CH(CH3) -OH formula (IV-4) or-CH 2—CH2—CH2—CH2-OH formula (IV-5), -CH (CH)3)—CH2—CH2-OH formula (IV-6), -CH2—CH(CH3)—CH2-OH formula (IV-7) or-CH2—CH2—CH(CH3) -OH formula (IV-8) — CH (CH)3)—CH(CH3) -OH formula (IV-9) — C (CH)3)(CH3) —CH2-OH formula (IV-10) or-CH2—C(CH3)(CH3) -OH formula (IV-11); more preferably formula (V) is: -CH2—CH2—NH2The formulae (V-1) — CH2—CH2—CH2—NH2The formulae (V-2), -CH (CH)3)—CH2—NH2The formulae (V-3) — CH2—CH(CH3)—NH2The formulae (V-4) — CH2—CH2—CH2—CH2—NH2The formulae (V-5) — CH (CH)3)—CH2—CH2—NH2The formulae (V-6) — CH2—CH(CH3)—CH2—NH2The formulae (V-7) — CH2—CH2—CH(CH3)—NH2The formulae (V-8), -CH (CH)3)—CH(CH3)—NH2The formulae (V-9) — C (CH)3)(CH3) —CH2—NH2The formulae (V-10) — CH2—C(CH3)(CH3)—NH2Formula (V-11).
C1-C4 alkyl-substituted cycloalkanols, i.e. said unsubstituted cycloalkanols have one or several hydrogen atoms in the alicyclic ring replaced by C1-C4 alkyl, e.g. one or two hydrogen atoms in the alicyclic ring are replaced by methyl, ethyl, propyl, isopropyl, butyl, n-butyl or isobutyl. The C1-C4 alkyl substituted cycloalkanol compound preferably has the following structure:
Figure BDA0003508314450000042
Figure BDA0003508314450000051
wherein R is7Is C1-C4 alkyl, which may be methyl, ethyl, propyl, isopropyl, butyl, n-butyl or isobutyl, preferably methyl or ethyl.
In the preparation of the polyether polyol of the present invention, one or more of the unsubstituted cycloalkanol compound and the C1-C4 alkyl-substituted cycloalkanol compound may be used as an initiator, or one or more of the unsubstituted cycloalkanol compound and the C1-C4 alkyl-substituted cycloalkanol compound may be used as an initiator together with at least one of polyhydroxy compounds or polyamino compounds known in the art, and preferably, the total weight of the unsubstituted cycloalkanol compound and the C1-C4 alkyl-substituted cycloalkanol compound is at least 5 wt% of the initiator, and more preferably, 20-100 wt%.
The preparation method of the polyether polyol adopts the known technology in the field, and in order to further ensure that the polyether polyol has higher functionality and lower viscosity, one or more of glycerol, ethylene glycol and propylene glycol are preferably used as an initiator together with the unsubstituted cycloalkanol compound and/or the C1-C4 alkyl substituted cycloalkanol compound. In order to shorten the mold release time, at least one of 1- (2-hydroxy-ethylamino) -propan-2-ol, monoethanolamine, diethanolamine, monoisopropanolamine, diisopropanolamine, ethylenediamine, triethylamine, triethanolamine, toluenediamine, phenylenediamine, aniline, or toluidine may be preferably used as a starter together with the unsubstituted cycloalkanol compound and/or the C1-C4 alkyl-substituted cycloalkanol compound. The alkylene oxide reacted with the initiator is at least one of propylene oxide, ethylene oxide or butylene oxide.
Third embodiment: the alicyclic group is introduced by the alkylene oxide and the initiator together, namely the alkylene oxide containing the alicyclic structure and the initiator containing the alicyclic structure are subjected to ring-opening polymerization reaction, so that the polyether polyol containing the structure of the formula (I) and/or the structure of the formula (I) in which hydrogen of the alicyclic ring is replaced by an inert group is obtained. The preferred alicyclic structure-containing alkylene oxide is the same as in the first embodiment, and the preferred alicyclic structure-containing initiator is the same as in the second embodiment, and will not be described in detail here. When the polyether polyol is prepared, preferably, the alkylene oxide with the alicyclic structure and the initiator containing the alicyclic structure are firstly subjected to alkoxylation, then are subjected to ring-opening polymerization with the C2-C3 alkylene oxide to obtain a polyether crude product, and the polyether polyol is obtained after refining treatment.
The hydroxyl value of the polyether polyol obtained by the three embodiments is preferably 160-650 mgKOH/g, more preferably 200-520 mgKOH/g, and even more preferably 280-468 mgKOH/g, so as to optimize the cell structure, enhance the strength of the cells, and take other excellent properties of the foam into account. The viscosity of the preferred polyether polyol at 25 ℃ is 2000-200000 cps, which is beneficial to improving the filling performance of the foam, reducing the total amount of the used polyurethane raw materials and further reducing the core density of the polyurethane foam.
Further, the unsubstituted cycloalkanol compound is obtained by reacting unsubstituted epoxy cycloalkane with an amine compound, and the C1-C4 alkyl-substituted cycloalkanol compound is obtained by reacting C1-C4 alkyl-substituted epoxy cycloalkane with an amine compound; wherein the unsubstituted epoxy cycloalkane is any one of 1, 2-epoxy cyclobutane, 1, 2-epoxy cyclopentane, 1, 2-epoxy cyclohexane, 1, 2-epoxy cycloheptane or 1, 2-epoxy cyclooctane, and the amine compound is primary amine or secondary amine. The unsubstituted cycloalkanol compound or the C1-C4 alkyl substituted cycloalkanol compound prepared by adopting the raw materials is less influenced by impurities, the polyether polyol obtained by the invention cannot be influenced by the existence of reaction byproducts, and the raw materials do not need to use catalysts, so that the raw material cost is lower. Among them, preferred unsubstituted epoxycycloalkanes and C1-C4 alkyl-substituted epoxycycloalkanes are the same as those in the first embodiment, and will not be described in detail herein.
Further, in order to reduce waste of raw materials and improve utilization efficiency of petrochemical resources, it is preferable that the initiator is a mixture S directly obtained after reacting epoxycycloalkane with the amine compound, wherein the epoxycycloalkane includes at least one of unsubstituted epoxycycloalkane and C1-C4 alkyl-substituted epoxycycloalkane. Namely, the mixture S is a mixture of unsubstituted cycloalkanols and/or C1-C4 alkyl-substituted cycloalkanols and residual raw materials, byproducts and the like, wherein the proportion of the total weight of the unsubstituted cycloalkanols and the C1-C4 alkyl-substituted cycloalkanols in the mixture S is preferably 66-100 wt%.
Further, in order to reduce side reactions, the preparation method of the mixture S comprises the following steps: the epoxy cycloalkane is added to the amine compound in batches, the reaction temperature is 100-160 ℃, the reaction pressure is more than 0MP and less than 1MPa, and the preferable range is 0.2-0.7 MPa. The mixture obtained after the reaction was completed was used as the mixture S without further purification treatment. The reaction can be carried out under the condition of not adding a catalyst, so that the step of removing the catalyst is omitted, and the production process is simplified. Furthermore, in order to improve the yield of the polyether polyol of the present invention, the ratio of the total moles of the epoxycycloalkane to the total moles of the amine compound is preferably 1 (0.7-2), and more preferably 1 (1-1.5).
Further, in order to improve the reaction efficiency of the mixture S and the selectivity of the structures of the formula (II) and the formula (III), the amine compound preferably comprises C2-C4 alkyl alcohol amine compounds, unsubstituted C2-C4 alkyl diamine compounds and C2-C4 alkyl diamine compounds substituted by C2-C3 hydroxyalkyl groups. Wherein the C2-C4 alkyl alcohol amine compound refers to alcohol amine compound which contains at least one hydroxyl group and at least one amino or imino group in the molecule and has 2-4 carbon atoms, and further preferably has the following structure shown in formula (VI): NH (NH)2—CpH2pOH or formula (VII): cpH2pOH—NH—CpH2pOH, wherein p is any natural number of 2-4. The C2-C4 alkylolamines of formula (VI) can be selected from, but are not limited to, the following: 2-amino-1-ethanol, 1-amino-2-propanol, 2-amino-1-propanol, 3-amino-1-propanol, 4-amino-1-butanol, 3-amino-2-methyl-1-propanol, 4-amino-2-butanol, 3-amino-2-butanol, 2-amino-2-methyl-1-propanol, 1-amino-2-methyl-2-propanol, C2 to C4 alkylolamines of formula (VII) may be selected from, but are not limited to, the following: diethanolamine, bis- (3-hydroxypropyl) -amine, bis- (2-hydroxy-1-methyl-ethyl) -amine, bis- (2-hydroxypropyl) -amine, bis- (2-hydroxy-1-methyl-propyl) -amine, bis- (3-hydroxy-butyl) amine, diisobutanolamine, bis- (3-hydroxy-1-methyl-propyl) -amine, di-N-butanolamine, N-bis (2-methyl-3-hydroxypropyl-2) amine, N-bis (2-methyl-2-hydroxypropyl) amine . The unsubstituted C2-C4 alkyldiamine refers to an amine compound containing two amino groups in the molecule and having 2-4 carbon atoms, and preferably has a structure represented by formula (VIII): NH (NH)2—CvH2v—NH2Wherein v is any natural number from 2 to 4, and can be selected from but not limited to the following substances: ethylenediamine, 1, 3-propanediamine, 1, 2-propanediamine, 1, 4-butanediamine, 1, 3-butanediamine, 2-methyl-1, 3-propanediamine, 2, 3-butanediamine, 1, 2-diamino-2-methylpropane. C2-C4 alkyldiamines substituted by C2-C3 hydroxyalkyl means that one or two hydrogens on the nitrogen atom of C2-C4 alkyldiamine are replaced by C2-C3 hydroxyalkyl, which can be selected from, but is not limited to, the following: n- (2-hydroxyethyl) ethylenediamine, N- (2-hydroxypropyl) ethylenediamine, N '-bis (2-hydroxyethyl) ethylenediamine, N' -bis (2-hydroxypropyl) propylenediamine, N-bis (2-hydroxyethyl) ethylenediamine, N-bis (2-hydroxyethyl) butylenediamine, N-bis (2-hydroxypropyl) ethylenediamine, 1- [2- (2-hydroxyethylamino) ethylamino]Propan-2-ol, 1- [ 2-aminoethyl (2-hydroxyethyl) amino]Propan-2-ol. The above-mentioned substances can give consideration to both the releasability and the dimensional stability of the polyurethane foam.
The polyether polyol containing the alicyclic group of the formula (I) and the polyether polyol containing the structure in which hydrogen on the alicyclic ring of the formula (I) is substituted by an inert group may be used alone or in combination to prepare a composition capable of reacting with isocyanate, the composition capable of reacting with isocyanate may be prepared by a method known in the art, and various combinations of raw materials may be selected according to the application field and the process parameter requirements, and generally the composition capable of reacting with isocyanate includes a complex polyol, a complex catalyst, a foam stabilizer and water.
The inventor of the present application has unexpectedly found in the research process that a composition capable of reacting with isocyanate, which is prepared by using a polyether polyol containing an alicyclic group of formula (I) and/or a polyether polyol containing a structure in which hydrogen on the alicyclic ring of formula (I) is substituted by an inert group, has a high reactivity, and is advantageous for improving the compatibility between a physical blowing agent and a polyurethane reaction raw material, shortening the demolding time, and simultaneously reducing the foam deformation, thereby taking into account the stability to environmental changes under a low-density condition and the stability after demolding. The ratio of the total weight of the polyether polyol containing the alicyclic group shown in the formula (I) and the polyether polyol containing the structure that hydrogen on the alicyclic ring shown in the formula (I) is replaced by the inert group to the total weight of the composite polyol is as follows: 3-65 wt%, and more preferably 10-50% to achieve better optimization effect. Further, the hydroxyl value of the polyether polyol containing the alicyclic group of the formula (I) or the polyether polyol containing the structure in which hydrogen on the alicyclic ring of the formula (I) is substituted by an inert group is preferably 160-650 mgKOH/g, and more preferably 200-520 mgKOH/g, so that the cell structure is further optimized, the stability of cells is enhanced, and the excellent performance of the foam is also considered.
Further, on the basis of the weight of the composite polyol, the composite polyol also comprises 35-97 wt% of a polyol mixture, and the polyol mixture contains at least one of polyether polyol B, bio-based polyol and polyester polyol, wherein the polyether polyol B is conventional polyether in the polyurethane field, namely polyether polyol prepared by ring-opening polymerization of an epoxide and polyhydroxy and/or amine compounds serving as an initiator. Further, in the present invention, it is preferable that the polyol initiator used for the polyether polyol B is one or more selected from diethylene glycol, propylene glycol, ethylene glycol, sorbitol, glycerin and sucrose, and the amine initiator used for the polyether polyol B is an aromatic amine such as phenylenediamine, toluenediamine, aniline and toluidine, an alkylalcohol amine such as ethanolamine and isopropanolamine, and an alkylamine such as ethylenediamine. The preferable using amount of the polyether glycol B is 25-85 wt% of the total amount of the composite polyol. Further, the epoxide used for preparing the polyether polyol B is preferably at least one of propylene oxide, ethylene oxide and butylene oxide, and propylene oxide is more preferably contained therein to improve compatibility with alkane blowing agents. The bio-based polyol is a polyol compound prepared by using a vegetable oil, preferably, but not limited to, soybean oil, castor oil, rapeseed oil, jatropha oil, olive oil, palm oil, and the like, as a raw material, and is preferably a polyol compound prepared by using a vegetable oil of a known variety in the art, a modified vegetable oil obtained by ring-opening modification of a vegetable oil by epoxidation, and a vegetable oil derivative prepared by subjecting a vegetable oil to a reaction such as alcoholysis or transesterification. The polyols prepared from the raw materials can be used in the invention, such as epoxidized soybean oil polyol, castor oil derivative polyol and the like, and the preferable dosage of the bio-based polyol is 0-35 wt% of the total amount of the composite polyol. Polyester polyols include conventional polyester polyols, polycaprolactone polyols, and polycarbonate polyols. The conventional polyester polyol is a polyester polyol obtained by polycondensation of a polybasic acid with a polyhydric alcohol or the like, such as a phthalic anhydride polyester polyol. The polycaprolactone polyol is prepared by ring-opening polymerization of epsilon-caprolactone and an initiator under the action of a catalyst. The polycarbonate polyol can be produced by transesterification, or can be produced using carbon dioxide and propylene oxide as raw materials. The amount of the polyester polyol is preferably 0 to 25 wt%, and more preferably 5 to 25 wt% of the total amount of the composite polyol.
The composite catalyst used in the present invention can be prepared by the techniques known in the art, and generally includes an intumescent catalyst, a gel catalyst and a trimerization catalyst, wherein the intumescent catalyst includes, but is not limited to, any one or more of pentamethyldiethylenetriamine, bis (dimethylaminoethyl) ether and tetramethylhexanediamine, the gel catalyst includes, but is not limited to, any one or more of dibutyltin dilaurate, N-ethylmorpholine, N-dimethylcyclohexylamine, triethylenediamine, 1, 2-dimethylimidazole and dimethylbenzylamine, and the trimerization catalyst includes, but is not limited to, 1, 3, 5-tris (dimethylaminopropyl) hexahydrotriazine, 2, 4, 6-tris (dimethylaminomethyl) phenol, methyl quaternary ammonium salt, potassium caprylate, potassium acetate, (2-hydroxypropyl) trimethyl ammonium formate, potassium caprylate, potassium acetate, sodium hydrogen carbonate, sodium carbonate, One or more of ethyl quaternary ammonium salt and octyl quaternary ammonium salt. When two or more catalysts are selected, a mixture thereof at an arbitrary ratio may be used. The composite catalyst of the invention can reduce the anisotropy of cells, optimize the cell structure and further reduce the thermal conductivity.
Further, in order to reduce the tendency of cell combination, it is preferable that the foam stabilizer contains a polysiloxane-oxyalkylene block copolymer, and further, in order to obtain a smaller cell size, it is preferable that the weight ratio of the polysiloxane-oxyalkylene block copolymer is 1.1 to 4.0 wt% based on the total weight of the composition. Can be selected from any one or more of commercially available brands of M-8805, M-8860, M-88312, M-8815, M-88308, M-8860, M-8830, B8460, B8462, B8461, B8544, B8494, B8532, B8465, B8471, B8474, B8476, B8481, L6900, L6863, L6912 and L6989. When two or more foam stabilizers are selected, they may be mixed in any ratio.
Further, in order to achieve better foam performance and production process matching, the composition comprises the following substances in percentage by weight based on the weight of the composition capable of reacting with isocyanate: 71-91 wt% of composite polyol, 3.2-5.2 wt% of composite catalyst, 1.1-4.0 wt% of foam stabilizer, 1.1-2.5 wt% of water and 0-20 wt% of physical foaming agent.
Further, the physical blowing agent may be one or more of blowing agents known in the art, such as alkane blowing agents, hydrofluorocarbon blowing agents, fluoroolefin blowing agents, carbon dioxide, and methyl formate. Wherein the alkane blowing agent can be selected from but not limited to cyclopentane, isopentane, n-pentane, n-butane, isobutane, propane, hexane, heptane, the hydrofluorocarbon blowing agent is selected from but not limited to pentafluoropropane, pentafluorobutane, difluoroethane, tetrafluoroethane, and the fluoroolefin blowing agent can be selected from but not limited to trifluoropropene, tetrafluoropropene, pentafluoropropene, hexafluoropropene, hexafluorobutene. Because the GWP value of the hydrofluorocarbon foaming agent is higher and is unfavorable for the environment, the invention is preferably an environment-friendly foaming agent, such as one or more of alkane foaming agents, fluoroolefin foaming agents and methyl formate. The alkane blowing agent is preferably at least one of cyclopentane, n-pentane, isopentane, n-butane and isobutane, and the fluoroolefin blowing agent is preferably at least one of cis-1, 1,1,4,4, 4-hexafluoro-2-butene, trans-1-chloro-3, 3, 3-trifluoropropene, cis-1-chloro-2, 3,3, 3-tetrafluoropropene, trans-1, 3,3, 3-tetrafluoropropene and 2,3,3, 3-tetrafluoropropene. The foaming agent has zero or approximately zero Ozone Depletion Potential (ODP) value and low Global Warming Potential (GWP) value, can reduce the influence on greenhouse effect and is environment-friendly.
When the composition capable of reacting with isocyanates contains no physical blowing agent, it preferably consists of the following substances in percentages by weight: 88-91 wt% of composite polyol, 4.0-5.2 wt% of composite catalyst, 1.4-4.0 wt% of foam stabilizer and 1.3-2.5 wt% of water; when the composition capable of reacting with isocyanates contains all the physical blowing agents required for the polyurethane foaming reaction, the following compositions in percentage by weight are preferred: 71-75 wt% of composite polyol, 3.2-4.3 wt% of composite catalyst, 1.1-3.2 wt% of foam stabilizer, 1.1-2.0 wt% of water and 17-20 wt% of physical foaming agent.
Meanwhile, in order to further optimize the cell structure and obtain uniform and fine foam, auxiliary agents such as perfluoroolefin, perfluoroalkane, fluorine-containing alkyl ether and the like can be added into the composition capable of reacting with isocyanate, wherein the perfluoroolefin can be selected from at least one of hexafluoropropylene, hexafluoropropylene dimer, hexafluoropropylene trimer, perfluorobutadiene, perfluoro-4-methyl-2-pentene, octafluorocyclopentene, perfluoro-1-heptene and perfluorohexene; the fluorine-containing alkyl ether is an ether containing a fluorine-containing alkyl group in a molecular chain, and can be selected from at least one of 1,1,3,3, 3-pentafluoro-2-trifluoromethylpropylmethyl ether, perfluorobutyl methyl ether, 2, 2-difluoroethyltrifluoromethyl ether, trifluoromethyltrifluorovinyl ether, perfluoropropylvinyl ether, 1,1,1,3,3, 3-hexafluoroisopropylmethyl ether, 2,2,3,3, 3-pentafluoropropylmethyl ether and 2,2, 2-trifluoroethyl methyl ether; the perfluoroalkane is selected from the group consisting of C5-18 perfluoroalkanes. In order to take cost and performance into consideration, the total addition amount of the substances such as perfluoroolefin, perfluoroalkane, fluorine-containing alkyl ether and the like is preferably 0.3-2 wt% of the total weight of the composite polyol.
Finally, the present invention provides a class of polyurethane foams comprising formula (I)
Figure BDA0003508314450000091
An alicyclic group having a structure and/or an alicyclic group having 1 to 2 hydrogen atoms in the alicyclic ring of the formula (I) substituted with an inert group, wherein n is an arbitrary natural number of 2 to 6, m is 1 or 2, and the inert group is a C1-C4 alkyl group, and the polyurethane foam of the present invention containing the alicyclic group can be usedThe polyether polyol can be prepared by taking the polyether polyol as one of the composite polyol components to prepare a composition capable of reacting with isocyanate and then reacting with a physical foaming agent and isocyanate, and can also be prepared by using the composite polyol, the composite catalyst, a foam stabilizer, water, the physical foaming agent, the isocyanate, an auxiliary agent and the like. The raw materials of the polyurethane foam are preferably: 34-37 wt% of composite polyol, 1.6-2.2 wt% of composite catalyst, 0.6-1.5 wt% of foam stabilizer, 0.6-0.9 wt% of water, 8.0-9.9 wt% of physical foaming agent, 0-0.7 wt% of auxiliary agent and 49-54 wt% of isocyanate. The foam has low density and high stability, is beneficial to the saving of fossil energy, has no loss of heat insulation performance, good stability and long service life, and is beneficial to energy conservation and emission reduction.
The preparation method of the rigid polyurethane foam of the invention adopts the known technology in the field, and the following three modes are preferred:
The method I comprises the following steps: firstly, mixing raw materials such as composite polyol, composite catalyst, foam stabilizer, water and the like to form a composition capable of reacting with isocyanate, then mixing the composition with a physical foaming agent, and then uniformly stirring and mixing the composition with isocyanate at a high speed to perform a polyurethane reaction;
the second method comprises the following steps: mixing a physical foaming agent with raw materials such as composite polyol, a composite catalyst, a foam stabilizer, water and the like to form a composition capable of reacting with isocyanate, and then uniformly stirring and mixing the composition and the isocyanate at a high speed to perform a polyurethane reaction;
the third method comprises the following steps: dividing a physical foaming agent into two parts, mixing one part of the physical foaming agent with isocyanate to form an isocyanate mixture, then obtaining a composition capable of reacting with the isocyanate according to the first mode, mixing the composition with the other part of the physical foaming agent, and then uniformly stirring and mixing the composition with the isocyanate mixture at a high speed to perform a polyurethane reaction;
or mixing the other part of the physical foaming agent with raw materials such as the composite polyol, the composite catalyst, the foam stabilizer, the water and the like according to the second mode to obtain a composition capable of reacting with the isocyanate, and then uniformly stirring and mixing the composition and the isocyanate mixture at a high speed to perform a polyurethane reaction.
In the preparation method, the first mode and the second mode are conventional modes, so that the use convenience is realized, and the third mode can further improve the fluidity of reaction raw materials in the cavity filling process, thereby being beneficial to reducing the foam density and saving the raw material cost.
Besides rigid polyurethane foam, the polyether polyol containing the structure of the formula (I) can be used for preparing soft foam, elastomer and the like, and the polyether polyol containing the structure of the formula (I) has low unsaturation degree (< 0.1mol/kg), so that the strength of a polyurethane material is improved.
The isocyanate used in the present invention may be any known isocyanate in the art, and may be polymethylene polyphenyl polyisocyanate (abbreviated as polymeric MDI), toluene diisocyanate (abbreviated as TDI), modified isocyanate, or the like, and when two or more isocyanates are selected, they may be mixed in any ratio. Wherein, the average functionality of the polymeric MDI is preferably 2.7-2.9, so as to ensure the heat conductivity of the polyurethane rigid foam. The polymeric MDI having an average functionality of 2.7 may be selected from
Figure BDA0003508314450000101
PM200、
Figure BDA0003508314450000102
44v20L、
Figure BDA0003508314450000103
M20s、
Figure BDA0003508314450000104
In any of PM2010, the polymeric MDI having an average functionality of 2.9 may be selected from
Figure BDA0003508314450000105
M50、
Figure BDA0003508314450000106
PM400、
Figure BDA0003508314450000107
44V40L、
Figure BDA0003508314450000108
2085. The industrial TDI is usually a mixture of 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate, and TDI-65, TDI-80, TDI-100 and the like can be used in the invention according to the mass ratio of 2, 4-toluene diisocyanate in the mixture. The modified isocyanate is obtained by reacting polyol with isocyanate, wherein the polyol can be polyether polyol taking glycerol, ethylene glycol, diethylene glycol, pentaerythritol and the like as initiators, or phthalic anhydride polyester polyol, and also can be bio-based polyol. The bio-based polyol is a polyol compound prepared from soybean oil, castor oil, rapeseed oil, jatropha curcas oil, olive oil, palm oil, or derivatives thereof, such as castor oil polyol, olive oil polyol, palm oil polyol, and castor oil derivative polyol.
Overall, the combined advantages of the present application are:
(1) good dimensional stability under low density, is beneficial to reducing the use amount of raw materials, and has a core density less than 27kg/m3The high-temperature dimensional deformation rate is less than or equal to 0.2 percent, and the low-temperature dimensional deformation rate is less than 0.1 percent;
(2) the deformation after short-time demoulding is small, which is beneficial to improving the production efficiency, and the deformation after 2min demoulding is less than 1.5%;
(3) low heat conductivity coefficient, high compression strength and excellent foam performance.
The specific implementation mode is as follows:
in order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Examples 1 to 9 and 21 to 25 the method for preparing polyether polyol is as follows:
adding raw materials such as an initiator into a reaction kettle, replacing by inert gas, vacuumizing, keeping the temperature of the kettle at 100-180 ℃, keeping the temperature of the kettle after vacuumizing is stopped, adding unsubstituted epoxy cycloalkane or C1-C4 alkyl substituted epoxy cycloalkane according to the mole number ratio of the unsubstituted epoxy cycloalkane to the initiator being (1-2): 1 or the mole number ratio of the C1-C4 alkyl substituted epoxy cycloalkane to the initiator being (1-2): 1, adding propylene oxide and/or ethylene oxide, wherein the reaction pressure is more than 0MPa and less than 1MPa, obtaining a crude polyether product after the reaction is finished, and obtaining polyether polyol after refining treatment.
Example 10-example 20 the method for preparing polyether polyol is as follows:
adding unsubstituted epoxy cycloalkane or C1-C4 alkyl substituted epoxy cycloalkane into an amine compound in batches, wherein the ratio of the total mole number of the unsubstituted epoxy cycloalkane to the total mole number of the amine compound or the ratio of the total mole number of the C1-C4 alkyl substituted epoxy cycloalkane to the total mole number of the amine compound is 1 (0.7-2), the reaction temperature is 100-160 ℃, the reaction pressure is less than 1MPa, and a mixture S is obtained after the reaction is finished. Adding the mixture S and an alkali metal catalyst into a reaction kettle, replacing with inert gas, vacuumizing, keeping the kettle temperature at 100-180 ℃, stopping vacuumizing, adding propylene oxide and/or ethylene oxide, keeping the reaction pressure less than 1MPa, obtaining a polyether crude product after the reaction is finished, and refining to obtain polyether polyol.
The purification treatment methods used in examples 1 to 25 were: adding pure water and 20-60 wt% of phosphoric acid solution into the crude polyether product at the temperature of 50-90 ℃, adjusting the pH to 5-6.5, adding magnesium silicate, continuously stirring, vacuumizing, dehydrating, and filtering to obtain polyether polyol.
Example 1
Sorbitol is used as an initiator, sorbitol and potassium hydroxide are added into a reaction kettle, inert gas is used for displacement and vacuum pumping, the temperature of the reaction kettle is 130-150 ℃, the vacuum pumping is stopped, the temperature of the reaction kettle is kept, 1, 2-epoxycyclohexane is added according to the mole number ratio of 1, 2-epoxycyclohexane to sorbitol being 1:1, propylene oxide is added according to the mole number ratio of propylene oxide to sorbitol being 4.8:1 after reaction, the reaction pressure is 0.3-0.5 MPa, a polyether crude product is obtained after the reaction is finished, polyether polyol A-1# is obtained after refining treatment, and the hydroxyl value is 590 # 620mgKOH/g, the molecule contains the structure of formula (I-1-1):
Figure 2
example 2
Glycerol is used as an initiator, glycerol and potassium hydroxide are added into a reaction kettle, inert gas is used for displacement and vacuum pumping, the kettle temperature is 140-160 ℃, the vacuum pumping is stopped, the kettle temperature is kept, 4-methyl-1, 2-epoxycyclohexane is added according to the molar ratio of 4-methyl-1, 2-epoxycyclohexane to glycerol being 2:1, propylene oxide and ethylene oxide are added according to the molar ratio of propylene oxide to ethylene oxide to glycerol being 9.6:1.4:1, the reaction pressure is 0.2-0.3 MPa, a crude polyether product is obtained after the reaction is finished, polyether polyol A-2# is obtained after refining treatment, the hydroxyl value is 160-180 mgKOH/g, and the molecule contains a structure shown in a formula (I-1-2):
Figure BDA0003508314450000121
example 3
Adding a 1# mixed initiator and potassium hydroxide into a reaction kettle, wherein the 1# mixed initiator is sorbitol and glycol with the mole ratio of 2:1, displacing by inert gas, vacuumizing, keeping the kettle at 100-130 ℃, stopping vacuumizing, keeping the kettle at the temperature, adding 1, 2-epoxy-3-methyl-cyclopentane according to the mole ratio of 1, 2-epoxy-3-methyl-cyclopentane to the 1# mixed initiator being 1:1, adding propylene oxide according to the mole ratio of 8.5:1 of propylene oxide to the 1# mixed initiator after reaction under the reaction pressure of 0.3-0.4 MPa, obtaining a polyether crude product after the reaction is finished, refining to obtain polyether polyol A-3#, the hydroxyl value of which is 350-365 mgKOH/g, and the molecule contains a structure shown in a formula (I-1-3):
Figure BDA0003508314450000122
Example 4
Trimethylolpropane is used as an initiator, trimethylolpropane and potassium hydroxide are added into a reaction kettle, inert gas is used for displacement and vacuum pumping is carried out, the kettle temperature is 160-180 ℃, the vacuum pumping is stopped, the kettle temperature is kept, and the 1, 2-epoxycyclooctane is used as a raw materialAdding 1, 2-epoxycyclooctane according to the molar ratio of 1:1 of alkane to trimethylolpropane, adding propylene oxide and ethylene oxide according to the molar ratio of 1.8:0.2:1 of propylene oxide to trimethylolpropane after reaction, wherein the reaction pressure is 0.3-0.5 MPa, obtaining a crude polyether product after the reaction is finished, and obtaining polyether polyol A-4 after refining treatment, wherein the hydroxyl value is 463-475 mgKOH/g, and the molecule contains a structure shown in a formula (I-1-4):
Figure 1
example 5
Adding a 2# mixed initiator and potassium hydroxide into a reaction kettle, wherein the 2# mixed initiator is sorbitol and glycerol with the mole ratio of 3:1, displacing by inert gas, vacuumizing, keeping the kettle at 100-120 ℃, stopping vacuumizing, keeping the kettle at the temperature, adding 1, 2-epoxy-3-methyl-cyclobutane according to the molar ratio of 1, 2-epoxy-3-methyl-cyclobutane to the 2# mixed initiator being 1.5:1, adding propylene oxide according to the molar ratio of the propylene oxide to the 2# mixed initiator being 5.4:1 after reaction, wherein the reaction pressure is 0.1-0.2 MPa, obtaining a polyether crude product after the reaction is finished, and obtaining polyether polyol A-5# after refining treatment, wherein the hydroxyl value is 482-492 mgKOH/g, and the molecule contains a structure shown in a formula (I-1-5):
Figure BDA0003508314450000124
Example 6
Adding xylitol and potassium hydroxide into a reaction kettle by taking xylitol as an initiator, replacing with inert gas, vacuumizing, keeping the kettle at 110-130 ℃, keeping the kettle at the temperature after vacuumizing is stopped, adding 1, 2-epoxy-3-isopropyl-cyclopentane according to the molar ratio of 1, 2-epoxy-3-isopropyl-cyclopentane to xylitol of 1.5:1, adding ethylene oxide according to the molar ratio of ethylene oxide to xylitol of 3.3:1 after reaction under the reaction pressure of 0.3-0.4 MPa, obtaining a polyether crude product after the reaction is finished, and refining to obtain polyether polyol A-6#, wherein the hydroxyl value is 573-586 mgKOH/g, and the molecule contains a structure represented by formula (I-1-6):
Figure BDA0003508314450000131
example 7
Adding ethylenediamine as an initiator into a reaction kettle, performing inert gas displacement and vacuum pumping, keeping the kettle temperature at 150-170 ℃, keeping the kettle temperature after stopping vacuum pumping, adding 1, 2-epoxy-3-ethyl-cyclohexane according to the mole ratio of the 1, 2-epoxy-3-ethyl-cyclohexane to the ethylenediamine of 2:1, adding potassium hydroxide after reaction, adding propylene oxide according to the mole ratio of the propylene oxide to the ethylenediamine of 2.2:1 under the reaction pressure of 0.2-0.3 MPa, obtaining a polyether crude product after the reaction is finished, and refining to obtain polyether polyol A-7#, wherein the hydroxyl value is 501-510 mgKOH/g, and the molecule contains a structure shown in formula (I-2-1):
Figure BDA0003508314450000132
Example 8
Adding monoethanolamine into a reaction kettle, replacing by inert gas, vacuumizing, keeping the kettle at 160-180 ℃, keeping the kettle at the temperature after vacuumizing is stopped, adding 1-methyl-1, 2-epoxycycloheptane according to the molar ratio of 1-methyl-1, 2-epoxycycloheptane to monoethanolamine of 1.5:1, adding potassium hydroxide after reaction, adding epoxypropane and ethylene oxide according to the molar ratio of epoxypropane to monoethanolamine of 2.4:0.24:1, wherein the reaction pressure is 0.4-0.6 MPa, obtaining a polyether crude product after the reaction is finished, and obtaining polyether polyol A-8# after refining treatment, wherein the hydroxyl value is 415-430 mgKOH/g, and the molecule contains a structure shown in formula (I-2-2):
Figure BDA0003508314450000133
example 9
Adding a 3# mixed initiator and potassium hydroxide into a reaction kettle, wherein the 3# mixed initiator is 4-methyl o-phenylenediamine and glycerol with the mole ratio of 4:1, replacing with inert gas, vacuumizing, keeping the kettle temperature at 110-130 ℃, stopping vacuumizing, keeping the kettle temperature, adding 1, 2-epoxycyclopentane according to the mole ratio of 1:1 of 1, 2-epoxycyclopentane to the 3# mixed initiator, reacting, and adding epoxypropane and cyclo-cyclopentane according to the mole ratio of 1:1Adding propylene oxide and ethylene oxide into the 3# mixed initiator at a molar ratio of 3:0.12:1, wherein the reaction pressure is 0.3-0.5 MPa, obtaining a polyether crude product after the reaction is finished, refining to obtain polyether polyol A-9, wherein the hydroxyl value is 510-520 mgKOH/g, and the molecule contains a structure shown in a formula (I-2-3):
Figure 3
Example 10
Dropwise adding 1, 2-epoxycyclohexane into 2-amino-1-ethanol within 1-2 h, wherein the ratio of the total molar number of the 1, 2-epoxycyclohexane to the total molar number of the 2-amino-1-ethanol is 1:1, the reaction temperature is 110-120 ℃, the reaction pressure is 0.5-0.7 MPa, and after the reaction is finished, a mixture S-1# is obtained, wherein the mixture S-1# contains a structure shown in a formula (II-3-1):
Figure BDA0003508314450000141
taking the mixture S-1# as an initiator, adding the mixture S-1# and potassium hydroxide into a reaction kettle, displacing by inert gas, vacuumizing, keeping the kettle temperature at 120-130 ℃, keeping the kettle temperature after stopping vacuumizing, adding propylene oxide according to the molar ratio of the propylene oxide to the mixture S-1# of 2.8:1, wherein the reaction pressure is 0.4-0.5 MPa, obtaining a polyether crude product after the reaction is finished, refining to obtain polyether polyol A-10#, wherein the hydroxyl value is 512-522 mgKOH/g, and the molecule contains a structure shown in a formula (I-2-4):
Figure BDA0003508314450000142
example 11
Dropwise adding 1, 2-epoxycyclopentane into 1-amino-2-propanol within 1-2 h, wherein the ratio of the total mole number of the 1, 2-epoxycyclopentane to the total mole number of the 1-amino-2-propanol is 1:1, the reaction temperature is 110-120 ℃, the reaction pressure is 0.4-0.5 MPa, and after the reaction is finished, a mixture S-2#, wherein the mixture S-2# contains a structure of a formula (II-2-1):
Figure BDA0003508314450000143
taking the mixture S-2# as an initiator, and reacting the mixture S-2#, Adding potassium hydroxide into a reaction kettle, replacing with inert gas, vacuumizing, keeping the kettle at 120-150 ℃, keeping the kettle at the temperature after vacuumizing is stopped, adding propylene oxide according to the mole ratio of 4:1 of propylene oxide to the mixture S-2#, wherein the reaction pressure is 0.2-0.4 MPa, obtaining a polyether crude product after the reaction is finished, refining to obtain polyether polyol A-11#, the hydroxyl value is 415-430 mgKOH/g, and the molecule contains a structure shown in a formula (I-2-3):
Figure 4
example 12
Dropwise adding 1, 2-epoxy-3-methyl-cyclobutane into 3-amino-2-butanol within 1-2 h, wherein the ratio of the total molar number of the 1, 2-epoxy-3-methyl-cyclobutane to the total molar number of the 3-amino-2-butanol is 1:2, the reaction temperature is 100-105 ℃, the reaction pressure is 0.3-0.5 MPa, and after the reaction is finished, a mixture S-3#, wherein the structure of the formula (II-1-1) is obtained:
Figure BDA0003508314450000145
taking the mixture S-3# as an initiator, adding the mixture S-3# and potassium hydroxide into a reaction kettle, replacing with inert gas, vacuumizing, keeping the kettle temperature at 100-110 ℃, keeping the kettle temperature after stopping vacuumizing, adding propylene oxide and ethylene oxide according to the molar ratio of the propylene oxide to the ethylene oxide to the mixture S-3# of 10.4:0.7:1, wherein the reaction pressure is 0.3-0.5 MPa, obtaining a polyether crude product after the reaction is finished, refining to obtain polyether polyol A-12#, wherein the hydroxyl value is 200-220 mgKOH/g, and the molecule contains a structure shown in a formula (I-2-5):
Figure BDA0003508314450000146
Example 13
Dropwise adding 1, 2-epoxy-3-n-butyl-cyclohexane into ethylenediamine within 1-2 h, wherein the ratio of the total mole number of the 1, 2-epoxy-3-n-butyl-cyclohexane to the total mole number of the ethylenediamine is 1:0.7, the reaction temperature is 115-125 ℃, the reaction pressure is 0.5-0.6 MPa, and after the reaction is finished, a mixture S-4# is obtained, wherein the mixture S-4# contains a structure shown in a formula (II-3-2):
Figure BDA0003508314450000151
taking the mixture S-4# as an initiator, adding the mixture S-4# and potassium hydroxide into a reaction kettle, displacing by inert gas, vacuumizing, keeping the kettle temperature at 110-130 ℃, keeping the kettle temperature after stopping vacuumizing, adding propylene oxide according to the molar ratio of the propylene oxide to the mixture S-4# of 5.2:1, wherein the reaction pressure is 0.2-0.3 MPa, obtaining a polyether crude product after the reaction is finished, refining to obtain polyether polyol A-13#, wherein the hydroxyl value is 475-485 mgKOH/g, and the molecule contains a structure shown in a formula (I-2-6):
Figure BDA0003508314450000152
example 14
Dropwise adding 1, 2-epoxy cycloheptane into diethanol amine within 1-2 h, wherein the ratio of the total moles of 1, 2-epoxy cycloheptane to the total moles of diethanol amine is 1:2, the reaction temperature is 125-135 ℃, the reaction pressure is 0.5-0.7 MPa, and a mixture S-5# is obtained after the reaction is finished, wherein the mixture S-5# contains a structure of a formula (II-4-1):
Figure BDA0003508314450000153
taking the mixture S-5# as an initiator, adding the mixture S-5# and potassium hydroxide into a reaction kettle, replacing with inert gas, vacuumizing, keeping the kettle temperature at 120-140 ℃, keeping the kettle temperature after vacuumizing is stopped, adding propylene oxide and ethylene oxide according to the molar ratio of the propylene oxide to the ethylene oxide to the mixture S-5# of 4.8:0.2:1, wherein the reaction pressure is 0.3-0.5 MPa, obtaining a polyether crude product after the reaction is finished, refining to obtain polyether polyol A-14#, wherein the hydroxyl value is 353-363 mgKOH/g, and the molecule contains a structure shown in a formula (I-2-7):
Figure BDA0003508314450000154
Example 15
Dropwise adding 5-methyl-1, 2-epoxycyclooctane into 1, 2-propane diamine within 1-2 h, wherein the ratio of the total moles of the 5-methyl-1, 2-epoxycyclooctane to the total moles of the 1, 2-propane diamine is 1:1.5, and the reaction temperature is140-160 ℃, the reaction pressure is 0.2-0.5 MPa, and a mixture S-6# is obtained after the reaction is finished, wherein the mixture S-6# contains a structure of a formula (II-5-1):
Figure 5
taking the mixture S-6# as an initiator, adding the mixture S-6# and potassium hydroxide into a reaction kettle, displacing by inert gas, vacuumizing, keeping the kettle temperature at 160-180 ℃, keeping the kettle temperature after stopping vacuumizing, adding propylene oxide according to the mole ratio of 3:1 of propylene oxide to the mixture S-6# and the reaction pressure of 0.2-0.3 MPa, obtaining a polyether crude product after the reaction is finished, refining to obtain polyether polyol A-15#, wherein the hydroxyl value is 630-650 mgKOH/g, and the molecule contains a structure shown in a formula (I-2-8):
Figure 6
example 16
Dropwise adding 1, 2-epoxycyclohexane into N- (2-hydroxypropyl) ethylenediamine within 1-2 h, wherein the ratio of the total molar number of the 1, 2-epoxycyclohexane to the total molar number of the N- (2-hydroxypropyl) ethylenediamine is 1:1.2, the reaction temperature is 110-120 ℃, the reaction pressure is 0.4-0.6 MPa, and after the reaction is finished, a mixture S-7# is obtained, wherein the mixture S-7# contains a structure of a formula (III-3-1):
Figure BDA0003508314450000163
Taking the mixture S-7# as an initiator, adding the mixture S-7# and potassium hydroxide into a reaction kettle, displacing by inert gas, vacuumizing, keeping the kettle temperature at 120-130 ℃, keeping the kettle temperature after stopping vacuumizing, adding propylene oxide according to the molar ratio of the propylene oxide to the mixture S-7# of 3.2:1, wherein the reaction pressure is 0.2-0.3 MPa, obtaining a polyether crude product after the reaction is finished, refining to obtain polyether polyol A-16#, the hydroxyl value is 566-576 mgKOH/g, and the molecule contains a structure shown in a formula (I-2-4):
Figure BDA0003508314450000164
example 17
Dripping 1 into N, N' -bis (2-hydroxypropyl) propane diamine within 1-2 h,the ratio of the total mole number of 1, 2-epoxy-3-isopropyl-cyclopentane to the total mole number of N, N' -bis (2-hydroxypropyl) propylenediamine is 1:1, the reaction temperature is 100-105 ℃, the reaction pressure is 0.3-0.5 MPa, and a mixture S-8# is obtained after the reaction is finished, wherein the mixture S-8# contains a structure represented by a formula (III-2-1):
Figure BDA0003508314450000165
taking the mixture S-8# as an initiator, adding the mixture S-8# and potassium hydroxide into a reaction kettle, displacing by inert gas, vacuumizing, keeping the kettle temperature at 100-120 ℃, keeping the kettle temperature after stopping vacuumizing, adding propylene oxide according to the molar ratio of the propylene oxide to the mixture S-8# of 1:1, wherein the reaction pressure is 0.2-0.3 MPa, obtaining a polyether crude product after the reaction is finished, refining to obtain polyether polyol A-17#, wherein the hydroxyl value is 601-611 mgKOH/g, and the molecule contains a structure shown in a formula (I-2-9):
Figure BDA0003508314450000171
Example 18
Dropwise adding 1, 2-epoxycyclobutane into N, N-bis (2-hydroxyethyl) butanediamine within 1-2 h, wherein the ratio of the total molar number of the 1, 2-epoxycyclobutane to the total molar number of the N, N-bis (2-hydroxyethyl) butanediamine is 1:1, the reaction temperature is 100-110 ℃, the reaction pressure is 0.3-0.4 MPa, and a mixture S-9# is obtained after the reaction is finished, wherein the mixture S-9# contains a structure shown in a formula (III-1-1):
Figure BDA0003508314450000172
taking the mixture S-9# as an initiator, adding the mixture S-9# and potassium hydroxide into a reaction kettle, displacing by inert gas, vacuumizing, keeping the kettle temperature at 100-110 ℃, keeping the kettle temperature after stopping vacuumizing, adding propylene oxide according to the mole ratio of 2.8:1 of propylene oxide to the mixture S-9# and the reaction pressure of 0.1-0.3 MPa, obtaining a polyether crude product after the reaction is finished, refining to obtain polyether polyol A-18#, wherein the hydroxyl value is 542-552 mgKOH/g, and the molecule contains a structure shown in a formula (I-2-10):
Figure BDA0003508314450000173
example 19
Dropwise adding 1, 2-epoxy cycloheptane into N, N '-bis (2-hydroxypropyl) ethylenediamine within 1-2 h, wherein the ratio of the total molar number of 1, 2-epoxy cycloheptane to the total molar number of N, N' -bis (2-hydroxypropyl) ethylenediamine is 1:1, the reaction temperature is 130-150 ℃, the reaction pressure is 0.5-0.6 MPa, and after the reaction is finished, a mixture S-10#, wherein the structure of the formula (III-4-1) is obtained:
Figure BDA0003508314450000174
Taking a mixture S-10# as an initiator, adding the mixture S-10# and potassium hydroxide into a reaction kettle, displacing by inert gas, vacuumizing, keeping the kettle temperature at 140-160 ℃, keeping the kettle temperature after stopping vacuumizing, adding propylene oxide according to the molar ratio of the propylene oxide to the mixture S-10# of 3.3:1, controlling the reaction pressure to be 0.3-0.5 MPa, obtaining a polyether crude product after the reaction is finished, refining to obtain polyether polyol A-19#, controlling the hydroxyl value to be 458-468 mgKOH/g, and controlling the molecular weight to be in a structure of a formula (I-2-7):
Figure BDA0003508314450000175
example 20
1- [2- (2-hydroxyethyl amino) ethylamino within 1-2 h]1, 2-epoxycyclooctane is added into the propane-2-alcohol in drops, the total mole number of the 1, 2-epoxycyclooctane and 1- [2- (2-hydroxyethyl amino) ethylamino]The ratio of the total mole number of the propyl-2-alcohol is 1:1, the reaction temperature is 120-140 ℃, the reaction pressure is 0.3-0.5 MPa, and a mixture S-11# is obtained after the reaction is finished, wherein the mixture S-11# contains a structure of a formula (III-5-1):
Figure BDA0003508314450000181
taking the mixture S-11# as an initiator, adding the mixture S-11# and potassium hydroxide into a reaction kettle, replacing with inert gas, vacuumizing, keeping the kettle temperature at 120-140 ℃, keeping the kettle temperature after stopping vacuumizing, adding propylene oxide according to the molar ratio of the propylene oxide to the mixture S-11# of 8.8:1, and reacting under pressure The force is 0.3-0.5 MPa, a polyether crude product is obtained after the reaction is finished, polyether polyol A-20# is obtained after refining treatment, the hydroxyl value is 270-280 mgKOH/g, and the molecule contains a structure shown in a formula (I-2-11):
Figure BDA0003508314450000182
example 21
To be provided with
Figure BDA0003508314450000183
Taking cyclohexanol and triethanolamine with a structure shown as a formula (II-3-3) as a 4# mixed initiator, wherein the weight of cyclohexanol with a structure shown as a formula (II-3-3) accounts for 5 wt% of the total weight of the 4# mixed initiator, performing inert gas replacement and vacuum pumping, keeping the temperature of a kettle at 120-140 ℃ after the vacuum pumping is stopped, adding propylene oxide and ethylene oxide according to the molar ratio of the propylene oxide to the ethylene oxide to the 4# mixed initiator of 5.41:0.37:1, wherein the reaction pressure is 0.3-0.4 MPa, obtaining a crude polyether product after the reaction is finished, and obtaining polyether polyol A-21#, the hydroxyl value is 335-350 mgKOH/g, and the molecule contains a structure shown as a formula (I-2-4):
Figure BDA0003508314450000184
example 22
To be provided with
Figure BDA0003508314450000185
The method comprises the following steps of taking cycloheptanol with a structure shown in a formula (II-4-2) and propylene glycol as a 5# mixed initiator, wherein the weight of the cycloheptanol with the structure shown in the formula (II-4-2) accounts for 20 wt% of the total weight of the 5# mixed initiator, replacing with inert gas, vacuumizing, keeping the temperature of a kettle at 150-180 ℃, keeping the temperature of the kettle after vacuumizing is stopped, adding propylene oxide according to the molar ratio of the propylene oxide to the 5# mixed initiator of 3.44:1, wherein the reaction pressure is 0.2-0.4 MPa, obtaining a crude polyether product after the reaction is finished, refining to obtain polyether polyol A-22#, the hydroxyl value is 405-415 mgKOH/g, and the molecule contains a structure shown in the formula (I-2-7):
Figure BDA0003508314450000191
Example 23
To be provided with
Figure BDA0003508314450000192
Taking cyclopentanol with a structure of a formula (II-2-2) and glycerol as a 6# mixed initiator, wherein the cyclopentanol with a structure of a formula (II-2-2) accounts for 50 wt% of the total weight of the 6# mixed initiator, replacing with inert gas, vacuumizing, keeping the temperature of a kettle at 120-140 ℃, keeping the temperature of the kettle after stopping vacuumizing, adding epoxypropane and 1, 2-epoxycyclohexane according to the molar ratio of the epoxypropane to the 1, 2-epoxycyclohexane to the 6# mixed initiator of 4.69:0.31:1, keeping the reaction pressure at 0.3-0.5 MPa, obtaining a polyether crude product after the reaction is finished, refining to obtain polyether polyol A-23#, the hydroxyl value is 435-450 mgKOH/g, and the molecule contains a structure of a formula (I-2-3):
Figure 7
example 24
To be provided with
Figure BDA0003508314450000194
The method comprises the following steps of (1) taking cyclohexanol with a structure shown in a formula (III-3-2), 4-methyl o-phenylenediamine and ethylene glycol as a 7# mixed initiator, (III-3-2) taking the weight of cyclohexanol with the formula (III-3-2) accounting for 80% of the total weight of the 7# mixed initiator, taking the weight of ethylene glycol accounting for 10% of the total weight of the 7# mixed initiator, performing inert gas replacement and vacuum pumping, keeping the temperature of a kettle at 130-150 ℃, keeping the temperature of the kettle after the vacuum pumping is stopped, adding propylene oxide according to the mole ratio of 3:1 of the propylene oxide to the 7# mixed initiator at the reaction pressure of 0.2-0.3 MPa, obtaining a crude polyether product after the reaction is finished, and obtaining polyether polyol A-24# after refining treatment, wherein the hydroxyl value is 510-515 mgKOH/g, and the molecule contains a structure shown in a formula (I-2-12):
Figure 8
Example 25
To be provided with
Figure BDA0003508314450000201
Formula (I)II-2-2) cyclopentanol as an initiator, performing inert gas displacement and vacuumizing, keeping the temperature of the kettle at 120-140 ℃, the reaction pressure at 0.2-0.4 MPa, stopping vacuumizing after the reaction is finished, keeping the temperature of the kettle, adding propylene oxide according to the molar ratio of the propylene oxide to the initiator of 5.6:1 to obtain a polyether crude product, and refining to obtain polyether polyol A-25#, wherein the hydroxyl value is 481-498 mgKOH/g, and the molecule contains a structure shown in a formula (I-2-3):
Figure 9
the detection method of the compatibility of the polyether polyol comprises the following steps:
the solubility is adopted to represent the compatibility of cyclopentane and polyether polyol, and the specific steps are as follows: weighing 100g of polyether polyol, placing the polyether polyol in a glass bottle, adding cyclopentane into the glass bottle, recording the weight of the cyclopentane corresponding to a turbid material system, standing the turbid material system for 1 day at normal temperature, and observing whether the system is layered or not, wherein if the system is not layered, the compatibility is good. The characterization results of examples 1 to 25 are shown in Table 1.
TABLE 1 compatibility of polyether polyols
Figure BDA0003508314450000203
As can be seen from the data in Table 1, the polyether polyol disclosed by the invention is good in compatibility with cyclopentane, 50-60 g of cyclopentane can be dissolved in every 100g of polyether polyol, and the polyether polyol is not layered within 1 day, so that the compatibility with polyurethane reaction raw materials is favorably improved. Meanwhile, the viscosity of the polyether polyol prepared in the embodiment 1-25 is 2000cps at the lowest and 200000cps at 25 ℃, and the lower density can be considered. The unsaturation degree of the polyether polyol is less than 0.1mol/kg, so that the polyurethane foam can have high specific strength.
Examples 26 to 44 are the preparation of isocyanate-reactive compositions and polyurethane foams by the following method, but the effect of the invention is not limited to this method: according to the formula shown in tables 2-4, the raw materials such as the composite polyol, the composite catalyst, the foam stabilizer, the water and the like are mixed to form a composition capable of reacting with the isocyanate, the composition is mixed with the physical foaming agent, and then the mixture is stirred and mixed with the isocyanate at a high speed and then injected into a mold cavity to obtain the polyurethane foam.
Some of the raw materials used in examples 26-44 are as follows:
the polyether polyol B-1 takes cane sugar and ethylene glycol as mixed initiators, and the hydroxyl value is 335-365 mgKOH/g;
the polyether polyol B-2 takes sorbitol and propylene glycol as mixed initiators, and the hydroxyl value is 450-490 mgKOH/g;
the polyether polyol B-3 takes glycerol as a mixed initiator, and the hydroxyl value is 225-255 mgKOH/g;
the polyether polyol B-4 takes sucrose and diethylene glycol as mixed initiators, and the hydroxyl value is 400-460 mgKOH/g;
the polyether polyol B-5 takes toluenediamine as an initiator, and the hydroxyl value is 390-430 mgKOH/g;
the polyether polyol B-6 takes ethylene diamine as an initiator, and the hydroxyl value is 440-460 mgKOH/g.
The epoxy soybean oil polyol has a hydroxyl value of 315-345 mgKOH/g; the castor oil derivative polyol has a hydroxyl value of 265-285 mgKOH/g; the hydroxyl value of the poly (propylene carbonate) polyol is 28-42 mgKOH/g; polycaprolactone polyol with a hydroxyl value of 210-220 mgKOH/g; the hydroxyl value of the phthalic anhydride polyester polyol is 340-360 mgKOH/g.
The composite catalyst is prepared from the following substances in percentage by weight: 15-25 wt% of foaming catalyst, 51-61 wt% of gel catalyst and 20-31 wt% of trimerization catalyst.
The characterization method of the performance of the rigid polyurethane foam comprises the following steps:
the dimensional stability characterization is adopted for the stability of environmental change, and the method is carried out according to GB/T26689 & lt 2011 rigid polyurethane foam for refrigerators and freezers.
The stability after demolding is characterized by adopting a 2-min after-demolding expansion rate, wherein the 2-min after-demolding expansion rate is the thickness change rate of the foam measured from the beginning of material injection to 2min after demolding, and the thickness change rate is the percentage of the difference between the maximum foam thickness after demolding and the mold thickness in the mold thickness. The smaller the thickness change rate, the lower the expansion rate after 2min of mold release, and the better the mold release property. When the expansion rate is less than 2 percent after demoulding within 2min, the demoulding can be carried out within 2 min.
The core density, thermal conductivity and compressive strength were all carried out according to the method described in GB/T26689 & lt 2011 rigid polyurethane foams for refrigerators and freezers.
TABLE 2 examples 26 to 31 raw material compositions
Figure BDA0003508314450000211
Figure BDA0003508314450000221
Figure BDA0003508314450000231
TABLE 3 examples 31 to 38 raw material compositions
Figure BDA0003508314450000232
Figure BDA0003508314450000241
TABLE 4 raw material compositions of examples 39-44 and comparative example 1
Figure BDA0003508314450000242
Figure BDA0003508314450000251
Rigid polyurethane foam is prepared according to the raw materials and the method, and the performance of the foam prepared in the examples 26 to 44 is characterized, and the results are shown in tables 5 to 7.
TABLE 5 foam characterization results for examples 26-31
Figure BDA0003508314450000261
TABLE 6 results of foam characterization in examples 32-38
Figure BDA0003508314450000262
TABLE 7 foam characterization results for examples 39-44 and comparative example 1
Figure BDA0003508314450000263
Figure BDA0003508314450000271
As can be seen from the data in the table, the rigid polyurethane foam prepared by the invention has higher stability under lower density, the low-temperature dimensional deformation rate of the examples 26-44 is less than 0.1%, the wet-heat dimensional deformation rate is less than or equal to 0.2%, the stability to environmental change is good, and the raw materials and the production cost are saved; in examples 26 to 44, the 2min post-demolding expansion rate was < 1.5%, which indicates that the invention has excellent stability after demolding, can greatly reduce the demolding time, and improve the production efficiency. Meanwhile, the invention has better compression strength and lower heat conductivity coefficient while ensuring lower moulding core density, and the comprehensive performance of the foam is excellent. In contrast, comparative example 1, in the case where the polyether polyol of the present invention was not used, had a high core density and poor dimensional stability of foam, which was disadvantageous in saving raw materials and improving production efficiency.

Claims (11)

1. Polyether polyol, characterized in that the polyether polyol contains an alicyclic group, and the alicyclic group has the structure of formula (I):
Figure FDA0003508314440000011
wherein n is any natural number from 2 to 6, and m is 1 or 2.
2. Polyether polyol according to claim 1, wherein 1 to 2 hydrogen atoms of the alicyclic group in the alicyclic group are substituted with an inert group, and the inert group is a C1 to C4 alkyl group.
3. Polyether polyol according to claim 1 or 2, wherein the alicyclic group is introduced by an alkylene oxide comprising at least one of an unsubstituted epoxycycloalkane and a C1-C4 alkyl-substituted epoxycycloalkane, wherein the unsubstituted epoxycycloalkane is at least one of 1, 2-epoxycyclobutane, 1, 2-epoxycyclopentane, 1, 2-epoxycyclohexane, 1, 2-epoxycycloheptane or 1, 2-epoxycyclooctane.
4. Polyether polyol according to claim 3, wherein the polyether polyol is prepared by reacting the alkylene oxide with an initiator, wherein the initiator is at least one of ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylolpropane, sorbitol, sucrose, glycerol or xylitol.
5. Polyether polyol according to claim 1 or 2, wherein the alicyclic group is introduced by an initiator comprising at least one of unsubstituted cycloalkanols and C1-C4 alkyl substituted cycloalkanols; the structure of the unsubstituted cycloalkanol compound is shown as a formula (II) or a formula (III),
The formula (II) is:
Figure FDA0003508314440000012
wherein x is any natural number from 2 to 6, R1Is H or R2Is C2-C4 hydroxyalkyl or C2-C4 aminoalkyl, or R1And R2Are all C2-C4 hydroxyalkyl;
formula (III) is:
Figure FDA0003508314440000013
wherein y is any natural number of 2-6, R3Is C2-C4 alkylene, R4Is hydrogen or C2-C3 hydroxyalkyl, R5Is hydrogen or C2-C3 hydroxyalkyl, R6Is C2-C3 hydroxyalkyl.
6. Polyether polyol according to claim 5, wherein the unsubstituted cycloalkanol compound is obtained by reacting an unsubstituted epoxycycloalkane with an amine compound, and the C1-C4 alkyl-substituted cycloalkanol compound is obtained by reacting a C1-C4 alkyl-substituted epoxycycloalkane with an amine compound;
wherein the unsubstituted epoxy cycloalkane is any one of 1, 2-epoxy cyclobutane, 1, 2-epoxy cyclopentane, 1, 2-epoxy cyclohexane, 1, 2-epoxy cycloheptane or 1, 2-epoxy cyclooctane, and the amine compound is primary amine or secondary amine.
7. Polyether polyol according to claim 6, wherein said initiator is a mixture S, said mixture S being a substance directly obtained after the reaction of said epoxycycloalkane with said amine compound, said epoxycycloalkane comprising at least one of an unsubstituted epoxycycloalkane and a C1-C4 alkyl-substituted epoxycycloalkane.
8. Polyether polyol according to claim 7, characterized in that said mixture S is prepared by: and adding the epoxy cycloalkane into the amine compound in batches, wherein the reaction temperature is 100-160 ℃, and the reaction pressure is more than 0MPa and less than 1 MPa.
9. Polyether polyol according to any of claims 5 to 8, wherein the amine compound comprises at least one of C2-C4 alkyl alcohol amine compounds, unsubstituted C2-C4 alkyl diamine compounds and C2-C4 alkyl diamine compounds substituted by C2-C3 hydroxyalkyl groups.
10. Polyether polyol according to claim 1 or 2, wherein the polyether polyol has a hydroxyl value of 160 to 650 mgKOH/g.
11. A polyurethane foam characterized by having a structure containing the alicyclic group of claim 1, wherein hydrogen atoms of the alicyclic group are unsubstituted or 1 to 2 hydrogen atoms of the alicyclic group are substituted with an inert group, and the inert group is a C1-C4 alkyl group.
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