CN105315450A - Preparation method of polyether polyol used for total-moisture rigid polyurethane foam - Google Patents
Preparation method of polyether polyol used for total-moisture rigid polyurethane foam Download PDFInfo
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- CN105315450A CN105315450A CN201510834789.5A CN201510834789A CN105315450A CN 105315450 A CN105315450 A CN 105315450A CN 201510834789 A CN201510834789 A CN 201510834789A CN 105315450 A CN105315450 A CN 105315450A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention belongs to the technical field of polyether polyol synthesis and particularly relates to a preparation method of polyether polyol used for total-moisture rigid polyurethane foam. The preparation method includes the steps that saccharose, pentaerythritol, glycerin and n-methy-o-phenylendiamine serve as a compound starting agent, KOH serves as a catalyst, epoxypropane is added for conducting a polymerization reaction, then neutralization, adsorption, drying and filtering are conducted, and the polyether polyol is obtained. According to the preparation method, the compound starting agent is adopted, the obtained polyether polyol prepared through the preparation method is low in viscosity, high in strength, good in base material caking property and size stability, suitable for construction and production of total-moisture system component materials, capable of effectively lowering the heat conduction coefficient of total-moisture system polyurethane foam and improving heat preservation performance and particularly applicable to the field of electrical appliances, such as refrigerators and freezers which have high requirements for heat insulation performance and energy consumption and meets the high-standard requirements of saving energy, lowering energy consumption and being environmental friendly.
Description
Technical field
The invention belongs to polyether glycol synthesis technical field, be specifically related to a kind of preparation method of full-water type polyurethane polyether polyvalent alcohol.
Background technology
Polyether glycol is the main raw material producing hard polyurethane foam.Hard polyurethane foams has that density is little, thermal conductivity is low, cohesive strength high, be widely used in refrigerator, refrigerator and the industry such as automobile, building, but the fluorochlorohydrocarbon CFC-11 whipping agent used due to it has destruction to atmospheric ozone layer, in order to safeguard ecotope, international convention has been produced it and has been used and made strict restriction and regulation, is the key subjects of polyurethane foam industry with zero or the whipping agent replacement fluorine chlorocarbon of low ODP value.
Full water foamed technology, principle is that water and polyisocyanates react and generate CO
2, CO
2stay the whipping agent as porous plastics in abscess, this system ODP value is zero, nontoxic, environmental protection, simple process, low without particular requirement, cost to equipment, is the important line that CFC-11 substitutes.But full water foamed system also exists many deficiencies, such as do not have the solvent cut effect of pneumatogen, the viscosity of combined polyether material is comparatively large, Combination is poor; When preparing low density and hard bubbling, because water consumption is comparatively large, causes foam crisp, with the bad adhesion of base material, dimensional stability and poor insulation property etc., thus limit application and the popularization of full water foamed polyurethane foam.
In addition, full aqueous systems foam thermal conductivity is higher, is restricted in the promotion and application of field of household appliances.
Summary of the invention
For the deficiencies in the prior art, the object of this invention is to provide a kind of preparation method of full-water type polyurethane polyether polyvalent alcohol, obtained polyether glycol has that viscosity is low, intensity is high, the feature of base material cohesiveness and good stability of the dimension, is applicable to construction and the production of full aqueous systems premixed systems.
The preparation method of full-water type polyurethane polyether polyvalent alcohol of the present invention, with sucrose, tetramethylolmethane, glycerine and methyl-o-phenylenediamine for compound initiator, adopt KOH as catalyzer, add propylene oxide and carry out polyreaction, then neutralize, adsorb, dry and after filtering, obtain polyether glycol.
The preparation method of described full-water type polyurethane polyether polyvalent alcohol, preferably comprises the steps:
(1) in reactor, add compound initiator and catalyzer, vacuumize after nitrogen replacement, stir and heat up, add the reaction of PART EPOXY propane, then vacuum is aging;
(2) adding remaining propylene oxide, reacting aging to continuing during constant pressure;
(3) add at 85 ~ 90 DEG C water and phosphoric acid carry out in and, then add adsorbent, dehydrate and filter, obtain full-water type polyurethane polyether polyvalent alcohol.
Wherein:
The mass ratio of described sucrose, tetramethylolmethane, glycerine and methyl-o-phenylenediamine is 342:68.1:196.9:61.
Described compound initiator and the mass ratio of propylene oxide are 668:3306.5 ~ 4029.1.
Described catalyst levels is 0.2 ~ 0.3% of compound initiator and propylene oxide total mass.
In step (1), when adding compound initiator, again the mixture of the two is added in the lump after methyl-o-phenylenediamine is first dissolved with glycerine.
In step (1), when stirring is warming up to 85 DEG C, add the reaction of PART EPOXY propane; The amount of described propylene oxide accounts for 8 ~ 10% of compound initiator and propylene oxide total mass; Described temperature of reaction is 80 ~ 90 DEG C, and reaction pressure is 0.1 ~ 0.3MPa, reacts to constant pressure.
In step (2), temperature of reaction is 100 ~ 120 DEG C, and reaction pressure controls at 0.1 ~ 0.3MPa.
In step (1), (2), described aging temperature is 90 ~ 110 DEG C, and digestion time is 1 ~ 3h.
In step (3), described phosphoric acid is the phosphoric acid of 85%; Described sorbent material is the mixture of Magnesium Silicate q-agent and pure aluminium silicate, and the two mass ratio is 1:1 ~ 2, and consumption is 0.2 ~ 0.3% of compound initiator and propylene oxide total mass.
Compared with prior art, beneficial effect of the present invention is as follows:
(1) the present invention's sucrose of adopting functionality higher and the very regular tetramethylolmethane of molecular structure are as main initiator, ensure that the high strength of polyether glycol and splendid dimensional stability, have lower hydroxyl value, the polyurethane foam base material adhesive property obtained with it is good simultaneously.
(2) introduce methyl-o-phenylenediamine in initiator simultaneously, with the rigid-foam polyether that it is produced, there is better mutual solubility, the polyurethane foam made is more even, abscess is finer and smoother, can not cause contraction, improve heat-proof quality and the Low-Temperature Size performance of foam.
(3) when adding compound initiator, add in the lump again after first methyl-o-phenylenediamine glycerine being dissolved, solve its unstable easily variable color and insufficient difficult problem of solid reaction in atmosphere, make the index stability of the polyether glycol different batches of preparation better.
(4) in preparation process, propylene oxide is added in batches, add propylene oxide at a lower temperature and activate polyreaction smoothly, avoid the generation directly carrying out pyroreaction by product, more be conducive to the stability of polyether glycol synthesis index, and the properties of preparation polyurethane foam is more excellent.
(5) the present invention adopts compound initiator, the polyether glycol viscosity obtained in conjunction with described preparation method is low, intensity is high, base material cohesiveness and good stability of the dimension, be applicable to construction and the production of full aqueous systems premixed systems, and effectively can reduce the thermal conductivity of full aqueous systems polyurethane foam, improve heat-insulating property, be specially adapted to such as refrigerator, refrigerator household appliances to heat-proof quality and the higher field of horsepower requirements, meet the high standard requirement of energy-conservation, consumption reduction, environmental protection.
Embodiment
Below in conjunction with embodiment, the present invention will be further described.
The all raw materials used in embodiment, except specified otherwise, are commercial.
Embodiment 1
(1) in the autoclave that agitator, gauger, heating and temperature controlling device, refrigerating unit and pressure transmitter are housed, sucrose 342g, tetramethylolmethane 68.1g, glycerine 196.9g, methyl-o-phenylenediamine 61g and catalyzer KOH14.1g is added, nitrogen replacement 6 times, and to be evacuated to pressure be-0.1MPa, when stirring is warming up to 85 DEG C, continuous dropping 470g propylene oxide, temperature of reaction controls at 85 ± 5 DEG C, reaction pressure controls at 0.2 ± 0.1MPa, when reaction no longer changes to pressure, the aging 2h of pressure in continuing at 100 ± 10 DEG C;
(2) be warming up to 105 DEG C, drip 3559.1g propylene oxide continuously, temperature of reaction controls at 110 ± 10 DEG C, and reaction pressure controls at 0.2 ± 0.1MPa, reacts after no longer changing to pressure, continues aging 2h at 100 ± 10 DEG C;
(3) 87.5 ± 2.5 DEG C time, 27.5g phosphoric acid is added and 187.8g water carries out neutralization reaction, 4.7g Magnesium Silicate q-agent and 4.7g adsorbin is added after reaction 1h, stir 40min final vacuum dehydration 3h, then filter, obtain full-water type polyurethane polyether polyvalent alcohol.
Obtained polyether glycol character index is as follows:
Outward appearance: pale yellow to brown yellow transparent liquid;
Functionality: 4.5;
Hydroxyl value: 231.7mgKOH/g;
Viscosity (25 DEG C): 936mPas;
Moisture: 0.017%;
pH：6.41；
Potassium ion: 1.15ppm.
Embodiment 2
(1) in the autoclave that agitator, gauger, heating and temperature controlling device, refrigerating unit and pressure transmitter are housed, sucrose 342g, tetramethylolmethane 68.1g, glycerine 196.9g, methyl-o-phenylenediamine 61g and catalyzer KOH8.6g is added, nitrogen replacement 7 times, and to be evacuated to pressure be-0.1MPa, when stirring is warming up to 85 DEG C, continuous dropping 387g propylene oxide, temperature of reaction controls at 85 ± 5 DEG C, reaction pressure controls at 0.2 ± 0.1MPa, after reaction no longer changes to pressure, the aging 1h of pressure in continuing at 100 ± 10 DEG C;
(2) be warming up to 105 DEG C, drip 3250.6g propylene oxide continuously, temperature of reaction controls at 110 ± 10 DEG C, and reaction pressure controls at 0.2 ± 0.1MPa, reacts after no longer changing to pressure, continues aging 3h at 100 ± 10 DEG C;
(3) 87.5 ± 2.5 DEG C time, 25.2g phosphoric acid is added and 172.2g water carries out neutralization reaction, 4.3g Magnesium Silicate q-agent and 6.45g adsorbin is added after reaction 1h, stir 40min final vacuum dehydration 3h, then filter, obtain full-water type polyurethane polyether polyvalent alcohol.
Obtained polyether glycol character index is as follows:
Outward appearance: pale yellow to brown yellow transparent liquid;
Functionality: 4.5;
Hydroxyl value: 240.6mgKOH/g;
Viscosity (25 DEG C): 1013mPas;
Moisture: 0.022%;
pH：6.32；
Potassium ion: 0.095ppm.
Embodiment 3
(1) in the autoclave that agitator, gauger, heating and temperature controlling device, refrigerating unit and pressure transmitter are housed, sucrose 342g, tetramethylolmethane 68.1g, glycerine 196.9g, methyl-o-phenylenediamine 61g and catalyzer KOH11.9g is added, nitrogen replacement 8 times, and to be evacuated to pressure be-0.1MPa, when stirring is warming up to 85 DEG C, continuous dropping 318g propylene oxide, temperature of reaction controls at 85 ± 5 DEG C, reaction pressure controls at 0.2 ± 0.1MPa, after reaction no longer changes to pressure, the aging 3h of pressure in continuing at 100 ± 10 DEG C;
(2) be warming up to 105 DEG C, drip 2988.4g propylene oxide continuously, temperature of reaction controls at 110 ± 10 DEG C, and reaction pressure controls at 0.2 ± 0.1MPa, reacts after no longer changing to pressure, continues aging 1h at 100 ± 10 DEG C;
(3) 87.5 ± 2.5 DEG C time, 23.2g phosphoric acid is added and 158.9g water carries out neutralization reaction, 4.0g Magnesium Silicate q-agent and 8.0g adsorbin is added after reaction 1h, stir 40min final vacuum dehydration 3h, then filter, obtain full-water type polyurethane polyether polyvalent alcohol.
Obtained polyether glycol character index is as follows:
Outward appearance: pale yellow to brown yellow transparent liquid;
Functionality: 4.5;
Hydroxyl value: 252.1mgKOH/g;
Viscosity (25 DEG C): 1130mPas;
Moisture: 0.019%;
pH：6.63；
Potassium ion: 1.33ppm.
The polyether glycol adopting embodiment 1-3 to prepare prepares full water premixed systems, carry out the Performance Detection of hard polyurethane foam, hard polyurethane foams prepared by the full aqueous systems premixed systems adopting same recipe to prepare with conventional commercial polyether glycol contrasts, and comparing result is in table 1.
The performance comparison of hard polyurethane foam prepared by table 1
Claims (10)
1. the preparation method of a full-water type polyurethane polyether polyvalent alcohol, it is characterized in that: with sucrose, tetramethylolmethane, glycerine and methyl-o-phenylenediamine for compound initiator, adopt KOH as catalyzer, add propylene oxide and carry out polyreaction, then neutralize, adsorb, dry and after filtering, obtain polyether glycol.
2. the preparation method of full-water type polyurethane polyether polyvalent alcohol according to claim 1, is characterized in that: comprise the steps:
(1) in reactor, add compound initiator and catalyzer, vacuumize after nitrogen replacement, stir and heat up, add the reaction of PART EPOXY propane, then vacuum is aging;
(2) adding remaining propylene oxide, reacting aging to continuing during constant pressure;
(3) add at 85 ~ 90 DEG C water and phosphoric acid carry out in and, then add adsorbent, dehydrate and filter, obtain full-water type polyurethane polyether polyvalent alcohol.
3. the preparation method of full-water type polyurethane polyether polyvalent alcohol according to claim 1, is characterized in that: the mass ratio of described sucrose, tetramethylolmethane, glycerine and methyl-o-phenylenediamine is 342:68.1:196.9:61.
4. the preparation method of full-water type polyurethane polyether polyvalent alcohol according to claim 1, is characterized in that: described compound initiator and the mass ratio of propylene oxide are 668:3306.5 ~ 4029.1.
5. the preparation method of full-water type polyurethane polyether polyvalent alcohol according to claim 1, is characterized in that: described catalyst levels is 0.2 ~ 0.3% of compound initiator and propylene oxide total mass.
6. the preparation method of full-water type polyurethane polyether polyvalent alcohol according to claim 2, it is characterized in that: in step (1), when adding compound initiator, again the mixture of the two is added in the lump after methyl-o-phenylenediamine is first dissolved with glycerine.
7. the preparation method of full-water type polyurethane polyether polyvalent alcohol according to claim 2, is characterized in that: in step (1), when stirring is warming up to 85 DEG C, adds the reaction of PART EPOXY propane; The amount of described propylene oxide accounts for 8 ~ 10% of compound initiator and propylene oxide total mass; Described temperature of reaction is 80 ~ 90 DEG C, and reaction pressure is 0.1 ~ 0.3MPa, reacts to constant pressure.
8. the preparation method of full-water type polyurethane polyether polyvalent alcohol according to claim 2, is characterized in that: in step (2), temperature of reaction is 100 ~ 120 DEG C, and reaction pressure controls at 0.1 ~ 0.3MPa.
9. the preparation method of full-water type polyurethane polyether polyvalent alcohol according to claim 2, it is characterized in that: in step (1), (2), described aging temperature is 90 ~ 110 DEG C, and digestion time is 1 ~ 3h.
10. the preparation method of full-water type polyurethane polyether polyvalent alcohol according to claim 2, it is characterized in that: in step (3), described phosphoric acid is the phosphoric acid of 85%; Described sorbent material is the mixture of Magnesium Silicate q-agent and pure aluminium silicate, and the two mass ratio is 1:1 ~ 2, and consumption is 0.2 ~ 0.3% of compound initiator and propylene oxide total mass.
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| CN105860051A (en) * | 2016-06-29 | 2016-08-17 | 句容宁武新材料股份有限公司 | Method for preparing low-odor polyether for polyurethane foam and application of prepared products |
| CN109134811A (en) * | 2017-06-28 | 2019-01-04 | 盛势达技研株式会社 | Urethane composition |
| CN110885418A (en) * | 2019-12-16 | 2020-03-17 | 山东一诺威新材料有限公司 | Polyurethane rigid foam for on-line tube heat collector and preparation method thereof |
| CN111471170A (en) * | 2020-04-22 | 2020-07-31 | 山东福瑞斯新材料科技有限公司 | Preparation process of environment-friendly polyurethane all-water composite material |
| CN111978533A (en) * | 2020-08-25 | 2020-11-24 | 江苏德励达新材料有限公司 | Method for preparing polyether polyol with good pentane compatibility and high functionality |
| CN113174038A (en) * | 2021-04-12 | 2021-07-27 | 浙江理工大学 | Preparation method of polyether polyol |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105860051A (en) * | 2016-06-29 | 2016-08-17 | 句容宁武新材料股份有限公司 | Method for preparing low-odor polyether for polyurethane foam and application of prepared products |
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| CN111471170A (en) * | 2020-04-22 | 2020-07-31 | 山东福瑞斯新材料科技有限公司 | Preparation process of environment-friendly polyurethane all-water composite material |
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| CN113174038A (en) * | 2021-04-12 | 2021-07-27 | 浙江理工大学 | Preparation method of polyether polyol |
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