CN101058637A - Method of preparing fatty acid polyether polyhydric alcohol by using recovery grease - Google Patents
Method of preparing fatty acid polyether polyhydric alcohol by using recovery grease Download PDFInfo
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- CN101058637A CN101058637A CNA200710021804XA CN200710021804A CN101058637A CN 101058637 A CN101058637 A CN 101058637A CN A200710021804X A CNA200710021804X A CN A200710021804XA CN 200710021804 A CN200710021804 A CN 200710021804A CN 101058637 A CN101058637 A CN 101058637A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a making method of aliphatic polyether polyol through the recycled fat, which comprises the following steps: blending 50-350wt% recycled fat, 1-10wt% catalyst and 0-200wt% micromolecular alcohol evenly; heating to 130-150 deg. c protected by N2; aerating 10-500wt% epoxyethane and 10-500wt% epoxypropane; circulating 2-8 times for 30-60 min for each time; keeping the reacting pressure at 0. 3-1. 0Mpa; 0. 3-1. 0Mpa after reacting; obtaining the rough product; purifying the rough product to obtain the fine product.
Description
One, technical field
The invention belongs to organic high molecular compound is the preparation of compositions method of base-material, particularly a kind of method that reclaims the oil and fat preparation fatty acid polyether polyhydric alcohol of utilizing.
Two, background technology
Prior art: well-known, the starting material of chemical industry use are at present all taken from petroleum resources, face oil shortage and rise in price, and biomass resource are unique inexhaustible.Lipid acid is exactly more a kind of of occupancy volume in numerous biomass resources.Lipid acid can be made by following raw material: rape seed oil, soybean oil, Oleum Cocois, plam oil, peanut oil, perhaps also can with among them through the discarded recovery grease (to call refiltered oil fat in the following text) after the food-processing.Whole nation waste grease total amount is at 6,000,000 tons/year-7,000,000 tons/year, and price has the big characteristics of low price stock number about 2000 yuan/ton.In numerous synthetic materialss, polyurethane products such as flexible polyurethane, rigid foam are one of the fastest industry of modern plastics industrial development, because of its heat insulating ability is good, electric property, acoustical behavior and chemical resistance are superior, easy construction, thereby the fields such as household electrical appliances, petrochemical industry, building, vehicle, aviation, machinery instrument that are widely used in are as thermal insulation material or structured material.The full water foamed rigid urethane foam of spary coating type is wherein a kind of product of urethane foam.The full water foamed rigid urethane foam stoste of spary coating type is made up of isocyanate component and polyol component.Wherein polyol component is divided into the pure and mild polyether glycol of polyester polyols by compound chemical structure.The CN1621429A[2005.6.1 of Bayer (China) Co., Ltd.], use polyester polyols based on aromatic anhydride pure and mild based on the single ` two of aliphatic series-or the polyethylene oxide/propylene oxide polyether glycol of polyamines, be used for rigid urethane foam.The CN1732196A[2006.2.8 of LG-DOW Universal Tech. Corp.]; The Holland CN1082516C[2002.4.10 of Shell Internationale Research Maatschappij B.V]; ShenYang Polyurethane Chemical Industry Inst CN1009005B[1990.8.1], obtain polyether glycol with aromatic hydrocarbons as reaction substrate.The CN1817930A[2006.8.16 of South China Science ﹠ Engineering University]; CN1189497C[2005.2.16], use polyureas and urea to obtain polyether glycol as reaction substrate.Ai Yu sound CN1075528C[2001.11.28]; The CN1237088C[2006.1.18 of Korea Gas Co.], use Sorbitol Powder, tetramethylolmethane, sucrose, seminose to obtain polyether glycol as reaction substrate.In sum, the polyether glycol of different compound structures is used for rigid urethane foam, can obtain various use properties.At present, the starting material that people use in producing rigid urethane foam are all taken from petroleum resources, face oil shortage and rise in price and environmental issue.
Three, summary of the invention
The present invention is directed to above-mentioned technical problem, a kind of method that reclaims the oil and fat preparation fatty acid polyether polyhydric alcohol of utilizing is provided.
Technical solution of the present invention is:
1. preparation method who prepares fatty acid polyether polyhydric alcohol with refiltered oil.This method is made by following raw material: rape seed oil, soybean oil, Oleum Cocois, plam oil, peanut oil, and perhaps with the discarded recovery grease after the process food-processing among them.
2. fatty acid polyether polyhydric alcohol can be made by following method:
The recovery grease of 50-350 part quality, the catalyzer of 1-10 part quality, the small molecular alcohol of 0-200 part quality are mixed in reactor, and it is in N to make this mixture
2In the atmosphere, make temperature be in 130-150 ℃ again, circulation feeds the oxyethane of 10-500 part quality and the propylene oxide of 10-500 part quality, in the circulation feeding process, after having led to each time, constant reaction 30-60min, and reaction pressure remained on 0.3-1.0MPa, after reaction finished, underpressure distillation obtained the fatty acid polyether polyhydric alcohol raw product.Wherein, small molecular alcohol is one of following alcohol or their optional several mixtures: dibasic alcohol: glycol ether, 1,4-butyleneglycol, triglycol, ethylene glycol, propylene glycol, glycerol, three hydroxyl first class propane, tetramethylolmethane, methyl glucoside, N.F,USP MANNITOL, sorbyl alcohol; Catalyzer is a kind of in KOH, NaOH, potassium methylate, the glycerol potassium.
3. get 100 mass parts fatty acid polyether polyhydric alcohol raw product,, mixed 0.5-1 hour, filter at 80 ℃ with 1-10 mass parts acidic white earth.Remove low fraction at 100-110 ℃/10 * 133.322Pa, obtain corps polyether acid polyvalent alcohol.
4. the application in rigid urethane foam:
(1) preparation of combination polyvalent alcohol:
Get fatty acid polyether polyhydric alcohol 40-100 part, other polyethers (ester) polyvalent alcohol (hydroxyl value 250～450mgKOH/g) 0-60 parts, catalyzer 0.1-5 part, suds-stabilizing agent 0.5-5 part, water 0.01-5 part, wherein catalyzer: be generally composite catalyst; Can be amines catalyst or amines catalyst and tin class mixture of catalysts.Wherein, amines catalyst is selected from: N, N ,-dimethylcyclohexylamine, triethylenediamine, dimethyl benzylamine, trolamine, Yi Bingchunan, quaternary amine or similar catalyzer, can be one of above-mentioned substance, also can two or more mixtures with arbitrary proportion.Tin class catalyzer is selected from: di-n-butyltin dilaurate and similar catalyzer.
(2) preparation of rigid urethane foam:
1. whipping agent: HCFC-141b, pentamethylene, iso-pentane, HFC-245fa, HFC-365mfc etc. choose any one kind of them or multiple mixture with arbitrary proportion.
The mass parts ratio is 100: 0～35 when 2. making up polyvalent alcohol and mixing with whipping agent.
3. isocyanic ester can be selected from: tolylene diisocyanate, Xylene Diisocyanate, polymethine polyphenyl polyisocyanate (PAPI), and preferred PAPI, trade names are: Desmodur N, the 44V20L of Bayer company, 44V10L etc.; Huntsman Corporation's Super ace5005,2085 etc.; The PAP127 of DOW company; The MR200 of BASF AG; The PM2010 of Yantai Wan Hua company etc.
Isocyanic ester and combined polyether (ester) are 1.0～2.5 by the mol ratio of NCO/OH when 4. foaming.
The present invention obtains following technique effect:
1. utilize a kind of biomass resource rape seed oil, soybean oil, Oleum Cocois, plam oil, peanut oil or obtain fatty acid polyether polyhydric alcohol through the process epoxidation reactions such as discarded recovery grease after the food-processing among them.Make the especially discarded recovery grease of biomass grease resource obtain high-quality industrial chemicals by deep process technology of the present invention.
2. the fatty acid polyether polyhydric alcohol that obtains is used for rigid urethane foam, and its performance is compared with other raw materials, as polyether glycol 635.Show that it has good heat-resistant, intensity, resistance to tearing.Because fatty acid polyether polyhydric alcohol except the active group hydroxyl, also has the long chain alkane base in molecule,, in prescription, good mutual solubility is arranged with other reagent so increased oil soluble.
3. biomass resource rape seed oil, soybean oil, Oleum Cocois, plam oil, peanut oil or be renewable resources among them through the discarded recovery grease after the food-processing etc., be not subjected to the influence of oil price.China is especially oil resource big producing country of agricultural, polyether glycol by the refiltered oil preparation uses in rigid urethane foam, with mention in the above patent with based on the polyether glycol of aromatic anhydride with based on the single ` two of aliphatic series-or the polyethylene oxide/propylene oxide polyether glycol of polyamines etc. serve as that the polyether glycol of basis preparation is compared, have good heat retaining property and good temperature resistance energy, good intensity, resistance to tearing.
4. show in the subordinate list, the fatty acid polyether polyhydric alcohol that embodiment 3～18 obtains, in application, show the combination polyvalent alcohol of fatty acids polyether glycol of the present invention and the rigid urethane foam sample that whipping agent (the white material of combination material), isocyanic ester compound (the black material of combination material) prepare, polyester polyol with other compound structures is compared, the porous plastics of fatty acids, reactive behavior, thermotolerance, compressive strength, these technical performance indexs are good.
Four, embodiment
Embodiment 1
A kind of with the preparation method who reclaims the oil and fat preparation fatty acid polyether polyhydric alcohol.This method is made by following raw material: rape seed oil, soybean oil, Oleum Cocois, plam oil, peanut oil, and perhaps with the discarded recovery grease after the process food-processing among them.
The preparation method is as follows:
1. the recovery grease of 50-350 mass parts, the catalyzer of 1-10 mass parts, the small molecular alcohol of 0-200 mass parts are mixed in reactor, the mass fraction of refiltered oil can be chosen for: 60 parts, and 80 parts, 90 parts, 120 parts, 170 parts, 220 parts, 260 parts, 290 parts, 320 parts, 335 parts, the mass fraction of catalyzer can be chosen for: 2 parts, 3 parts, 5 parts, 8 parts, 9 parts, the mass fraction of small molecular alcohol can be chosen for 20 parts, 40 parts, 50 parts, 70 parts, 80 parts, 90 parts, 120 parts, 150 parts, 170 parts, 185 parts, 195 parts, and it is in N to make this mixture
2(can be evacuated down to less than 0.098MPa and use N then in the atmosphere
2Displacement, 3 times repeatedly.), make temperature be in 130-150 ℃ again, for example can be chosen for 135 ℃, 142 ℃, 146 ℃, 148 ℃, circulation feeds the oxyethane of 10-500 mass parts and the propylene oxide of 10-500 mass parts, the mass fraction of oxyethane can be chosen for 50 parts, and 80 parts, 120 parts, 150 parts, 220 parts, 280 parts, 320 parts, 370 parts, 420 parts, 460 parts, 480 parts, in the circulation feeding process, after having led to each time, constant reaction 30-60min, the reaction times can be chosen for, 35 minutes, 40 minutes, 50 minutes, 55 minutes, and reaction pressure remained on 0.3-1.0MPa, for example can be chosen for 0.5MPa, 0.8MPa, 0.9MPa, after reaction finishes, underpressure distillation (for example 100-130 ℃/10mm Hg decompression find time 30-60min) obtains the fatty acid polyether polyhydric alcohol raw product, and the method that circulation feeds can hocket for feeding oxyethane and propylene oxide, cycle index is generally 2-8 time, wherein, small molecular alcohol is one of following alcohol or their optional several mixtures: dibasic alcohol: glycol ether, 1, the 4-butyleneglycol, triglycol, ethylene glycol, propylene glycol, glycerol, three hydroxyl first class propane, tetramethylolmethane, methyl glucoside, N.F,USP MANNITOL, sorbyl alcohol; Catalyzer is a kind of in KOH, NaOH, potassium methylate, the glycerol potassium.
2. the described fatty acid polyether polyhydric alcohol that is used for rigid urethane foam, it is characterized in that described lipid acid is obtained by following raw material: rape seed oil, soybean oil, Oleum Cocois, plam oil, peanut oil, perhaps also can with among them through the discarded recovery grease (to call refiltered oil fat in the following text) after the food-processing.
3. get 100 mass parts fatty acid polyether polyhydric alcohol raw product,, mixed 0.5-1 hour, acidic white earth is removed by filter at 80 ℃ with 1-10 mass parts acidic white earth.Remove at 100-110 ℃/10 * 133.322Pa and to anhydrate and low fraction such as small molecular alcohol, obtain corps polyether acid polyvalent alcohol.
Embodiment 2
The recovery grease of 50-350 mass parts, the catalyzer of 1-10 mass parts, the small molecular alcohol of 0-200 mass parts are mixed in reactor, and the mass fraction of refiltered oil can be chosen for: 60 parts, and 80 parts, 90 parts, 120 parts, 170 parts, 220 parts, 260 parts, 290 parts, 320 parts, 335 parts, the mass fraction of catalyzer can be chosen for: 2 parts, 3 parts, 5 parts, 8 parts, 9 parts, the mass fraction of small molecular alcohol can be chosen for 20 parts, 40 parts, 50 parts, 70 parts, 80 parts, 90 parts, 120 parts, 150 parts, 170 parts, 185 parts, 195 parts, and it is in N to make this mixture
2(can be evacuated down to less than 0.098MPa and use N then in the atmosphere
2Displacement, 3 times repeatedly.), make temperature be in 130-150 ℃ again, for example can be chosen for 135 ℃, 142 ℃, 146 ℃, 148 ℃, circulation feeds the oxyethane of 10-500 mass parts and the propylene oxide of 10-500 mass parts, the mass fraction of oxyethane can be chosen for 50 parts, and 80 parts, 120 parts, 150 parts, 220 parts, 280 parts, 320 parts, 370 parts, 420 parts, 460 parts, 480 parts, in the circulation feeding process, after having led to each time, constant reaction 30-60min, the reaction times can be chosen for, 35 minutes, 40 minutes, 50 minutes, 55 minutes, and reaction pressure remained on 0.3-1.0MPa, for example can be chosen for 0.5MPa, 0.8MPa, 0.9MPa, after reaction finishes, underpressure distillation (for example 100-130 ℃/10mm Hg decompression find time 30-60min) obtains the fatty acid polyether polyhydric alcohol raw product, and the method that circulation feeds can hocket for feeding oxyethane and propylene oxide, cycle index is generally 2-8 time, wherein, small molecular alcohol is one of following alcohol or their optional several mixtures: dibasic alcohol: glycol ether, 1, the 4-butyleneglycol, triglycol, ethylene glycol, propylene glycol, glycerol, three hydroxyl first class propane, tetramethylolmethane, methyl glucoside, N.F,USP MANNITOL, sorbyl alcohol; If mixture, its proportioning can be any proportioning.Catalyzer is a kind of in KOH, NaOH, potassium methylate, the glycerol potassium.Described lipid acid is obtained by following raw material: rape seed oil, soybean oil, Oleum Cocois, plam oil, peanut oil, perhaps also can with among them through the discarded recovery grease (to call refiltered oil fat in the following text) after the food-processing.
Get 100 mass parts fatty acid polyether polyhydric alcohol raw product,, mixed 0.5-1 hour, acidic white earth is removed by filter at 80 ℃ with 1-10 mass parts acidic white earth.Remove at 100-110 ℃/10 * 133.322Pa and to anhydrate and low fraction such as small molecular alcohol, obtain corps polyether acid polyvalent alcohol.
Embodiment 3
The preparation of fatty acid polyether polyhydric alcohol takes by weighing reclaims 50 parts of greases, 1 part of catalyzer KOH, 20 parts of glycol ethers, is added to withstand voltage still.Be evacuated down to less than 0.098MP and use N then
2Displacement, 3 times so repeatedly.Be warmed up to 130 ℃, the equivalent circulation feeds 10 parts of oxyethane, 10 parts of propylene oxide.135 ℃ of temperature of reaction, reaction pressure 0.4MPa reaction.When equivalent circulation feeds oxyethane, propylene oxide, led to epoxide each time after, constant reaction 30min.Lead to the epoxide afterreaction and finished emptying.At 100 ℃/10mm Hg, the 30min that finds time reduces pressure.Remove lower-boiling impurity, obtain the fatty acid polyether polyhydric alcohol raw product.Get 100 mass parts fatty acid polyether polyhydric alcohol raw product,, mixed 0.5 hour, acidic white earth is removed by filter at 80 ℃ with 1 mass parts acidic white earth.Remove at 100-110 ℃/10 * 133.322Pa and to anhydrate and low fraction such as small molecular alcohol, obtain the finished product, sampling analysis: outward appearance, light yellow transparent liquid; Hydroxyl value 240mgKOH/g; Moisture, 0.1%; Viscosity (25 ℃) 980mpa.s.
Embodiment 4
The preparation of fatty acid polyether polyhydric alcohol takes by weighing reclaims 50 parts of greases, 10 parts of catalyzer potassium ethylates, 200 parts of propylene glycol, to withstand voltage still.Be evacuated down to less than 0.098MP and use N then
2Displacement, 3 times repeatedly.Be warmed up to 150 ℃, the equivalent circulation feeds 500 parts of oxyethane, 500 parts of propylene oxide.150 ℃ of temperature of reaction, reaction pressure 1.0MP reaction.When equivalent circulation feeds oxyethane, propylene oxide, led to epoxide each time after, constant reaction 60min.Having led to the epoxide afterreaction finishes.Stopped reaction.Emptying.At 130 ℃/10mm Hg, the 30min that finds time reduces pressure.Obtain the fatty acid polyether polyhydric alcohol raw product.Get 100 mass parts fatty acid polyether polyhydric alcohol raw product,, mixed 0.7 hour, acidic white earth is removed by filter at 80 ℃ with 2 mass parts acidic white earths.Remove at 100-110 ℃/10 * 133.322Pa and to anhydrate and low fraction such as small molecular alcohol, obtain the finished product, sampling analysis: outward appearance, light yellow transparent liquid; Hydroxyl value 250mgKOH/g; Moisture, 0.09%; Viscosity (25 ℃) 1280mpa.s.
Embodiment 5
The preparation of fatty acid polyether polyhydric alcohol takes by weighing reclaims 150 parts of greases, 9 parts of catalyzer potassium methylates, 120 parts of glycerol, to withstand voltage still.Be evacuated down to less than 0.098MP and use N then
2Displacement, 3 times repeatedly.Be warmed up to 140 ℃, the equivalent circulation feeds 200 parts of oxyethane, 200 parts of propylene oxide.130 ℃ of temperature of reaction, reaction pressure 0.6MP reaction.When equivalent circulation feeds oxyethane, propylene oxide, led to epoxide each time after, constant reaction 60min.Having led to the epoxide afterreaction finishes.Stopped reaction.Emptying.At 120 ℃/10mm Hg, the 40min that finds time reduces pressure.Obtain the fatty acid polyether polyhydric alcohol raw product.Get 100 mass parts fatty acid polyether polyhydric alcohol raw product,, mixed 1 hour, acidic white earth is removed by filter at 80 ℃ with 10 mass parts acidic white earths.Remove at 100-110 ℃/10 * 133.322Pa and to anhydrate and low fraction such as small molecular alcohol, obtain the finished product, sampling analysis: outward appearance, light yellow transparent liquid; Hydroxyl value 420mgKOH/g; Moisture, 0.08%; Viscosity (25 ℃) 2500mpa.s.
Embodiment 6
The preparation of fatty acid polyether polyhydric alcohol takes by weighing reclaims 50 parts of greases, 1 part of catalyzer KOH, 20 parts of triglycols, to withstand voltage still.Be evacuated down to less than 0.098MP and use N then
2Displacement, 3 times repeatedly.Be warmed up to 150 ℃, the equivalent circulation feeds 10 parts of oxyethane, 10 parts of propylene oxide.130 ℃ of temperature of reaction, reaction pressure 0.3MP reaction.When equivalent circulation feeds oxyethane, propylene oxide, led to epoxide each time after, constant reaction 30min.Having led to the epoxide afterreaction finishes.Stopped reaction.Emptying.At 100 ℃/10mm Hg, the 30min that finds time reduces pressure.Obtain the fatty acid polyether polyhydric alcohol raw product.Get 100 mass parts fatty acid polyether polyhydric alcohol raw product,, mixed 1 hour, acidic white earth is removed by filter at 85 ℃ with 8 mass parts acidic white earths.Remove at 100-110 ℃/10 * 133.322Pa and to anhydrate and low fraction such as small molecular alcohol, obtain the finished product, sampling analysis: outward appearance, light yellow transparent liquid; Hydroxyl value 406mgKOH/g; Moisture, 0.09%; Viscosity (25 ℃) 1080mpa.s.
Embodiment 7
The preparation of fatty acid polyether polyhydric alcohol takes by weighing reclaims 150 parts of greases, 1 part of catalyzer KOH, 26 parts of sorbyl alcohols, to withstand voltage still.Be evacuated down to less than 0.098MP and use N then
2Displacement, 3 times repeatedly.Be warmed up to 150 ℃, the equivalent circulation feeds 110 parts of oxyethane, 110 parts of propylene oxide.130 ℃ of temperature of reaction, reaction pressure 0.9MP reaction.When equivalent circulation feeds oxyethane, propylene oxide, led to epoxide each time after, constant reaction 30min.Having led to the epoxide afterreaction finishes.Stopped reaction.Emptying.At 100 ℃/10mm Hg, the 30min that finds time reduces pressure.Obtain the fatty acid polyether polyhydric alcohol raw product.Get 100 mass parts fatty acid polyether polyhydric alcohol raw product,, mixed 0.5 hour, acidic white earth is removed by filter at 75 ℃ with 1 mass parts acidic white earth.Remove at 100-110 ℃/10 * 133.322Pa and to anhydrate and low fraction such as small molecular alcohol, obtain the finished product, sampling analysis: outward appearance, light yellow transparent liquid; Hydroxyl value 422mgKOH/g; Moisture, 0.08%; Viscosity (25 ℃) 920mpa.s.
Embodiment 8
The preparation of fatty acid polyether polyhydric alcohol takes by weighing reclaims 350 parts of greases, 6 parts in catalyzer glycerol potassium, 120 parts in three hydroxyl first class propane, to withstand voltage still.Be evacuated down to less than 0.098MP and use N then
2Displacement, 3 times repeatedly.Be warmed up to 140 ℃, the equivalent circulation feeds 410 parts of oxyethane, 410 parts of propylene oxide.140 ℃ of temperature of reaction, reaction pressure 0.8MP reaction.When equivalent circulation feeds oxyethane, propylene oxide, led to epoxide each time after, constant reaction 40min.Having led to the epoxide afterreaction finishes.Stopped reaction.Emptying.At 110 ℃/10mm Hg, the 30min that finds time reduces pressure.Obtain the fatty acid polyether polyhydric alcohol raw product.Get 100 mass parts fatty acid polyether polyhydric alcohol raw product,, mixed 1 hour, acidic white earth is removed by filter at 80 ℃ with 10 mass parts acidic white earths.Remove at 100-110 ℃/10 * 133.322Pa and to anhydrate and low fraction such as small molecular alcohol, obtain the finished product, sampling analysis: outward appearance, light yellow transparent liquid; Hydroxyl value 395mgKOH/g; Moisture, 0.08%; Viscosity (25 ℃) 880mpa.s.
Embodiment 9
The preparation of fatty acid polyether polyhydric alcohol takes by weighing reclaims 350 parts of greases, 1 part of catalyzer KOH, 120 parts in three hydroxyl first class propane, to withstand voltage still.Be evacuated down to less than 0.098MP and use N then
2Displacement, 3 times repeatedly.Be warmed up to 150 ℃, the equivalent circulation feeds 180 parts of oxyethane, 180 parts of propylene oxide.130 ℃ of temperature of reaction, reaction pressure 0.9MP reaction.When equivalent circulation feeds oxyethane, propylene oxide, led to epoxide each time after, constant reaction 30min.Having led to the epoxide afterreaction finishes.Stopped reaction.Emptying.At 110 ℃/10mm Hg, the 30min that finds time reduces pressure.Obtain the fatty acid polyether polyhydric alcohol raw product.Get 100 mass parts fatty acid polyether polyhydric alcohol raw product,, mixed 0.8 hour, acidic white earth is removed by filter at 80 ℃ with 1 mass parts acidic white earth.Remove at 100-110 ℃/10 * 133.322Pa and to anhydrate and low fraction such as small molecular alcohol, obtain the finished product, sampling analysis: outward appearance, light yellow transparent liquid; Hydroxyl value 500mgKOH/g; Moisture, 0.09%; Viscosity (25 ℃) 800mpa.s.
Embodiment 10
The preparation of fatty acid polyether polyhydric alcohol takes by weighing reclaims 1 part of 50 parts of grease, catalyzer KOH, 1, and 20 parts of 4-butyleneglycols are to withstand voltage still.Be evacuated down to less than 0.098MP and use N then
2Displacement, 3 times repeatedly.Be warmed up to 150 ℃, the equivalent circulation feeds 10 parts of oxyethane, 10 parts of propylene oxide.130 ℃ of temperature of reaction, reaction pressure 0.3MP reaction.When equivalent circulation feeds oxyethane, propylene oxide, led to epoxide each time after, constant reaction 30min.Having led to the epoxide afterreaction finishes.Stopped reaction.Emptying.At 100 ℃/10mm Hg, the 30min that finds time reduces pressure.Obtain the fatty acid polyether polyhydric alcohol raw product.Get 100 mass parts fatty acid polyether polyhydric alcohol raw product,, mixed 0.5 hour, acidic white earth is removed by filter at 80 ℃ with 6 mass parts acidic white earths.Remove at 100-110 ℃/10 * 133.322Pa and to anhydrate and low fraction such as small molecular alcohol, obtain the finished product, sampling analysis: outward appearance, light yellow transparent liquid; Hydroxyl value 311mgKOH/g; Moisture, 0.1%; Viscosity (25 ℃) 980mpa.s.
Embodiment 11
The preparation of fatty acid polyether polyhydric alcohol takes by weighing reclaims 3 parts of 450 parts of greases, catalyzer potassium methylate, 1, and 20 parts of 4-butyleneglycols are to withstand voltage still.Be evacuated down to less than 0.098MP and use N then
2Displacement, 3 times repeatedly.Be warmed up to 150 ℃, the equivalent circulation feeds 410 parts of oxyethane, 410 parts of propylene oxide.130 ℃ of temperature of reaction, reaction pressure 1.0MP reaction.When equivalent circulation feeds oxyethane, propylene oxide, led to epoxide each time after, constant reaction 30min.Having led to the epoxide afterreaction finishes.Stopped reaction.Emptying.At 120 ℃/10mm Hg, the 30min that finds time reduces pressure.Obtain the fatty acid polyether polyhydric alcohol raw product.Get 100 mass parts fatty acid polyether polyhydric alcohol raw product,, mixed 0.5 hour, acidic white earth is removed by filter at 80 ℃ with 1 mass parts acidic white earth.Remove at 100-110 ℃/10 * 133.322Pa and to anhydrate and low fraction such as small molecular alcohol, obtain the finished product, sampling analysis: outward appearance, light yellow transparent liquid; Hydroxyl value 420mgKOH/g; Moisture, 0.05%; Viscosity (25 ℃) 1180mpa.s.
Embodiment 12
The preparation of fatty acid polyether polyhydric alcohol takes by weighing reclaims 50 parts of greases, 1 part of catalyzer KOH, 20 parts in N.F,USP MANNITOL, to withstand voltage still.Be evacuated down to less than 0.098MP and use N then
2Displacement, 3 times repeatedly.Be warmed up to 150 ℃, the equivalent circulation feeds 10 parts of oxyethane, 10 parts of propylene oxide.130 ℃ of temperature of reaction, reaction pressure 0.3MP reaction.When equivalent circulation feeds oxyethane, propylene oxide, led to epoxide each time after, constant reaction 30min.Having led to the epoxide afterreaction finishes.Stopped reaction.Emptying.At 100 ℃/10mm Hg, the 30min that finds time reduces pressure.Obtain the fatty acid polyether polyhydric alcohol raw product.Get 100 mass parts fatty acid polyether polyhydric alcohol raw product,, mixed 1 hour, acidic white earth is removed by filter at 80 ℃ with 10 mass parts acidic white earths.Remove at 100-110 ℃/10 * 133.322Pa and to anhydrate and low fraction such as small molecular alcohol, obtain the finished product, sampling analysis: outward appearance, light yellow transparent liquid; Hydroxyl value 311mgKOH/g; Moisture, 0.1%; Viscosity (25 ℃) 980mpa.s.
Embodiment 13
The preparation of fatty acid polyether polyhydric alcohol takes by weighing reclaims 1 part of 150 parts of grease, catalyzer KOH, 1, and 20 parts of 4-butyleneglycols are to withstand voltage still.Be evacuated down to less than 0.098MP and use N then
2Displacement, 3 times repeatedly.Be warmed up to 150 ℃, the equivalent circulation feeds 10 parts of oxyethane, 10 parts of propylene oxide.130 ℃ of temperature of reaction, reaction pressure 0.3MP reaction.When equivalent circulation feeds oxyethane, propylene oxide, led to epoxide each time after, constant reaction 30min.Having led to the epoxide afterreaction finishes.Stopped reaction.Emptying.At 100 ℃/10mm Hg, the 30min that finds time reduces pressure.Obtain the fatty acid polyether polyhydric alcohol raw product.Get 100 mass parts fatty acid polyether polyhydric alcohol raw product,, mixed 0.5 hour, acidic white earth is removed by filter at 80 ℃ with 1 mass parts acidic white earth.Remove at 100-110 ℃/10 * 133.322Pa and to anhydrate and low fraction such as small molecular alcohol, obtain the finished product, sampling analysis: outward appearance, light yellow transparent liquid; Hydroxyl value 410mgKOH/g; Moisture, 0.07%; Viscosity (25 ℃) 900mpa.s.
Embodiment 14
The preparation of fatty acid polyether polyhydric alcohol takes by weighing reclaims 400 parts of greases, 1 part of catalyst n aOH, 60 parts of glycerol, to withstand voltage still.Be evacuated down to less than 0.098MP and use N then
2Displacement, 3 times repeatedly.Be warmed up to 150 ℃, the equivalent circulation feeds 90 parts of oxyethane, 90 parts of propylene oxide.130 ℃ of temperature of reaction, reaction pressure 0.3MP reaction.When equivalent circulation feeds oxyethane, propylene oxide, led to epoxide each time after, constant reaction 30min.Having led to the epoxide afterreaction finishes.Stopped reaction.Emptying.At 120 ℃/10mm Hg, the 30min that finds time reduces pressure.Obtain the fatty acid polyether polyhydric alcohol raw product.Get 100 mass parts fatty acid polyether polyhydric alcohol raw product,, mixed 1 hour, acidic white earth is removed by filter at 80 ℃ with 5 mass parts acidic white earths.Remove at 100-110 ℃/10 * 133.322Pa and to anhydrate and low fraction such as small molecular alcohol, obtain the finished product, sampling analysis: outward appearance, light yellow transparent liquid; Hydroxyl value 380mgKOH/g; Moisture, 0.06%; Viscosity (25 ℃) 1320mpa.s.
Embodiment 15
The preparation of fatty acid polyether polyhydric alcohol takes by weighing reclaims 350 parts of greases, 1 part of catalyzer KOH, 20 parts in N.F,USP MANNITOL, to withstand voltage still.Be evacuated down to less than 0.098MP and use N then
2Displacement, 3 times repeatedly.Be warmed up to 150 ℃, the equivalent circulation feeds 300 parts of oxyethane, 300 parts of propylene oxide.130 ℃ of temperature of reaction, reaction pressure 0.3MP reaction.When equivalent circulation feeds oxyethane, propylene oxide, led to epoxide each time after, constant reaction 30min.Having led to the epoxide afterreaction finishes.Stopped reaction.Emptying.At 120 ℃/10mm Hg, the 30min that finds time reduces pressure.Obtain the fatty acid polyether polyhydric alcohol raw product.Get 100 mass parts fatty acid polyether polyhydric alcohol raw product,, mixed 1 hour, acidic white earth is removed by filter at 80 ℃ with 10 mass parts acidic white earths.Remove at 100-110 ℃/10 * 133.322Pa and to anhydrate and low fraction such as small molecular alcohol, obtain the finished product, sampling analysis: outward appearance, light yellow transparent liquid; Hydroxyl value 290mgKOH/g; Moisture, 0.06%; Viscosity (25 ℃) 800mpa.s.
Embodiment 16
The preparation of fatty acid polyether polyhydric alcohol takes by weighing reclaims 350 parts of greases, 1 part of catalyzer KOH, 20 parts of ethylene glycol, to withstand voltage still.Be evacuated down to less than 0.098MP and use N then
2Displacement, 3 times repeatedly.Be warmed up to 130 ℃, the equivalent circulation feeds 80 parts of oxyethane, 80 parts of propylene oxide.125 ℃ of temperature of reaction, reaction pressure 0.8MP reaction.When equivalent circulation feeds oxyethane, propylene oxide, led to epoxide each time after, constant reaction 30min.Having led to the epoxide afterreaction finishes.Stopped reaction.Emptying.At 120 ℃/10mm Hg, the 30min that finds time reduces pressure.Obtain the fatty acid polyether polyhydric alcohol raw product.Get 100 mass parts fatty acid polyether polyhydric alcohol raw product,, mixed 0.5 hour, acidic white earth is removed by filter at 80 ℃ with 1 mass parts acidic white earth.Remove at 100-110 ℃/10 * 133.322Pa and to anhydrate and low fraction such as small molecular alcohol, obtain the finished product, sampling analysis: outward appearance, light yellow transparent liquid; Hydroxyl value 360mgKOH/g; Moisture, 0.12%; Viscosity (25 ℃) 1950mpa.s.
Embodiment 17
The preparation of fatty acid polyether polyhydric alcohol takes by weighing reclaims 350 parts of greases, 1 part in catalyzer glycerol potassium, 120 parts of glycol ethers, to withstand voltage still.Be evacuated down to less than 0.098MP and use N then
2Displacement, 3 times repeatedly.Be warmed up to 150 ℃, the equivalent circulation feeds 90 parts of oxyethane, 90 parts of propylene oxide.120 ℃ of temperature of reaction, reaction pressure 0.9MP reaction.When equivalent circulation feeds oxyethane, propylene oxide, led to epoxide each time after, constant reaction 30min.Having led to the epoxide afterreaction finishes.Stopped reaction.Emptying.At 120 ℃/10mm Hg, the 30min that finds time reduces pressure.Obtain the fatty acid polyether polyhydric alcohol raw product.Get 100 mass parts fatty acid polyether polyhydric alcohol raw product,, mixed 1 hour, acidic white earth is removed by filter at 80 ℃ with 10 mass parts acidic white earths.Remove at 100-110 ℃/10 * 133.322Pa and to anhydrate and low fraction such as small molecular alcohol, obtain the finished product, sampling analysis: outward appearance, light yellow transparent liquid; Hydroxyl value 300mgKOH/g; Moisture, 0.07%; Viscosity (25 ℃) 900mpa.s.
Embodiment 18
The preparation of fatty acid polyether polyhydric alcohol takes by weighing reclaims 50 parts of greases, 1 part of catalyst n aOH, 20 parts of tetramethylolmethanes, to withstand voltage still.Be evacuated down to less than 0.098MP and use N then
2Displacement, 3 times repeatedly.Be warmed up to 150 ℃, the equivalent circulation feeds 10 parts of oxyethane, 10 parts of propylene oxide.130 ℃ of temperature of reaction, reaction pressure 0.3MP reaction.When equivalent circulation feeds oxyethane, propylene oxide, led to epoxide each time after, constant reaction 50min.Having led to the epoxide afterreaction finishes.Stopped reaction.Emptying.At 100 ℃/10mm Hg, the 60min that finds time reduces pressure.Obtain the fatty acid polyether polyhydric alcohol raw product.Get 100 mass parts fatty acid polyether polyhydric alcohol raw product,, mixed 0.5 hour, acidic white earth is removed by filter at 80 ℃ with 1 mass parts acidic white earth.Remove at 100-110 ℃/10 * 133.322Pa and to anhydrate and low fraction such as small molecular alcohol, obtain the finished product, sampling analysis: outward appearance, light yellow transparent liquid; Hydroxyl value 310mgKOH/g; Moisture, 0.04%; Viscosity (25 ℃) 1580mpa.s.
Embodiment 19
The preparation of fatty acid polyether polyhydric alcohol takes by weighing reclaims 50 parts of greases, 1 part of catalyzer KOH, 120 parts of glycerol, to withstand voltage still.Be evacuated down to less than 0.098MP and use N then
2Displacement, 3 times repeatedly.Be warmed up to 150 ℃, the equivalent circulation feeds 410 parts of oxyethane, 410 parts of propylene oxide.150 ℃ of temperature of reaction, reaction pressure 0.8MP reaction.When equivalent circulation feeds oxyethane, propylene oxide, led to epoxide each time after, constant reaction 40min.Having led to the epoxide afterreaction finishes.Stopped reaction.Emptying.At 110 ℃/10mm Hg, the 40min that finds time reduces pressure.Obtain the fatty acid polyether polyhydric alcohol raw product.Get 100 mass parts fatty acid polyether polyhydric alcohol raw product,, mixed 0.5 hour, acidic white earth is removed by filter at 80 ℃ with 2 mass parts acidic white earths.Remove at 100-110 ℃/10 * 133.322Pa and to anhydrate and low fraction such as small molecular alcohol, obtain the finished product, sampling analysis: outward appearance, light yellow transparent liquid; Hydroxyl value 411mgKOH/g; Moisture, 0.11%; Viscosity (25 ℃) 1990mpa.s.
Embodiment 20
The preparation of fatty acid polyether polyhydric alcohol takes by weighing reclaims 150 parts of greases, 1 part of catalyzer KOH, 200 parts of ethylene glycol, to withstand voltage still.Be evacuated down to less than 0.098MP and use N then
2Displacement, 3 times repeatedly.Be warmed up to 150 ℃, the equivalent circulation feeds 500 parts of oxyethane, 500 parts of propylene oxide.130 ℃ of temperature of reaction, reaction pressure 1.0MP reaction.When equivalent circulation feeds oxyethane, propylene oxide, led to epoxide each time after, constant reaction 30min.Having led to the epoxide afterreaction finishes.Stopped reaction.Emptying.At 100 ℃/10mm Hg, the 30min that finds time reduces pressure.Obtain the fatty acid polyether polyhydric alcohol raw product.Get 100 mass parts fatty acid polyether polyhydric alcohol raw product,, mixed 1 hour, acidic white earth is removed by filter at 80 ℃ with 10 mass parts acidic white earths.In 100-110 ℃/10 * 133.322Pa distillation, remove and anhydrate and low fraction such as small molecular alcohol, obtain the finished product, sampling analysis: outward appearance, light yellow transparent liquid; Hydroxyl value 500mgKOH/g; Moisture, 0.1%; Viscosity (25 ℃) 800mpa.s.
Embodiment 21
Fatty acid polyether polyhydric alcohol 40-100 part, other polyethers (ester) polyvalent alcohol (hydroxyl value 250～450mgKOH/g) 0-60 parts, catalyzer 0.1-5 part, suds-stabilizing agent 0.5-5 part, water 0.01-5 part, wherein catalyzer: be generally composite catalyst are got in the preparation of combination polyvalent alcohol; Can be amines catalyst or amines catalyst and tin class mixture of catalysts.Wherein, amines catalyst is selected from: N, N ,-dimethylcyclohexylamine, triethylenediamine, dimethyl benzylamine, trolamine, Yi Bingchunan, quaternary amine or similar catalyzer, can be one of above-mentioned substance, also can two or more mixtures with arbitrary proportion.Tin class catalyzer is selected from: di-n-butyltin dilaurate and similar catalyzer.
The fatty acid polyether polyhydric alcohol that table 1 embodiment 3～20 obtains is used to make up the prescription (part) of polyvalent alcohol
| Embodiment | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 |
| Fatty acid polyether | 45 | 40 | 35 | 50 | 55 | 60 | 65 | 70 | 75 |
| Polyethers 635 | 50 | 55 | 60 | 45 | 40 | 35 | 30 | 25 | 20 |
| Suds-stabilizing agent | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 |
| Catalyzer | 1.8 | 2.0 | 1.5 | 1.6 | 1.6 | 1.7 | 1.8 | 1.9 | 1.5 |
| Water | 2.0 | 1.5 | 1.0 | 1.0 | 0.9 | 1.1 | 2.6 | 2.1 | 1.7 |
| Whipping agent | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 |
| NCO/OH | 1.05 | 1.10 | 1.14 | 1.02 | 1.08 | 1.10 | 1.07 | 1.08 | 1.08 |
| Embodiment | 12 | 13 | 14 | 15 | 16 | 17 | 18 | 19 | 20 | Reference example |
| Fatty acid polyether | 80 | 85 | 90 | 95 | 58 | 68 | 78 | 88 | 84 | 0 |
| Polyethers 635 | 15 | 10 | 5 | 0 | 37 | 27 | 17 | 7 | 11 | 95 |
| Suds-stabilizing agent | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 |
| Catalyzer | 1.8 | 2.0 | 1.5 | 1.6 | 1.6 | 2.1 | 1.8 | 1.9 | 1.7 | 2.2 |
| Water | 2.0 | 1.5 | 1.0 | 1.0 | 0.9 | 1.1 | 2.6 | 2.1 | 2.0 | 2.2 |
| Whipping agent | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 |
| NCO/OH | 1.15 | 1.20 | 1.30 | 1.22 | 1.18 | 1.10 | 1.27 | 1.08 | 1.14 | 1.08 |
Suds-stabilizing agent: mainly be silicon-oxygen or silicon-charcoal type tensio-active agent, dolantin generation wound company produces suds-stabilizing agent AK8805, AK8815, AK8812, AK8809 etc.; German Sa company: B8460, B8481, B8474, B8471, B8476, B8481 etc.Suds-stabilizing agent can be one of above-mentioned also can be that two or more arbitrary proportion mixes and uses.The prescription that more than provides is the most basic proportioning of the present invention, and wherein representative detailed formulation data sees attached list 1.
Table 2 combination polyvalent alcohol is used for urethane foam formula for a product and plastic prod performance
| Embodiment | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 |
| Combination polyvalent alcohol (part) | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 |
| PAPI (part) | 170 | 175 | 170 | 165 | 160 | 160 | 170 | 160 | 165 |
| Foam density, kg/m 3 | 35.2 | 33.6 | 35.6 | 36.0 | 35.5 | 34.7 | 35.7 | 34.8 | 33.5 |
| Thermal conductivity, W/m.k | 0.020 | 0.019 | 0.018 | 0.019 | 0.019 | 0.019 | 0.019 | 0.017 | 0.018 |
| Dimensional stability (30 ℃, 24h), % | 0.18 | 0.18 | 0.15 | 0.14 | 0.10 | 0.09 | 0.08 | 0.11 | 0.10 |
| Compressive strength KPa | 188 | 180 | 184 | 158 | 167 | 177 | 169 | 184 | 174 |
| Heat decomposition temperature, ℃ | 256 | 255 | 250 | 250 | 260 | 265 | 261 | 260 | 261 |
| Embodiment | 12 | 13 | 14 | 15 | 16 | 17 | 18 | 19 | 20 | Reference example |
| Combination polyvalent alcohol (part) | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 |
| PAPI (part) | 165 | 155 | 155 | 145 | 160 | 160 | 165 | 160 | 170 | 180 |
| Foam density, kg/m 3 | 36.2 | 34.6 | 35.6 | 36.1 | 36.5 | 34.7 | 35.7 | 34.8 | 35.0 | 34.8 |
| Thermal conductivity, W/m.k | 0.021 | 0.019 | 0.018 | 0.019 | 0.021 | 0.019 | 0.019 | 0.021 | 0.017 | 0.018 |
| Dimensional stability (30 ℃, 24h), % | 0.18 | 0.18 | 0.15 | 0.14 | 0.10 | 0.09 | 0.08 | 0.11 | 0.17 | 0.12 |
| Compressive strength KPa | 198 | 185 | 184 | 168 | 177 | 176 | 169 | 178 | 182 | 154 |
| Heat decomposition temperature, ℃ | 265 | 266 | 268 | 269 | 262 | 259 | 262 | 265 | 266 | 235 |
Embodiment 22
The preparation of rigid urethane foam: whipping agent: HCFC-141b, pentamethylene, iso-pentane, HFC-245fa, HFC-365mfc etc. choose any one kind of them or multiple mixture with arbitrary proportion.Weight ratio 100: 0～35 when the combination polyvalent alcohol mixes with whipping agent.Isocyanic ester can be selected from: tolylene diisocyanate, Xylene Diisocyanate, polymethine polyphenyl polyisocyanate (PAPI), and preferred PAPI, trade names are: Desmodur N, the 44V20L of Bayer company, 44V10L etc.; Huntsman Corporation's Super ace5005,2085 etc.; The PAPI27 of DOW company; The MR200 of BASF AG; The PM2010 of Yantai Wan Hua company etc.Isocyanic ester and combined polyether (ester) are 1.0～2.5 by the mol ratio of NCO/OH during foaming.The prescription that more than provides is the most basic proportioning of the present invention, and wherein best representative detailed formulation data sees attached list 1.
Embodiment 23
The preparation of rigid urethane foam: the fatty acid polyether polyhydric alcohol that earlier embodiment 3～20 is obtained is used to make up polyvalent alcohol, by mixing under electronic stirring with whipping agent after the prescription weighing in the table 1 again.Press the NCO/OH value again and calculate, press in the table 2 after the prescription weighing, high-speed stirring 10-30s after isocyanic ester, combination polyvalent alcohol are mixed; Pour in the mould slaking 48h into.The fatty acid polyether polyhydric alcohol that embodiment 3～20 obtains is used for urethane foam product performance analysis in table 2.
Embodiment 24
The fatty acid polyether polyhydric alcohol preparation method:
The first step is used for the fatty acid polyether polyhydric alcohol of rigid urethane foam, and its lipid acid is obtained by following raw material:
Rape seed oil, soybean oil, Oleum Cocois, plam oil, peanut oil, perhaps also can with among them through the discarded recovery grease (to call refiltered oil fat in the following text) after the food-processing.
Second step, the preparation of fatty acid polyether polyhydric alcohol
1. raw material:
The recovery grease that the first step obtains; Small molecular alcohol: can adopt one of following alcohol or their optional several mixtures: dibasic alcohol: glycol ether, 1,4-butyleneglycol, triglycol, ethylene glycol, propylene glycol; Trivalent alcohol: glycerol, three hydroxyl first class propane; Tetravalent alcohol: tetramethylolmethane, methyl glucoside; Hexavalent alcohol: N.F,USP MANNITOL, sorbyl alcohol; Catalyzer: KOH, NaOH, potassium methylate, glycerol potassium; Propylene oxide (PO) (technical grade); Oxyethane (EO) (technical grade).
2. reaction unit: the withstand voltage still of MZS-A type.Specification; 2L.
Operation steps: add and reclaim grease 50-350 part, catalyzer 1-10 part, small molecular alcohol 0-200 part, to withstand voltage still.Be evacuated down to less than 0.098MP and use N then
2Displacement, 3 times repeatedly.Be evacuated down to less than 0.098MP and use N then
2Displacement, 3 times repeatedly.Be warmed up to 130-150 ℃, circulation feeds 10-500 part oxyethane, 10-500 part propylene oxide.Temperature of reaction 130-150 ℃, reaction pressure 0.3-1.0MP, led to epoxide each time after, constant reaction 30-60min, stopped reaction.Emptying.At the 100-130 ℃/10mm Hg decompression 30-60min that finds time.Obtain the fatty acid polyether polyhydric alcohol raw product.3. the fatty acid polyether polyhydric alcohol raw product is refining: get 100 mass parts fatty acid polyether polyhydric alcohol raw product, with 1-10 mass parts acidic white earth, mixed 0.5-1 hour at 80 ℃, acidic white earth is removed by filter.In 100-110 ℃/10 * 133.322Pa distillation, remove and anhydrate and low fraction such as small molecular alcohol, obtain corps polyether acid polyvalent alcohol.
The 3rd step, the application in rigid urethane foam:
(1) preparation of combination polyvalent alcohol:
Fatty acid polyether polyhydric alcohol 40-100 part, other polyethers (ester) polyvalent alcohol (hydroxyl value 250～450mgKOH/g) 0-60 parts, catalyzer 0.1-5 part, suds-stabilizing agent 0.5-5 part, water 0.01-5 part catalyzer: be generally composite catalyst; Can be amines catalyst or amines catalyst and tin class mixture of catalysts.Wherein, amines catalyst is selected from: N, N ,-dimethylcyclohexylamine, triethylenediamine, dimethyl benzylamine, trolamine, Yi Bingchunan, quaternary amine or similar catalyzer, can be one of above-mentioned substance, also can two or more mixtures with arbitrary proportion.Tin class catalyzer is selected from: di-n-butyltin dilaurate and similar catalyzer.
Suds-stabilizing agent: mainly be silicon-oxygen or silicon-charcoal type tensio-active agent, dolantin generation wound company produces suds-stabilizing agent AK8805, AK8815, AK8812, AK8809 etc.; German Sa company: B8460, B8481, B8474, B8471, B8476, B8481 etc.Suds-stabilizing agent can be one of above-mentioned also can be that two or more arbitrary proportion mixes and uses.
(2) preparation of rigid urethane foam:
5. whipping agent: HCFC-141b, pentamethylene, iso-pentane, HFC-245fa, HFC-365mfc etc. choose any one kind of them or multiple mixture with arbitrary proportion.
The mass parts ratio is 100: 0～35 when 6. making up polyvalent alcohol and mixing with whipping agent.
7. isocyanic ester can be selected from: tolylene diisocyanate, Xylene Diisocyanate, polymethine polyphenyl polyisocyanate (PAPI), and preferred PAPI, trade names are: Desmodur N, the 44V20L of Bayer company, 44V10L etc.; Huntsman Corporation's Super ace5005,2085 etc.; The PAPI27 of DOW company; The MR200 of BASF AG; The PM2010 of Yantai Wan Hua company etc.Isocyanic ester and combined polyether (ester) are 1.0～2.5 by the mol ratio of NCO/OH during foaming.
Claims (5)
1. one kind is utilized the method that reclaims the oil and fat preparation fatty acid polyether polyhydric alcohol, it is characterized in that preparation process is: the recovery grease of 50～350 mass parts, the catalyzer of 1～10 mass parts, the small molecular alcohol of 0～200 mass parts are mixed, at N
2Under the atmosphere protection; temperature is heated to 130～150 ℃; circulation feeds the oxyethane of 10～500 mass parts and the propylene oxide of 10～500 mass parts then; cycle index is 2～8 times; afterreaction 30～the 60min that circulates each time, and reaction pressure remained on 0.3～1.0MPa, reaction finishes the back distillation; the distillation residuum be the fatty acid polyether polyhydric alcohol raw product, at last raw product is purified the fatty acid polyether polyhydric alcohol highly finished product.
2. the method for oil and fat preparation fatty acid polyether polyhydric alcohol is reclaimed in utilization as claimed in claim 1, it is characterized in that described method of purification is: get 100 mass parts fatty acid polyether polyhydric alcohol raw product, with 1～10 mass parts acidic white earth, mixed 0.5～1 hour at 75～85 ℃, with acidic white earth remove after filtration clear liquid, in 100～110 ℃/10 * 133.322Pa distillation, the distillation residuum is corps polyether acid polyvalent alcohol with clear liquid.
3. the method for oil and fat preparation fatty acid polyether polyhydric alcohol is reclaimed in utilization as claimed in claim 1, it is characterized in that described recovery grease is rape seed oil, soybean oil, Oleum Cocois, plam oil, peanut oil, or they are through the discarded recovery grease after the food-processing.
4. the method for oil and fat preparation fatty acid polyether polyhydric alcohol is reclaimed in utilization as claimed in claim 1, it is characterized in that described catalyzer is KOH, NaOH, potassium methylate or glycerol potassium.
5. the method for oil and fat preparation fatty acid polyether polyhydric alcohol is reclaimed in utilization as claimed in claim 1, it is characterized in that described small molecular alcohol is a glycol ether, 1, a kind of or any several mixture in 4-butyleneglycol, triglycol, ethylene glycol, propylene glycol, glycerol, three hydroxyl first class propane, tetramethylolmethane, methyl glucoside, N.F,USP MANNITOL or the sorbyl alcohol.
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| CN101955649A (en) * | 2010-09-19 | 2011-01-26 | 江苏强林生物能源有限公司 | Rigid polyurethane foam plastics prepared from epoxy vegetable oil and one-step preparation method |
| CN102336901A (en) * | 2011-08-03 | 2012-02-01 | 句容宁武新材料发展有限公司 | Method for preparing polyurethane polyether polyol by waste oil |
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| CN102585201B (en) * | 2011-12-30 | 2014-04-02 | 高春青 | Method for preparing polyol for hard polyurethane foam by using kitchen waste |
| CN103709393A (en) * | 2013-12-06 | 2014-04-09 | 江苏盈天化学有限公司 | Method for preparing hydrophilic polyether polyol by utilization of recycled alcohols and EO |
| CN106336505A (en) * | 2015-09-25 | 2017-01-18 | 中国石油化工股份有限公司 | Preparation method of polyether polyol |
| CN110885437A (en) * | 2019-11-25 | 2020-03-17 | 滨化集团股份有限公司 | Preparation method of high-functionality hard foam polyether polyol |
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