CN112661951A - Preparation method of polyether polyol for shoe material - Google Patents
Preparation method of polyether polyol for shoe material Download PDFInfo
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- CN112661951A CN112661951A CN202011465486.8A CN202011465486A CN112661951A CN 112661951 A CN112661951 A CN 112661951A CN 202011465486 A CN202011465486 A CN 202011465486A CN 112661951 A CN112661951 A CN 112661951A
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- polyether polyol
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- shoe materials
- propylene oxide
- ethylene oxide
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- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 90
- 229920000570 polyether Polymers 0.000 title claims abstract description 90
- 229920005862 polyol Polymers 0.000 title claims abstract description 89
- 150000003077 polyols Chemical class 0.000 title claims abstract description 89
- 239000000463 material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 150000007524 organic acids Chemical class 0.000 claims abstract description 9
- 239000000835 fiber Substances 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 57
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 37
- 229910052757 nitrogen Inorganic materials 0.000 claims description 29
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 28
- 238000006116 polymerization reaction Methods 0.000 claims description 26
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- 239000000178 monomer Substances 0.000 claims description 23
- 238000007334 copolymerization reaction Methods 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 230000001502 supplementing effect Effects 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 9
- 150000001340 alkali metals Chemical class 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 230000000977 initiatory effect Effects 0.000 claims description 8
- 238000006386 neutralization reaction Methods 0.000 claims description 8
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- 230000005587 bubbling Effects 0.000 claims description 6
- 239000006227 byproduct Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 229920002522 Wood fibre Polymers 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 4
- 239000002025 wood fiber Substances 0.000 claims description 4
- 229920003043 Cellulose fiber Polymers 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 11
- 239000000047 product Substances 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 7
- 229920002635 polyurethane Polymers 0.000 abstract description 6
- 239000004814 polyurethane Substances 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
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- 239000007795 chemical reaction product Substances 0.000 abstract description 3
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- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- 210000000459 calcaneus Anatomy 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000002683 foot Anatomy 0.000 description 1
- 235000019589 hardness Nutrition 0.000 description 1
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- 150000004678 hydrides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
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- 238000007670 refining Methods 0.000 description 1
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- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Polyethers (AREA)
Abstract
The invention belongs to the technical field of polyether polyol synthesis, and particularly relates to a preparation method of polyether polyol for shoe materials. The invention innovatively adopts a double-catalysis system to synthesize polyether polyol for shoe materials, KOH is used as a main catalyst, a phosphazene catalyst is used as a cocatalyst, organic acid is neutralized, organic fibers are used for assisting filtration, the activity of a reaction process is high, and side reaction products are few. Compared with the polyether polyol synthesized by the traditional market KOH catalytic process, the polyether polyol product has low unsaturation degree, narrow molecular weight distribution and high primary hydroxyl end capping rate, and can endow polyurethane shoe materials with higher curing speed and more excellent performance.
Description
Technical Field
The invention belongs to the technical field of polyether polyol synthesis, and particularly relates to a preparation method of polyether polyol for shoe materials.
Background
The polyurethane sole material has the advantages of comfort, lightness, wear resistance, good elasticity, high strength and the like, and the forming process is simple and can have various densities and hardnesses. The sole mainly comprises an outsole, a mid-sole and an insole 3. The insole and the insole are important components for ensuring good cushioning, shock absorption and energy return of the sole, and directly influence the function and comfort of the shoe. The polyurethane insole that possesses high resilience shock attenuation performance can make human weight distribute more rationally in each part of foot, and the shock that the cushioning movement led to the fact brain, calcaneus and other positions of health has guaranteed the travelling comfort demand of shoes. The quality of raw materials supports the performance of products, and with the continuous and deep research on low-density polyurethane shoe materials in China, the production process is continuously improved and optimized, and the requirements of manufacturers on polyether polyol are higher and higher.
The domestic use of more polyether polyols for shoe materials is a KOH catalytic system, and the products have two functionalities and relative molecular mass of about 4000. Limited by a catalytic system, the existing polyether polyol for shoe materials is difficult to further reduce side reactions, obtain products with lower unsaturation degree, and limit the development of polyurethane shoe materials to lower cost and higher quality.
Chinese patent 104497298B provides a method for preparing polyether polyol with low unsaturation degree, high molecular weight and high activity, which uses organic alkoxide as catalyst, and uses active hydride and olefin oxide to make polymerization reaction, but the preparation process of organic alkoxide in the invention is complex, and the cost of industrial application is high. Chinese patent 106947074B provides a method for preparing polyether polyol with low unsaturation degree and high activity, which comprises using cesium hydroxide as a catalyst, firstly adding propylene oxide and an initiator to carry out a ring-opening reaction, after the ring-opening reaction is finished, adding ethylene oxide to carry out end capping, and finally refining to obtain the finished polyether polyol. Chinese patent 104109234B provides a method for preparing a polyether polyol with high molecular weight, low unsaturation degree and high primary hydroxyl content, which comprises the steps of treating the polyether polyol with high molecular weight and low unsaturation degree containing a bimetallic catalyst DMC by using a treating agent, then adding ethylene oxide for carrying out a capping reaction, treating a capped product by using an adsorbent, and finally filtering to obtain the polyether polyol with high molecular weight, low unsaturation degree and high activity, but the operation process is complex, and the higher primary hydroxyl capping rate is difficult to obtain due to the restriction of the catalytic capability of alkali metal. Chinese patent 109485844A provides a preparation method of polyether polyol with high activity, high molecular weight and low unsaturation degree, which is characterized in that a di-functionality mixed initiator and a tri-functionality mixed initiator are adopted, a phosphazene catalyst is used for catalysis, and the traditional acid water process is adopted for neutralization, so that the prepared polyether polyol has the characteristics of high activity, low volatile organic content and small smell, but the single phosphazene catalyst has high usage, and the traditional phosphoric acid neutralization process cannot meet the higher requirements of the market on environmental protection and low smell. Based on the above reasons, a more efficient and simple catalytic system is needed to further reduce the degree of unsaturation, increase the primary hydroxyl content, and meet the development requirements of high molecular weight and high activity polyether polyol, especially for shoe materials.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the preparation method overcomes the defects of the prior art, provides the preparation method of the polyether polyol for the shoe material, innovatively adopts a double-catalysis system, takes KOH as a main catalyst and a phosphazene catalyst as a cocatalyst, and is neutralized by organic acid, so that organic fibers assist filtration, the reaction process activity is high, and side reaction products are few; the prepared polyether polyol product has low unsaturation degree, narrow molecular weight distribution, high primary hydroxyl content and low smell, and can endow polyurethane shoe materials with more excellent performance.
The preparation method of the polyether polyol for the shoe material comprises the following steps:
(1) under the action of an alkali metal catalyst, carrying out primary polymerization reaction on a small molecular initiator and propylene oxide to obtain an intermediate polyether polyol;
(2) under the action of a phosphazene catalyst, adding propylene oxide into the intermediate polyether polyol to carry out initiation reaction, adding propylene oxide and ethylene oxide to carry out copolymerization reaction after initiation, and adding ethylene oxide to carry out end capping polymerization reaction after the reaction is finished to obtain crude polyether polyol;
(3) and adding an organic acid neutralizer into the crude polyether polyol for neutralization, then adding a filter aid, and drying and filtering to obtain the polyether polyol for the shoe material.
Wherein:
the micromolecule initiator in the step (1) is at least one of ethylene glycol, propylene glycol, diethylene glycol or dipropylene glycol.
The alkali metal catalyst in the step (1) is potassium hydroxide, and the addition amount of the alkali metal catalyst is 1-2%, preferably 1-1.5% of the designed mass of the intermediate polyether polyol.
The adding amount of the phosphazene catalyst in the step (2) is 0.5-3.5 per mill of the designed mass of the crude polyether polyol, and preferably 1.5-2.5 per mill.
The temperature for initiating the reaction of propylene oxide in the step (2) is 90 to 105 ℃, preferably 95 to 100 ℃, and the temperature for copolymerizing propylene oxide and ethylene oxide is 90 to 105 ℃, preferably 95 to 100 ℃.
In the step (2), the copolymerization amount of the ethylene oxide for copolymerization is 5-10% of the designed mass of the crude polyether polyol, and the mass ratio of the propylene oxide to the ethylene oxide for copolymerization is 3: 1.
The temperature of the ethylene oxide end-capping polymerization reaction in the step (2) is 105-125 ℃, preferably 110-120 ℃, and the amount of the ethylene oxide subjected to the end-capping polymerization reaction is 15-25%, preferably 18-23% of the designed mass of the crude polyether polyol.
The organic acid neutralizer in the step (3) is one or two of citric acid or adipic acid.
The filter aid in the step (3) is a compound of high specific surface area Cartidge P and a three-dimensional network structure organic filter aid, the Cartidge P is a product of special absorbent of Dallas (Qingdao) and the adding amount is 0.05-0.08% of the mass of polyether polyol, the organic filter aid is at least one of wood fiber, plant fiber or high-purity cellulose fiber with a fiber structure, and the adding amount is 0.1-0.3% of the mass of polyether polyol.
Further, the preparation method of the polyether polyol for the shoe material comprises the following steps:
(1) adding a small molecular initiator and an alkali metal catalyst into a pressure-resistant reaction kettle for mixing, replacing the oxygen content in the kettle by nitrogen until the oxygen content is less than 50ppm, then heating to 105-115 ℃ and adding propylene oxide for primary polymerization reaction, continuing the internal pressure reaction for 1.5-3.5h after the reaction is finished, and removing unreacted monomers to obtain an intermediate polyether polyol;
(2) adding the intermediate polyether polyol and the phosphazene catalyst in the step (1) into a pressure-resistant reaction kettle, replacing nitrogen until the oxygen content in the kettle is less than 50ppm, carrying out nitrogen bubbling for 1-3h under the condition that the vacuum degree is lower than-0.09 MPa at 90-115 ℃, adding propylene oxide after timing is finished to carry out initiation polymerization reaction, continuing carrying out internal pressure reaction for 3.5-5.5h after the reaction is finished, removing unreacted monomers, supplementing nitrogen to 0.05-0.08MPa, adding propylene oxide and ethylene oxide to carry out copolymerization reaction, removing unreacted monomers after 1-3h after the internal pressure is finished, supplementing nitrogen to 0.05-0.08MPa, then adding ethylene oxide to carry out end capping polymerization reaction, and removing unreacted residual monomers and micromolecular byproducts after 1-3h after the reaction is finished to obtain crude polyether polyol;
(3) and (3) adding the polyether polyol crude polymer prepared in the step (2) into an organic acid neutralizer for neutralization, then adding a filter aid, and then drying and filtering to obtain the polyether polyol for shoe materials.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention innovatively adopts a double-catalysis system, takes KOH as a main catalyst and takes a phosphazene catalyst as a cocatalyst to synthesize the polyether polyol for the shoe material, the reaction activity is high, the side reaction products are few, and the product has lower unsaturation degree and narrower molecular weight distribution.
(2) Compared with the traditional phosphoric acid neutralization process, the organic acid neutralization process has the advantages that the odor of the obtained polyether product is lower, and the generation amount of waste residues is less.
(3) The filter aid Cartidge P adopted by the invention has large specific surface area, small dosage and good filter aid effect, the organic fiber filter aid forms a three-dimensional network structure, the polyether polyol can be rapidly filtered under the synergistic effect of the organic fiber filter aid and the polyether polyol, and the organic filter aid is degradable and has the advantage of environmental protection.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples.
The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.
Example 1
Adding 62g of ethylene glycol, 106g of diethylene glycol and 15g of potassium hydroxide into a pressure-resistant reaction kettle, replacing with nitrogen to ensure that the oxygen content in the kettle is less than 50ppm, then adding 1117g of propylene oxide to carry out primary polymerization reaction at the temperature of 108-110 ℃, and continuing internal pressure reaction for 3 hours after the reaction is finished to ensure that the added propylene oxide fully reacts, and removing unreacted monomers to obtain the intermediate polyether polyol.
Adding 500g of intermediate polyether polyol and 2.15g of phosphazene catalyst into a pressure-resistant reaction kettle, mixing, replacing with nitrogen to ensure that the oxygen content in the kettle is less than 50ppm, and carrying out nitrogen bubbling for 2 hours under the conditions that the temperature is 93-95 ℃ and the vacuum degree is less than-0.09 MPa. And adding 903g of propylene oxide to carry out polymerization reaction after timing is finished, continuing internal pressure reaction for 5h after the reaction is finished to ensure that the added propylene oxide fully reacts, removing unreacted monomers, supplementing nitrogen to 0.04MPa, feeding 645g of propylene oxide and 215g of ethylene oxide in equal proportion to carry out copolymerization reaction, continuing internal pressure reaction for 2h after the reaction is finished, removing the unreacted monomers, supplementing nitrogen to 0.08MPa, adding 387g of ethylene oxide to carry out end-capping polymerization reaction, continuing internal pressure for 2h after the reaction is finished, and removing unreacted residual monomers and micromolecular byproducts to obtain the crude polyether polyol.
Adding 11.1g of citric acid and 100g of water into the crude polyether polyol, then adding 1.2g of cartidge P and 4g of wood fiber, drying and filtering to obtain the polyether polyol for the shoe material.
Example 2
Adding 76g of propylene glycol, 134g of dipropylene glycol and 11g of potassium hydroxide into a pressure-resistant reaction kettle, replacing with nitrogen to ensure that the oxygen content in the kettle is less than 50ppm, then adding 1005g of propylene oxide to carry out primary polymerization reaction at the temperature of 108-110 ℃, and continuing internal pressure reaction for 3 hours after the reaction is finished to ensure that the added propylene oxide fully reacts, and removing unreacted monomers to obtain the intermediate polyether polyol.
Adding 500g of intermediate polyether polyol and 3.2g of phosphazene catalyst into a pressure-resistant reaction kettle, mixing, replacing with nitrogen to ensure that the oxygen content in the kettle is less than 50ppm, and carrying out nitrogen bubbling for 2 hours under the conditions that the temperature is 93-95 ℃ and the vacuum degree is less than-0.09 MPa. Adding 1290g of propylene oxide to carry out polymerization reaction after timing is finished, continuing internal pressure reaction for 5h after the reaction is finished to ensure that the added propylene oxide fully reacts, removing unreacted monomers, supplementing nitrogen to 0.04MPa, feeding 324g of propylene oxide and 108g of ethylene oxide in equal proportion to carry out copolymerization reaction, continuing internal pressure reaction for 2h after the reaction is finished, removing the unreacted monomers, supplementing nitrogen to 0.08MPa, adding 430g of ethylene oxide to carry out end-capping polymerization reaction, continuing internal pressure for 2h after the reaction is finished, and removing unreacted residual monomers and micromolecular byproducts to obtain the crude polyether polyol.
Adding 8.6g of citric acid and 100g of water into the crude polyether polyol, then adding 1.6g of cartidge P and 6g of cellulose fiber, drying and filtering to obtain the polyether polyol for the shoe material.
Example 3
Adding 180g of diethylene glycol and 13g of potassium hydroxide into a pressure-resistant reaction kettle, replacing with nitrogen to ensure that the oxygen content in the kettle is less than 50ppm, then adding 1917g of propylene oxide to carry out primary polymerization reaction at the temperature of 108-110 ℃, and continuing internal pressure reaction for 3 hours after the reaction is finished to ensure that the added propylene oxide fully reacts, and removing unreacted monomers to obtain the intermediate polyether polyol.
Adding 500g of intermediate polyether polyol and 4.3g of phosphazene catalyst into a pressure-resistant reaction kettle, mixing, replacing with nitrogen to ensure that the oxygen content in the kettle is less than 50ppm, and carrying out nitrogen bubbling for 2 hours under the conditions that the temperature is 93-95 ℃ and the vacuum degree is less than-0.09 MPa. 1182g of propylene oxide is added after timing is finished to carry out polymerization reaction, internal pressure reaction is continued for 5h after the reaction is finished, the added propylene oxide is fully reacted, unreacted monomers are removed, nitrogen is supplemented to 0.04MPa, 324g of propylene oxide and 108g of ethylene oxide are fed in an equal proportion to carry out copolymerization reaction, internal pressure reaction is continued for 2h after the reaction is finished, the unreacted monomers are removed, nitrogen is supplemented to 0.08MPa, 538g of ethylene oxide is added to carry out end-capping polymerization reaction, internal pressure is continued for 2h after the reaction is finished, and unreacted residual monomers and micromolecular byproducts are removed, so that the crude polyether polyol is prepared.
Adding 16.8g of adipic acid and 80g of water into the crude polyether polyol, then adding 1g of Cartridge P and 4g of wood fiber, and drying and filtering to obtain the polyether polyol for the shoe material.
Comparative example 1
500g of the intermediate polyether polyol obtained in example 1 was put into a pressure-resistant reaction vessel and mixed, the oxygen content in the vessel was adjusted to less than 50ppm by nitrogen substitution, and nitrogen bubbling was carried out at a temperature of 93 to 95 ℃ and a vacuum degree of less than-0.09 MPa for 2 hours. And adding 903g of propylene oxide to carry out polymerization reaction after timing is finished, continuing internal pressure reaction for 5h after the reaction is finished to ensure that the added propylene oxide fully reacts, removing unreacted monomers, supplementing nitrogen to 0.04MPa, feeding 645g of propylene oxide and 215g of ethylene oxide in equal proportion to carry out copolymerization reaction, continuing internal pressure reaction for 2h after the reaction is finished, removing the unreacted monomers, supplementing nitrogen to 0.08MPa, adding 387g of ethylene oxide to carry out end-capping polymerization reaction, continuing internal pressure for 2h after the reaction is finished, and removing unreacted residual monomers and micromolecular byproducts to obtain the crude polyether polyol.
Adding 18.6g of phosphoric acid (with the concentration of 71%) and 100g of water into the crude polyether polyol, then adding 3g of magnesium aluminum silicate for adsorption, and then drying and filtering to obtain the polyether polyol with high molecular weight and high activity.
The polyether polyols prepared in examples 1 to 3 and comparative example 1 were subjected to a performance test according to the current national standard, the test results being shown in table 1.
TABLE 1 polyether polyol test results prepared in examples 1-3 and comparative example 1
Of course, the foregoing is only a preferred embodiment of the invention and should not be taken as limiting the scope of the embodiments of the invention. The present invention is not limited to the above examples, and equivalent changes and modifications made by those skilled in the art within the spirit and scope of the present invention should be construed as being included in the scope of the present invention.
Claims (10)
1. A preparation method of polyether polyol for shoe materials is characterized by comprising the following steps: the method comprises the following steps:
(1) under the action of an alkali metal catalyst, carrying out primary polymerization reaction on a small molecular initiator and propylene oxide to obtain an intermediate polyether polyol;
(2) under the action of a phosphazene catalyst, adding propylene oxide into the intermediate polyether polyol to carry out initiation reaction, adding propylene oxide and ethylene oxide to carry out copolymerization reaction after initiation, and adding ethylene oxide to carry out end capping polymerization reaction after the reaction is finished to obtain crude polyether polyol;
(3) and adding an organic acid neutralizer into the crude polyether polyol for neutralization, then adding a filter aid, and drying and filtering to obtain the polyether polyol for the shoe material.
2. The method for producing polyether polyol for shoe materials according to claim 1, characterized in that: the micromolecule initiator in the step (1) is at least one of ethylene glycol, propylene glycol, diethylene glycol or dipropylene glycol.
3. The method for producing polyether polyol for shoe materials according to claim 1, characterized in that: the alkali metal catalyst in the step (1) is potassium hydroxide, and the addition amount of the alkali metal catalyst is 1-2% of the designed mass of the intermediate polyether polyol.
4. The method for producing polyether polyol for shoe materials according to claim 1, characterized in that: the adding amount of the phosphazene catalyst in the step (2) is 0.5-3.5 per mill of the designed mass of the crude polyether polyol.
5. The method for producing polyether polyol for shoe materials according to claim 1, characterized in that: the initiation reaction temperature of the propylene oxide in the step (2) is 90-105 ℃, and the copolymerization reaction temperature of the propylene oxide and the ethylene oxide is 90-105 ℃.
6. The method for producing polyether polyol for shoe materials according to claim 1, characterized in that: in the step (2), the copolymerization amount of the ethylene oxide for copolymerization is 5-10% of the designed mass of the crude polyether polyol, and the mass ratio of the propylene oxide to the ethylene oxide for copolymerization is 3: 1.
7. The method for producing polyether polyol for shoe materials according to claim 1, characterized in that: the temperature of the ethylene oxide end capping polymerization reaction in the step (2) is 105-125 ℃, and the amount of the ethylene oxide for end capping polymerization reaction is 15-25% of the designed mass of the crude polyether polyol.
8. The method for producing polyether polyol for shoe materials according to claim 1, characterized in that: the organic acid neutralizer in the step (3) is one or two of citric acid or adipic acid.
9. The method for producing polyether polyol for shoe materials according to claim 1, characterized in that: the filter aid in the step (3) is a compound of filter aid Cartidge P and an organic filter aid, and the organic filter aid is at least one of wood fiber with a fiber structure, plant fiber or high-purity cellulose fiber.
10. The method for producing polyether polyol for shoe materials according to claim 1, characterized in that: the method comprises the following steps:
(1) adding a small molecular initiator and an alkali metal catalyst into a pressure-resistant reaction kettle for mixing, replacing the oxygen content in the kettle by nitrogen until the oxygen content is less than 50ppm, then heating to 105-115 ℃ and adding propylene oxide for primary polymerization reaction, continuing the internal pressure reaction for 1.5-3.5h after the reaction is finished, and removing unreacted monomers to obtain an intermediate polyether polyol;
(2) adding the polyether polyol intermediate and the phosphazene catalyst in the step (1) into a pressure-resistant reaction kettle, replacing nitrogen until the oxygen content in the kettle is less than 50ppm, carrying out nitrogen bubbling for 1-3h under the condition that the vacuum degree is lower than-0.09 MPa at 90-115 ℃, adding propylene oxide after timing is finished to carry out initiation polymerization reaction, continuing carrying out internal pressure reaction for 3.5-5.5h after the reaction is finished, removing unreacted monomers, supplementing nitrogen to 0.05-0.08MPa, adding propylene oxide and ethylene oxide to carry out copolymerization reaction, removing unreacted monomers after 1-3h after the internal pressure is finished, supplementing nitrogen to 0.05-0.08MPa, then adding ethylene oxide to carry out end capping polymerization reaction, and removing unreacted residual monomers and micromolecular byproducts after 1-3h after the reaction is finished to obtain crude polyether polyol;
(3) and (3) adding the polyether polyol crude polymer prepared in the step (2) into an organic acid neutralizer for neutralization, then adding a filter aid, and then drying and filtering to obtain the polyether polyol for shoe materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011465486.8A CN112661951A (en) | 2020-12-14 | 2020-12-14 | Preparation method of polyether polyol for shoe material |
Applications Claiming Priority (1)
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| CN104910370A (en) * | 2015-06-11 | 2015-09-16 | 山东一诺威新材料有限公司 | Preparation method of high-activity low-unsaturation-degree polyether polyol for shoe materials |
| CN105814113A (en) * | 2013-12-18 | 2016-07-27 | 科思创德国股份有限公司 | Method for working up alkaline polyether polyols |
| CN110922580A (en) * | 2019-12-12 | 2020-03-27 | 山东一诺威新材料有限公司 | Preparation method of high molecular weight high activity polyether polyol |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105814113A (en) * | 2013-12-18 | 2016-07-27 | 科思创德国股份有限公司 | Method for working up alkaline polyether polyols |
| CN104910370A (en) * | 2015-06-11 | 2015-09-16 | 山东一诺威新材料有限公司 | Preparation method of high-activity low-unsaturation-degree polyether polyol for shoe materials |
| CN110922580A (en) * | 2019-12-12 | 2020-03-27 | 山东一诺威新材料有限公司 | Preparation method of high molecular weight high activity polyether polyol |
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