CN106700012A - Method for preparing polyurethane rigid foam - Google Patents
Method for preparing polyurethane rigid foam Download PDFInfo
- Publication number
- CN106700012A CN106700012A CN201611068064.0A CN201611068064A CN106700012A CN 106700012 A CN106700012 A CN 106700012A CN 201611068064 A CN201611068064 A CN 201611068064A CN 106700012 A CN106700012 A CN 106700012A
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- CN
- China
- Prior art keywords
- flame
- retardant
- polyurethane foam
- preparation
- reactor
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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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
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5075—Polyethers having heteroatoms other than oxygen having phosphorus
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention relates to a method for preparing polyurethane rigid foam and belongs to the field of material preparation. The method is characterized by comprising the following steps: (1) adding THPO and a KOH catalyst into a stainless-steel reactor, and replacing air in the reactor with nitrogen gas for 5 times; (2) adding PO in accordance with that the mass ratio of THPO/PO is 5: 11; (3) relieving pressure of the reactor, adding phosphoric acid and a refining agent into the reactor, carrying out vacuum dehydrating, and carrying out filtrating, so as to obtain a phosphorus-containing flame-retardant polyether polyol; and (4) weighing the phosphorus-containing flame-retardant polyether polyol, a stabilizer and a catalyst, putting the weighed phosphorus-containing flame-retardant polyether polyol, stabilizer and catalyst into a plastic cup, carrying out uniform mixing and stirring, then, injecting the mixture into a mold for free foaming molding, then, taking out foam, and carrying out standing for 75 hours at room temperature, thereby preparing the polyurethane rigid foam. The flame retardance of the polyurethane foam can be improved through increasing the consumption of a flame retardant and an isocyanate index. The flame-retardant effect is more obvious and can be achieved generally through only adding the flame retardant, and for higher flame-retardant requirements, the flame-retardant polyether polyol is required to be added, and meanwhile, the isocyanate index is required to be increased.
Description
Technical field
The invention belongs to field of material preparation, more particularly to a kind of preparation method of hard polyurethane foam.
Background technology
At present, the fire-retardant of polyurethane material is broadly divided into two kinds：One kind is outer addition fire retardant type, and another kind is in molecule
Ignition-proof element and heteroaromatic structure are introduced in structure.The former can make the mechanical performance of polyurethane material when addition is larger
It is decreased obviously, while also there are problems that occurring to migrate and fire resistance because of fire retardant, but still is fire-retardant polyurethane material
It is required that most popular flame-retarded technology when relatively low；The latter is mainly by the addition in the formula of polyurethane material containing fire-retardant
The polyalcohol of element or heterocycle structure, the method for reactive flame retardant realize, with fire resistance persistently, influence mechanicalness
The small advantage of energy.
Ying matter Ju urethanes foam is with unique heat preservation and insulation, lightweight, specific strength is big, it is simple etc. excellent to construct
Good characteristic, at the same also sound insulation, it is cold-resistant, heat-resisting, corrosion-resistant the features such as, be that thermal conductivity factor is most in current organic and inorganic materials
A kind of low insulation material.Therefore it is widely used in the heat preserving and insulating material of external wall, freezer, pipeline, refrigerator ice cabinet etc..
The content of the invention
Present invention seek to address that above mentioned problem, there is provided a kind of preparation method of hard polyurethane foam.
The technical scheme is that：
A kind of preparation method of hard polyurethane foam, comprises the following steps：
（1）THPO, KOH catalyst are added in 2L stainless steel cauldrons, with air in nitrogen displacement kettle 3-5 times；
（2）5 are respectively according to THPO/PO mass ratioes：11、7：11 and 9:11 add PO, and temperature then is risen into 110 DEG C, pressure
Below 0.6MPa is maintained at, reaction carries out 4h；
（3）Reactor pressure is shed, phosphoric acid, refining agent is added, vacuum dehydration, filtering can obtain phosphor-containing flame-proof polyether polyols
Alcohol；
（4）Weigh phosphor-containing flame-proof PPG, stabilizer, catalyst to be placed in 500mL plastic cups, by temperature adjustment to 25 DEG C
After mix, after being stirred under 2000r/min rotating speeds inject mould in free foaming shaping, mold temperature control at 45 DEG C simultaneously
2h is maintained, foams is then taken out and is placed 72-75h completion preparations in room temperature.With in polyurethane foam system, isocyanates refers to
Several raisings, the oxygen index (OI) of polyurethane foam becomes larger, but after isocyanate index brings up to 200, limited oxygen index
Improve few.In addition excessive isocyanates can form tripolymer under catalyst action, can improve the compression of polyurethane foam
Intensity, heat resistance.
The preparation method of hard polyurethane foam of the present invention, step（1）Described in reactor temperature be 80 DEG C, reaction
Time is 0.5h.
The preparation method of hard polyurethane foam of the present invention, step（3）Described in dewatering time be 2-3h.
The preparation method of hard polyurethane foam of the present invention, step（4）Described in mixing time be 30s.
The technical effects of the invention are that：
The preparation method of hard polyurethane foam of the present invention, improving amount of flame-retardant agent and isocyanate index can improve poly- ammonia
The fire resistance of ester foam.The effect of fire retardant becomes apparent from, general only to be can reach by adding fire retardant, when it is higher it is fire-retardant will
Flame retardant polyether polyol need to be added when asking, while improving isocyanate index.
Specific embodiment
Embodiment 1
A kind of preparation method of hard polyurethane foam, comprises the following steps：
（1）THPO, KOH catalyst are added in 2L stainless steel cauldrons, with air in nitrogen displacement kettle 3 times；
（2）5 are respectively according to THPO/PO mass ratioes：11 add PO, and temperature then is risen into 110 DEG C, and pressure is maintained at 0.6MPa
Hereinafter, reaction carries out 4h；
（3）Reactor pressure is shed, phosphoric acid, refining agent is added, vacuum dehydration, filtering can obtain phosphor-containing flame-proof polyether polyols
Alcohol；
（4）Weigh phosphor-containing flame-proof PPG, stabilizer, catalyst to be placed in 500mL plastic cups, by temperature adjustment to 25 DEG C
After mix, after being stirred under 2000r/min rotating speeds inject mould in free foaming shaping, mold temperature control at 45 DEG C simultaneously
2h is maintained, foams is then taken out and is placed 72h completion preparations in room temperature.
The preparation method of hard polyurethane foam of the present invention, step（1）Described in reactor temperature be 80 DEG C, reaction
Time is 0.5h.
The preparation method of hard polyurethane foam of the present invention, step（3）Described in dewatering time be 2h.
The preparation method of hard polyurethane foam of the present invention, step（4）Described in mixing time be 30s.
The limited oxygen index of the polyurethane foam of common polyether polyalcohol synthesis is only 18.7%, and is not added with fire retardant
Flame retardant polyether polyol prepare RPUF limited oxygen index minimum 24.5%, and compressive strength and
Variable density is little.As the increase of the phosphorus content in flame retardant polyether polyol, flame retardant effect increase, limited oxygen index is reachable
25.6%, but being decreased obviously occurs in compressive strength.Oxygen index (OI) is the important indicator for characterizing polyurethane foam fire resistance, general oxygen
Index is bigger, and fire resistance is more excellent.With the increase of amount of flame-retardant agent, the oxygen index (OI) of polyurethane foam increases.When being added to matter
It is using the polyurethane foam F0 limited oxygen indexs of common polyether polyols preparation up to 26.1% therefore past during amount fraction 30%
Toward when limited oxygen index is less than less than 26%, addition fire retardant is the fire resistance that can be required in actual applications.When
The use of flame retardant polyether polyol is optimal selection when higher to flame-retardancy requirements, when fire retardant mass fraction 30% is added, hard bubbles
The limited oxygen index of sample F 3 can reach 30.5%.
Isocyanate index can directly affect the oxygen index (OI) of polyurethane foam, be primarily due to excessive isocyanates generation
Isocyanic acid urea ester group, can improve the fire resistance of system.With the raising of isocyanate index in polyurethane foam system, gather
The oxygen index (OI) of urethane foam becomes larger, but after isocyanate index brings up to 200, limited oxygen index improves few.This
Outer excessive isocyanates can form tripolymer under catalyst action, can improve compressive strength, the heat resistance of polyurethane foam.
Isocyanate index can select 170.
Embodiment 2
A kind of preparation method of hard polyurethane foam, comprises the following steps：
（1）THPO, KOH catalyst are added in 2L stainless steel cauldrons, with air in nitrogen displacement kettle 5 times；
（2）9 are respectively according to THPO/PO mass ratioes:11 add PO, and temperature then is risen into 110 DEG C, and pressure is maintained at 0.6MPa
Hereinafter, reaction carries out 4h；
（3）Reactor pressure is shed, phosphoric acid, refining agent is added, vacuum dehydration, filtering can obtain phosphor-containing flame-proof polyether polyols
Alcohol；
（4）Weigh phosphor-containing flame-proof PPG, stabilizer, catalyst to be placed in 500mL plastic cups, by temperature adjustment to 25 DEG C
After mix, after being stirred under 2000r/min rotating speeds inject mould in free foaming shaping, mold temperature control at 45 DEG C simultaneously
2h is maintained, foams is then taken out and is placed 75h completion preparations in room temperature.
The preparation method of hard polyurethane foam of the present invention, step（1）Described in reactor temperature be 80 DEG C, reaction
Time is 0.5h.
The preparation method of hard polyurethane foam of the present invention, step（3）Described in dewatering time be 3h.Step（4）In
The mixing time is 30s.
When at 250 DEG C, phosphor-containing flame-proof polyurethane foam heat endurance reduction, hence it is evident that not as conventional polyurethanes foam is former
Because being probably, because the thermal degradation activation energy of the phosphorous segment in resistance combustion polyurethane foam is low, to promote phosphorous segment in relatively low temperature
Degree is decomposed.In addition the polyurethane foam that prepared by flame retardant polyether polyol terminates substantially in 500 DEG C of burnings, but F0 is until 600
Just terminate substantially after DEG C.At 800 DEG C, apparently higher than F0, this is primarily due to phosphorus element-containing to the residual rate of phosphorous polyurethane foam
Introducing, polyphosphoric acid, pyrophosphoric acid etc. are generated under the high temperature conditions and promote polyurethane foam dehydration carbonization, the residue of formation sinks
Product surface, completely cut off with appearance air exchange and heat transfer, delayed burning time, so as to improve polyurethane foam
Fire resistance.The phosphorus content of F2 is less than F3, but final carbon yield is 20%, higher than the latter, illustrates that hard polyurethane foam oxygen refers to
Number is not necessarily consistent with the change of carbon yield.
Phosphor-containing flame-proof PPG is prepared for by raw material of THPO, the chemical constitution of phosphorous PPG is characterized, with
The increase of THPO consumptions, phosphorus content, hydroxyl value, viscosity increase therewith.Hard polyurethane foam tool prepared by phosphor-containing flame-proof PPG
There is fire resistance higher, oxygen index (OI) is up to 25.6%.
Claims (4)
1. a kind of preparation method of hard polyurethane foam, it is characterised in that comprise the following steps：
（1）THPO, KOH catalyst are added in 2L stainless steel cauldrons, with air in nitrogen displacement kettle 3-5 times；
（2）5 are respectively according to THPO/PO mass ratioes：11、7：11 and 9:11 add PO, and temperature then is risen into 110 DEG C, pressure
Below 0.6MPa is maintained at, reaction carries out 4h；
（3）Reactor pressure is shed, phosphoric acid, refining agent is added, vacuum dehydration, filtering can obtain phosphor-containing flame-proof polyether polyols
Alcohol；
（4）Weigh phosphor-containing flame-proof PPG, stabilizer, catalyst to be placed in 500mL plastic cups, by temperature adjustment to 25 DEG C
After mix, after being stirred under 2000r/min rotating speeds inject mould in free foaming shaping, mold temperature control at 45 DEG C simultaneously
2h is maintained, foams is then taken out and is placed 72-75h completion preparations in room temperature.
2. the preparation method of hard polyurethane foam according to claim 1, it is characterised in that：Step（1）Described in reactor
Temperature be 80 DEG C, the reaction time is 0.5h.
3. the preparation method of hard polyurethane foam according to claim 1, it is characterised in that：Step（3）Described in when being dehydrated
Between be 2-3h.
4. the preparation method of hard polyurethane foam according to claim 1, it is characterised in that：Step（4）Described in when stirring
Between be 30s.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611068064.0A CN106700012A (en) | 2016-11-29 | 2016-11-29 | Method for preparing polyurethane rigid foam |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611068064.0A CN106700012A (en) | 2016-11-29 | 2016-11-29 | Method for preparing polyurethane rigid foam |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106700012A true CN106700012A (en) | 2017-05-24 |
Family
ID=58934932
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611068064.0A Pending CN106700012A (en) | 2016-11-29 | 2016-11-29 | Method for preparing polyurethane rigid foam |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106700012A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021047977A1 (en) | 2019-09-12 | 2021-03-18 | Huntsman International Llc | A tris (hydroxymethyl) phosphine oxide based polyester polyol and a resin composition obtained therefrom |
| CN115232287A (en) * | 2022-08-08 | 2022-10-25 | 南京金栖化工集团有限公司 | Flame-retardant slow-rebound polyurethane sponge and preparation method thereof |
-
2016
- 2016-11-29 CN CN201611068064.0A patent/CN106700012A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021047977A1 (en) | 2019-09-12 | 2021-03-18 | Huntsman International Llc | A tris (hydroxymethyl) phosphine oxide based polyester polyol and a resin composition obtained therefrom |
| US12049536B2 (en) | 2019-09-12 | 2024-07-30 | Huntsman International Llc | Tris (hydroxymethyl) phosphine oxide based polyester polyol and a resin composition obtained therefrom |
| CN115232287A (en) * | 2022-08-08 | 2022-10-25 | 南京金栖化工集团有限公司 | Flame-retardant slow-rebound polyurethane sponge and preparation method thereof |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170524 |
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| WD01 | Invention patent application deemed withdrawn after publication |