CN114763409A - Graphite oxide polyether polyol, preparation method and application - Google Patents

Graphite oxide polyether polyol, preparation method and application Download PDF

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Publication number
CN114763409A
CN114763409A CN202110053256.9A CN202110053256A CN114763409A CN 114763409 A CN114763409 A CN 114763409A CN 202110053256 A CN202110053256 A CN 202110053256A CN 114763409 A CN114763409 A CN 114763409A
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polyether polyol
catalyst
graphite oxide
oxide
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牟砚圃
朱霞林
叶俊
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Wanhua Chemical Yantai Rongwei Polyurethane Co Ltd
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Wanhua Chemical Yantai Rongwei Polyurethane Co Ltd
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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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
    • C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
    • 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
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/482—Mixtures of polyethers containing at least one polyether containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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

Abstract

The invention provides a graphite oxide polyether polyol and a preparation method and application thereof. The preparation method comprises the following steps: (1) taking graphite oxide as a raw material, and mixing the graphite oxide with a solvent; (2) graphite oxide and ethylene oxide are subjected to addition reaction under the action of a catalyst to obtain a mixed solution containing an intermediate product; (3) and (3) carrying out addition reaction on the mixed solution obtained in the step (2) and an epoxide under the action of a catalyst to obtain the graphite oxide polyether polyol. When the modified graphite oxide polyether polyol is applied to preparation of polyurethane rigid foam, the nucleation and stability of the foam can be effectively improved, the foam holes are uniform and fine, the heat conductivity coefficient is reduced, and the strength and dimensional stability of the foam are improved.

Description

Graphite oxide polyether polyol, preparation method and application
Technical Field
The invention relates to a preparation method of Graphite Oxide (GO) polyether polyol and polyurethane rigid foam.
Background
The polyurethane is a microporous foam body with a compact structure, which is polymerized by using isocyanate and polyol as basic raw materials, and has the excellent performances of light weight, high specific strength, water impermeability, no moisture absorption, insulation, shock resistance, sound absorption, oil resistance, chemical corrosion resistance and the like. The polyurethane hard foam is an important component of white household appliances such as refrigerators, freezers and the like. With the technological progress, the perfection of national standards and specifications and the improvement of requirements of people on living quality, the formula system of the polyurethane rigid foam is continuously and iteratively upgraded and is improved towards the directions of low cost, low heat conduction, low pollution, quick demoulding, high strength and the like. According to the direction requirements of national energy conservation and emission reduction, manufacturers of large refrigerators and freezers also have the requirement of updating low energy consumption.
The energy consumption of the existing refrigerator and freezer mainly comprises three aspects: the first aspect is that the electric energy used in the process of producing cold by the compressor through the Carnot cycle and the self energy conversion can not reach 100 percent, which causes heat loss; the second aspect is that the position of the inner components of the refrigerator, such as the evaporation tube, is reasonably arranged, and the efficiency of absorbing and radiating heat is high and low; the third aspect is the ability of the polyurethane foam to provide insulation against heat exchange between the space within the cavity and the outside environment.
The heat insulation performance of polyurethane foam plays a decisive role in heat preservation, so that a great deal of literature is also available for researching and proposing a plurality of theoretical models of heat preservation of a microporous structure and schemes for improving the heat insulation performance of the foam. The key to the heat insulation of polyurethane rigid foam is that the foam has countless closed micropores, gases with low heat conductivity are locked inside the micropores, the solid phase is used as a continuous phase and is the framework support of the whole foam, the micropores like small cells are used as beams and columns, and the foaming agent is used as a dispersed phase to play a heat insulation role. The polyurethane foam as a whole can have good heat insulation effect.
The combined polyether polyol in the foaming system of the existing polyurethane rigid foam is mainly sugar ether, amine ether, oil ether and micromolecular polyether. The system has several problems, firstly, the sugar ether and the amine ether with higher strength have higher viscosity and are limited to be applied, and on the other hand, although the viscosity of the polyether can be effectively regulated and controlled by the oleyl ether and the micromolecule polyether, the cross-linking performance of the synthesized polyether is relatively poorer due to the chemical structure of the long chain of the oleyl ether and the micromolecule polyether; the high viscosity results in uneven mixing of the conjugate polyether with the isocyanate to cause problems such as cracking, while insufficient strength results in poor properties such as dimensional stability, mold release properties and damping resistance of the foam.
Therefore, a low-viscosity and strong-crosslinking polyether monomer needs to be developed, so that the low-viscosity mixing effect is ensured, the high strength of the produced polyurethane foam is ensured, the supporting strength of a foam framework is further ensured, the foam heat insulation performance is improved, and the purpose of reducing the energy consumption of a refrigerator and a freezer is further achieved.
Disclosure of Invention
In order to solve the problems, the invention provides a novel polyether composite material technology of polyurethane rigid foam, which comprises the steps of firstly taking graphite oxide as a raw material, and carrying out addition reaction with alkylene oxide under relatively mild synthesis conditions to obtain graphite oxide polyether polyol with amphiphilic characteristics, wherein the graphite oxide polyether polyol contains polar groups such as hydroxyl, carboxyl and carbonyl and two non-polar groups such as a reticular six-membered carbocyclic ring.
The graphite oxide polyether polyol can be used as an emulsifier in a polyether composite material formula, can be well dissolved with other polar and non-polar components in the composite material after physical mixing, can reduce the mixing difficulty of other components in the composite polyether polyol, and forms a mixed solution with uniform appearance and long-term stability. The nano-scale graphite oxide sheets in the graphite oxide polyether polyol are dispersed in the composite material polyether as solids, and can provide nucleation points for the vaporization of the foaming agent in the early stage of the reaction, so that the initiation time of each part in the whole foam is more consistent, the pore diameter of the pores is more consistent, and the heat conductivity coefficient of the polyurethane foam is reduced. The skeleton of the graphite oxide is a ring-shaped six-membered carbon ring, which has the rigidity of a carbon-carbon bond and the toughness of a net, the polar organic functional group connected to the carbon ring provides a site for reacting with an epoxy compound, and the average functionality of the polyether monomer is increased by phase change, so that the mechanical strength and the weather resistance are increased.
In order to achieve the purpose, the invention adopts the following technical scheme:
the graphite oxide polyether polyol has the following structural formula:
Figure BDA0002899912080000031
wherein: i, j, m, n, s, t, u, v, x, y are each independently an integer of not less than 0, preferably each independently an integer of 1 to 3; r is CnH2n-1N is 0 to 3, preferably n is 1.
The preparation method of the graphite oxide polyether polyol comprises the following steps:
(1) mixing graphite oxide serving as a raw material with a solvent;
(2) carrying out addition reaction on graphite oxide and ethylene oxide under the action of a catalyst to obtain a mixed solution containing an intermediate product;
(3) and (3) carrying out addition reaction on the mixed solution obtained in the step (2) and an epoxide under the action of a catalyst to obtain the graphite oxide polyether polyol.
In the step (1), the solvent is water and/or alcohol, and the alcohol can be glycerol, ethylene glycol, propylene glycol, diethylene glycol, preferably diethylene glycol and/or glycerol;
in the step (1), the mass ratio of the graphite oxide to the solvent is 1: (0.1-50), preferably 1: (1-20); the mixing temperature is 10-90 deg.C, preferably 50-80 deg.C; the mixing time is 10-60min, preferably 20-30 min.
In the step (2), the mass ratio of the graphite oxide to the ethylene oxide is 1 (1-80), preferably 1 (5-50);
in the step (2), the catalyst is inorganic base and/or organic amine, the inorganic base is selected from KOH and NaOH, the organic amine is selected from ethylenediamine, dimethylamine and the like, and the catalyst is preferably KOH solid. The amount of the catalyst accounts for 0.1-1.0 wt% of the mass of the reaction system (graphite oxide, ethylene oxide and solvent); the reaction temperature is 90-150 ℃, and the reaction time is 2-4 h.
In step (3), the epoxide may be ethylene oxide, propylene oxide, butylene oxide or the like, preferably propylene oxide;
the mass ratio of the graphite oxide to the epoxide added initially is 1 (10-400), preferably 1 (30-200);
the catalyst is inorganic base and/or organic amine, the inorganic base is selected from KOH and NaOH, the organic amine is selected from ethylenediamine, dimethylamine and the like, and the catalyst is preferably KOH. The amount of the catalyst accounts for 0.01-1 wt% of the mass of the reaction system (the solvent, graphite oxide, ethylene oxide and epoxide which are added initially); the reaction temperature is 90-150 ℃, the preferable temperature is 80-120 ℃, and the reaction time is 1-8h, and the preferable time is 2-4 h.
Adding 5-10 times of water into the obtained reactant, centrifuging or standing until the upper layer and the lower layer are clearly separated, taking the lower layer black mixed solution, and repeatedly adding water to dilute until the pH value of the lower layer solution reaches 6.0-7.0. And drying the subnatant to obtain a graphite oxide polyether polyol product.
The invention also relates to application of the graphite oxide polyether polyol in preparation of polyurethane rigid foam.
The graphite oxide polyether polyol is used as an emulsifier to prepare polyurethane foam, so that the nucleation number of the foam can be increased, the foam holes are finer and finer, the heat conductivity coefficient is lower, and the energy consumption of a refrigerator, a freezer and the like is reduced; the high strength characteristic of the graphite oxide can also improve the strength of polyurethane foam, reduce the filling amount and reduce the foaming cost.
The invention also provides a polyurethane rigid foam, which is prepared from the following raw materials in parts by weight:
(a) 91.5-106 parts of combined polyether;
(b) 12.5-19 parts of foaming agent, such as 15 parts and 16 parts
(c) And (b) 160 parts of polyisocyanate 130, such as 145 parts and 150 parts.
Wherein the conjugate polyether comprises: 87-93 parts of polyether composition, 1.5-3.5 parts of surfactant, 1.5-3.5 parts of combined catalyst, 1-3 parts of water and 0.5-3 parts of emulsifier, wherein the emulsifier is the graphite oxide polyether polyol disclosed by the invention;
the polyether composition comprises the following raw materials in parts by weight: 0-50 parts of sucrose and propylene glycol polyether polyol, preferably 25-40 parts; 0-50 parts of sorbitol polyether polyol, preferably 25-40 parts; 0-40 parts of o-toluenediamine polyether polyol, preferably 10-30 parts; 0-40 parts of cane sugar, palm oil and diethylene glycol polyether polyol, preferably 25-35 parts; 0-15 parts of glycerol polyether polyol, preferably 6-13 parts; wherein the dosage of each component is not 0 at the same time;
wherein, preferably, the sucrose and propylene glycol polyether polyol is prepared by the addition reaction of sucrose and propylene glycol as common initiators and propylene oxide, the viscosity is 20000-30000mpa.s, the hydroxyl value is 380-520mgKOH/g, and the functionality is 5.4-6.7;
preferably, the sorbitol polyether polyol is prepared by taking a sorbitol aqueous solution as an initiator and carrying out addition reaction with propylene oxide, and has the viscosity of 22000-32000mpa.s, the hydroxyl value of 400-500mgKOH/g and the functionality of 4.9-6.0;
preferably, the sucrose, palm oil and diethylene glycol polyether polyol are prepared by the addition reaction of sucrose, palm oil and diethylene glycol which are used as common initiators and propylene oxide, and have the viscosity of 3000-7000mpa.s, the hydroxyl value of 350-450mgKOH/g and the functionality of 5.4-6.7.
Preferably, the o-toluenediamine polyether polyol is prepared by taking o-toluenediamine as an initiator, firstly performing addition reaction with ethylene oxide and then performing addition reaction with propylene oxide, wherein the viscosity is 35000-55000mpa.s, the hydroxyl value is 340-460mgKOH/g, and the functionality is 3.4-3.9;
preferably, the glycerol polyether polyol is prepared by the addition reaction of glycerol serving as an initiator and propylene oxide, and has the viscosity of 300-800mpa.s, the hydroxyl value of 500-700mgKOH/g and the functionality of 2.9-3.0;
the surfactant is a silicon surfactant, preferably an organosilicon surfactant, and most preferably one or more of silicone oil L6863, silicone oil MG291, silicone oil RW-E, Y16239 and silicone oil B84813;
preferably, the combined catalyst comprises a foaming catalyst, a gel catalyst and a trimerization catalyst, wherein the mass ratio of the foaming catalyst to the gel catalyst to the trimerization catalyst is preferably 1: 2-8: 1-4; wherein, preferably, the foaming catalyst is one or a mixture of more of pentamethyl diethylenetriamine, tetramethyl hexanediamine and bis-dimethyl aminoethyl ether in any proportion; preferably, the gel catalyst is one or a mixture of more than one of dimethylbenzylamine, dimethylcyclohexylamine and triethylene diamine in any proportion; preferably, the trimerization catalyst is hexahydrotriazine and/or potassium acetate.
The foaming agent is a mixed system of one or more than two of cyclopentane, isopentane, n-pentane, HFC-134a, HFC-245fa, HFC-152a and HFO-1336 mzz.
The polyisocyanate is polymeric MDI, preferably polymeric MDI with NCO content of 30-32%; most preferably one or more of Wanhua PM-200, PM-2010 and PM-400.
The preparation method of the polyurethane rigid foam comprises the following steps:
s1: uniformly mixing the graphite oxide polyether polyol, the combined catalyst and water to obtain a mixture A;
s2: mixing the polyether composition with a surfactant, uniformly mixing the mixture with the mixture A to obtain combined polyether, and cooling to below 15 ℃;
s3: adding a foaming agent into the combined polyether, uniformly mixing, standing and defoaming to obtain a mixture B;
s4: and respectively adding the mixture B and the polyisocyanate into independent charging pots, mixing and foaming by a high-pressure foaming machine, and striking into a fixed mold to prepare the polyurethane rigid foam.
Preferably, in S4, the flow rate of the foaming machine is 400-600g/S, the temperature of the charging bucket is 15-18 ℃, and the pressure is 100-150bar (gauge pressure).
Preferably, the die is a horizontal die or a vertical die, further the horizontal die dimension is 70 x 40 x 10cm and the vertical die dimension is 110 x 30 x 5 cm. The mold temperature is 35-50 ℃, and the overfilling rate is 15-25%.
The technical scheme provided by the invention has the following beneficial effects:
1) the graphite oxide component structure introduced into the graphite oxide polyether polyol provided by the invention contains the nonpolar hydrophobic groups such as six-membered carbon rings and the like, and also contains the polar group hydrophilic groups such as hydroxyl, carboxyl, carbonyl and the like with lone electron pairs, so that the miscibility of the amphiphilic molecules containing polar and nonpolar groups in the system is obviously enhanced, meanwhile, the compatibility of the original system and a foaming agent is also obviously improved, and the mixing easiness and the long-term placing stability of the combined material are effectively improved;
2) the graphite oxide is stably present in a combined material system after being stirred and dispersed at a high speed in a polyether system, dispersed graphite oxide sheets can be used as preferable nucleation points of heterogeneous nucleation, nucleation of a foaming agent can be preferentially attached to the graphite oxide sheets, the nucleation is more uniform, the nucleation time is more concentrated, and cells are finer and more uniform;
3) the matrix of the graphite oxide used in the invention is a regular hexagonal network structure consisting of six-membered carbon rings, and strength support can be provided in the polyurethane rigid foam in uniform dispersion. After hydroxyl and carboxyl on the carbocycle react with the epoxy compound, the crosslinking degree among polyether polyol molecules is increased, so that the test results of the compressive strength, the high and low temperature dimensional stability and the compressive strength of the pressure tank of the foam in multiple directions are improved;
4) the graphite oxide used in the invention belongs to a pollution-free green environment-friendly additive, does not increase the difficulty and cost of environment-friendly treatment, and is an environment-friendly product. And the synthesis process of the graphite oxide is mature, and the industrial popularization is easy. Compared with the classical synthesis process, the synthesis of the polyether composition does not need equipment modification.
Drawings
FIG. 1 is a XPS oxygen peak subdivision plot of the graphite oxide polyether polyol of example 1;
wherein peak I is located at 531.0-531.9eV, and is attributed to C ═ O double bonds such as quinone group and lactone, and peak II is located at 532.3-532.8eV, and is attributed to hydroxyl C-OH bonds; peak III is located at 533.1-533.8eV and is attributed to an ester group and an anhydride C-O bond; peak IV is located at 534.3-535.4eV and is attributed to COOH carboxyl bond; peak V is located at 536-536.5eV and is attributed to O adsorbed in graphite oxide micropores2And H2Oxygen element in O.
FIG. 2 is a XPS carbon peak subdivision plot of the graphite oxide polyether polyol of example 1;
the main peak (peak 1) is located at 284.8eV, and is mainly composed of carbon atoms of a graphite layer structure on the surface of the graphite oxide polyol; the second peak (peak 2) is located at 286.0-286.3eV, and is mainly composed of C-O functional groups on the surface of graphite oxide; the third peak (peak 3) is located between 287.3 and 287.6eV, which is mainly composed of C ═ O groups in the carbonyl and keto groups; the fourth peak (peak 4) is located at 288.8-289.1eV, which is composed mainly of carboxyl groups and O-C ═ O groups in the lactone; the fifth peak (peak 5) mainly refers to CO adsorbed in the micropores of the graphite oxide2。
Detailed Description
The technical solutions of the present invention are further described by the following specific examples, but the scope of the present invention is not limited thereto, and variations or substitutions of the same or similar technical features within the technical scope of the present invention are included in the scope of the present invention.
The sources of the main materials and reagents of the examples of the invention are shown in table 1:
table 1 examples main material and reagent sources
Name of raw materials Manufacturer(s)
Polyether polyol A Wanhua chemical (cigarette holder) container
Polyether polyol B Wanhua chemical (cigarette holder) container
Polyether polyol C Wanhua chemical (cigarette holder) container
Polyether polyol D Wanhua chemical (cigarette holder) container
Polyether polyol E Wanhua chemical (cigarette holder) container
Graphite oxide polyether polyol Self-made
Silicon surfactant MG291 Mai chart
Combined catalyst Air chemical engineering, solvay and Wanshengdai Wei
Cyclopentane (I) Meilong Co Ltd
Polymeric MDI PM-200 Wanhua chemistry
Polyether polyol A: the sucrose and propylene glycol polyether polyol is prepared by the addition reaction of sucrose and propylene glycol which are used as common initiators and propylene oxide, and has the viscosity of 20000-30000mpa.s, the hydroxyl value of 380-520mgKOH/g and the functionality of 5.4-6.7.
Polyether polyol B: the sorbitol polyether polyol is prepared by taking a sorbitol aqueous solution as an initiator and carrying out addition reaction with propylene oxide, and has the viscosity of 22000-32000mpa.s, the hydroxyl value of 400-500mgKOH/g and the functionality of 4.9-6.0.
Polyether polyol C: the sucrose, palm oil and diethylene glycol polyether polyol is prepared by the addition reaction of sucrose, palm oil and diethylene glycol which are used as common initiators and propylene oxide, and has the viscosity of 3000-7000mpa.s, the hydroxyl value of 350-450mgKOH/g and the functionality of 5.4-6.7.
Polyether polyol D: the o-toluenediamine polyether polyol is prepared by taking o-toluenediamine as an initiator, firstly performing addition reaction with ethylene oxide and then reacting with propylene oxide, and has the viscosity of 35000-55000mpa.s, the hydroxyl value of 340-460mgKOH/g and the functionality of 3.4-3.9.
Polyether polyol E: the glycerol polyether polyol is prepared by the addition reaction of glycerol as an initiator and propylene oxide, and has the viscosity of 300-800mpa.s, the hydroxyl value of 500-700mgKOH/g and the functionality of 2.9-3.0.
Combination catalyst: the foaming catalyst is pentamethyldiethylenetriamine, the gel catalyst is dimethylcyclohexylamine, and the trimerization catalyst is hexahydrotriazine; pentamethyldiethylenetriamine: dimethyl cyclohexylamine: hexahydrotriazine (mass ratio) 1:3.5:1.2
Example 1
The preparation method of the graphite oxide polyether polyol comprises the following steps:
1) weighing 10g of graphite oxide, adding 15g of glycerol, stirring and mixing at 70 ℃ at the rotating speed of 1000r/min for 60 minutes, adding 500g of ethylene oxide, adding 3g of potassium hydroxide as a catalyst, adjusting the rotating speed of a stirrer to 1000r/min, heating to 100 ℃, and carrying out addition reaction for 4 hours to obtain a mixed solution.
2) Adding 1500g of propylene oxide into the mixed solution obtained in the step 1), adding 5g of potassium hydroxide as a catalyst, adjusting the rotating speed of a stirrer to 1000r/min, heating to 140 ℃, and carrying out addition reaction for 4 h.
3) And (3) adding 5 times of deionized water into the product obtained in the step 2), centrifuging, layering clearly from top to bottom, and repeatedly adding water into the lower-layer black mixed solution to dilute until the pH value of the lower-layer solution reaches 6.0-7.0. Drying the lower layer liquid at 100 ℃.
The resulting product was analyzed by XPS for carbon and oxygen peaks and further subdivided into different oxygen-containing functional group structures, with XPS spectra as shown in FIGS. 1 and 2.
Example 2
The preparation of the oxidized graphite polyether polyol comprises the following steps:
1) weighing 10g of graphite oxide, adding 20g of propylene glycol, stirring and mixing at 80 ℃ at a rotation speed of 1000r/min for 45 minutes, adding 800g of ethylene oxide, adding 2g of potassium hydroxide serving as a catalyst, adjusting the rotation speed of a stirrer to 1000r/min, heating to 100 ℃, and carrying out addition reaction for 3 hours to obtain a mixed solution.
2) Adding 1000g of propylene oxide into the mixed solution obtained in the step 1), adding 15g of 40% dimethylamine solution as a catalyst, adjusting the rotating speed of a stirrer to 1000r/min, heating to 140 ℃, and carrying out addition reaction for 6 hours.
3) Taking the product obtained in the step 2), adding 5 times of deionized water into the obtained reactant, centrifuging, layering clearly from top to bottom, taking the lower layer black mixed solution, and repeatedly adding water to dilute until the pH value of the lower layer solution reaches 6.0-7.0. Drying the lower layer liquid at 100 ℃.
Example 3
1) Weighing 50g of graphite oxide, adding 400g of diethylene glycol, stirring and mixing at 90 ℃ at the rotating speed of 1000r/min for 40 minutes, adding 600g of ethylene oxide, adding 10g of potassium hydroxide as a catalyst, adjusting the rotating speed of a stirrer to 1000r/min, heating to 140 ℃, and carrying out addition reaction for 2 hours to obtain a mixed solution.
2) Gradually adding 2000g of epoxy butane into the mixed solution obtained in the step 1), adding 20g of potassium hydroxide as a catalyst, adjusting the rotating speed of a stirrer to 1000r/min, heating to 110 ℃, and carrying out addition reaction for 7 hours.
3) Taking the product obtained in the step 2), adding 5 times of deionized water into the obtained reactant, centrifuging, layering clearly from top to bottom, taking the lower layer black mixed solution, and repeatedly adding water to dilute until the pH value of the lower layer solution reaches 6.0-7.0. Drying the lower layer liquid at 100 ℃.
Example 4
A polyurethane rigid foam containing emulsifier graphite oxide polyether polyol comprises the following raw materials in parts by weight:
(a) polyether composition: (polyether composition 91.5 parts, surfactant (MG291)2.5 parts, combined catalyst 3 parts, water 2 parts, graphite oxide polyether polyol (example 1)1 part);
wherein the polyether composition comprises: 36.5 parts of polyether polyol A, 30 parts of polyether polyol C, 20 parts of polyether polyol D and 5 parts of polyether polyol E.
(b) Cyclopentane: 13 parts.
(c) PM-200: 135.6 parts.
The preparation method of the polyurethane hard foam comprises the following steps:
1) uniformly mixing the oxidized graphite polyether polyol, the combined catalyst and water to obtain a mixture A;
2) mixing the polyether composition and the surfactant, adding the mixture A, uniformly mixing to obtain combined polyether, and cooling to 15 ℃;
3) adding cyclopentane into the cooled composite polyether, shaking uniformly, standing for defoaming for 2h, and pumping into a composite material tank by using a pneumatic pump;
4) and (3) mixing and foaming the mixture obtained in the step 3) and PM-200 at high pressure, wherein the material temperature is 17 ℃, the pressure of a gun head is 125bar, the flow of a foaming machine is 600g/s, the mixture is hit into a vertical mold with the temperature of 45 ℃, and the curing time is 240s, so that the polyurethane hard foam is prepared.
Example 5
A polyurethane rigid foam containing emulsifier oxidized graphite polyether polyol comprises the following raw materials:
(a) a conjugate polyether (88 parts of polyether composition, 1.5 parts of surfactant (Y16239), 1.8 parts of conjugate catalyst, 1.5 parts of water, 0.5 part of graphite oxide polyether polyol (example 2)); (b) 16 parts of cyclopentane; (c) 145 parts of polyisocyanate.
Wherein the polyether composition comprises: 38 parts of polyether polyol B, 15 parts of polyether polyol C, 25 parts of polyether polyol D and 10 parts of polyether polyol E.
The polyurethane rigid foam was prepared in the same manner as in example 4.
Example 6
A polyurethane rigid foam containing emulsifier oxidized graphite polyether polyol comprises the following raw materials:
(a) a conjugate polyether (93 parts of polyether composition, 3.5 parts of surfactant (silicone oil B84813), 3.5 parts of conjugate catalyst, 2.8 parts of water, 2.5 parts of graphite oxide polyether polyol (example 3)); (b) 18.5 parts of cyclopentane; (c) 158.2 parts of polyisocyanate.
Wherein the polyether composition comprises: 28 parts of polyether polyol A, 15 parts of polyether polyol B, 20 parts of polyether polyol C, 15 parts of polyether polyol D and 15 parts of polyether polyol E.
The polyurethane rigid foam was prepared in the same manner as in example 4.
Comparative example 1
On the basis of example 4, 1 part of the graphite oxide polyether polyol is removed, and 1 part of polyether polyol E is added, and the conditions are the same as in example 4.
Comparative example 2
Based on example 4, 1 part of graphite oxide polyether polyol was replaced with 1 part of 3M-5056 (product of 3M company, emulsifier), and the other conditions were the same as in example 4.
Table 2: examples 4 to 6 and comparative examples 1 to 2 polyurethane rigid foam raw material compositions (parts by weight) and Performance parameters
Figure BDA0002899912080000121
Note: the foam density, the compressive strength, the thermal conductivity and the dimensional stability are determined according to the national standard:
foam core density test according to standard: GB/T6343-2009;
foam thermal conductivity test according to standard: GB/T10295-;
foam compression strength test according to the standard: GB/T8813-2008;
foam dimensional stability test according to the standard: GB/T8811-.

Claims (10)

1. A graphite oxide polyether polyol has a structural formula as follows:
Figure FDA0002899912070000011
wherein: i. j, m, n, s, t, u, v, x, y are each independently an integer of not less than 0, preferably 1 to 3; r is CnH2n-1N is 0 to 3, preferably n is 1.
2. A method of preparing a graphite oxide polyether polyol, comprising:
(1) taking graphite oxide as a raw material, and mixing the graphite oxide with a solvent;
(2) carrying out addition reaction on graphite oxide and ethylene oxide under the action of a catalyst to obtain a mixed solution containing an intermediate product;
(3) and (3) carrying out addition reaction on the mixed liquid obtained in the step (2) and an epoxide under the action of a catalyst to obtain the graphite oxide polyether polyol.
3. The method of claim 2, wherein in step (1), the solvent is water and/or an alcohol selected from the group consisting of glycerol, ethylene glycol, propylene glycol, diethylene glycol,
the mass ratio of the graphite oxide to the solvent is 1: (0.1-50), preferably 1: (1-20).
4. The method according to claim 2 or 3, wherein in the step (2), the mass ratio of the graphite oxide to the ethylene oxide is 1 (1-80), the reaction temperature is 90-150 ℃, and the reaction time is 2-4 h.
5. The method according to any one of claims 2 to 4, wherein in the step (2), the catalyst is an inorganic base and/or an organic amine, the inorganic base is selected from KOH and NaOH, the organic amine is selected from ethylenediamine and dimethylamine, and the amount of the catalyst is 0.1 to 1.0 wt% of the mass of the reaction system (graphite oxide + ethylene oxide + solvent).
6. The method according to any one of claims 2 to 5, wherein in the step (3), the epoxide comprises ethylene oxide, propylene oxide and butylene oxide, the mass ratio of the graphite oxide to the epoxide is 1 (10-400), the reaction temperature is 90-150 ℃, and the reaction time is 1-8 h.
7. The method according to any one of claims 2 to 6, wherein in the step (3), the catalyst is an inorganic base and/or an organic amine, the inorganic base is selected from KOH and NaOH, the organic amine is selected from ethylenediamine and dimethylamine, and the amount of the catalyst is 0.01 to 1 wt% of the mass of the reaction system (the initially added solvent, graphite oxide, ethylene oxide and epoxide).
8. The rigid polyurethane foam is prepared from raw materials including a combined polyether, a foaming agent and polyisocyanate, and comprises the following components in percentage by weight:
(a) 91.5-106 parts of combined polyether;
(b) 12.5 to 19 portions of foaming agent,
(c) 130-160 parts of polyisocyanate,
wherein the conjugate polyether comprises: 87-93 parts of polyether composition, 1.5-3.5 parts of surfactant, 1.5-3.5 parts of combined catalyst, 1-3 parts of water and 0.5-3 parts of emulsifier, wherein the emulsifier is the graphite oxide polyether polyol in any one of claims 1-7.
9. The rigid polyurethane foam according to claim 8, wherein the polyether composition comprises the following raw materials in parts by weight:
0-50 parts of sucrose and propylene glycol polyether polyol, preferably 25-40 parts; 0-50 parts of sorbitol polyether polyol, preferably 25-40 parts; 0-40 parts of o-tolylenediamine polyether polyol, preferably 10-30 parts; 0-40 parts of cane sugar, palm oil and diethylene glycol polyether polyol, preferably 25-35 parts; 0-15 parts of glycerol polyether polyol, preferably 6-13 parts;
preferably, the sucrose and propylene glycol polyether polyol is prepared by the addition reaction of sucrose and propylene glycol as co-initiators and propylene oxide, and has the viscosity of 20000-30000mpa.s, the hydroxyl value of 380-520mgKOH/g and the functionality of 5.4-6.7;
preferably, the sorbitol polyether polyol is prepared by taking a sorbitol aqueous solution as an initiator and carrying out addition reaction with propylene oxide, and has the viscosity of 22000-32000mpa.s, the hydroxyl value of 400-500mgKOH/g and the functionality of 4.9-6.0;
preferably, the sucrose, palm oil and diethylene glycol polyether polyol is prepared by the addition reaction of sucrose, palm oil and diethylene glycol which are used as common initiators and propylene oxide, and has the viscosity of 3000-7000mpa.s, the hydroxyl value of 350-450mgKOH/g and the functionality of 5.4-6.7.
Preferably, the o-toluenediamine polyether polyol is prepared by taking o-toluenediamine as an initiator, firstly performing addition reaction with ethylene oxide and then performing addition reaction with propylene oxide, wherein the viscosity is 35000-55000mpa.s, the hydroxyl value is 340-460mgKOH/g, and the functionality is 3.4-3.9;
preferably, the glycerol polyether polyol is prepared by the addition reaction of glycerol as an initiator and propylene oxide, and has the viscosity of 300-800mpa.s, the hydroxyl value of 500-700mgKOH/g and the functionality of 2.9-3.0.
10. The rigid polyurethane foam according to claim 8 or 9, wherein the surfactant is a silicone surfactant, preferably a silicone surfactant, most preferably one or more of silicone oil L6863, silicone oil MG291, silicone oil RW-E, Y16239 and silicone oil B84813; and/or:
the foaming agent is one or more of cyclopentane, isopentane, n-pentane, HFC-134a, HFC-245fa, HFC-152a and HFO-1336 mzz; and/or:
the polyisocyanate is polymeric MDI, preferably polymeric MDI with NCO content of 30-32%; and/or:
the combined catalyst comprises a foaming catalyst, a gel catalyst and a trimerization catalyst, wherein the mass ratio of the foaming catalyst to the gel catalyst to the trimerization catalyst is 1: 2-8: 1-4; the foaming catalyst is one or more of pentamethyldiethylenetriamine, tetramethylhexamethylenediamine and bis-dimethylaminoethylether, the gel catalyst is one or more of dimethylbenzylamine, dimethylcyclohexylamine and triethylenediamine, and the trimerization catalyst is hexahydrotriazine and/or potassium acetate.
CN202110053256.9A 2021-01-15 2021-01-15 Graphite oxide polyether polyol, preparation method and application Pending CN114763409A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3546145A (en) * 1966-05-26 1970-12-08 Naphtachimie Sa Polyurethane foams prepared from mixtures of polyether polyols
CN110016132A (en) * 2019-04-30 2019-07-16 万华化学（宁波）容威聚氨酯有限公司 Carbon nano-fiber polyether polyol emulsifier and its preparation method and application
CN110078890A (en) * 2019-04-30 2019-08-02 万华化学（宁波）容威聚氨酯有限公司 A kind of hard polyurethane foam and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3546145A (en) * 1966-05-26 1970-12-08 Naphtachimie Sa Polyurethane foams prepared from mixtures of polyether polyols
CN110016132A (en) * 2019-04-30 2019-07-16 万华化学（宁波）容威聚氨酯有限公司 Carbon nano-fiber polyether polyol emulsifier and its preparation method and application
CN110078890A (en) * 2019-04-30 2019-08-02 万华化学（宁波）容威聚氨酯有限公司 A kind of hard polyurethane foam and preparation method thereof

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