CN113845640B - Polyether polyol for polyurethane foam plastic and preparation method and application thereof - Google Patents
Polyether polyol for polyurethane foam plastic and preparation method and application thereof Download PDFInfo
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- CN113845640B CN113845640B CN202111351663.4A CN202111351663A CN113845640B CN 113845640 B CN113845640 B CN 113845640B CN 202111351663 A CN202111351663 A CN 202111351663A CN 113845640 B CN113845640 B CN 113845640B
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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
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5075—Polyethers having heteroatoms other than oxygen having phosphorus
- C08G18/5081—Polyethers having heteroatoms other than oxygen having phosphorus having phosphorus bound to oxygen only
- C08G18/5084—Phosphate compounds
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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
- C08G2101/00—Manufacture of cellular products
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Abstract
The polyether polyol for polyurethane foam plastics, which is prepared on the basis of the polyether polyol, has the advantages of high compressive strength, good dimensional stability, less moisture absorption and swelling problems in rainy days, excellent solvent resistance and flame retardance, and can well meet the application requirements of polyurethane spraying. The preparation method of the polyether polyol for the polyurethane foam provided by the invention comprises the following steps: s1, carrying out phosphorylation modification on polyether polyol by polyphosphoric acid to generate polyether polyol phosphate, wherein the polyether polyol phosphate contains partial hydroxyl; and S2, carrying out epoxidation modification on the polyether polyol phosphate obtained in the step S1 by adopting epoxy resin to generate the polyether polyol for the polyurethane foam, wherein the molecular structure of the epoxy resin contains benzene rings.
Description
Technical Field
The invention relates to modified polyether polyol, in particular to polyether polyol for polyurethane foam plastic and a preparation method and application thereof.
Background
Polyurethane is a kind of high molecular material containing urethane repeating structural unit, can be made into products with various shapes, such as foamed plastics, elastomers, adhesives, synthetic leather coating resins and the like, and has wide application in the fields of clothing and eating, industrial and agricultural production, building, traffic, medical treatment and the like. The polyurethane material has various performance advantages, such as a layer of polyurethane rigid foam sprayed on the surface of the inner wall of the refrigeration house, and has the advantages of heat preservation, heat insulation, water resistance and energy conservation. However, the common polyurethane foam plastic has the defects of poor mechanical property, poor dimensional stability, easy moisture absorption, poor solvent resistance, poor flame retardance and the like, is very easy to deform under pressure under the action of external force, and is easy to shrink in size even without the action of external force; when the weather is rainy, the phenomenon of moisture absorption and bulging can occur, and the application range of the paint is greatly limited. CN1515602A discloses an asphalt polyurethane hard foam, which adopts potassium alkoxide composite catalyst to improve the dimensional stability of the hard foam, but because the amount of the catalyst used in the system is very small, the two main raw materials, polyether and isocyanate, are not changed, so the improvement effect of the dimensional stability is very limited.
The cured epoxy resin has the advantages of high mechanical strength, good dimensional stability, strong hydrophobicity, good heat resistance, safety, environmental protection and the like, and can improve the application performance of the polyurethane foam plastic by utilizing the epoxy resin. CN102924692A adopts epoxy resin blending modified polyurethane to prepare an epoxy resin-polyurethane interpenetrating network material, but because of the different solubility of epoxy resin and polyurethane, two phases in the system are separated to a certain degree, and the performance improvement effect is greatly reduced. CN111269647A uses epoxy resin to chemically modify polyurethane coating to enhance its wear resistance, moisture permeability and oxidation resistance, but its chemical modification principle is very fuzzy, and the change of properties such as mechanical strength of modified coating is not discussed.
In order to solve the problems, the industry needs to develop a novel polyurethane foam plastic which has good mechanical property, good dimensional stability and difficult moisture absorption so as to expand the application of the polyurethane foam plastic in the fields of refrigeration house spraying, pipeline heat preservation, plate filling, household appliance heat insulation and the like.
Disclosure of Invention
The polyether polyol for the polyurethane foam is obtained by reacting the polyether polyol modified by phosphoric acid esterification with epoxy resin, and the polyurethane foam prepared based on the polyether polyol for the polyurethane foam has the advantages of high compression strength, good dimensional stability, less moisture absorption and swelling problems in rainy days, excellent solvent resistance and flame retardance, and capability of well meeting the application requirements of polyurethane spraying.
In order to realize the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a preparation method of polyether polyol for polyurethane foam, which comprises the following steps:
s1, carrying out phosphorylation modification on polyether polyol by adopting polyphosphoric acid to generate polyether polyol phosphate, wherein the polyether polyol phosphate contains partial hydroxyl;
and S2, carrying out epoxidation modification on the polyether polyol phosphate obtained in the step S1 by adopting epoxy resin to generate the polyether polyol for the polyurethane foam, wherein the molecular structure of the epoxy resin contains benzene rings.
Further, the polyether polyol in step S1 has the following chemical formula (II):
wherein R is 1 Is alkyl or hydrogen, n is the polymerization degree of polyether polyol, x is the functionality of an initiator used for preparing the polyether polyol shown in the formula (II), x is more than or equal to 3, and Y is a structure of the initiator after active hydrogen is removed; the initiator may be those commonly used in the art for preparing polyether polyols, such as polyols, polyamines, or other active hydrogen-containing compounds, as exemplified by xylitol as the initiator
Then Y is
The polyether polyol for the polyurethane foam provided by the invention has hydroxyl, and epoxy groups, benzene rings and phosphorus elements are introduced into molecules, so that when the polyether polyol is used as one of main raw materials of the polyurethane foam, the mechanical property, the dimensional stability and the solvent resistance of the foam can be effectively improved, the moisture absorption and swelling phenomenon of spraying the foam is improved, and the flame retardant property is remarkably improved. In some embodiments, the polyether polyol for polyurethane foam of the present invention may be represented by the following structural expression (I):
in the formula (I), Y and R 1 N, x have the same meaning as described above in relation to formula (II), and are not described in detail. q is the number of hydroxyl groups participating in the phosphorylation reaction, and q is less than x; r is 2 Is Ep; r 3 Is Ep or hydrogen; wherein Ep is a structure of an epoxy group of an epoxy resin molecule after ring opening, the epoxy resin molecule contains a benzene ring, and for example, bisphenol A diglycidyl ether type epoxy resin molecules are as follows:
wherein Ep formed after ring opening of one epoxy group is:
and m is the polymerization degree of the epoxy resin.
In some embodiments, the polyether polyol phosphate obtained in step S1 may be represented by the following structural formula (III):
in terms of reaction kinetics, it is not controllable that a part of or all of the hydroxyl groups on the polyether polyol (represented by formula (II)) in step S1 participate in the phosphorylation reaction. The invention solves the problem by controlling the feeding amount of polyphosphoric acid, and the prepared polyether polyol phosphate not only contains phosphate groups, but also keeps partial hydroxyl (shown as a formula III). Preferably, in step S1, the ratio of the polyphosphoric acid to the polyether polyol (formula (II)) is controlled to be 1 (1.8-2.2) in terms of the molar ratio of phosphorus atoms in the polyphosphoric acid to hydroxyl groups in the polyether polyol. When the feeding ratio is higher than 1.8, phosphorus atoms are relatively excessive, the hydroxyl groups of the reacted polyether polyol are few, and the reaction activity and the mechanical strength are obviously reduced when the polyether polyol is used for polyurethane foaming; when the feeding ratio is lower than 1.
Preferably, in step S1, the polyphosphoric acid is diluted with a solvent before feeding, and added to the reaction system in a dropwise manner after dilution; preferably, the mass ratio of the polyphosphoric acid to the solvent is 1: (0.8-1.2). The present inventors have surprisingly found through studies that it is not feasible to react pure polyphosphoric acid with a polyfunctional polyether polyol and that the reaction mass changes from colorless to dark brown to black in a short time, because the dehydration properties of polyphosphoric acid are close to those of concentrated sulfuric acid, resulting in slight charring of the reaction mass. The invention reduces the dehydration property of polyphosphoric acid by diluting the polyphosphoric acid with a solvent, effectively solves the problem and enables the reaction to be carried out stably. Preferably, the solvent is selected from one or more of ethanol, dichloromethane, chloroform, dimethyl carbonate, methyl acetate and ethyl acetate. More preferably ethanol is the solvent. The method adopts a dropwise adding mode to add the polyphosphoric acid solution into the polyether polyol, can ensure the stable reaction, and avoids dehydration and carbonization of reactants caused by over violent reaction and over quick heat release.
In some embodiments, in step S1, the temperature of the reaction system is preheated to 50-60 ℃ in advance, and after the temperature of the reaction system is stable (for example, the temperature fluctuation range is within ± 1 ℃), the temperature is raised to 75-85 ℃ for reaction for 2-6 hours; preferably, the temperature rise is performed in a slow temperature rise manner, for example, the temperature rise rate of the temperature rise is 3 ℃/min.
In some embodiments, the post-treatment operation after the reaction of step S1 is completed comprises: extracting the resulting product with ethyl acetate and retaining the organic phase, then washing the organic phase with deionized water, repeating the extraction, the washing operation a plurality of times (e.g., 3 times) until the aqueous phase is added dropwise to the CaCl 2 No precipitate is separated out from the saturated aqueous solution; then dried (e.g. with anhydrous Na) 2 SO 4 Drying) the organic phase, filtering, and removing the solvent (e.g., by rotary evaporation) to obtain the target product, polyether polyol phosphate; the amount of the extractant ethyl acetate used is not particularly limited, so that the aqueous phase is finally added dropwise to the CaCl 2 No precipitate is precipitated in the saturated aqueous solution.
Preferably, in step S2, the epoxy resin is one or more of glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, and alicyclic epoxy resin, each of which has a molecular structure containing a benzene ring.
Preferably, the charging ratio of the phosphorus atom of the target product obtained in the step S1 to the epoxy resin molecule in the step S2 is 1 (1.0-1.3); by adopting the molar ratio, more epoxy resin molecules can be grafted to the phosphate group, and the product contains both the hydroxyl group and the epoxy group of the polyol.
Preferably, the reaction of step S2 is carried out at room temperature for a reaction time of 0.5 to 1 hour. The room temperature varies according to the environment, and in the present invention, the room temperature may be between 10 and 30 ℃. The target product obtained in step S2 does not require post-treatment.
The invention also provides polyether polyol for polyurethane foam, which is prepared by the method.
The present invention also provides a polyurethane foam prepared using a composition comprising an isocyanate and the above-mentioned polyether polyol for polyurethane foam;
preferably, the component comprises a component A, a component B and a component C, wherein the total mass of the component A and the component B is 100 percent:
and (2) component A:
and the component B comprises:
2-3.5wt% of catalyst,
7-17wt% of curing agent;
the component C is isocyanate, and the ratio of the total mass of the component A and the component B to the mass of the component C is 1: (1-1.7).
Wherein, the foam stabilizer is preferably one or more of Jiangsu Meiside chemical M-8809, M-8803, M-8806, mi Tu L6900 and Yingchuang B8545, preferably one or more of M-8809, M-8803 and M-8806;
preferably, the foaming agent is one or more of chlorofluorocarbon, alkane or hydrofluorocarbon foaming agents, preferably hydrofluorocarbon foaming agents, more preferably one or two of HONEYWELL HFC-245fa and HFC-365 mfc;
preferably, the catalyst is a tertiary amine or organotin catalyst, preferably N, N-dimethylcyclohexylamine, organotin or a complex catalyst, more preferably warfarin
PMDETA, new classical chemical T-12,
One or more of SPs 703.
Preferably, the curing agent is one or more of 4, 4-diaminodicyclohexylmethane, 3-aminomethyl-3, 5-trimethylcyclohexylamine or polyetheramine, preferably Wanhua
2110、
PACM、
IPDA or
8100.
Preferably, the isocyanate is a polymeric isocyanate, preferably a polymethylene polyphenyl isocyanate, more preferably Wanhua
PM-200、
One or two of PM-400.
In some embodiments, before the polyurethane foam is applied, the mixing method of the three components A, B and C comprises the following steps:
(1) Respectively and uniformly mixing the component A and the component B at the temperature of 10-40 ℃, and respectively discharging, sealing and storing;
(2) At the temperature of 10-40 ℃, respectively mixing the component A and the component B with the component C according to the mass ratio (A + B): c =1: (1-1.7) and mixing uniformly.
The invention also provides application of the polyurethane foam plastic, and the polyurethane foam plastic is applied to the fields of refrigeration house spraying, pipeline heat preservation, plate filling and household appliance heat insulation (such as refrigerator heat preservation). In some embodiments, the specific application method is as follows: when the coating is applied to spraying of a refrigeration house, respectively and uniformly mixing A and B by using a spraying machine, then uniformly mixing A, B and C, directly spraying the mixture on the wall surface of the refrigeration house, and foaming and curing at the temperature of 10-40 ℃; when the composite material is applied to pipeline heat insulation, the uniformly mixed components A, B and C are extruded, injected or sprayed and wound on the surface of a pipeline, and are foamed and cured at the temperature of 10-30 ℃; when the foaming agent is applied to plate filling, the uniformly mixed three components A, B and C are coated on the surface of a plate, and the foaming, molding, curing and demolding are carried out at the temperature of 10-30 ℃; when the polyurethane foam is applied to heat preservation of a refrigerator, the three components A, B and C which are uniformly mixed are injected into a mold for foaming, molding and curing to obtain the required polyurethane foam.
The polyurethane foam plastic prepared from the polyether polyol for polyurethane foam plastic has high compression strength, low dimensional change rate, excellent hydrophobicity, solvent resistance and flame retardance under the room temperature condition, and meets the requirements of the polyurethane foam plastic industry. For example, some embodiments achieve a compressive strength of 0.52MPa (0.12 MPa at the national standard) and dimensional change rates of less than 0.8% (70 ℃, 4% at the national standard), + -0.3% (-20 ℃, 1% at the national standard).
The invention adopts a chemical modification mode to introduce the epoxy resin with a benzene ring structure into the field of polyurethane foam plastics. When the polyether polyol is subjected to phosphorylation modification, the polyphosphoric acid is diluted by a solvent and then reacts with the polyether polyol in a dropwise manner, so that dehydration and carbonization of reactants caused by over violent reaction and over quick heat release are effectively avoided; the phosphoric acid esterification is used as a bridge for introducing epoxy resin into polyether polyol, and partial epoxidation of the polyether polyol is realized by reasonably controlling the feeding amount of polyphosphoric acid and the epoxy resin, so that a target product has the performances of phosphate and the epoxy resin; compared with the common polyether polyol, the epoxy resin molecular chain segment containing benzene rings is introduced into the prepared polyurethane foam plastic, the mechanical property and the size stability are obviously improved, the compression deformation under the action of external force and the size shrinkage without the external force are effectively reduced, the problem that the polyurethane foam is easy to absorb moisture and swell in rainy days is solved, meanwhile, the solvent resistance and the flame retardant property of the foam plastic are further improved due to the introduction of benzene rings and phosphorus elements, and the application range of the polyurethane foam plastic is greatly expanded.
The technical scheme provided by the invention has the following beneficial effects:
(1) The invention introduces epoxy resin into polyether polyol molecules by adopting a chemical modification method, applies the scheme to the field of polyurethane foam plastics for the first time, has wide sources of raw materials of epoxy resin and polyether polyol, simple preparation process conditions and high production efficiency, and is easy to realize industrialization. In the prior art, an epoxy compound with a benzene ring is introduced when polyether polyol is synthesized by using an initiator directly at the upstream, the process needs to involve the use of a catalyst, a polymerization inhibitor and a blocking agent, and strict temperature control and strict catalyst dosage control are needed to prepare epoxy modified polyether polyol with specific molecular weight, so that the process requirement is strict; compared with the prior art, the invention has the advantages of relatively loose process conditions, no use of the reagent and easy process implementation and control.
(2) When the modified polyether polyol is prepared, epoxy resin molecules containing a benzene ring structure are adopted for modification, and the polyether polyol prepared by the method is used as a raw material for polyurethane spraying, so that the prepared polyurethane foam plastic is high in compression strength and good in size stability, and can effectively resist size shrinkage in a long-term use process and compression deformation under the action of external force; the solvent resistance of the foam is further improved.
(3) Meanwhile, the hydrophobic property of the polyether polyol is greatly improved by introducing the epoxy resin into the polyether polyol molecular chain segment, and the problem of moisture absorption and swelling of the foam plastic can be obviously improved in the polyurethane spraying construction process.
(4) In addition, the polyether polyol prepared by the method is rich in phosphorus elements, and the polyether polyol is used as a main raw material of polyurethane foam, so that the overall flame retardant property of the plastic is obviously improved.
(5) In terms of reaction kinetics, part of or all of the hydroxyl groups of the polyether polyol participate in the phosphorylation reaction, which is an uncontrollable process. According to the invention, by controlling the feeding amount of polyphosphoric acid, the novel polyether polyol molecule containing epoxy groups and phosphoric ester bonds and retaining part of hydroxyl groups is synthesized, so that the novel polyurethane foam plastic with the performance advantages is prepared, the industry development trend is met, and the market prospect is wide.
Detailed Description
In order to better understand the technical solution of 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.
Information on the main raw materials used:
polyphosphoric acid: shanghai Aladdin Biotechnology GmbH;
polyether polyol:
r2403, wanhua chemistry, formula;
wherein R is 1 Is methyl, n =1,x =4,Y is
Glycidyl ether type epoxy resin: WSR618, blue star nantong star synthetic materials ltd;
glycidyl amine type epoxy resin: syna Epoxy S-720, new Nantong Xinnaxi Material Co., ltd;
glycidyl ether type epoxy resin: WSR6101, blue star southwestern stars synthetic materials ltd;
foam stabilizer: m-8809, M-8806, maxwell chemical Co., ltd;
foaming agent: HFC-24lfa, honeywell;
catalyst:
PMDETA, wanhua chemistry;
catalyst:
SP703, wanhua chemistry;
catalyst: t-12, new classical chemical materials (Shanghai) Inc.;
curing agent:
2110, warewashing chemistry;
curing agent:
8100, wanhua chemistry;
curing agent:
PACM，Evonik；
polymeric isocyanate:
PM-200, wanhua chemistry;
the test method comprises the following steps:
compressive strength: refer to GB/T8813-2020 determination of compressibility of rigid foam plastics;
dimensional stability: refer to GB/T8811-2008 rigid foam plastic dimensional stability test method;
water absorption: refer to GB/T8810-2005 determination of water absorption of rigid foam plastics;
solvent resistance: preparing polyurethane foam into small blocks with the specification of 15mm multiplied by 15mm, putting the blocks into an oven to be completely dried and weighed, then soaking the blocks for 14 days at room temperature by using 10wt% hydrochloric acid, 10wt% acetic acid and 10wt% ethanol water solution, airing the surfaces, weighing again, and calculating the solvent-resistant swelling ratio eta according to the following formula:
η＝(m-m 0 )/m 0 ×100％
in the formula, m represents the mass of a sample block after being soaked for 14 days, and g represents the mass of the sample block;
m 0 -mass of sample block before soaking, g;
flame retardant property: the 2 nd part of the combustion behavior is determined by oxygen index method with reference to GB/T2406.2-2009 plastics: room temperature test ";
hydroxyl value: refer to GB 12008.3-1989 method for determining hydroxyl value in polyether polyol.
[ example 1 ]
Polyether polyol # 1 for polyurethane foam was prepared as follows:
169g of polyphosphoric acid is dissolved in 169g of absolute ethanol to prepare an absolute ethanol solution of polyphosphoric acid, and then the solution is dropwise added to 300g of polyether polyol in 3 batches
In R2403 (ensuring that the molar ratio of phosphorus atoms of polyphosphoric acid to hydroxyl groups in the polyether polyol raw material is 1, 2), preheating the temperature of a reaction system to 50-60 ℃, and raising the temperature to 80 ℃ after the temperature of the system is stabilized at 55 ℃ for reacting for 4 hours. And (3) extracting the product by using ethyl acetate (the volume ratio of the extracting agent to the extracted liquid is 1) 2 No precipitate is separated out from the saturated solution, and anhydrous Na is used 2 SO 4 Drying the organic phase, filtering, and removing the solvent by rotary evaporation to obtain the target product polyether polyol phosphate (the hydroxyl value of the polyether polyol is reduced from 760mgKOH/g to 382mgKOH/g before and after the reaction).
Taking 460g of polyether polyol phosphate and 748g of glycidyl ether type epoxy resin WSR618 (the molar ratio of phosphorus atoms to epoxy resin molecules is 1.1), stirring and reacting for 45min under the room temperature condition, and obtaining the target product polyether polyol for polyurethane foam without post-treatment.
[ example 2 ] A method for producing a polycarbonate
Polyether polyol # 2 for polyurethane foam was prepared as follows:
169g of polyphosphoric acid are dissolved in 135g of dichloromethane to prepare an absolute ethanol solution of polyphosphoric acid, and then the solution is dropwise added to 270g of polyether polyol in 3 batches
R2403 (ensuring that the molar ratio of phosphorus atoms of polyphosphoric acid to hydroxyl groups in the polyether polyol raw material is 1.8), preheating the temperature of a reaction system to 50-60 ℃, and heating to 75 ℃ after the temperature of the system is stabilized at 50 ℃ for reacting for 6 hours. And (3) extracting the product by using ethyl acetate (the volume ratio of the extracting agent to the extracted liquid is 1) 2 No precipitate is separated out from the saturated solution, and anhydrous Na is used 2 SO 4 Drying the organic phase, filtering, and removing the solvent by rotary evaporation to obtain the target product polyether polyol phosphate (the hydroxyl value of the polyether polyol before and after the reaction is reduced from 760mgKOH/g to 353 mgKOH/g).
460g of polyether polyol phosphate and 845g of glycidyl amine type Epoxy resin Syna Epoxy S-720 (the molar ratio of phosphorus atoms to Epoxy resin molecules is 1.
[ example 3 ] A method for producing a polycarbonate
Polyether polyol # 3 for polyurethane foam was prepared as follows:
169g of polyphosphoric acid was dissolved in 152g of dimethyl carbonate to prepare an absolute ethanol solution of polyphosphoric acid, which was then added dropwise to 330g of polyether polyol in 3 batches
In R2403 (ensuring that the molar ratio of phosphorus atoms of polyphosphoric acid to hydroxyl groups in the polyether polyol raw material is 1: 2.2), preheating the temperature of a reaction system to 50-60 ℃, and heating to 85 ℃ after the temperature of the system is stabilized at 60 ℃ for reacting for 2 hours. And (3) extracting the product by using ethyl acetate (the volume ratio of the extracting agent to the extracted liquid is 1) 2 No precipitate is separated out from the saturated solution, and then anhydrous Na is used 2 SO 4 Drying the organic phase, filtering, and removing the solvent by rotary evaporation to obtain the target product polyether polyol phosphate (the hydroxyl value of the polyether polyol before and after the reaction is reduced from 760mgKOH/g to 416 mgKOH/g).
460g of polyether polyol phosphate and 1091g of epoxy resin WSR6101 (the molar ratio of phosphorus atoms to epoxy resin molecules is 1.2) are stirred and reacted for 30min under the condition of room temperature, so that the polyether polyol for the target product polyurethane foam is obtained, and the product does not need post-treatment.
[ example 4 ] A method for producing a polycarbonate
Polyether polyol # 4 for polyurethane foam was prepared as follows:
169g of polyphosphoric acid are dissolved in 186g of methyl acetate to prepare an absolute ethanol solution of polyphosphoric acid, and then the solution is dropwise added to 285g of polyether polyol in 3 batches
In R2403 (ensuring that the molar ratio of phosphorus atoms of polyphosphoric acid to hydroxyl groups in the polyether polyol raw material is 1.9), preheating the temperature of a reaction system to 50-60 ℃, and heating to 78 ℃ after the temperature of the system is stabilized at 53 ℃ for reacting for 3 hours. And (3) extracting the product by using ethyl acetate (the volume ratio of the extracting agent to the extracted liquid is 1) 2 No precipitate is separated out from the saturated solution, and anhydrous Na is used 2 SO 4 Drying the organic phase, filtering, and removing the solvent by rotary evaporation to obtain the target product polyether polyol phosphate (the hydroxyl value of the polyether polyol before and after the reaction is reduced from 760mgKOH/g to 361 mgKOH/g).
Taking 460g of polyether polyol phosphate and 885g of epoxy resin WSR618 (the molar ratio of phosphorus atoms to epoxy resin molecules is 1.3).
[ example 5 ]
Polyether polyol # 5 for polyurethane foam was prepared as follows:
169g of polyphosphoric acid was dissolved in 203g of ethyl acetate to prepare an absolute ethanol solution of polyphosphoric acid, which was then added dropwise to 315g of polyether polyol in 3 batches
In R2403 (ensuring the molar ratio of phosphorus atoms to hydroxyl groups to be 1, 2.1), preheating the temperature of a reaction system to 50-60 ℃, and raising the temperature to 83 ℃ after the temperature of the system is stabilized at 58 ℃ for reaction for 5 hours. And (3) extracting the product by using ethyl acetate (the volume ratio of the extracting agent to the extracted liquid is 1) 2 No precipitate is separated out from the saturated solution, and anhydrous Na is used 2 SO 4 Drying the organic phase, filtering, and removing the solvent by rotary evaporation to obtain the target product polyether polyol phosphate (the hydroxyl value of the polyether polyol before and after the reaction is reduced from 760mgKOH/g to 402 mgKOH/g).
Taking 460g of polyether polyol phosphate and 930g of Epoxy resin Syna Epoxy S-720 (the molar ratio of phosphorus atoms to Epoxy resin molecules is 1.1).
[ example 6 ]
Polyurethane foams were prepared as follows:
respectively preparing a component A, a component B and a component C:
the component A comprises: 630g of polyether polyol 1#,15g of foam stabilizer M-8809, 250g of foaming agent HFC-24wfa and 15g of water for polyurethane foam are fully and uniformly mixed.
And the component B comprises: 10g of catalyst
PMDETA,10g catalyst
SP703, 40g curing agent
2110 30g of curing agent
IPDA (Wanhua chemical) was mixed well.
Component C is polymeric isocyanate
PM-200。
Respectively and uniformly mixing A and B by using a spraying machine at 25 ℃, and then mixing A, B and C according to the mass ratio (A + B): c =1:1.3, mixing evenly and spraying the mixture on the wall surface of a cold storage, foaming and curing at 25 ℃ to obtain the polyurethane foam plastics, wherein the performance test results are shown in tables 1 and 2.
[ example 7 ] A method for producing a polycarbonate
Polyurethane foams were prepared as follows:
respectively preparing components A, B and C:
the component A comprises: 580g of polyether polyol 2# for polyurethane foam, 20g of foam stabilizer M-8803, 240g of foaming agent HFC-365mfc and 13g of water are fully and uniformly mixed.
And the component B comprises: 14g of catalyst
PMDETA,13g catalyst
SP703, 60g curing agent
2110 60g of curing agent
8110 mixing well.
The component C is polymeric isocyanate
PM-400 (Wanhua chemistry).
Respectively and uniformly mixing A and B by using a spraying machine at 25 ℃, and then mixing A, B and C according to the mass ratio (A + B): c =1:1, uniformly mixing and directly spraying the mixture on the wall surface of a cold storage, foaming and curing at 25 ℃ to obtain the polyurethane foam plastics, wherein the performance test results are shown in tables 1 and 2.
[ example 8 ]
Polyurethane foams were prepared as follows:
respectively preparing a component A, a component B and a component C:
and (2) component A: 680g of polyurethane foam plastic polyether polyol No. 3, 10g of foam stabilizer M-8806, 200g of foaming agent cyclopentane and 6g of water are mixed evenly.
And B component: 19g of catalyst
PMDETA,15g of catalyst T-12, 40g of curing agent
PACM,30g curing agent
8100 mixing well.
The component C is polymeric isocyanate
PM-200。
Respectively and uniformly mixing A and B by using a spraying machine at 25 ℃, and then mixing A, B and C according to the mass ratio (A + B): c =1:1.7, mixing evenly and spraying the mixture on the wall surface of a cold storage, foaming and curing at 25 ℃ to obtain the polyurethane foam plastics, wherein the performance test results are shown in tables 1 and 2.
[ example 9 ]
Polyurethane foams were prepared as follows:
respectively preparing components A, B and C:
the component A comprises: 580g of polyether polyol 4# for polyurethane foam, 10g of foam stabilizer L6900, 200g of foaming agent 141b and 6g of water are fully and uniformly mixed.
And B component: 16g of catalyst
PMDETA,19g catalyst
SP70, 79g curing agent
PACM,90g curing agent
The IPDA is mixed thoroughly and homogeneously.
Component C is polymeric isocyanate
PM-400。
Respectively and uniformly mixing A and B by using a spraying machine at 25 ℃, and then mixing A, B and C according to the mass ratio (A + B): c =1:1.5, mixing evenly and spraying the mixture on the wall surface of a cold storage, foaming and curing at 25 ℃ to obtain the polyurethane foam plastics, wherein the performance test results are shown in tables 1 and 2.
[ example 10 ] A method for producing a polycarbonate
Polyurethane foams were prepared as follows:
respectively preparing a component A, a component B and a component C:
the component A comprises: 580g of polyether polyol 5# for polyurethane foam, 10g of foam stabilizer B8545 and 200g of foaming agent CFC-11,6g of water are fully and uniformly mixed.
And B component: 16g of catalyst
PMDETA,18g catalyst
SP703, 80g curing agent
2110 90g of curing agent
8100 mixing well.
Component C is polymeric isocyanate
PM-200。
Respectively and uniformly mixing A and B by using a spraying machine at 25 ℃, and then mixing A, B and C according to the mass ratio (A + B): c =1:1.1, mixing uniformly and spraying the mixture on the wall surface of a cold storage directly, foaming and curing at 25 ℃ to obtain the polyurethane foam plastics, wherein the performance test results are shown in tables 1 and 2.
Comparative example 1
Polyether polyol # 6 was prepared according to the procedure for example 1, except that:
the polyphosphoric acid is not diluted by absolute ethyl alcohol solvent and is directly mixed with polyether polyol
R2403. The reaction product turns from colorless to dark brown and then to black in a short time, slight carbonization occurs, and the target product cannot be obtained.
Comparative example 2
Polyether polyol # 7 was prepared according to the method of example 1, except that:
phosphorus atom and polyether polyol in polyphosphoric acid
The molar ratio of hydroxyl groups in R2403 was 1.05, and the amount of epoxy WSR618 was increased simultaneously to 1496g (ensuring a molar ratio of phosphorus atoms to epoxy molecules of 1.
Polyurethane foam was prepared by polyether polyol # 7 by the method of example 6, and the system was not foamed after mixing A, B and C, and polyurethane foam could not be obtained because the most of the hydroxyl groups in polyether polyol were consumed by polyphosphoric acid due to excess polyphosphoric acid (the hydroxyl value of polyether polyol before and after the reaction was reduced from 760mgKOH/g to 3 mgKOH/g), and the prepared polyether polyol # 7 could not be foamed.
Comparative example 3
Polyether polyol # 8 was prepared according to the method of example 1, except that:
phosphorus atom and polyether polyol in polyphosphoric acid
The molar ratio of hydroxyl groups in R2403 is 1.5 (the hydroxyl value of polyether polyol before and after reaction is reduced from 760mgKOH/g to 504 mgKOH/g), and the amount of the epoxy resin WSR618 is synchronously reduced to 599g (ensuring that the molar ratio of phosphorus atoms to epoxy resin molecules is 1.1, the same as in example 1).
The results of the performance tests on the polyurethane foam epoxy resin compositions obtained in this comparative example are shown in Table 1.
Comparative example 4
A polyurethane foam was prepared as in example 6, except that:
with unmodified conventional polyether polyols
R2403 is used to replace polyether polyol 1# for polyurethane foam in the component A, and the performance test results of the polyurethane foam obtained in this comparative example are shown in Table 1.
The polyurethane foams prepared in examples 6 to 10 and comparative examples 3 to 4 were subjected to the tests for compressive strength, dimensional stability, water absorption, solvent resistance and flame retardancy, and the test results are shown in tables 1 and 2:
TABLE 1 partial Performance test results for polyurethane foams
TABLE 2 results of solvent resistance test of polyurethane foams
| Eta (hydrochloric acid) /) | Eta (acetic acid)/%) | Eta (ethanol) /) | |
| Example 6 | 15 | 65 | 38 |
| Example 7 | 17 | 64 | 40 |
| Example 8 | 18 | 63 | 39 |
| Example 9 | 19 | 68 | 35 |
| Example 10 | 17 | 70 | 42 |
| Comparative example 3 | 24 | 81 | 52 |
| Comparative example 4 | 35 | 103 | 69 |
And (4) analyzing results:
examples 6-10 polyurethane foams were prepared using the polyether polyol prepared according to the present invention, and comparative example 4 polyurethane foams were prepared using an unmodified conventional polyether polyol, as can be seen from Table 1, the compressive strength and dimensional stability of examples 6-10 were greatly improved as compared to comparative example 4. In comparative example 3, since the feed molar ratio of phosphorus atoms to hydroxyl groups of polyether polyol in step S1 is less than 1.2, the amount of polyphosphoric acid is relatively small, the degree of reaction is reduced, the effect of epoxy resin-modified polyether polyol is limited, and the compressive strength and dimensional stability are slightly inferior to those of examples 6 to 10.
The lower the water absorption of the polyurethane foam, the better the hydrophobicity, and as can be seen from table 1, the comparative example 4 shows that the hydrophobicity of examples 6-10 is obviously improved, and the improvement of the hydrophobicity can effectively alleviate the problem that the foam absorbs moisture and bulges in rainy days.
The oxygen index can represent the flame retardant property of the polyurethane foam, and the higher the oxygen index is, the better the flame retardant property is. As can be seen from Table 1, the flame retardant properties of examples 6-10 also have significant advantages over comparative example 4; the solvent resistance is characterized by the magnitude of η, the greater η, the more solvent imbibed within the plastic and the poorer the solvent resistance, as can be seen from table 2, the superior solvent resistance compared to comparative example 4, examples 6-10. The flame retardant and solvent resistance of comparative example 3 are slightly inferior to those of examples 6 to 10.
In conclusion, the polyether polyol provided by the invention is used as a raw material to prepare polyurethane foam plastics, so that the polyurethane foam plastics are excellent in mechanical property, dimensional stability, solvent resistance and flame retardance, and the problem that the foam plastics absorb moisture and swell in rainy days can be effectively solved.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for a person skilled in the art, several modifications and additions can be made without departing from the method of the present invention, and these modifications and additions should also be considered as the protection scope of the present invention.
Claims (14)
1. A preparation method of polyether polyol for polyurethane foam is characterized by comprising the following steps:
s1, carrying out phosphorylation modification on polyether polyol by polyphosphoric acid to generate polyether polyol phosphate, wherein the polyether polyol phosphate contains partial hydroxyl; the feeding ratio of the polyphosphoric acid to the polyether polyol is controlled to be 1 (1.8-2.2) by the molar ratio of phosphorus atoms in the polyphosphoric acid to hydroxyl groups of the polyether polyol; diluting the polyphosphoric acid with a solvent before feeding;
and S2, carrying out epoxidation modification on the polyether polyol phosphate obtained in the step S1 by adopting epoxy resin to generate the polyether polyol for the polyurethane foam, wherein the molecular structure of the epoxy resin contains benzene rings.
2. The process according to claim 1, wherein the polyether polyol in step S1 has the following formula (II):
wherein R is 1 Is alkyl or hydrogen, n is the polymerization degree of polyether polyol, x is the functionality of an initiator used for preparing the polyether polyol shown in the formula (II), x is more than or equal to 3, and Y is the structure of the initiator after active hydrogen is removed.
3. The production method according to claim 1,
in step S1, the polyphosphoric acid is diluted and then added dropwise to the reaction system.
4. The method according to claim 1, wherein in step S1, the mass ratio of the polyphosphoric acid to the solvent is 1: (0.8-1.2).
5. The method according to claim 1, wherein in step S1, the solvent is one or more selected from the group consisting of ethanol, dichloromethane, chloroform, dimethyl carbonate, methyl acetate, and ethyl acetate.
6. The process according to claim 3, wherein in step S1, the temperature of the reaction system is preheated to 50 to 60 ℃ in advance, and after the temperature of the reaction system is stabilized, the temperature is raised to 75 to 85 ℃ to react for 2 to 6 hours.
7. The method according to claim 6, wherein the post-treatment operation after the reaction of step S1 is completed comprises: extracting the obtained product with ethyl acetate and keeping the organic phase, then washing the organic phase with deionized water, repeating the extraction and washing operations for a plurality of times until the water phase is dripped into CaCl 2 No precipitate is separated out from the saturated aqueous solution; and then drying the organic phase, filtering and removing the solvent to obtain the target product polyether polyol phosphate.
8. The method according to any one of claims 1 to 6, wherein in step S2, the epoxy resin is one or more of glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, and alicyclic epoxy resin having a molecular structure containing a benzene ring.
9. The method according to claim 8, wherein in step S2, the ratio of the phosphorus atom to the epoxy resin molecule in the target product obtained in step S1 is 1 (1.0-1.3).
10. The method according to claim 9, wherein the reaction of step S2 is carried out at room temperature for 0.5 to 1 hour.
11. Polyether polyol for polyurethane foams, characterized in that it is obtained by the process according to any one of claims 1 to 10.
12. A polyurethane foam obtained from a composition comprising an isocyanate and the polyether polyol for polyurethane foam of claim 11.
13. The polyurethane foam according to claim 12, wherein the component comprises a component A, a component B and a component C, wherein the total mass of the component A and the component B is 100%, and the total mass of the component A and the component B comprises the following components:
and (2) component A:
and B component:
2 to 3.5 weight percent of catalyst,
7-17wt% of curing agent;
the component C is isocyanate, and the ratio of the total mass of the component A and the component B to the mass of the component C is 1: (1-1.7).
14. The use of the polyurethane foam according to claim 12 or 13, wherein the polyurethane foam is used in the fields of cold storage spraying, pipeline insulation, plate filling and household appliance insulation.
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