CN105315450B - The preparation method of full-water type polyurethane polyether polyalcohol - Google Patents
The preparation method of full-water type polyurethane polyether polyalcohol Download PDFInfo
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- CN105315450B CN105315450B CN201510834789.5A CN201510834789A CN105315450B CN 105315450 B CN105315450 B CN 105315450B CN 201510834789 A CN201510834789 A CN 201510834789A CN 105315450 B CN105315450 B CN 105315450B
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Abstract
The invention belongs to PPG synthesis technical field, and in particular to a kind of preparation method of full-water type polyurethane polyether polyalcohol.Described preparation method, using sucrose, pentaerythrite, glycerine and methyl-o-phenylenediamine as compound initiator, using KOH as catalyst, adds expoxy propane and carries out polymerisation, after then neutralizing, adsorb, drying and filter, obtains PPG.The present invention uses compound initiator, the PPG viscosity with reference to made from the preparation method is low, intensity is high, base material caking property and good stability of the dimension, the construction and production of material are combined suitable for full aqueous systems, and it can effectively reduce the thermal conductivity factor of full aqueous systems polyurethane foam, improve heat-insulating property, such as refrigerator, refrigerator the household appliances field higher to heat-proof quality and horsepower requirements is particularly suitable for use in, meets energy-conservation, consumption reduction, the high standards of environmental protection.
Description
Technical field
The invention belongs to PPG synthesis technical field, and in particular to a kind of full-water type polyurethane polyether is more
The preparation method of first alcohol.
Background technology
PPG is the primary raw material for producing hard polyurethane foam.Hard polyurethane foams have that density is small, lead
The features such as hot coefficient is low, adhesion strength is high, is widely used in the industries such as refrigerator, refrigerator and automobile, building, but used due to it
Fluorochlorohydrocarbon CFC-11 foaming agents have destruction to atmospheric ozone layer, and in order to safeguard ecological environment, international convention is produced to it
With using strict limitation and regulation is made that, it is polyurethane foam industry to substitute fluorochlorohydrocarbon with the foaming agent of zero or low ODP values
Key subjects.
Full water foamed technology, principle is water and polyisocyanates reaction generation CO2, CO2Stay in abscess as foamed plastics
Foaming agent, system ODP values are zero, nontoxic, environmentally friendly, technique is easy, to equipment without particular/special requirement, low cost, be CFC-11
The important line substituted.But, there is also many deficiencies, such as solvent without physical blowing agent are dilute for full water foamed system
Release effect, the viscosity of combined polyether material is larger, Combination is poor；When preparation low-density is hard bubbled, because water consumption is larger, cause
Foam is crisp, the bad adhesion with base material, dimensional stability and poor insulation property etc., so as to limit full water foamed polyurethane foam
The application of foam and popularization.
In addition, full aqueous systems foam thermal conductivity is higher, it is restricted in the promotion and application of field of household appliances.
The content of the invention
In view of the shortcomings of the prior art, it is an object of the invention to provide a kind of full-water type polyurethane polyether polyalcohol
Preparation method, obtained PPG has that viscosity is low, intensity is high, base material caking property and the characteristics of good stability of the dimension,
The construction and production of material are combined suitable for full aqueous systems.
The preparation method of full-water type polyurethane polyether polyalcohol of the present invention, with sucrose, pentaerythrite, sweet
Oil and methyl-o-phenylenediamine are compound initiator, using KOH as catalyst, add expoxy propane and carry out polymerisation, then
Neutralize, absorption, dry and after filtering, obtain PPG.
The preparation method of described full-water type polyurethane polyether polyalcohol, preferably comprises following steps：
(1) vacuumized after adding compound initiator and catalyst, nitrogen displacement into reactor, stirring heating, addition portion
Divide expoxy propane reaction, then vacuum aging；
(2) add remaining expoxy propane, reaction to pressure it is constant when continue aging；
(3) add water at 85~90 DEG C and phosphoric acid is neutralized, then add adsorbent absorption, dehydrate and mistake
Filter, produces full-water type polyurethane polyether polyalcohol.
Wherein：
Described sucrose, pentaerythrite, the mass ratio of glycerine and methyl-o-phenylenediamine are 342：68.1：196.9：61.
Described compound initiator and the mass ratio of expoxy propane are 668：3306.5~4029.1.
Described catalyst amount is the 0.2~0.3% of compound initiator and expoxy propane gross mass.
In step (1), when adding compound initiator, again by the mixing of the two after methyl-o-phenylenediamine is first dissolved with glycerine
Thing is added in the lump.
In step (1), when stirring is warming up to 85 DEG C, the reaction of PART EPOXY propane is added；The amount of the expoxy propane accounts for multiple
Close the 8~10% of initiator and expoxy propane gross mass；The reaction temperature be 80~90 DEG C, reaction pressure be 0.1~
0.3MPa, reaction to constant pressure.
In step (2), reaction temperature is 100~120 DEG C, and reaction pressure is controlled in 0.1~0.3MPa.
In step (1), (2), described aging temperature is 90~110 DEG C, and ageing time is 1~3h.
In step (3), the phosphoric acid that described phosphoric acid is 85%；The adsorbent is the mixture of magnesium silicate and alumina silicate,
The two mass ratio is 1：1~2, consumption is the 0.2~0.3% of compound initiator and expoxy propane gross mass.
Compared with prior art, beneficial effects of the present invention are as follows：
(1) present invention is used as main starting using the higher sucrose of degree of functionality and molecular structure extremely regular pentaerythrite
Agent, it is ensured that the high intensity of PPG and splendid dimensional stability, while there is relatively low hydroxyl value, it is obtained poly- with it
Urethane foam substrate adhesive property is good.
(2) methyl-o-phenylenediamine is introduced simultaneously in initiator, there is more preferable intersolubility with its rigid-foam polyether produced,
The polyurethane foam being made more uniform, abscess is finer and smoother, will not cause contraction, improve the heat-proof quality and low temperature of foam
Dimensional performance.
(3) it is another after first methyl-o-phenylenediamine glycerine is dissolved and add when adding compound initiator, solve it
Unstable easy discoloration and the insufficient problem of solid reaction, make the index of the PPG different batches of preparation in atmosphere
Stability is more preferable.
(4) expoxy propane is added in batches in preparation process, expoxy propane is added at a lower temperature, and smoothly activation is poly-
Close reaction, it is to avoid directly carry out the generation of pyroreaction accessory substance, be more beneficial for the stability that PPG synthesizes index,
And it is more excellent to prepare the properties of polyurethane foam.
(5) present invention uses compound initiator, and the PPG viscosity with reference to made from the preparation method is low, intensity
High, base material caking property and good stability of the dimension, it is adaptable to the construction and production of full aqueous systems combination material, and can effectively reduce
The thermal conductivity factor of full aqueous systems polyurethane foam, improves heat-insulating property, is particularly suitable for use in such as refrigerator, refrigerator household appliances to heat-insulated
Performance and the higher field of horsepower requirements, meet energy-conservation, consumption reduction, the high standards of environmental protection.
Embodiment
With reference to embodiment, the present invention will be further described.
All raw materials used in embodiment unless otherwise specified, are purchased in market.
Embodiment 1
(1) in the autoclave equipped with agitator, meter, heating and temperature controlling device, cooling device and pressure sensor
Middle addition sucrose 342g, pentaerythrite 68.1g, glycerine 196.9g, methyl-o-phenylenediamine 61g and catalyst KOH 14.1g, nitrogen
Displacement 6 times, and pressure is evacuated to for -0.1MPa, it is continuous that 470g expoxy propane, reaction temperature is added dropwise when stirring is warming up to 85 DEG C
Degree control is at 85 ± 5 DEG C, and reaction pressure control is in 0.2 ± 0.1MPa, when reaction to pressure no longer changes, at 100 ± 10 DEG C after
Continuous internal pressure aging 2h；
(2) 105 DEG C are warming up to, continuous that 3559.1g expoxy propane is added dropwise, reaction temperature is controlled in 110 ± 10 DEG C, reaction pressure
Power control is in 0.2 ± 0.1MPa, after reaction no longer changes to pressure, continues aging 2h at 100 ± 10 DEG C；
(3) 27.5g phosphoric acid is added at 87.5 ± 2.5 DEG C and 187.8g water carries out addition after neutralization reaction, reaction 1h
Vacuum dehydration 3h after 4.7g magnesium silicates and 4.7g adsorbins, stirring 40min, is then filtered, and is produced complete water type and is gathered
Urethane polyether polyalcohol.
Obtained PPG property index is as follows：
Outward appearance：It is pale yellow to brown yellow transparent liquid；
Degree of functionality：4.5；
Hydroxyl value：231.7mgKOH/g；
Viscosity (25 DEG C)：936mPa·s；
Moisture：0.017%；
pH：6.41；
Potassium ion：1.15ppm.
Embodiment 2
(1) in the autoclave equipped with agitator, meter, heating and temperature controlling device, cooling device and pressure sensor
Middle addition sucrose 342g, pentaerythrite 68.1g, glycerine 196.9g, methyl-o-phenylenediamine 61g and catalyst KOH 8.6g, nitrogen
Displacement 7 times, and pressure is evacuated to for -0.1MPa, it is continuous that 387g expoxy propane, reaction temperature is added dropwise when stirring is warming up to 85 DEG C
Degree control is at 85 ± 5 DEG C, and reaction pressure control is in 0.2 ± 0.1MPa, after reaction no longer changes to pressure, at 100 ± 10 DEG C after
Continuous internal pressure aging 1h；
(2) 105 DEG C are warming up to, continuous that 3250.6g expoxy propane is added dropwise, reaction temperature is controlled in 110 ± 10 DEG C, reaction pressure
Power control is in 0.2 ± 0.1MPa, after reaction no longer changes to pressure, continues aging 3h at 100 ± 10 DEG C；
(3) 25.2g phosphoric acid is added at 87.5 ± 2.5 DEG C and 172.2g water carries out addition after neutralization reaction, reaction 1h
Vacuum dehydration 3h after 4.3g magnesium silicates and 6.45g adsorbins, stirring 40min, is then filtered, and is produced complete water type and is gathered
Urethane polyether polyalcohol.
Obtained PPG property index is as follows：
Outward appearance：It is pale yellow to brown yellow transparent liquid；
Degree of functionality：4.5；
Hydroxyl value：240.6mgKOH/g；
Viscosity (25 DEG C)：1013mPa·s；
Moisture：0.022%；
pH：6.32；
Potassium ion：0.095ppm.
Embodiment 3
(1) in the autoclave equipped with agitator, meter, heating and temperature controlling device, cooling device and pressure sensor
Middle addition sucrose 342g, pentaerythrite 68.1g, glycerine 196.9g, methyl-o-phenylenediamine 61g and catalyst KOH 11.9g, nitrogen
Displacement 8 times, and pressure is evacuated to for -0.1MPa, it is continuous that 318g expoxy propane, reaction temperature is added dropwise when stirring is warming up to 85 DEG C
Degree control is at 85 ± 5 DEG C, and reaction pressure control is in 0.2 ± 0.1MPa, after reaction no longer changes to pressure, at 100 ± 10 DEG C after
Continuous internal pressure aging 3h；
(2) 105 DEG C are warming up to, continuous that 2988.4g expoxy propane is added dropwise, reaction temperature is controlled in 110 ± 10 DEG C, reaction pressure
Power control is in 0.2 ± 0.1MPa, after reaction no longer changes to pressure, continues aging 1h at 100 ± 10 DEG C；
(3) 23.2g phosphoric acid is added at 87.5 ± 2.5 DEG C and 158.9g water carries out addition after neutralization reaction, reaction 1h
Vacuum dehydration 3h after 4.0g magnesium silicates and 8.0g adsorbins, stirring 40min, is then filtered, and is produced complete water type and is gathered
Urethane polyether polyalcohol.
Obtained PPG property index is as follows：
Outward appearance：It is pale yellow to brown yellow transparent liquid；
Degree of functionality：4.5；
Hydroxyl value：252.1mgKOH/g；
Viscosity (25 DEG C)：1130mPa·s；
Moisture：0.019%；
pH：6.63；
Potassium ion：1.33ppm.
Full water combination material is prepared using the embodiment 1-3 PPGs prepared, the performance of hard polyurethane foam is carried out
Detection, the full aqueous systems prepared with conventional commercial PPG using same recipe combine hard polyurethane foams prepared by material
Contrasted, comparing result is shown in Table 1.
The performance comparison of hard polyurethane foam prepared by table 1
Claims (7)
1. a kind of preparation method of full-water type polyurethane polyether polyalcohol, it is characterised in that：With sucrose, pentaerythrite,
Glycerine and methyl-o-phenylenediamine are compound initiator, using KOH as catalyst, add expoxy propane and carry out polymerisation, so
Neutralize, adsorb, dry and after filtering afterwards, obtain PPG；
Specifically include following steps：
（1）Vacuumized after adding compound initiator and catalyst, nitrogen displacement into reactor, stirring heating adds part ring
Ethylene Oxide reacts, then vacuum aging；
（2）Add remaining expoxy propane, reaction to pressure it is constant when continue aging；
（3）Water is added at 85~90 DEG C and phosphoric acid is neutralized, and is then added adsorbent absorption, is dehydrated and filter, i.e.,
Obtain full-water type polyurethane polyether polyalcohol；
Described sucrose, pentaerythrite, the mass ratio of glycerine and methyl-o-phenylenediamine are 342：68.1：196.9：61；
Step（1）In, when adding compound initiator, again by the mixture one of the two after methyl-o-phenylenediamine is first dissolved with glycerine
And add.
2. the preparation method of full-water type polyurethane polyether polyalcohol according to claim 1, it is characterised in that：Institute
The compound initiator and the mass ratio of expoxy propane stated are 668：3306.5~4029.1.
3. the preparation method of full-water type polyurethane polyether polyalcohol according to claim 1, it is characterised in that：Institute
The catalyst amount stated is the 0.2~0.3% of compound initiator and expoxy propane gross mass.
4. the preparation method of full-water type polyurethane polyether polyalcohol according to claim 1, it is characterised in that：Step
Suddenly（1）In, when stirring is warming up to 85 DEG C, add the reaction of PART EPOXY propane；The amount of the expoxy propane account for compound initiator with
The 8~10% of expoxy propane gross mass；The reaction temperature is 80~90 DEG C, and reaction pressure is 0.1~0.3MPa, reaction to perseverance
Constant-pressure.
5. the preparation method of full-water type polyurethane polyether polyalcohol according to claim 1, it is characterised in that：Step
Suddenly（2）In, reaction temperature is 100~120 DEG C, and reaction pressure is controlled in 0.1~0.3MPa.
6. the preparation method of full-water type polyurethane polyether polyalcohol according to claim 1, it is characterised in that：Step
Suddenly（1）、（2）In, described aging temperature is 90~110 DEG C, and ageing time is 1~3h.
7. the preparation method of full-water type polyurethane polyether polyalcohol according to claim 1, it is characterised in that：Step
Suddenly（3）In, the phosphoric acid that described phosphoric acid is 85%；The adsorbent is the mixture of magnesium silicate and alumina silicate, and the two mass ratio is
1：1~2, consumption is the 0.2~0.3% of compound initiator and expoxy propane gross 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 |
| JP6909074B2 (en) * | 2017-06-28 | 2021-07-28 | サンスター技研株式会社 | Polyurethane 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 |
| CN118186624A (en) * | 2024-05-20 | 2024-06-14 | 晋江安润纺织有限公司 | Preparation method of bio-based polyurethane elastic fiber |
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| CN103554427A (en) * | 2013-10-31 | 2014-02-05 | 淄博德信联邦化学工业有限公司 | Preparation method of all-water foamed polyurethane rigid foams |
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