CN106832248A - The preparation method of fast demoulding rigid-foam polyether polyol - Google Patents
The preparation method of fast demoulding rigid-foam polyether polyol Download PDFInfo
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- CN106832248A CN106832248A CN201710050981.4A CN201710050981A CN106832248A CN 106832248 A CN106832248 A CN 106832248A CN 201710050981 A CN201710050981 A CN 201710050981A CN 106832248 A CN106832248 A CN 106832248A
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- polyether polyol
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/3311—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing a hydroxy group
- C08G65/3314—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing a hydroxy group cyclic
- C08G65/3315—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing a hydroxy group cyclic aromatic
- C08G65/3317—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing a hydroxy group cyclic aromatic phenolic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polyethers (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention belongs to polyurethanes technology field, and in particular to a kind of preparation method of fast demoulding rigid-foam polyether polyol.The present invention introduces some cyclic groups by the design process of PPG, the deformation of molecule interchain is reduced, so as to improve release property.Synthesis of sucrose PPG, according to different formulations system and customer demand, adjusts the hydroxyl value of Sucrose polyethers polyalcohol, viscosity and activity first；Then it is modified with Hydroxybenzenes compound；Finally carry out refinement treatment and obtain the PPG with excellent releasability from mode.Simple production process of the present invention, existing working condition can meet demand, it is not necessary to extra production auxiliary equipment, product favorable reproducibility, steady quality, and material system intersolubility is good with combining；The polyurethane foam release property of preparation is good, and good stability of the dimension disclosure satisfy that the demand of different clients.
Description
Technical field
The invention belongs to polyurethanes technology field, and in particular to a kind of preparation side of fast demoulding rigid-foam polyether polyol
Method.
Background technology
PPG is one of primary raw material of polyurethane industrial, can be used to manufacture household electrical appliances, utilidor, sheet material, vapour
The product in the fields such as in-car decorations, coating.In these industrial goods, the initiator class of different product to raw material PPG
Type, molecular structure, degree of functionality, molecular weight and activity have different requirements.Demoulding time is the important of measurement polyurethane foam
Index, in order to shorten molding open time in soft brewage, reduces mold temperature, and energy saving is often using high activity
The PPG of high proportion of primary OH groups.For the production of rigid foam, PPG typically uses high functionality and hydroxyl high
The polyethers system of value, or even amidogen ether of the collocation with special amine as initiator, so can not only influence the mobility of foam, and
Foam production cost can be increased using amidogen ether.
Hard polyurethane foams are the effectively insulating insulation materials uniquely used currently as refrigerator, no matter foam physics
The processing performance that can still produce all almost Perfects.Hard polyurethane foam component generally with pour mode be added to refrigerator or
The intermediate course of ice tank body, for ensure the overall flatness of refrigerator product after cast curing, it is necessary to dwell time more long or
Demoulding time, the raising of serious restriction production efficiency, and the too fast demoulding ahead of time can also cause the decline of foamed product properties,
Even ftracture, be deformed into waste product.The demoulding time of usual foaming system is according to model of refrigerator size, production technology and heat-insulation layer
Thickness is different and different.It is improve production efficiency, reduces cost, during the highly desirable shortening demoulding for producer
Between, the production cycle for shortening product is always the direction that each producer makes great efforts, and the demoulding time needed for polyurethane foam is influence
The principal element of polyurethane products production efficiency.
For a long time, material supplier is the competitive advantage of raising raw material, is devoted to developing the hard polyurethane of fast demoulding
Ester foam component.PPG as hard polyurethane foam component chief component, to fast demoulding
Play vital effect.Therefore, people have carried out more detailed formula and technical study in recent years.
The content of the invention
It is an object of the invention to provide a kind of preparation method of fast demoulding rigid-foam polyether polyol, by PPG
Design process introduces the group of some ring-types, the deformation of molecule interchain is reduced, so as to improve release property；The PPG hydroxyl
Value, viscosity and degree of functionality are adjustable, and tolerance is strong in material formula system is combined, and hard polyurethane foams release property improves bright
Aobvious, foam stability is good.
The preparation method of fast demoulding rigid-foam polyether polyol of the present invention, comprises the following steps：
(1) sucrose, low molecule weight initiator and oxyalkylene are reacted in the presence of base catalyst, is obtained sucrose
PPG；
(2) to Hydroxybenzenes compound is added in Sucrose polyethers polyalcohol, it is well mixed, adds condensing agent to carry out polycondensation anti-
Should, obtain modified Sucrose polyethers polyalcohol；
(3) refinement treatment is carried out to addition water, acid and adsorbent in modified Sucrose polyethers polyalcohol, obtains fast demoulding
Rigid-foam polyether polyol.
Wherein：
Reaction condition described in step (1) is 60-120 DEG C of oxygen-free atmosphere, and reaction pressure is 0.1-0.5MPa, oxidation
After olefin feedstocks are finished, pressure reacts less than -0.04MPa and completes.
Low molecule weight initiator described in step (1) is glycerine, propane diols, diethylene glycol, triethanolamine, diethanol amine or
One or more in water, base catalyst is the one kind in potassium hydroxide or NaOH, oxyalkylene be expoxy propane or
One or two in oxirane.
Hydroxybenzenes compound described in step (2) is in 2- hydroxyls-paraxylene, phenol, bisphenol-A or salicylic acid
One or more；Condensing agent is formaldehyde or paraformaldehyde.
Described formaldehyde is the technical grade formalin of mass fraction 37%, 44% or 50%, the paraformaldehyde degree of polymerization
It is 10-100.
After reaction condition described in step (2) is under no oxygen airtight condition, to add condensing agent reaction 0.5-1.5h, open
Beginning is warming up to 90-110 DEG C and is dehydrated continuation reacts 1.5-3h.
Acid described in step (3) is the one kind in oxalic acid or phosphoric acid, and adsorbent is magnesium silicate, alumina silicate or aluminium-magnesium silicate
In one or more.
Reaction condition described in step (3) is 70-90 DEG C of oxygen-free atmosphere, is reacted 1-3 hours under normal pressure.
Sucrose, low molecule weight initiator, oxyalkylene, base catalyst, Hydroxybenzenes compound, condensing agent, water, acid and suction
Attached dose of mass ratio is 300-350:150-250:5-8:1000-1400:80-220:25-30:100-150:8-11:2-8.
Beneficial effects of the present invention are as follows：
The present invention introduces the group of some ring-types by the design process of PPG, reduces the deformation of molecule interchain,
So as to improve release property.Synthesis of sucrose PPG, according to different formulations system and customer demand, adjusts Sucrose polyethers first
The hydroxyl value of polyalcohol, viscosity and activity；Then it is modified with Hydroxybenzenes compound；Refinement treatment is finally carried out to obtain
PPG with excellent releasability from mode.Simple production process of the present invention, existing working condition can meet demand, be not required to
Want extra production auxiliary equipment.Product favorable reproducibility, steady quality, material system intersolubility is good with combining；The polyurethane of preparation
Foam release property is good, good stability of the dimension, disclosure satisfy that the demand of different clients.
Specific embodiment
The present invention is described further with reference to embodiments.
Embodiment 1
It is being equipped with agitator, meter, heating temperature control device, cooling device (including external jacket and inner coil pipe) and pressure
In the 2L autoclaves of sensor, add sucrose 342g, glycerine 178g and potassium hydroxide 5g to be heated to 85 DEG C, gradually add 1030g
Expoxy propane, keeps pressure to be less than 0.2MPa.When pressure is less than -0.04MPa, 70 DEG C are cooled the temperature to, then 94g phenol,
80g formalins (37%) are added after stirring evenly to continue to react 1.0 hours, are then gradually heating to 105 DEG C of dehydrations and are continued anti-
Answer 3 hours.Then modified sugar polyethers is transferred to drying kettle, 100g water is added when temperature is down to 80 DEG C, added after stirring evenly
The phosphoric acid of 9.8g 85%, then the magnesium silicate and 2g adsorbins of 3g are added after stirring evenly, after continuing to stir 1h, start to warm up
Dehydration, last dry filter obtains fast demoulding rigid-foam polyether polyol.
The fast demoulding PPG of synthesis has following property：
Hydroxyl value：448mgKOH/g
25 DEG C of viscosity：9370mPas
Outward appearance：Light yellow clear
Release property：1.4%
Comparative example 1
It is being equipped with agitator, meter, heating temperature control device, cooling device (including external jacket and inner coil pipe) and pressure
In the 2L autoclaves of sensor, add sucrose 342g, glycerine 178g and potassium hydroxide 5g to be heated to 85 DEG C, gradually add 1030g
Expoxy propane, keeps pressure to be less than 0.2MPa.When question response pressure is basically unchanged, nitrogen is mended small to 0.15MPa continuation reactions 3
When.Then Sucrose polyethers are transferred to drying kettle, and 100g water is added when temperature is down to 80 DEG C, add 9.8g's 85% after stirring evenly
Phosphoric acid, then the magnesium silicate and 2g adsorbins of 3g are added after stirring evenly, after continuing to stir 1h, dehydration is started to warm up, finally do
It is dry to be filtrated to get rigid-foam polyether polyol.
The PPG of synthesis has following property：
Hydroxyl value：500mgKOH/g
25 DEG C of viscosity：11500mPas
Outward appearance：Light yellow clear
Release property：3.2%
Embodiment 2
It is being equipped with agitator, meter, heating temperature control device, cooling device (including external jacket and inner coil pipe) and pressure
In the 2L autoclaves of sensor, sucrose 342g, glycerine 89g, triethanolamine 144g and potassium hydroxide 5.8g is added to be heated to 85 DEG C,
1240g expoxy propane is gradually added, keeps pressure to be less than 0.2MPa.When pressure is less than -0.04MPa, 70 DEG C are cooled the temperature to,
Then 94g phenol, adds 80g formalins (37%) and continues to react 1.0 hours after stirring evenly, and is then gradually heating to 105
DEG C dehydration continue react 3 hours.Then modified sugar polyethers is transferred to drying kettle, 116g is added when temperature is down to 80 DEG C
Water, adds the phosphoric acid of 11.4g 85% after stirring evenly, then 3.5g magnesium silicates and 2.3g adsorbins are added after stirring evenly, and continues to stir
After mixing 1h, dehydration is started to warm up, last dry filter obtains fast demoulding rigid-foam polyether polyol.
The fast demoulding PPG of synthesis has following property：
Hydroxyl value：396mgKOH/g
25 DEG C of viscosity：10400mPas
Outward appearance：Light yellow clear
Release property：1.1%
Comparative example 2
It is being equipped with agitator, meter, heating temperature control device, cooling device (including external jacket and inner coil pipe) and pressure
In the 2L autoclaves of sensor, sucrose 342g, glycerine 89g, triethanolamine 144g and potassium hydroxide 5.8g is added to be heated to 85 DEG C,
1240g expoxy propane is gradually added, keeps pressure to be less than 0.2MPa.When question response pressure is basically unchanged, nitrogen to 0.15MPa is mended
Continue to react 3 hours.Then Sucrose polyethers are transferred to drying kettle, and 116g water is added when temperature is down to 80 DEG C, are added after stirring evenly
The phosphoric acid of 11.4g 85%, then 3.5g magnesium silicates and 2.3g adsorbins are added after stirring evenly, after continuing to stir 1h, start to rise
Temperature dehydration, last dry filter obtains rigid-foam polyether polyol.
The PPG of synthesis has following property：
Hydroxyl value：427mgKOH/g
25 DEG C of viscosity：11200mPas
Outward appearance：Light yellow clear
Release property：2.6%
Embodiment 3
It is being equipped with agitator, meter, heating temperature control device, cooling device (including external jacket and inner coil pipe) and pressure
In the 2L autoclaves of sensor, add sucrose 342g, glycerine 215g and potassium hydroxide 6.3g to be heated to 85 DEG C, gradually add
1320g expoxy propane, keeps pressure to be less than 0.2MPa.When pressure is less than -0.04MPa, 70 DEG C are cooled the temperature to, then 200g
Bisphenol-A, adds 80g formalins (37%) and continues to react 1.0 hours after stirring evenly, be then gradually heating to 105 DEG C of dehydrations
Continue to react 3 hours.Then modified sugar PPG is transferred to drying kettle, 126g is added when temperature is down to 80 DEG C
Water, adds the phosphoric acid of 12.4g 85% after stirring evenly, then 4.2g magnesium silicates and 2.1g adsorbins are added after stirring evenly, and continues to stir
After mixing 1h, dehydration is started to warm up, last dry filter obtains fast demoulding rigid-foam polyether polyol.
The fast demoulding PPG of synthesis has following property：
Hydroxyl value：402mgKOH/g
25 DEG C of viscosity：9560mPas
Release property：1.5%
Comparative example 3
In 2L autoclaves, add sucrose 342g, glycerine 215g and potassium hydroxide 6.3g to be heated to 85 DEG C, gradually add
1320g expoxy propane, keeps pressure to be less than 0.2MPa.When question response pressure is basically unchanged, mends nitrogen and continue to react to 0.15MPa
3 hours.Then Sucrose polyethers are transferred to drying kettle, and 126g water is added when temperature is down to 80 DEG C, and 12.4g is added after stirring evenly
85% phosphoric acid, then 4.2g magnesium silicates and 2.1g adsorbins are added after stirring evenly, after continuing to stir 1h, start to warm up de-
Water, last dry filter obtains rigid-foam polyether polyol.
The PPG of synthesis has following property：
Hydroxyl value：450mgKOH/g
25 DEG C of viscosity：10560mPas
Release property：3.6%.
Claims (9)
1. a kind of preparation method of fast demoulding rigid-foam polyether polyol, it is characterised in that comprise the following steps：
(1) sucrose, low molecule weight initiator and oxyalkylene are reacted in the presence of base catalyst, is obtained Sucrose polyethers
Polyalcohol；
(2) to Hydroxybenzenes compound is added in Sucrose polyethers polyalcohol, it is well mixed, adds condensing agent to carry out polycondensation reaction,
Obtain modified Sucrose polyethers polyalcohol；
(3) refinement treatment is carried out to addition water, acid and adsorbent in modified Sucrose polyethers polyalcohol, obtains fast demoulding and hard bubble
PPG.
2. the preparation method of fast demoulding rigid-foam polyether polyol according to claim 1, it is characterised in that：Step (1)
Described in reaction condition be 60-120 DEG C of oxygen-free atmosphere, reaction pressure is 0.1-0.5MPa, after oxyalkylene charging is finished,
Pressure reacts less than -0.04MPa and completes.
3. the preparation method of fast demoulding rigid-foam polyether polyol according to claim 1 and 2, it is characterised in that：Step
(1) low molecule weight initiator described in for the one kind in glycerine, propane diols, diethylene glycol, triethanolamine, diethanol amine or water or
Several, base catalyst is the one kind in potassium hydroxide or NaOH, and oxyalkylene is in expoxy propane or oxirane
One or two.
4. the preparation method of fast demoulding rigid-foam polyether polyol according to claim 1, it is characterised in that：Step (2)
Described in Hydroxybenzenes compound be one or more in 2- hydroxyls-paraxylene, phenol, bisphenol-A or salicylic acid；Condensation
Agent is formaldehyde or paraformaldehyde.
5. the preparation method of fast demoulding rigid-foam polyether polyol according to claim 4, it is characterised in that：Described first
Aldehyde is the technical grade formalin of mass fraction 37%, 44% or 50%, and the paraformaldehyde degree of polymerization is 10-100.
6. the preparation method of the fast demoulding rigid-foam polyether polyol according to claim 4 or 5, it is characterised in that：Step
(2) after reaction condition described in is under no oxygen airtight condition, to add condensing agent reaction 0.5-1.5h, start to warm up to 90-
110 DEG C and be dehydrated continuation react 1.5-3h.
7. the preparation method of fast demoulding rigid-foam polyether polyol according to claim 1, it is characterised in that：Step (3)
Described in acid be the one kind in oxalic acid or phosphoric acid, adsorbent is one or more in magnesium silicate, alumina silicate or aluminium-magnesium silicate.
8. the preparation method of fast demoulding rigid-foam polyether polyol according to claim 7, it is characterised in that：Step (3)
Described in reaction condition be 70-90 DEG C of oxygen-free atmosphere, under normal pressure react 1-3 hours.
9. the preparation method of fast demoulding rigid-foam polyether polyol according to claim 1, it is characterised in that：It is sucrose, small
The mass ratio of molecule initiator, oxyalkylene, base catalyst, Hydroxybenzenes compound, condensing agent, water, acid and adsorbent is
300-350:150-250:5-8:1000-1400:80-220:25-30:100-150:8-11:2-8。
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107151318A (en) * | 2017-06-28 | 2017-09-12 | 山东诺威新材料有限公司 | Sucrose polyethers polyalcohol and preparation method thereof |
| CN108047442A (en) * | 2017-12-20 | 2018-05-18 | 上海东大化学有限公司 | A kind of compound polyether polyol of rigid foam and preparation method thereof |
| CN115894260A (en) * | 2022-12-15 | 2023-04-04 | 红宝丽集团股份有限公司 | Co-production method of amino-terminated polyether and diol compounds |
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| US4383100A (en) * | 1980-09-19 | 1983-05-10 | E. I. Du Pont De Nemours And Company | Polyurethanes from oligomeric formal diols of THF copolymer glycols |
| JP2004027074A (en) * | 2002-06-27 | 2004-01-29 | Hitachi Home & Life Solutions Inc | Rigid polyurethane foam and heat insulator |
| CN102781997A (en) * | 2010-03-02 | 2012-11-14 | 巴斯夫欧洲公司 | Method for producing polyurethanes |
| CN105601978A (en) * | 2015-11-10 | 2016-05-25 | 南京红宝丽聚氨酯有限公司 | Hard polyurethane foam |
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2017
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4383100A (en) * | 1980-09-19 | 1983-05-10 | E. I. Du Pont De Nemours And Company | Polyurethanes from oligomeric formal diols of THF copolymer glycols |
| JP2004027074A (en) * | 2002-06-27 | 2004-01-29 | Hitachi Home & Life Solutions Inc | Rigid polyurethane foam and heat insulator |
| CN102781997A (en) * | 2010-03-02 | 2012-11-14 | 巴斯夫欧洲公司 | Method for producing polyurethanes |
| CN105601978A (en) * | 2015-11-10 | 2016-05-25 | 南京红宝丽聚氨酯有限公司 | Hard polyurethane foam |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107151318A (en) * | 2017-06-28 | 2017-09-12 | 山东诺威新材料有限公司 | Sucrose polyethers polyalcohol and preparation method thereof |
| CN107151318B (en) * | 2017-06-28 | 2019-07-12 | 山东一诺威新材料有限公司 | Sucrose polyethers polyalcohol and preparation method thereof |
| CN108047442A (en) * | 2017-12-20 | 2018-05-18 | 上海东大化学有限公司 | A kind of compound polyether polyol of rigid foam and preparation method thereof |
| CN108047442B (en) * | 2017-12-20 | 2020-02-07 | 上海东大化学有限公司 | Rigid foam composite polyether polyol and preparation method thereof |
| CN115894260A (en) * | 2022-12-15 | 2023-04-04 | 红宝丽集团股份有限公司 | Co-production method of amino-terminated polyether and diol compounds |
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| Publication number | Publication date |
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| CN106832248B (en) | 2019-01-29 |
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