CN102050945B - Polyether glycol, polyurethane rigid foamed plastic and preparation methods thereof - Google Patents
Polyether glycol, polyurethane rigid foamed plastic and preparation methods thereof Download PDFInfo
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- CN102050945B CN102050945B CN2010105856299A CN201010585629A CN102050945B CN 102050945 B CN102050945 B CN 102050945B CN 2010105856299 A CN2010105856299 A CN 2010105856299A CN 201010585629 A CN201010585629 A CN 201010585629A CN 102050945 B CN102050945 B CN 102050945B
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Abstract
The invention discloses a preparation method of polyether glycol. The method comprises the following step: preparing the polyether glycol from compound initiator, polyether glycol synthetic catalyst and propylene oxide by using a conventional polyether glycol synthesis method, wherein the compound initiator comprises the following components in parts by weight: 0.04-0.08 part of glycerol, 0.2-0.4 part of dihydroxymethylphenol and 0.56-0.72 part of sucrose; and the mass ratio of the propylene oxide to the compound initiator is 1.7-2.3. The invention also discloses polyether glycol prepared by using the method, a method for preparing polyurethane rigid foamed plastic from the polyether glycol, and polyurethane rigid foamed plastic. The polyether glycol disclosed by the invention has the advantages of low viscosity and high functionality, and has favorable processing properties when being used as a raw material. The polyurethane rigid foamed plastic prepared from the polyether glycol has the advantages of excellent high-temperature resistance, high flame resistance and high compression strength.
Description
Technical field
The present invention relates to a kind of polyether glycol and a kind of polyurethane rigid foam plastic, and their preparation method.
Background technology
Polyurethane rigid foam plastic has good physical and mechanical properties, acoustical behavior and chemical resistance, and especially thermal conductivity is low especially, is widely used in various field of thermal insulation such as household electrical appliances, building board, pipeline, exterior wall spraying.After country put into effect 65% building energy conservation policy and Copenhagen meeting, requiring of building energy conservation was increasingly high, and polyurethane rigid foam plastic is as the lagging material of excellence, and the urethane industry welcomes new development opportunity.Yet there are shortcomings such as resistance to elevated temperatures is poor, inflammable in common polyurethane foam, has influence on it in Application for Field such as building, sheet material and pipelines.
Exploitation has high thermal resistance and flame resistant polyurethane rigid foam plastic is one of research direction of present urethane industry.At present, to the research of resistance toheat, mainly concentrate in the industry, like 2010 1 phases of periodical " thermosetting resin " " the synthetic and thermotolerance research of novel Rosinpolyether polylol " with the Gum Rosin modified polyether polylol.Though the Gum Rosin modified polyether polylol can improve the resistance toheat of prepared hard polyurethane foam; But because the viscosity of Rosinpolyether polylol is too high, reach more than the 30000mPas, functionality is lower; Be merely about 3.0; Therefore influence foamy flowing property and later stage slaking performance, make the use characteristics variation of raw material, in sheet material and pipeline formula system, use and still be restricted.Therefore, it is better to need the exploitation performance badly, the high thermal resistance of application preferably and flame resistant polyurethane rigid foam plastic.
Summary of the invention
Technical problem to be solved by this invention is that the existing polyether glycol viscosity that is used for high thermal resistance, flame resistant polyurethane rigid foam plastic is high, functionality is low in order to overcome; Thereby influence the defective of use characteristics; And the polyether glycol that a kind of viscosity is lower, functionality is higher is provided; And by its polyurethane rigid foam plastic that makes, and their preparation method with excellent high thermal resistance, flame resistivity and compressive strength.
The present invention at first relates to a kind of preparation method of polyether glycol, and it comprises the steps: to adopt compound initiator, polyether glycol synthetic catalyst and propylene oxide to prepare polyether glycol by conventional polyether glycol compound method; Described compound initiator is 0.04～0.08 part of glycerine, 0.2～0.4 part of hydroxymethyl-phenol and 0.56～0.72 portion of sucrose, and described part is weight part; The quality ratio of described propylene oxide and compound initiator is 1.7～2.3.
Wherein, Described compound initiator is 0.04 part of glycerine, 0.4 part of hydroxymethyl-phenol and 0.56 portion of sucrose more preferably; Perhaps more preferably 0.08 part of glycerine, 0.2 part of hydroxymethyl-phenol and 0.72 portion of sucrose; Perhaps more preferably 0.08 part of glycerine, 0.2 part of hydroxymethyl-phenol and 0.56 portion of sucrose, perhaps more preferably 0.04 part of glycerine, 0.2 part of hydroxymethyl-phenol and 0.72 portion of sucrose.
Wherein, described polyether glycol synthetic catalyst can be this area synthesizing polyether glycol various catalyzer commonly used, like anionic polymerization catalyst (like KOH, NaOH, potassium alcoholate or sodium alkoxide etc.) or cationic polymerisation catalyst (like BF
3, TiCl
4Or SnCl
4Deng), the catalyzer of using always in the industrial preparation such as preferable use KOH or NaOH is main with KOH again wherein.The consumption of described polyether glycol synthetic catalyst is selected by conventional catalytically effective amount, is generally 0.1%～1% of propylene oxide quality like KOH.
Wherein, described propylene oxide is this area synthesizing polyether glycol monomer commonly used, and preferable specification requirement is: moisture≤0.01%, aldehyde (propionic aldehyde)≤0.01%, colourity (APHA)＜10, purity>=99.5/%; Per-cent is mass percent.
Adopt above-mentioned raw materials, popular response step and condition by this area polyether glycol compound method can make polyether glycol of the present invention.
Selection process is: adopting KOH or NaOH is the polyether glycol synthetic catalyst; Compound initiator and polyether glycol synthetic catalyst are mixed fusing, under the vacuum decompression condition, dewater afterwards, again products therefrom and propylene oxide are carried out polyreaction, get final product.What wherein, the described temperature that mixes was preferable is 80～90 ℃.What described vacuum decompression condition was preferable is lower than 1500Pa for vacuum tightness.What the temperature of described dehydration was preferable is 110～120 ℃, and better is 115 ℃.What the time of described dehydration was preferable is 1～2 hour.Described polyreaction is carried out under rare gas element (like nitrogen) protection by routine, and specifically the operation of logical nitrogen can be after dehydration, carries out nitrogen replacement, and the displacement number of times is preferably 3 times.The feed way of described propylene oxide can be batch charging or continuous charging.When adopting batch charging, what every batch feeding quantity was preferable be 6%～10% of propylene oxide total amount, and every batch reinforced preferable feeds in raw material when following and be advisable to reduce to 0.1Mpa when reaction kettle pressure.What the temperature of described polyreaction was preferable is 80～120 ℃, better for the initial reaction stage temperature is 80～90 ℃, 110～115 ℃ of reaction middle and later periods temperature.What the pressure of described polyreaction was preferable is below the 0.4MPa.The time of described polyreaction preferable for after adding propylene oxide, reacted again 0.5～1.5 hour, better for after adding propylene oxide, pressure reduce to about 0.1MPa stable after, 110～115 ℃ were reacted 1 hour again.After polyreaction finishes, can carry out aftertreatment, be generally again and neutralize, dewater and refinement treatment such as filtration by this area ordinary method.
The invention still further relates to the polyether glycol that makes by aforesaid method.In the preferred embodiments, polyether glycol hydroxyl value of the present invention is 390～460mg KOH/g, and functionality is 4.5～6, and viscosity is 5000～7000mPas; The theoretical value average molecular weight is 580～760.
The invention further relates to a kind of preparation method of polyurethane rigid foam plastic; It comprises the steps: under the effect of polyurethane rigid foam plastic catalyzer, whipping agent and water; Adopt polyether glycol of the present invention and isocyanate compound; Conventional polyurethanes rigid foam preparation method prepares by this area, gets final product.
Wherein, described isocyanic ester can adopt polyurethane rigid foam plastic field various isocyanic ester commonly used, like polymethylene multi-phenenyl isocyanate, and the polymethylene multi-phenenyl isocyanate PM200 of the preferred Yantai Wanhua Polyurethane Co., Ltd of the present invention.The consumption of described isocyanic ester is selected by conventional amount used, and preferable, the quality ratio of isocyanic ester and combined polyether glycol is 1.1～1.25, and better is 1.2.Described combined polyether glycol is all raw materials of other except that isocyanic ester in the raw material.
Wherein, described whipping agent can adopt this area routine hard bubble whipping agent, for example a fluorine ethylene dichloride (commercial goods such as HCFC-141b), 1,1; 1,3,3-3-pentafluorobutane (HFC-365mfc of commercial goods such as Solvay fluorochemical company) or mass ratio be 95: 51,1; 1,3,3-3-pentafluorobutane and 1,1; 1,3, the mixed foaming agent of 3-pentafluoropropane (HFC-245fa of commercial goods such as Honeywell company), the preferred fluorine ethylene dichloride of the present invention.The consumption of described whipping agent can be selected by conventional amount used, and that preferable is the 24-28% of polyether glycol quality, and better is 26%.
Wherein, the consumption of described water is selected by this area conventional amount used, and preferable is 1～3% of polyether glycol quality, and better is 2%.
Wherein, Described polyurethane rigid foam plastic catalyzer can adopt various polyurethane rigid foam plastic catalyzer commonly used in this area; Specifically can be according to the expansion rate of the foaming forming technique of selecting; Take into account the characteristic of polyether glycol of the present invention and the isocyanate compound of being selected for use, select by the conventional knowledge in this area.When adopting the low speed foaming forming technique, the present invention preferably includes five methyl diethylentriamine, dimethylcyclohexylamine and 1,3 especially, the composite catalyst of 5-three (dimethylamino-propyl)-Hexahydrotriazine, and what three's mass ratio was preferable is 0.2: 1: 0.6.Described polyurethane rigid foam plastic catalyst consumption is more than the catalytically effective amount.
As required, in the preparation process, also can add this area various auxiliary reagents commonly used, as in suds-stabilizing agent (the preferred silicone oil L6900 of the present invention), toughener, toughner, mould inhibitor and the anti-aging agent one or more etc.As required, by this area conventional polyurethanes rigid foam preparation method, select existing various hard polyurethane foam foaming forming technique and condition thereof to prepare, like manual foaming, pouring foaming or spray coating foaming etc.The present invention is that example describes with the hand dropping foaming.Behind the foaming, can carry out aftertreatment like slaking, cutting etc. by the conventional post-treating method in this area.
The present invention's one preferred embodiments is: with 100 parts of polyether glycols of the present invention (polyether glycol that preferably adopts aforementioned preferred compound initiator of the present invention to make); With comprise 0.2 part of five methyl diethylentriamine, 1 part of dimethylcyclohexylamine and 0.6 part 1,3, the composite catalyst of 5-three (dimethylamino-propyl)-Hexahydrotriazine; 26 parts of whipping agent one fluorine ethylene dichloride (like HCFC-141b); 2 parts of water and 2 parts of suds-stabilizing agent silicone oil L6900 mix down at 20～25 ℃, afterwards with 158 parts of isocyanic ester PM200 mixings, are poured into mould; Become mould under 38～42 ℃, promptly get the preferred polyurethane rigid foam plastic of the present invention.
The present invention further relates to the polyurethane rigid foam plastic that is made by aforesaid method again.
On the basis that meets this area general knowledge, above-mentioned each optimum condition, but arbitrary combination promptly get each preferred embodiments of the present invention.
Agents useful for same of the present invention and raw material are all commercially available to be got.
Positive progressive effect of the present invention is: polyether glycol viscosity of the present invention is lower, functionality is higher, and is good as the use characteristics of raw material.The polyurethane rigid foam plastic that is made by polyether glycol of the present invention not only has excellent high thermal resistance; Applicable to life-time service under the high temperature; Like fields such as gas transmission, oil pipelines, and also have excellent flame resistivity, avoided adding the negative impact that a large amount of fire retardants bring.In addition, it also has the compressive strength that significantly improves.
Embodiment
Mode through embodiment further specifies the present invention below, but does not therefore limit the present invention among the described scope of embodiments.
The preparation of embodiment 1 polyether glycol
In the polyether reactant still of 15L, add glycerine 25g, hydroxymethyl-phenol 250g, sucrose 350g and Pottasium Hydroxide 5g respectively, after 80 ℃ of fusings, 115 ℃ of vacuum (1500Pa) dehydration 2h makes potassium alkoxide solution.Temperature is reduced to 80 ℃, carries out nitrogen replacement, triplicate.
Afterwards, add propylene oxide 1100g in batches: add the propylene oxide of 80g, open stirring and be warming up to 80 ℃; The propylene oxide (dividing 2 addings, 1 hour time spent) that slowly adds 70g again, 80 ℃ are incubated 1 hour then, and the still internal pressure is reduced to 0.1MPa; Continue to add the propylene oxide of 100g, be warming up to 110 ℃; When treating that the still internal pressure is reduced to 0.1MPa, drop into propylene oxide 100g, along with the carrying out of thermopositive reaction, the temperature in the still can rise gradually; When reaching 120 ℃, the pressure in the still can descend rapidly, at once logical recirculated water cooling; Temperature is reduced to 110 ℃, and pressure is reduced to 0.1MPa, stops logical recirculated water; Continue to add the 100g propylene oxide, repeat above process, finish up to the propylene oxide interpolation.When treating that propylene oxide is added to 800g, speed of response is slower, and temperature of reaction is controlled at 115～120 ℃, with fast reaction speed.Feeding intake finishes, treat pressure reduce to 0.1MPa stable after, 115 ℃ of insulations 1 hour.In the entire reaction course, below the control still internal pressure 0.4MPa.
Aftertreatment: add the phosphatase 11 1g of 100g pure water and 80%, 110～115 ℃ of neutralization reaction half a hour.Afterwards, 110～115 ℃, under the vacuum tightness of 1300Pa, dewatered 2 hours; Charge into nitrogen.Treat that temperature reduces to 80 ℃, use 100 order filtering nets to filter and emit, promptly get polyether glycol of the present invention.
The preparation of embodiment 2 polyether glycols
In the composition of raw materials, the add-on of propylene oxide is outside the 1300g, other raw material types and consumption, and process operation and condition make polyether glycol of the present invention with embodiment 1.
The preparation of embodiment 3 polyether glycols
In the composition of raw materials, glycerine is 50g, and hydroxymethyl-phenol is 125g, and sucrose is 450g, and propylene oxide is 1150g, other raw material types and consumption, and process operation and condition make polyether glycol of the present invention with embodiment 1.
The preparation of embodiment 4 polyether glycols
In the composition of raw materials, propylene oxide is 1400g, other raw material types and consumption, and process operation and condition make polyether glycol of the present invention with embodiment 3.
The preparation of embodiment 5 polyether glycols
In the composition of raw materials, glycerine 59.5g, hydroxymethyl-phenol 148.8g, sucrose 416.7g, propylene oxide are 1400g, other raw material types and consumption, and process operation and condition make polyether glycol of the present invention with embodiment 1.
The preparation of embodiment 6 polyether glycols
In the composition of raw materials, glycerine 26g, hydroxymethyl-phenol 130g, sucrose 469g, propylene oxide are 1150g, other raw material types and consumption, and process operation and condition make polyether glycol of the present invention with embodiment 1.
The composition of raw materials of embodiment 1～6, and gained polyether glycol appraising datum is as shown in table 1.
Polyether glycol viscosity measurement GB/T 12008.8-1992
Polyether glycol hydroxy value measuring method GB/T 12008.3-1989
Polyether glycol composition of raw materials and the appraising datum of table 1 embodiment 1～6
The preparation of embodiment 7 polyurethane rigid foam plastics
1, raw material
Glycerine: technical grade, import (Malaysia).Sucrose: four directions, Xinjiang sugar industry ltd.Propylene oxide: technical grade, the big chemical industry ltd in east, Shandong.PC5 (five methyl diethylentriamine), PC8 (dimethylcyclohexylamine) and PC41 (1,3,5-three (dimethylamino-propyl)-Hexahydrotriazine): technical grade, U.S. aerification chemical product company.L-6900 (silicone oil): technical grade, Mitugao New Material Group.HCFC-141b (a fluorine ethylene dichloride): technical grade, Zhejiang Sanmei Chemical Co., Ltd..PM200 (polyphenyl polymethylene polyisocyanates): technical grade, Yantai Wanhua Polyurethane Co., Ltd.
Polyether glycol 4110: technical grade, Shandong Lanxing Dongda Chemical Co.,Ltd, initiator is sucrose and glycol ether or Ucar 35, hydroxyl value 400-430, viscosity 2000-3500mPas.
2, method and result
Take by weighing the made polyether glycol of polyether glycol 4110 and embodiment 1～4 as a comparison respectively by the prescription shown in the table 2; Mix with silicone oil, water, catalyzer and whipping agent material; 20～25 ℃ of control temperature of charge; By table 2 proportioning this material and polyphenyl polymethylene polyisocyanates PM200 are poured in the beaker of 500ml afterwards, agitator speed transfers to 3500 rev/mins, stirs fast 6～8 seconds; The raw material that stirs is poured into (40 ± 1 ℃ of control die temperatures) in the square dies of 300*300*100mm; Die sinking after 10 minutes promptly obtains polyurethane rigid foam plastic.
After the normal temperature slaking 24 as a child, use foam cutting machine, cut foam and get core, detect moulded foam density; Cut the core foam, three directions are respectively got 3 (specification 50*50*50mm) and are averaged, and detect foam compression intensity, average; Cut core foam (specification 100*100*25), detect the high low temperature dimensional stability of foamy.Composition of raw materials and performance test data are as shown in table 2.
Porous plastics and rubber apparent (volume) density inspect method GB/T 6343-1995
Rigid foam compression performance measuring method GB/T 8813-2008
Rigid foam dimensional stability testing method GB/T 8811-2008
Plastics combustionproperty testing method GB/T 2406-1993
Table 2 polyurethane rigid foam plastic composition of raw materials and performance test data (massfraction)
Visible by table 2, polyether glycol of the present invention, conventional sucrose system polyether glycol (like polyether glycol 4110) all is being significantly improved aspect high temperature resistant, dimensional stability and the flame resistivity.
Claims (14)
1. the preparation method of a polyether glycol is characterized in that it comprises the steps: to adopt compound initiator, polyether glycol synthetic catalyst and propylene oxide to prepare polyether glycol by conventional polyether glycol compound method; Described compound initiator is 0.04～0.08 part of glycerine, 0.2～0.4 part of hydroxymethyl-phenol and 0.56～0.72 portion of sucrose, and described part is weight part; The quality ratio of described propylene oxide and compound initiator is 1.7～2.3.
2. the method for claim 1; It is characterized in that: described compound initiator is 0.04 part of glycerine, 0.4 part of hydroxymethyl-phenol and 0.56 portion of sucrose; Perhaps be 0.08 part of glycerine, 0.2 part of hydroxymethyl-phenol and 0.72 portion of sucrose; Perhaps being 0.08 part of glycerine, 0.2 part of hydroxymethyl-phenol and 0.56 portion of sucrose, perhaps is 0.04 part of glycerine, 0.2 part of hydroxymethyl-phenol and 0.72 portion of sucrose; Described part is weight part.
3. the method for claim 1, it is characterized in that: described polyether glycol synthetic catalyst is KOH; The consumption of described polyether glycol synthetic catalyst is 0.1%～1% of a propylene oxide quality.
4. method as claimed in claim 2 is characterized in that: described polyether glycol synthetic catalyst is KOH; The consumption of described polyether glycol synthetic catalyst is 0.1%～1% of a propylene oxide quality.
5. like each described method of claim 1～4; It is characterized in that: described method is undertaken by following operation: compound initiator and polyether glycol synthetic catalyst are mixed fusing; Afterwards under the vacuum decompression condition; Dewater, again products therefrom and propylene oxide are carried out polyreaction, get final product.
6. method as claimed in claim 5 is characterized in that:
The described temperature that mixes is 80～90 ℃; Described vacuum decompression condition is that vacuum tightness is lower than 1500Pa; The temperature of described dehydration is 110～120 ℃; The time of described dehydration is 1～2 hour; Described polyreaction is carried out under protection of inert gas;
The feed way of described propylene oxide is batch charging or continuous charging; When adopting batch charging, every batch feeding quantity is 6%～10% of a propylene oxide total amount, and every batch reinforced feeds in raw material when following to reduce to 0.1MPa when reaction kettle pressure;
The temperature of described polyreaction is 80～120 ℃; The pressure of described polyreaction is below the 0.4MPa; The time of described polyreaction reacted 0.5～1.5 hour for after adding propylene oxide again;
And/or, after described polyreaction finishes, neutralize again, dehydration and filtering refinement treatment.
7. method as claimed in claim 6 is characterized in that: the temperature of said polyreaction is: the initial reaction stage temperature is 80～90 ℃, 110～115 ℃ of reaction middle and later periods temperature; The time of described polyreaction is for after adding propylene oxide, pressure reduce to 0.1MPa stable after, 110～115 ℃ were reacted 1 hour again.
8. the polyether glycol that makes like each described method of claim 1～7.
9. polyether glycol as claimed in claim 8 is characterized in that: the hydroxyl value of described polyether glycol is 390～460mg KOH/g, and functionality is 4.5～6, and viscosity is 5000～7000mPas.
10. the preparation method of a polyurethane rigid foam plastic; It is characterized in that it comprises the steps: under the effect of polyurethane rigid foam plastic catalyzer, whipping agent and water; Adopt like claim 8 or 9 described polyether glycol and isocyanate compounds; Conventional polyurethanes rigid foam preparation method prepares by this area, gets final product.
11. method as claimed in claim 10 is characterized in that:
Described isocyanic ester is a polymethylene multi-phenenyl isocyanate;
And/or described whipping agent is a fluorine ethylene dichloride, 1,1,1,3,3-3-pentafluorobutane or mass ratio be 95: 51,1,1,3,3-3-pentafluorobutane and 1,1,1,3, the mixed foaming agent of 3-pentafluoropropane;
And/or the consumption of described water is 1～3% of a polyether glycol quality;
And/or described polyurethane rigid foam plastic catalyzer is for comprising five methyl diethylentriamine, dimethylcyclohexylamine and 1,3, the composite catalyst of 5-three (dimethylamino-propyl)-Hexahydrotriazine;
And/or, in the process of described preparation, also add in suds-stabilizing agent, toughener, toughner, mould inhibitor and the anti-aging agent one or more.
12. method as claimed in claim 11 is characterized in that: the quality ratio of described isocyanic ester and combined polyether glycol is 1.1～1.25; Described combined polyether glycol is all raw materials of other except that isocyanic ester in the raw material; The consumption of described whipping agent is 24～28% of a polyether glycol quality.
13. like claim 11 or 12 described methods, it is characterized in that: described method is: with 100 parts like claim 8 or 9 described polyether glycols, and comprise 0.2 part of five methyl diethylentriamine, 1 part of dimethylcyclohexylamine and 0.6 part 1; 3; The composite catalyst of 5-three (dimethylamino-propyl)-Hexahydrotriazine, 26 parts of whipping agent one fluorine ethylene dichloride, 2 parts of water and 2 parts of suds-stabilizing agent silicone oil L6900 mix down at 20～25 ℃; Afterwards with 158 parts of isocyanic ester PM200 mixings; Be poured into mould, become mould under 38～42 ℃, get final product.
14. the polyurethane rigid foam plastic that makes like each described method of claim 10～13.
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| CN109535387B (en) * | 2018-10-30 | 2022-07-19 | 中国科学院上海有机化学研究所 | Method for preparing polyurethane foam plastic from TGIC (triglycidyl isocyanurate) by-product |
| CN110117358B (en) * | 2019-05-17 | 2021-10-22 | 万华化学集团股份有限公司 | High-functionality polyether polyol, preparation method and application thereof |
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| CN111518251A (en) * | 2020-04-08 | 2020-08-11 | 上海抚佳精细化工有限公司 | Polyurethane rigid foam and preparation method thereof |
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| CN116218607A (en) * | 2022-12-23 | 2023-06-06 | 中国林业科学研究院林产化学工业研究所 | Plant oil-based polyphenol and method for preparing recyclable polyurethane foam by using plant oil-based polyphenol |
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