CN104311816A - Method for preparing polyether glycol with rape stalks as raw materials - Google Patents
Method for preparing polyether glycol with rape stalks as raw materials Download PDFInfo
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Abstract
The invention discloses a method for preparing polyether glycol with rape stalks as raw materials. The method comprises the following steps: firstly, crushing and baking rape stalks to obtain stalk powder; adding a liquefying agent and a catalyst into a container in sequence according to a mass ratio of 100:(1-5); heating the liquefying agent and the catalyst to 100-150 DEG C while stirring the liquefying agent and the catalyst so as to obtain a mixed solution; adding the stalk powder to the mixed solution according to the fact that the mass ratio of the liquefying agent to the stalk powder is (4-8):1; continuing to heat obtained mixture to 120-170 DEG C, reacting for 60-180 min; naturally cooling to the room temperature; adjusting the pH value of a reaction liquid to 6-7; finally, carrying out filtering and reduced pressure distillation, so as to obtain the polyether glycol with the rape stalks as the raw materials. The polyether glycol with the rape stalks as the raw materials has infrared characteristic absorption peaks at two wave numbers of 1108-1112 cm<-1> and 3420-3440 cm<-1>, the hydroxyl value of the polyether glycol with the rape stalks as the raw material is 150-480 mg KOH/g, and the viscosity of the polyether glycol with the rape stalks as the raw material is 400-4500 mPa.s/25 DEG C.
Description
Technical field
The present invention relates to a kind of take rape stalk as the preparation method of the polyether glycol of raw material, belongs to polymer chemistry research field.
Background technology
Polyether glycol is one of most important raw material producing polyurethane material, its principal item has three classes: a kind of be with polyvalent alcohol or organic amine for initiator is by the polymkeric substance formed with propylene oxide or open-loop polymerizing ethylene oxide, be called polyether glycol (referred to as PPG); Another kind of modify and graft polyether glycol is based on PPG, then obtain through bulk polymerization in polyvalent alcohol with vinyl monomer, is called polymer polyatomic alcohol (referred to as POP), often and PPG with the use of; The third is by the polyvalent alcohol of tetrahydrofuran ring opening polymerization, this polyvalent alcohol generally by propylene oxide, oxyethane, propylene glycol, glycerol, sucrose and Sorbitol Powder and so on as initiator.Above three kinds of polyether glycols are all the derived product of petrochemical complex.
As everyone knows, fossil resources is Nonrenewable resources, and its quantity is day by day exhausted and hold at high price, and this not only greatly limits the sound development of polyurethane material, also because being difficult to the problem of environmental pollution unavoidably brought in nature degraded.
Along with the enhancing of social development and scientific-technical progress and people's environmental protection consciousness, it take biomass resource as the research that polyether glycol prepared by raw material that some research workers start to try to explore.
The research report of more existing employings as Material synthesis polyether glycol based on soybean oil, vegetable seed wet goods vegetables oil [repaiies beautiful English at present, Lu Bin, Luo Zhongyu, the preparation of soybean oil polyol and the application in hard polyurethane foam thereof, application chemical industry, 2008,37 (4): 416-418; Wen Chunjun, the biopolyol technique utilizing rapeseed oil to prepare and the application in polyurethane foam, Institutes Of Technology Of Nanjing's master thesis, 2011], can alleviating energy crisis problem to a certain extent.
As everyone knows, one of modal agriculture and forestry organic waste material of rape stalk system.Under normal circumstances, most of rape stalk is directly burned on the spot, generates a large amount of smog in combustion and forms haze, not only serious environment pollution, also causes a lot of traffic accident in the whole nation manyly.In addition, also have small part rape stalk to be used to prepare biofuel, but its added value produced is extremely low, country must gives special subsides and funds support.As can be seen here, existing rape stalk recovery and reuse technology added value is low, causes a large amount of wastes of resource.
From molecular composition, the main chemical compositions of rape stalk is Mierocrystalline cellulose (content 25% ~ 30%), hemicellulose (content 15% ~ 20%) and xylogen (content 20% ~ 30%), three's common feature is rich in hydroxyl in molecular structure, and hydroxyl is then the Basal activity group needed for polyether glycol preparation.
Because the method for above-mentioned Material synthesis polyether glycol based on soybean oil, vegetable seed wet goods vegetables oil exists complicated operation, needs to carry out the technical problems such as modification, side reaction be many to raw material, the present invention propose to solve this technical problem just a kind of take rape stalk as the preparation method of the polyether glycol of raw material, have not yet to see the research report about utilizing rape stalk to prepare biomass polyether glycol.Thus be the preparation method of the polyether glycol of raw material with rape stalk in the urgent need to development.
Summary of the invention
It take rape stalk as the preparation method of the polyether glycol of raw material that the object of the invention is to provide a kind of, this preparation method owing to taking rape stalk as raw material, therefore have technique simple, without the need to carrying out modification, operational safety, environmental protection, the advantage such as with low cost to raw material.Further, owing to taking rape stalk as raw material, thus solution rape stalk burns the Heavy environmental pollution problem brought, also overcome the technical barrier that rape stalk recycling added value of product is low simultaneously, and then provide one to be turned waste into wealth by discarded rape stalk, be prepared into the polyether glycol of high added value.
know-why of the present invention
Rape stalk is a kind of Biological resources of preciousness.From molecular composition, the main chemical compositions of rape stalk is Mierocrystalline cellulose (content 25% ~ 30%), hemicellulose (content 15% ~ 20%) and xylogen (content 20% ~ 30%), and three's common feature is rich in hydroxyl in molecular structure.Indicate in theory, it can introduce high reactivity reactive group after liquefaction activation treatment on its molecular structure, and then prepares biomass polyether glycol.
technical scheme of the present invention
Take rape stalk as a preparation method for the polyether glycol of raw material, specifically comprise the steps:
(1), by rape stalk be crushed to 30 ~ 120 orders, and toast 1 ~ 3 h at temperature 100 ~ 120 DEG C, obtain straw powder;
(2), according to the mass ratio of 100:1 ~ 5, liquefying agent and catalyzer are joined successively in container, warming while stirring to 100 ~ 150 DEG C, obtain mixed solution;
Described liquefying agent be glycerol, NSC 11801, propylene carbonate, butylene, ethylene glycol and molecular weight 200 ~ 1000 g/mol polyoxyethylene glycol in one or more mixture, preferred molecular weight be glycerol and molecular weight 400 g/mol polyoxyethylene glycol in mass ratio 3:1 ~ 9 form mixture;
Described catalyzer is sulfuric acid, hydrochloric acid, phosphoric acid or oxalic acid, preferably sulfuric acid;
(3), be 4 ~ 8:1 according to liquefying agent and straw powder mass ratio, step (1) gained straw powder is joined in step (2) gained mixed solution, continues to be warming up to 120 ~ 170 DEG C of reaction 60 ~ 180 min, be more naturally down to room temperature, obtain reaction solution;
The consumption of straw powder, calculates in mass ratio, straw powder: the liquefying agent in step (2) gained mixed solution is 1:4-8;
(4), be 6 ~ 7 with the pH of rapid (3) the gained reaction solution of pH adjusting agent pacing, carry out natural filtration subsequently, gained filtrate is underpressure distillation 2 h under vacuum tightness-0.5 ~-0.1 MPa, and it is the polyether glycol of raw material that gained viscous liquid is with rape stalk;
Described pH adjusting agent is potassium hydroxide, sodium hydroxide, calcium hydroxide, magnesium oxide, sodium carbonate, sodium bicarbonate, Sodium phosphate dibasic or ammoniacal liquor.
The polyether glycol of above-mentioned preparation method's gained, it is at 1108 ~ 1112 cm
-1, 3425 ~ 3440 cm
-1two wave number places have the infrared signature absorption peak of polyether glycol, and its hydroxyl value is 150.6 ~ 410 mgKOH/g, viscosity is 1583 ~ 3500 mPas/25 DEG C, therefore can be used to manufacture polyurethane rigid foam material, Polyurethane wood substitution, polyurethane-base composite wooden material etc.
Beneficial effect of the present invention
Of the present invention a kind of take rape stalk as the preparation method of the polyether glycol of raw material, due to be with agriculture and forestry organic waste material and rape stalk for raw material, utilize the hydroxyl on its molecular structure to obtain polyether glycol after liquefaction processing.The present invention is without the need to using expensive traditional petrochemical material, and greatly reduce the production cost of polyether glycol, the production for low cost polyether glycol provides a kind of brand-new technological approaches.
Further, conventional petroleum based polyether polyol is produced and must be carried out in high-temperature high-pressure reaction kettle, can produce a large amount of waste liquids simultaneously.And rape stalk only under middle normal temperature and pressure, need can be converted into polyether glycol by the present invention, and only produce water vapor in process of production.Thus have that mild condition, technique are simple, operational safety, environmental protection, feature with low cost.
Further, the polyether glycol of gained of the present invention, not only has the physicochemical property suitable with conventional petroleum based polyether polyol (hydroxyl value be 150 ~ 480 mgKOH/g, viscosity be 400 ~ 4500 mPas/25 DEG C), also has biodegradability properties.
Further, of the present invention take rape stalk as the preparation method of the polyether glycol of raw material, is turned waste into wealth by rape stalk, fundamentally can solve a recovery and reuse technology difficult problem for discarded rape stalk in prior art.
Accompanying drawing explanation
The infrared spectrogram of the polyether glycol of Fig. 1, embodiment 1 gained.
Embodiment
Also by reference to the accompanying drawings the present invention is described in further detail below by embodiment, but do not limit the present invention.
Liquefying agent NSC 11801, poly(oxyethylene glycol) 400, glycerol, ethylene glycol that the present invention is used, catalyst sulfuric acid, hydrochloric acid, phosphoric acid, and pH adjusting agent potassium hydroxide, sodium hydroxide, calcium hydroxide is all purchased from Shanghai traditional Chinese medicines group.
embodiment 1
Take rape stalk as a preparation method for the polyether glycol of raw material, specifically comprise the steps:
(1), by rape stalk be crushed to 30 orders, and toast 1h at temperature 120 DEG C, obtain straw powder;
(2), according to liquefying agent: the mass ratio of catalyzer is the ratio of 100:5, liquefying agent and catalyzer are joined successively and be equipped with in four neck shake flask volume of mechanical stirrer, prolong and thermometer, warming while stirring to 100 DEG C, obtains mixed solution;
Described liquefying agent is the polyoxyethylene glycol of glycerol and molecular weight 400 g/mol is mixture that the ratio of 3:9 forms in mass ratio;
Described catalyzer is sulfuric acid;
(3), by step (1) gained straw powder join in step (2) gained mixed solution, continue to be warming up to 120 DEG C of reaction 120 min, be more naturally down to room temperature, obtain reaction solution;
The consumption of above-mentioned straw powder, calculates in mass ratio, straw powder: the liquefying agent in step (2) gained mixed solution is 1:8;
(4), be 7 with the pH of rapid (3) the gained reaction solution of pH adjusting agent pacing, carry out natural filtration subsequently, gained filtrate is underpressure distillation 2h under vacuum tightness-0.1 MPa, and it is the polyether glycol of raw material that gained viscous liquid is with rape stalk;
Described pH adjusting agent is potassium hydroxide.
The polyether glycol of above-mentioned gained, through NEXUS870 type fourier transform infrared spectrometry (Nicolet company of the U.S.) scanning, the infrared spectrogram of gained as shown in Figure 1.As can be seen from Figure 1, at 1110 cm
-1, 3425 cm
-1two wave number places all have the infrared signature absorption peak of polyether glycol.
Adopt Tetra hydro Phthalic anhydride pyridine method (GB 12008.3-89), measuring its hydroxyl value is 160 mgKOH/g.
Adopt NDJ-8S automatic digital display viscosity apparatus (T=25 DEG C), measuring its viscosity is 1583 mPas/25 DEG C.
embodiment 2
Take rape stalk as a preparation method for the polyether glycol of raw material, specifically comprise the steps:
(1), by rape stalk be crushed to 30 orders, and toast 1 h at temperature 120 DEG C, obtain straw powder;
(2), according to liquefying agent: the mass ratio of catalyzer is the ratio of 100:3, liquefying agent and catalyzer are joined successively and be equipped with in four neck shake flask volume of mechanical stirrer, prolong and thermometer, warming while stirring to 140 DEG C, obtains mixed solution;
Described liquefying agent is the polyoxyethylene glycol of glycerol and molecular weight 400 g/mol is mixture that the ratio of 3:3 forms in mass ratio;
Described catalyzer is sulfuric acid;
(3), by step (1) gained straw powder join in step (2) gained mixed solution, after continuing to be warming up to 160 DEG C of reaction 140 min, be more naturally down to room temperature, obtain reaction solution;
The consumption of above-mentioned straw powder, calculates in mass ratio, straw powder: the liquefying agent in step (2) gained mixed solution is 1:6;
(4), be 7 with the pH of rapid (3) the gained reaction solution of pH adjusting agent pacing, carry out natural filtration subsequently, gained filtrate controls underpressure distillation 2 h under vacuum tightness-0.1 MPa, and it is the polyether glycol of raw material that gained viscous liquid is with rape stalk;
Described pH adjusting agent is sodium hydroxide.
The polyether glycol of above-mentioned gained, at 1109 cm
-1, 3440 cm
-1two wave number places all have the infrared signature absorption peak of polyether glycol.
Adopt Tetra hydro Phthalic anhydride pyridine method (GB 12008.3-89), measuring its hydroxyl value is 150.6 mgKOH/g.
Adopt NDJ-8S automatic digital display viscosity apparatus (T=25 DEG C), measuring its viscosity is 1785 mPas/25 DEG C.
embodiment 3
Take rape stalk as a preparation method for the polyether glycol of raw material, specifically comprise the steps:
(1), by rape stalk be crushed to 30 orders, and toast 1 h at temperature 120 DEG C, obtain straw powder;
(2), according to liquefying agent: the mass ratio of catalyzer is the ratio of 100:1, liquefying agent and catalyzer are joined successively and be equipped with in four neck shake flask volume of mechanical stirrer, prolong and thermometer, warming while stirring to 150 DEG C, obtains mixed solution;
Described liquefying agent is the polyoxyethylene glycol of glycerol and molecular weight 400 g/mol is mixture that the ratio of 3:1 forms in mass ratio;
Described catalyzer is sulfuric acid;
(3), by step (1) gained straw powder join in step (2) gained mixed solution, continue to be warming up to 170 DEG C of reaction 60 min, be more naturally down to room temperature, obtain reaction solution;
The consumption of straw powder, calculates in mass ratio, straw powder: the liquefying agent in step (2) gained mixed solution is 1:4;
(4), be 7 with the pH of rapid (3) the gained reaction solution of pH adjusting agent pacing, carry out natural filtration subsequently, gained filtrate is underpressure distillation 2h under vacuum tightness-0.1 MPa, and it is the polyether glycol of raw material that gained viscous liquid is with rape stalk;
Described pH adjusting agent is potassium hydroxide.
The polyether glycol of above-mentioned gained, it is at 1110cm
-1, 3435cm
-1two wave number places have the infrared signature absorption peak of polyether glycol.
Adopt Tetra hydro Phthalic anhydride pyridine method (GB 12008.3-89), measuring its hydroxyl value is 200.7mgKOH/g.
Adopt NDJ-8S automatic digital display viscosity apparatus (T=25 DEG C), measuring its viscosity is 1973mPas/25 DEG C.
embodiment 4
Take rape stalk as a preparation method for the polyether glycol of raw material, specifically comprise the steps:
(1), by rape stalk be crushed to 60 orders, and toast 2 h at temperature 110 DEG C, obtain straw powder;
(2), according to liquefying agent: the mass ratio of catalyzer is the ratio of 100:4, liquefying agent and catalyzer are joined successively and be equipped with in four neck shake flask volume of mechanical stirrer, prolong and thermometer, warming while stirring to 100 DEG C, obtains mixed solution;
Described liquefying agent is NSC 11801;
Described catalyzer is phosphoric acid;
(3), be 8:1 according to liquefying agent and straw powder mass ratio, step (1) gained straw powder is joined in step (2) gained mixed solution, continues to be warming up to 120 DEG C of reaction 120 min, be more naturally down to room temperature, obtain reaction solution;
The consumption of above-mentioned straw powder, calculates in mass ratio, straw powder: the liquefying agent in step (2) gained mixed solution is 1:8;
(4), be 7 with the pH of pH adjusting agent regulating step (3) gained reaction solution, carry out natural filtration subsequently, gained filtrate is underpressure distillation 2 h under vacuum tightness-0.1 MPa, and it is the polyether glycol of raw material that gained viscous liquid is with rape stalk;
Described pH adjusting agent is calcium hydroxide.
The polyether glycol of above-mentioned gained, it is at 1112 cm
-1, 3430 cm
-1two wave number places have the infrared signature absorption peak of polyether glycol.
Adopt Tetra hydro Phthalic anhydride pyridine method (GB 12008.3-89), measuring its hydroxyl value is 300.5 mgKOH/g.
Adopt NDJ-8S automatic digital display viscosity apparatus (T=25 DEG C), measuring its viscosity is 2583 mPas/25 DEG C.
embodiment 5
Take rape stalk as a preparation method for the polyether glycol of raw material, specifically comprise the steps:
(1), by rape stalk be crushed to 100 orders, and toast 3h at temperature 105 DEG C, obtain straw powder;
(2), according to liquefying agent: the mass ratio of catalyzer is the ratio of 100:3, liquefying agent and catalyzer are joined successively and be equipped with in four neck shake flask volume of mechanical stirrer, prolong and thermometer, warming while stirring to 100 DEG C, obtains mixed solution;
Described liquefying agent is the polyoxyethylene glycol of glycerol and molecular weight 400g/mol is mixture that the ratio of 3:1 forms in mass ratio;
Described catalyzer is sulfuric acid;
(3), by step (1) gained straw powder join in step (2) gained mixed solution, continue to be warming up to 120 DEG C of reaction 180 min, be more naturally down to room temperature, obtain reaction solution;
The consumption of above-mentioned straw powder, calculates in mass ratio, straw powder: the liquefying agent in step (2) gained mixed solution is 1:8;
(4), be 7 with the pH of pH adjusting agent regulating step (3) gained reaction solution, carry out natural filtration subsequently, gained filtrate is underpressure distillation 2 h under vacuum tightness-0.1 MPa, and it is the polyether glycol of raw material that gained viscous liquid is with rape stalk;
Described pH adjusting agent is potassium hydroxide.
The polyether glycol of above-mentioned gained, it is at 1108 cm
-1, 3437 cm
-1two wave number places have the infrared signature absorption peak of polyether glycol.
Adopt Tetra hydro Phthalic anhydride pyridine method (GB 12008.3-89), measuring its hydroxyl value is 254 mgKOH/g.
Adopt NDJ-8S automatic digital display viscosity apparatus (T=25 DEG C), measuring its viscosity is 2345 mPas/25 DEG C.
embodiment 6
Take rape stalk as a preparation method for the polyether glycol of raw material, specifically comprise the steps:
(1), by rape stalk be crushed to 120 orders, and toast 3 h at temperature 100 DEG C, obtain straw powder;
(2), according to liquefying agent: the mass ratio of catalyzer is the ratio of 100:1, liquefying agent and catalyzer are joined successively and be equipped with in four neck shake flask volume of mechanical stirrer, prolong and thermometer, warming while stirring to 100 DEG C, obtains mixed solution;
Described liquefying agent is NSC 11801;
Described catalyzer is sulfuric acid;
(3), by step (1) gained straw powder join in step (2) gained mixed solution, continue to be warming up to 120 DEG C of reaction 120 min, be more naturally down to room temperature, obtain reaction solution;
The consumption of above-mentioned straw powder, calculates in mass ratio, straw powder: the liquefying agent in step (2) gained mixed solution is 1:8;
(4), be 7 with the pH of pH adjusting agent regulating step (3) gained reaction solution, carry out natural filtration subsequently, gained filtrate controls underpressure distillation 2 h under vacuum tightness-0.1 MPa, and it is the polyether glycol of raw material that gained viscous liquid is with rape stalk;
Described pH adjusting agent is sodium hydroxide.
The polyether glycol of above-mentioned gained, at 1109 cm
-1, 3432 cm
-1two wave number places have the infrared signature absorption peak of polyether glycol.
Adopt Tetra hydro Phthalic anhydride pyridine method (GB 12008.3-89), measuring its hydroxyl value is 285 mgKOH/g.
Adopt NDJ-8S automatic digital display viscosity apparatus (T=25 DEG C), measuring its viscosity is 2473 mPas/25 DEG C.
embodiment 7
Take rape stalk as a preparation method for the polyether glycol of raw material, specifically comprise the steps:
(1), by rape stalk be crushed to 30 orders, and toast 1 h at temperature 120 DEG C, obtain straw powder;
(2), according to liquefying agent: the mass ratio of catalyzer is the ratio of 100:5, liquefying agent and catalyzer are joined successively and be equipped with in four neck shake flask volume of mechanical stirrer, prolong and thermometer, warming while stirring to 130 DEG C, obtains mixed solution;
Described liquefying agent is ethylene glycol;
Described catalyzer is sulfuric acid;
(3), by step (1) gained straw powder join in step (2) gained mixed solution, continue to be warming up to 150 DEG C of reaction 100 min, be more naturally down to room temperature, obtain reaction solution;
The consumption of above-mentioned straw powder, calculates in mass ratio, straw powder: the liquefying agent in step (2) gained mixed solution is 1:7;
(4), be 7 with the pH of pH adjusting agent regulating step (3) gained reaction solution, carry out natural filtration subsequently, gained filtrate is underpressure distillation 2h under vacuum tightness-0.1 MPa, and it is the polyether glycol of raw material that gained viscous liquid is with rape stalk;
Described pH adjusting agent is potassium hydroxide.
The polyether glycol of above-mentioned gained, it is at 1111 cm
-1, 3427cm
-1two wave number places have the infrared signature absorption peak of polyether glycol.
Adopt Tetra hydro Phthalic anhydride pyridine method (GB 12008.3-89), measuring its hydroxyl value is 410 mgKOH/g.
Adopt NDJ-8S automatic digital display viscosity apparatus (T=25 DEG C), measuring its viscosity is 3500 mPas/25 DEG C.
embodiment 8
Take rape stalk as a preparation method for the polyether glycol of raw material, specifically comprise the steps:
(1), by rape stalk be crushed to 30 orders, and toast 1 h at temperature 120 DEG C, obtain straw powder;
(2), according to liquefying agent: the mass ratio of catalyzer is the ratio of 100:1, liquefying agent and catalyzer are joined successively and be equipped with in four neck shake flask volume of mechanical stirrer, prolong and thermometer, warming while stirring to 110 DEG C, obtains mixed solution;
Described liquefying agent is ethylene glycol;
Described catalyzer is phosphoric acid;
(3), by step (1) gained straw powder join in step (2) gained mixed solution, continue to be warming up to 130 DEG C of reaction 80 min, be more naturally down to room temperature, obtain reaction solution;
The consumption of above-mentioned straw powder, calculates in mass ratio, straw powder: the liquefying agent in step (2) gained mixed solution is 1:5;
The add-on of straw powder, calculates in mass ratio, i.e. liquefying agent in the mixed solution of step (2) gained: straw powder is 5:1;
(4), be 7 with the pH of pH adjusting agent regulating step (3) gained reaction solution, carry out natural filtration subsequently, gained filtrate is underpressure distillation 2h under vacuum tightness-0.1 MPa, and it is the polyether glycol of raw material that gained viscous liquid is with rape stalk;
Described pH adjusting agent is potassium hydroxide.
The polyether glycol of above-mentioned gained, it is at 1112 cm
-1, 3439 cm
-1two wave number places have the infrared signature absorption peak of polyether glycol.
Adopt Tetra hydro Phthalic anhydride pyridine method (GB 12008.3-89), measuring its hydroxyl value is 350 mgKOH/g.
Adopt NDJ-8S automatic digital display viscosity apparatus (T=25 DEG C), measuring its viscosity is 3100 mPas/25 DEG C.
In sum, of the present invention a kind of take rape stalk as the preparation method of the polyether glycol of raw material, have that technique is simple, operational safety, environmental protection, feature with low cost.The hydroxyl value of prepared polyether glycol is 150.6 ~ 410 mgKOH/g, viscosity is 1583 ~ 3500 mPas/25 DEG C.
Above said content be only the present invention conceive under basic explanation, and according to any equivalent transformation that technical scheme of the present invention is done, all should protection scope of the present invention be belonged to.
Claims (10)
1. be a preparation method for the polyether glycol of raw material with rape stalk, it is characterized in that specifically comprising the steps:
(1), by rape stalk be crushed to 30 ~ 120 orders, and toast 1 ~ 3 h at temperature 100 ~ 120 DEG C, obtain straw powder;
(2), in liquefying agent: the mass ratio of catalyzer is the ratio of 100:1 ~ 5, and liquefying agent and catalyzer are joined successively in container, warming while stirring to 100 ~ 150 DEG C, obtain mixed solution;
Described liquefying agent be glycerol, NSC 11801, propylene carbonate, butylene, ethylene glycol and molecular weight 200 ~ 1000 g/mol polyoxyethylene glycol in one or more mixture;
Described catalyzer is sulfuric acid, hydrochloric acid, phosphoric acid or oxalic acid;
(3), by step (1) gained straw powder join in step (2) gained mixed solution, continue to be warming up to 120 ~ 170 DEG C of reaction 60 ~ 180 min, be more naturally down to room temperature, obtain reaction solution;
The consumption of straw powder, calculates in mass ratio, straw powder: the liquefying agent in step (2) gained mixed solution is 1:4-8;
(4), be 6 ~ 7 with the pH of rapid (3) the gained reaction solution of pH adjusting agent pacing, carry out natural filtration subsequently, gained filtrate is underpressure distillation 2h under vacuum tightness-0.5 ~-0.1 MPa, and it is the polyether glycol of raw material that gained viscous liquid is with rape stalk;
Described pH adjusting agent is potassium hydroxide, sodium hydroxide, calcium hydroxide, magnesium oxide, sodium carbonate, sodium bicarbonate, Sodium phosphate dibasic or ammoniacal liquor.
2. a kind of as claimed in claim 1 take rape stalk as the preparation method of the polyether glycol of raw material, it is characterized in that the liquefying agent described in step (2) be the polyoxyethylene glycol of glycerol and molecular weight 400g/mol is mixture that 3:1 ~ 9 form in mass ratio.
3. a kind of as claimed in claim 1 take rape stalk as the preparation method of the polyether glycol of raw material, it is characterized in that the mass ratio of the liquefying agent described in step (2) and catalyzer is 100:5, described liquefying agent is the polyoxyethylene glycol of glycerol and molecular weight 400 g/mol is the mixture of 1:3 composition in mass ratio, and described catalyzer is sulfuric acid;
The consumption of straw powder in step (3), calculate in mass ratio, straw powder: the liquefying agent in step (2) gained mixed solution is 1:8, temperature of reaction is 120 DEG C, time 120min.
4. a kind of as claimed in claim 1 take rape stalk as the preparation method of the polyether glycol of raw material, it is characterized in that the mass ratio of the liquefying agent described in step (2) and catalyzer is 100:3, described liquefying agent is the polyoxyethylene glycol of glycerol and molecular weight 400 g/mol is the mixture of 3:3 composition in mass ratio; Described catalyzer is sulfuric acid;
The consumption of straw powder in step (3), calculate in mass ratio, straw powder: the liquefying agent in step (2) gained mixed solution is 1:6, temperature of reaction is 160 DEG C, time 140 min.
5. a kind of as claimed in claim 1 take rape stalk as the preparation method of the polyether glycol of raw material, it is characterized in that the mass ratio of the liquefying agent described in step (2) and catalyzer is 100:1, described liquefying agent is the polyoxyethylene glycol of glycerol and molecular weight 400 g/mol is the mixture of 3:1 composition in mass ratio, and described catalyzer is sulfuric acid;
The consumption of straw powder in step (3), calculate in mass ratio, straw powder: the liquefying agent in step (2) gained mixed solution is 1:4, temperature of reaction is 170 DEG C, time 60min.
6. a kind of as claimed in claim 1 take rape stalk as the preparation method of the polyether glycol of raw material, it is characterized in that the mass ratio of the liquefying agent described in step (2) and catalyzer is 100:4, described liquefying agent is NSC 11801, and described catalyzer is phosphoric acid;
Liquefying agent described in step (3) and straw powder mass ratio are 8:1, and temperature of reaction is 120 DEG C, time 120 min.
7. a kind of as claimed in claim 1 take rape stalk as the preparation method of the polyether glycol of raw material, it is characterized in that the mass ratio of the liquefying agent described in step (2) and catalyzer is 100:3, described liquefying agent is the polyoxyethylene glycol of glycerol and molecular weight 400 g/mol is the mixture of 3:1 composition in mass ratio, and described catalyzer is sulfuric acid;
The consumption of straw powder in step (3), calculate in mass ratio, straw powder: the liquefying agent in step (2) gained mixed solution is 1:8, temperature of reaction is 120 DEG C, time 180 min.
8. a kind of as claimed in claim 1 take rape stalk as the preparation method of the polyether glycol of raw material, it is characterized in that the mass ratio of the liquefying agent described in step (2) and catalyzer is 100:1, described liquefying agent is NSC 11801, and described catalyzer is sulfuric acid;
The consumption of straw powder in step (3), calculate in mass ratio, straw powder: the liquefying agent in step (2) gained mixed solution is 1:8, temperature of reaction is 120 DEG C, time 120 min.
9. a kind of as claimed in claim 1 take rape stalk as the preparation method of the polyether glycol of raw material, it is characterized in that the mass ratio of the liquefying agent described in step (2) and catalyzer is 100:5, described liquefying agent is ethylene glycol, and described catalyzer is sulfuric acid;
The consumption of straw powder in step (3), calculate in mass ratio, straw powder: the liquefying agent in step (2) gained mixed solution is 1:7, temperature of reaction is 150 DEG C, time 100 min.
10. a kind of as claimed in claim 1 take rape stalk as the preparation method of the polyether glycol of raw material, it is characterized in that the mass ratio of the liquefying agent described in step (2) and catalyzer is 100:1, described liquefying agent is ethylene glycol, and described catalyzer is phosphoric acid;
The consumption of straw powder in step (3), calculate in mass ratio, straw powder: the liquefying agent in step (2) gained mixed solution is 1:5, temperature of reaction is 130 DEG C, time 80min.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104910368A (en) * | 2015-06-25 | 2015-09-16 | 淄博德信联邦化学工业有限公司 | Preparation method of straw oil polyether polyol |
| CN105601945A (en) * | 2016-02-01 | 2016-05-25 | 上海应用技术学院 | Method for preparing bio-based polyether polyol by carrying out microwave-assisted liquefaction on rape stalks |
| CN111303374A (en) * | 2020-04-02 | 2020-06-19 | 上海应用技术大学 | Brominated soybean oil modified pure water-based polyurethane nano-emulsion and preparation method thereof |
| CN113999361A (en) * | 2021-11-24 | 2022-02-01 | 浙江高裕家居科技股份有限公司 | Plant-based polyurethane material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000504750A (en) * | 1996-02-06 | 2000-04-18 | ヘンケル・コマンディットゲゼルシャフト・アウフ・アクチエン | Polyurethane material |
| CN102585141A (en) * | 2011-01-14 | 2012-07-18 | 中国林业科学研究院木材工业研究所 | Flame-retardant polyurethane foam and preparation method thereof |
| CN102633886A (en) * | 2011-02-11 | 2012-08-15 | 李翠花 | Method for preparing plant-based polyether polyol by straw liquefaction |
-
2014
- 2014-11-11 CN CN201410630057.XA patent/CN104311816A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000504750A (en) * | 1996-02-06 | 2000-04-18 | ヘンケル・コマンディットゲゼルシャフト・アウフ・アクチエン | Polyurethane material |
| CN102585141A (en) * | 2011-01-14 | 2012-07-18 | 中国林业科学研究院木材工业研究所 | Flame-retardant polyurethane foam and preparation method thereof |
| CN102633886A (en) * | 2011-02-11 | 2012-08-15 | 李翠花 | Method for preparing plant-based polyether polyol by straw liquefaction |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104910368A (en) * | 2015-06-25 | 2015-09-16 | 淄博德信联邦化学工业有限公司 | Preparation method of straw oil polyether polyol |
| CN105601945A (en) * | 2016-02-01 | 2016-05-25 | 上海应用技术学院 | Method for preparing bio-based polyether polyol by carrying out microwave-assisted liquefaction on rape stalks |
| CN111303374A (en) * | 2020-04-02 | 2020-06-19 | 上海应用技术大学 | Brominated soybean oil modified pure water-based polyurethane nano-emulsion and preparation method thereof |
| CN113999361A (en) * | 2021-11-24 | 2022-02-01 | 浙江高裕家居科技股份有限公司 | Plant-based polyurethane material and preparation method thereof |
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