CN104004179A - Method for preparation of polyether polyol and hard foam polyurethane from waste recovered material and products thereof - Google Patents
Method for preparation of polyether polyol and hard foam polyurethane from waste recovered material and products thereof Download PDFInfo
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- CN104004179A CN104004179A CN201410164328.7A CN201410164328A CN104004179A CN 104004179 A CN104004179 A CN 104004179A CN 201410164328 A CN201410164328 A CN 201410164328A CN 104004179 A CN104004179 A CN 104004179A
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
- Y02P20/143—Feedstock the feedstock being recycled material, e.g. plastics
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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Abstract
The invention discloses a method for preparation of polyether polyol and hard foam polyurethane from waste recovered material and products thereof. The method for preparation of polyether polyol includes: under the action of an ester exchange catalyst and in diol, the waste recovered material undergoes ester exchange reaction and vacuum dehydration reaction, terminating the reaction when the acid value of the reaction system is detected less than 10mgKOH/g so as to obtain a polyester polyol-containing reactant; taking the reactant and polyol as the co-initiator, under the action of a catalyst, letting alkylene oxide undergo ring-opening polymerization reaction, and terminating the reaction when the hydroxyl value of the reactant is detected 300-450mgKOH/g. The method provided by the invention adopts the waste recovered material as the raw material, the consumption of petroleum in the polyether polyol synthesis field is greatly reduced, the energy is saved, and the cost is low. The obtained polyether polyol can be used for preparing polyurethane hard foams with good compression resistant effect, bonding effect, flame retardant effect and thermal insulation effect, and the obtained hard foams have good dimensional stability.
Description
Technical field
The present invention relates to the polyether glycol that the waste and old regenerant of a kind of use is prepared the method for polyether glycol and made thus, and the hard polyurethane foam that adopts this polyether glycol to make.
Background technology
The polyether glycol that existing polyurethane heat insulation material is used is to be synthesized by polyvalent alcohol, oxyethane, propylene oxide, catalyzer substantially, these polyether glycols generally have following shortcoming: (1) flame retardant resistance is bad, when use, need to add in a large number fire retardant, increase cost.(2) foamy body cohesiveness is bad, easily comes off.(3) oxyethane, propylene oxide feedstock come from petroleum products, and polyether glycol has consumed petroleum resources, and bring impact to environment.(4) dimensional stability of polyurethane foam is bad, in actual application, easily ftractures.Based on current national energy-saving environmental requirement, in conjunction with the good heat insulation effect of polyurethane foam, polyurethane foam heat insulation material consumption is increased, but along with the consumption of national petroleum resources, for more and more nervous resource environment, schedule has been put in the utilization of junk.The polyether glycol tool that junk reclaims preparation has the following advantages: (1) environmental protection, has solved the recycling problem of waste; (2) polyurethane foam of its production, high insulating effect; (3) good in surface bonding; (4) have certain fire-retardant effect, toxicity is low; Have a wide range of applications space and market outlook.Based on this, need a kind of method that adopts junk to prepare polyether glycol.The useful waste in this area is prepared the method for polyester polyol at present, but while use, consistency is bad, and easily makes the foam contraction obtaining, and affects the physicals of foam.
Summary of the invention
Technical problem to be solved by this invention has been to overcome hard polyurethane foam that polyether glycol prepared by the waste and old regenerant of existing use prepares the defect of the problems such as contraction, a kind of use polyether glycol that waste and old regenerant is prepared the method for polyether glycol and made is thus provided, and has adopted hard polyurethane foam that this polyether glycol makes and preparation method thereof.Method of the present invention is taking waste and old regenerant as raw material, greatly reduce the consumption of the synthetic field of polyether glycol to oil, save the energy, with low cost, and the polyether glycol obtaining can be used in preparation resistance to compression effect, bond effect, flame retardant effect, hard polyurethane foam that heat insulation effect is good, and the rigid foam dimensional stability obtaining is good, cracking and deformation are few.
The invention provides a kind of waste and old regenerant and prepare the method for polyether glycol, it comprises the steps:
(1) prepare polyester polyol: under the effect of transesterification catalyst, in dibasic alcohol, waste and old regenerant generation transesterification reaction and vacuum hydro-extraction reaction, when detection reaction system acid number is less than 10mgKOH/g, termination reaction must be containing the reactant of polyester polyol; The material of wherein said waste and old regenerant is polyethylene terephthalate (being called for short PET), or the mixture of polyethylene terephthalate and polycarbonate; Described waste and old regenerant and the mass ratio of described dibasic alcohol are 100:40～100:80, and described waste and old regenerant and the mass ratio of described transesterification catalyst are 100:0.5～100:2.5;
(2) reactant containing polyester polyol obtaining taking step (1) and polyvalent alcohol are as being total to initiator, under the effect of catalyzer, epoxy alkane generation ring-opening polymerization, when detecting reactant hydroxyl value is 300～450mgKOH/g, when preferably hydroxyl value is 400～450mgKOH/g, termination reaction obtains polyether glycol; Described epoxy alkane is oxyethane and/or propylene oxide.
In step (1), described waste and old regenerant can be selected various forms of waste and old regenerants, is preferably polycarbonate fragment, mineral water bottle fragment and plastic beverage bottle fragment etc.
In step (1), described transesterification catalyst can adopt the conventional catalyst of this type of reaction of this area, is preferably zinc acetate, antimonous oxide or tetrabutyl titanate.
In step (1), described dibasic alcohol is preferably Diethylene Glycol and/or ethylene glycol.
In step (1), the condition of described transesterification reaction and vacuum hydro-extraction reaction can adopt the normal condition of this type of reaction of this area.The temperature of reaction of described transesterification reaction and vacuum hydro-extraction reaction is preferably 140～240 DEG C, is more preferably 200～240 DEG C.
In step (1), the vacuum tightness of described vacuum hydro-extraction reaction can adopt the conventional vacuum tightness of this type of reaction of this area, is preferably-0.1～-1.0MPa.
In step (2), the consumption of the described reactant containing polyester polyol is preferably 19～48 parts, and the consumption of described polyvalent alcohol is preferably 15～50 parts, and the consumption of described epoxy alkane is preferably 50～75 parts.
In step (2), in the time that described epoxy alkane is oxyethane and propylene oxide, the mass ratio of described oxyethane and described propylene oxide is preferably 1:3～1:8, is more preferably 1:4～1:6.
In step (2), described polyvalent alcohol is the polyvalent alcohol of functionality 2～8, preferably one or more in dibasic alcohol, trivalent alcohol and sucrose, described dibasic alcohol is preferably one or more in ethylene glycol, propylene glycol and Diethylene Glycol, and described trivalent alcohol is preferably glycerol.
In step (2), described catalyzer can adopt ring-opening polymerization in this area to prepare the conventional catalyzer using of polyether glycol, is preferably basic catalyst and/or dmc catalyst.Described basic catalyst is preferably amines catalyst and/or potassium hydroxide.Described amines catalyst is preferably one or more in dimethylamine, hexahydroaniline, Trimethylamine 99, tridecyl amine and lauryl amine.The consumption of described basic catalyst is preferably 0.5～1.2 part, and the consumption of described dmc catalyst is preferably 20～60ppm.
In step (2), the reaction conditions of described ring-opening polymerization can adopt the normal condition of this type of reaction of this area.The temperature of reaction of described ring-opening polymerization is preferably 90～135 DEG C, is more preferably 105～135 DEG C; The reaction pressure of described ring-opening polymerization is preferably below 0.5MPa.The reaction times of described ring-opening polymerization is preferably 0.5～5 hour, is more preferably 3～4 hours.
In step (2), described ring-opening polymerization can carry out in the various reactors of this area routine, preferably in the autoclave with outer circulation, carries out.
The polyether glycol that the present invention also provides a kind of method of preparing polyether glycol by above-mentioned waste and old regenerant to prepare.
The present invention also provides a kind of method of preparing hard polyurethane foam, and it comprises the steps: polyether glycol of the present invention and isocyanic ester mixing post-foaming; Described polyether glycol preferably mixes with isocyanic ester with the form of combined polyether.
Wherein, described polyether glycol preferably mixes with isocyanic ester with the form of combined polyether.Described combined polyether can comprise the component of each routine in the combined polyether of this area, preferably comprises the following component in weight part: 100 parts of polyether glycols of the present invention, 2 parts of foam stabilizers, 25 parts of whipping agents, 2.2 parts, 3 parts of catalyzer and water.
Wherein, the mass ratio of described combined polyether and described isocyanic ester is the mass ratio of this area routine, is preferably 1:1～1:1.05.
Wherein, described isocyanic ester can adopt the isocyanic ester of the various routines in this area, be preferably PAPI, such as, in the Hensel graceful 5005 of the pm200 of Yantai Wanhua Polyurethane Co., Ltd., the 44v20 series of Bayer A.G and Hensel Man etc. one or more.
The present invention also provides a kind of hard polyurethane foam being prepared by the above-mentioned method of preparing hard polyurethane foam, its transparent liquid that is light yellow thickness.
Meeting on the basis of this area general knowledge, above-mentioned each optimum condition, can arbitrary combination, obtains the preferred embodiments of the invention.
Agents useful for same of the present invention and raw material be commercially available obtaining all.
Positive progressive effect of the present invention is:
The present invention is taking existing waste and old polyester as polyvalent alcohol raw material, can in synthesizing formula, introduce the ring texture with certain flame retardant effect, make synthetic polyether glycol there is certain flame retardant effect, can reduce the consumption of fire retardant, reduce combined polyether production cost, and due to its special molecular structure, make its foam there is good dimensional stability and cohesiveness, reduce cracking and the deformation of foam, and its environmental protection object is self-evident.
Embodiment
Mode below by embodiment further illustrates the present invention, but does not therefore limit the present invention among described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example, according to ordinary method and condition, or selects according to catalogue.
In following embodiment, except special instruction, described umber is all mass parts.
Embodiment 1
(1) prepare polyester polyol: according to the composition of raw materials shown in table 1, in 100 parts of polyester fragments (deriving from is Chef Kang's mineral water bottle), 50 parts of dibasic alcohol (Diethylene Glycol) and 1.2 parts of input reactors of transesterification catalyst (zinc acetate), at 210 DEG C, carry out transesterification reaction and vacuum hydro-extraction reaction, vacuum tightness is-0.90MPa, to remove the small molecules such as the water of generation, when detection reaction system acid number is less than 10mgKOH/g (actual measurement is 9.7mgKOH/g), termination reaction obtains the reactant containing polyester polyol, lowers the temperature for subsequent use;
(2) prepare polyether glycol: according to the composition of raw materials shown in table 2 by containing 48 parts of the reactants of polyester polyol, 19 parts of polyvalent alcohols (sucrose), 1.2 parts of inputs of catalyzer (dimethylamine) are with in still in the autoclave of outer circulation, make 54 parts of propylene oxide carry out ring-opening polymerization, temperature of reaction is 105 DEG C, reaction pressure is less than 0.5MPa, approximately 4.5 hours reaction times, detect hydroxyl value 410mgKOH/g, termination reaction obtains the transparent liquid of brown color thickness, machinery-free impurity.
Embodiment 2
(1) prepare polyester polyol: according to the composition of raw materials shown in table 1, by polyester fragment, (Chef Kang's brand mineral water bottle accounts for 20wt%, other brands (heartily, NongFuShanQuan and ice reveal) mineral water bottle accounts for 80wt%, be colourless bottle) 100 parts, in 40 parts of dibasic alcohol (Diethylene Glycol) and 2.2 parts of input reactors of transesterification catalyst (antimonous oxide), at 220 DEG C, carry out transesterification reaction and vacuum hydro-extraction reaction, vacuum tightness is-0.85MPa, to remove the small molecules such as the water of generation, when detection reaction system acid number is less than 10mgKOH/g (actual detection as 8.2mgKOH/g), termination reaction obtains the reactant containing polyester polyol, lower the temperature for subsequent use,
(2) prepare polyether glycol: according to the composition of raw materials shown in table 2 by containing 19 parts of the reactants of polyester polyol, 19 parts of polyvalent alcohols (sucrose), 0.8 part of input of catalyzer (Trimethylamine 99) is with in still in the autoclave of outer circulation, make 70 parts, oxyethane carry out ring-opening polymerization, temperature of reaction is 105 DEG C, reaction pressure is less than 0.5MPa, approximately 4 hours reaction times, detect hydroxyl value 420mgKOH/g, termination reaction obtains the transparent liquid of light yellow thickness, machinery-free impurity.
Embodiment 3
(1) prepare polyester polyol: according to the composition of raw materials shown in table 1, by 100 parts of polyester fragments (the colourless mineral water bottle 80wt% of WAHAHA brand, Chef Kang's green tea drink bottle (green) 20wt%), in 50 parts of dibasic alcohol (ethylene glycol) and 0.5 part of input reactor of transesterification catalyst (tetrabutyl titanate), at 240 DEG C, carry out transesterification reaction and vacuum hydro-extraction reaction, vacuum tightness is-0.95MPa, to remove the small molecules such as the water of generation, react 8 hours, when detection reaction system acid number is less than 10mgKOH/g (actual measurement 9.8mgKOH/g), termination reaction obtains the reactant of light green containing polyester polyol, lower the temperature for subsequent use,
(2) prepare polyether glycol: according to the composition of raw materials shown in table 2 by containing 48 parts of the reactants of polyester polyol, 19 parts of polyvalent alcohols (sucrose), 0.5 part of input of catalyzer (potassium hydroxide) is with in still in the autoclave of outer circulation, make 50 parts of epoxy alkane (wherein 11 parts, oxyethane, 39 parts of propylene oxide) carry out ring-opening polymerization, temperature of reaction is 115 DEG C, reaction pressure is less than 0.5MPa, approximately 5 hours reaction times, detect hydroxyl value 440mgKOH/g, termination reaction obtains the transparent liquid of light yellow thickness, machinery-free impurity.
Embodiment 4
(1) prepare polyester polyol: according to the composition of raw materials shown in table 1, by 100 parts of polyester fragments (colourless mineral water bottle fragment 80wt%, green green tea drink bottle 20wt%), in 80 parts of dibasic alcohol (ethylene glycol) and 2.2 parts of input reactors of transesterification catalyst (tetrabutyl titanate), at 220 DEG C, carry out transesterification reaction and vacuum hydro-extraction reaction, vacuum tightness is-0.88MPa, to remove the small molecules such as the water of generation, react 5 hours, when detection reaction system acid number is less than 10mgKOH/g (actual measurement is 7.9mgKOH/g), termination reaction obtains the reactant containing polyester polyol, lower the temperature for subsequent use,
(2) prepare polyether glycol: according to the composition of raw materials shown in table 2 by containing 19 parts of the reactants of polyester polyol, 50 portions of (wherein 33 parts of sucrose of polyvalent alcohol, 17 parts of propylene glycol), 0.5 part of catalyzer (potassium hydroxide), drop into in still in the autoclave of outer circulation, make 54 parts of epoxy alkane (wherein 8 parts, oxyethane, 46 parts of propylene oxide) carry out ring-opening polymerization, temperature of reaction is 105 DEG C, reaction pressure is less than 0.5MPa, approximately 4 hours reaction times, detect hydroxyl value 450mgKOH/g, termination reaction obtains the transparent liquid of light yellow thickness, machinery-free impurity.
Embodiment 5
(1) prepare polyester polyol: according to the composition of raw materials shown in table 1, by 100 parts of polyester fragments (colourless mineral water bottle fragment 80wt%, green green tea drink bottle 20wt%), in 80 parts of dibasic alcohol (Diethylene Glycol) and 2.2 parts of input reactors of transesterification catalyst (tetrabutyl titanate), at 220 DEG C, carry out transesterification reaction and vacuum hydro-extraction reaction, vacuum tightness is-0.88MPa, to remove the small molecules such as the water of generation, react 5 hours, when detection reaction system acid number is less than 10mgKOH/g (actual measurement is 7.9mgKOH/g), termination reaction obtains the reactant containing polyester polyol, lower the temperature for subsequent use,
(2) prepare polyether glycol: according to the composition of raw materials shown in table 2 by containing 40 parts of the reactants of polyester polyol, polyvalent alcohol (wherein 18 parts of sucrose, 9 parts of glycerol) 27 parts, 1.2 parts of catalyzer (lauryl amine), drop into in still in the autoclave of outer circulation, make 74 parts of epoxy alkane (wherein 8 parts, oxyethane, 66 parts of propylene oxide) carry out ring-opening polymerization, temperature of reaction is 105 DEG C, reaction pressure is less than 0.5MPa, approximately 4 hours reaction times, termination reaction while detecting hydroxyl value 430mgKOH/g, obtain the transparent liquid of light yellow thickness, machinery-free impurity.
Embodiment 6
(1) prepare polyester polyol: according to the composition of raw materials shown in table 1, by 100 parts of polyester fragments (colourless mineral water bottle fragment 60wt%, green green tea drink bottle 40wt%), in 50 parts of dibasic alcohol (ethylene glycol) and 2.2 parts of input reactors of transesterification catalyst (tetrabutyl titanate), at 220 DEG C, carry out transesterification reaction and vacuum hydro-extraction reaction, vacuum tightness is-0.85MPa, to remove the small molecules such as the water of generation, react 5 hours, when detection reaction system acid number is less than 10mgKOH/g (actual measurement is 6.9mgKOH/g), termination reaction obtains the reactant containing polyester polyol, lower the temperature for subsequent use,
(2) prepare polyether glycol: according to the composition of raw materials shown in table 2 by containing 48 parts of the reactants of polyester polyol, polyvalent alcohol (wherein 11 parts of sucrose, 10 parts of Diethylene Glycols) 21 parts, 1.0 parts of catalyzer (tridecyl amine), drop into in still in the autoclave of outer circulation, make 54 parts of propylene oxide carry out ring-opening polymerization, temperature of reaction is 105 DEG C, reaction pressure is less than 0.4MPa, approximately 4 hours reaction times, detect hydroxyl value 433mgKOH/g, termination reaction obtains the transparent liquid of light yellow thickness, machinery-free impurity.
Embodiment 7
(1) prepare polyester polyol: according to the composition of raw materials shown in table 1, by 100 parts of polyester fragments (colourless mineral water bottle fragment 50wt%, green green tea drink bottle 50wt%), in 50 parts of dibasic alcohol (Diethylene Glycol) and 2.2 parts of input reactors of transesterification catalyst (tetrabutyl titanate), at 220 DEG C, carry out transesterification reaction and vacuum hydro-extraction reaction, vacuum tightness is-0.85MPa, to remove the small molecules such as the water of generation, react 5 hours, when detection reaction system acid number is less than 10mgKOH/g (actual measurement is 6.6mgKOH/g), termination reaction obtains the reactant containing polyester polyol, lower the temperature for subsequent use,
(2) prepare polyether glycol: according to the composition of raw materials shown in table 2 by containing 48 parts of the reactants of polyester polyol, 19 parts of polyvalent alcohols (sucrose), catalyzer (DMC) 40ppm, drop into in still in the autoclave of outer circulation, make 54 parts of epoxy alkane (wherein 8 parts, oxyethane, 46 parts of propylene oxide) carry out ring-opening polymerization, temperature of reaction is 135 DEG C, reaction pressure is less than 0.2MPa, approximately 0.5 hour reaction times, detect hydroxyl value 430mgKOH/g, termination reaction obtains the transparent liquid of light yellow thickness, machinery-free impurity.
Comparative example 1
(1) prepare polyester polyol: according to the composition of raw materials shown in table 1, in 100 parts of polyester fragments (the colourless mineral water bottle 100% of Chef Kang's brand), 50 parts of dibasic alcohol (Diethylene Glycol) and 0.2 part of input reactor of transesterification catalyst (tetrabutyl titanate), at 240 DEG C, carry out transesterification reaction and vacuum hydro-extraction reaction, vacuum tightness is-0.98MPa, to remove the small molecules such as the water of generation, react 12 hours, when detection reaction system acid number is 19mgKOH/g, termination reaction obtains the reactant of light green containing polyester polyol, lowers the temperature for subsequent use;
(2) prepare polyether glycol: according to the composition of raw materials shown in table 2 by containing 44 parts of the reactants of polyester polyol, 23 parts of polyvalent alcohols (sucrose), 0.8 part of catalyzer (potassium hydroxide), drop into in still in the autoclave of outer circulation, make 64 parts of epoxy alkane (wherein 9 parts, oxyethane, 55 parts of propylene oxide) carry out ring-opening polymerization, temperature of reaction is 115 DEG C, reaction pressure is less than 0.5MPa, approximately 5 hours reaction times, reaction as a child stopped 5, still internal pressure is too high, pressure release, detect hydroxyl value 540mgKOH/g, termination reaction obtains the transparent liquid of brown-green thickness, machinery-free impurity, yield 75%, be starkly lower than the yield (more than 86%) of embodiment 1-7.
Low former of yield because: transesterify is not thorough, and polyester acid number is too high, is unfavorable for the ring-opening polymerization of next step epoxide, proves that the catalytic amount of transesterification should be lower than 0.5 part, preferably 2.0 parts.
Comparative example 2
(1) prepare polyester polyol: according to the composition of raw materials shown in table 1, in 100 parts of polycarbonate fragments, 80 parts of dibasic alcohol (ethylene glycol) and 2.2 parts of input reactors of transesterification catalyst (tetrabutyl titanate), at 220 DEG C, carry out transesterification reaction and vacuum hydro-extraction reaction, vacuum tightness is-0.98MPa, to remove the small molecules such as the water of generation, react 9 hours, when detection reaction system acid number is 27.9mgKOH/g, termination reaction obtains the reactant of polyester polyol, lowers the temperature for subsequent use; The alcoholysis reaction of polycarbonate fragment is bad.
(2) prepare polyether glycol: according to the composition of raw materials shown in table 2 by containing 48 parts of the reactants of polyester polyol, polyvalent alcohol (sucrose 38,9 parts of propylene glycol, for mass fraction) 47 parts, 0.5 part of catalyzer (potassium hydroxide), drop into in still in the autoclave of outer circulation, make 64 parts of propylene oxide carry out ring-opening polymerization, temperature of reaction is 105 DEG C, and reaction pressure is less than 0.5MPa, approximately 7 hours reaction times, stopped reaction, because the high reaction of acid number is not thorough, obtain the transparent liquid of light brown viscous, machinery-free impurity.Detect hydroxyl value 585mgKOH/g, hydroxyl value is high, and yield is low, is 70%.
Table 1 polyester polyol composition of raw materials
Table 2 polyether glycol composition of raw materials
Effect embodiment
The polyether glycol that embodiment 1～7 is obtained is configured to combined polyether, with 1.05 parts of isocyanic ester after high pressure foaming machine high pressure mixing, obtain hard polyurethane foam, and detect rigid foam physicals according to country's north material examination criteria, test result is in table 3.
Combined polyether formula:
Table 3
The oxygen index that does not add the hard polyurethane foam of fire retardant is generally 16-18, and the oxygen index of visible hard polyurethane foam of the present invention, than the height that does not add fire retardant, has certain flame retardant properties.Be also shown in by table 3, the hard polyurethane foam that the present invention obtains all can be up to state standards, and resistance to compression is respond well, has solved the problem that junk reclaims, and has obvious environment protecting.
Claims (10)
1. waste and old regenerant is prepared a method for polyether glycol, and it comprises the steps:
(1) prepare polyester polyol: under the effect of transesterification catalyst, in dibasic alcohol, waste and old regenerant generation transesterification reaction and vacuum hydro-extraction reaction, when detection reaction system acid number is less than 10mgKOH/g, termination reaction must be containing the reactant of polyester polyol; The material of wherein said waste and old regenerant is polyethylene terephthalate, or the mixture of polyethylene terephthalate and polycarbonate; Described waste and old regenerant and the mass ratio of described dibasic alcohol are 100:40～100:80, and described waste and old regenerant and the mass ratio of described transesterification catalyst are 100:0.5～100:2.5;
(2) reactant containing polyester polyol obtaining taking step (1) and polyvalent alcohol are as being total to initiator, under the effect of catalyzer, epoxy alkane generation ring-opening polymerization, when detecting reactant hydroxyl value is 300～450mgKOH/g, termination reaction obtains polyether glycol; Described epoxy alkane is oxyethane and/or propylene oxide.
2. the method for claim 1, is characterized in that: in step (1), described transesterification catalyst is zinc acetate, antimonous oxide or tetrabutyl titanate; And/or described dibasic alcohol is Diethylene Glycol and/or ethylene glycol.
3. the method for claim 1, is characterized in that: in step (1), the temperature of reaction of described transesterification reaction and vacuum hydro-extraction reaction is 140～240 DEG C, is preferably 200～240 DEG C; And/or the vacuum tightness of described vacuum hydro-extraction reaction is-0.1～-1.0MPa.
4. the method for claim 1, is characterized in that: in step (2), the consumption of the described reactant containing polyester polyol is 19～48 parts, and the consumption of described polyvalent alcohol is 15～50 parts, and the consumption of described epoxy alkane is 50～75 parts.
5. the method for claim 1, it is characterized in that: in step (2), described polyvalent alcohol is the polyvalent alcohol of functionality 2～8, preferably one or more in dibasic alcohol, trivalent alcohol and sucrose, described dibasic alcohol is preferably one or more in ethylene glycol, propylene glycol and Diethylene Glycol, and described trivalent alcohol is preferably glycerol.
6. the method for claim 1, is characterized in that: in step (2), in the time that described epoxy alkane is oxyethane and propylene oxide, the mass ratio of described oxyethane and described propylene oxide is 1:3～1:8, is preferably 1:4～1:6;
And/or described catalyzer is basic catalyst and/or dmc catalyst; Described basic catalyst is preferably amines catalyst and/or potassium hydroxide; Described amines catalyst is preferably one or more in dimethylamine, hexahydroaniline, Trimethylamine 99, tridecyl amine and lauryl amine; And/or the consumption of described basic catalyst is 0.5～1.2 part, the consumption of described dmc catalyst is 20～60ppm.
7. the method for claim 1, is characterized in that: in step (2), the temperature of reaction of described ring-opening polymerization is 90～135 DEG C, is preferably 105～135 DEG C; And/or the reaction pressure of described ring-opening polymerization is below 0.5MPa; And/or the reaction times of described ring-opening polymerization is 0.5～5 hour, it is preferably 3～4 hours; And/or described ring-opening polymerization carries out in the autoclave with outer circulation.
8. the polyether glycol that the method as described in claim 1～7 any one prepares.
9. prepare a method for hard polyurethane foam, it comprises the steps: polyether glycol claimed in claim 8 and isocyanic ester mixing post-foaming.
10. the hard polyurethane foam that method as claimed in claim 9 prepares.
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| CN105175702A (en) * | 2015-09-09 | 2015-12-23 | 济南大学 | Preparation method for dihydric alcohol used for preparing polyurethane and application of dihydric alcohol |
| CN105693993A (en) * | 2016-04-12 | 2016-06-22 | 广州聚天化工科技有限公司 | Rigid polyurethane foam material on basis of polyurethane insole degradation products and method for preparing rigid polyurethane foam material |
| CN107556468A (en) * | 2017-09-11 | 2018-01-09 | 福建师范大学泉港石化研究院 | A kind of method that aromatic polyether ester polyol is prepared using waste PET as raw material |
| US10053533B1 (en) | 2017-04-13 | 2018-08-21 | Presidium Usa, Inc. | Oligomeric polyol compositions |
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| CN110092882A (en) * | 2019-05-31 | 2019-08-06 | 山东理工大学 | Method based on waste paint slag preparation flame retarded polyurethane-foam material |
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| CN109912961A (en) * | 2019-04-04 | 2019-06-21 | 张宏春 | A kind of production method of plastic pipe heat preservation layer material |
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