CN107602831A - The production method of hard bubble PEPA - Google Patents
The production method of hard bubble PEPA Download PDFInfo
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- CN107602831A CN107602831A CN201711049574.8A CN201711049574A CN107602831A CN 107602831 A CN107602831 A CN 107602831A CN 201711049574 A CN201711049574 A CN 201711049574A CN 107602831 A CN107602831 A CN 107602831A
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- dicarboxylic acids
- production method
- pepa
- hard bubble
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Abstract
It is that melamine and dicarboxylic acids or anhydride reaction is modified the present invention relates to a kind of production method of hard bubble PEPA, carrying out polycondensation reaction with small molecule polyol and dicarboxylic acids or acid anhydrides under catalyst action is made.Wherein：The mass fraction of melamine and dicarboxylic acids or acid anhydrides is as follows：70 85 parts of 15 30 parts of melamine, dicarboxylic acids or acid anhydrides.For overcome the deficiencies in the prior art, the present invention provides a kind of production method of hard bubble PEPA, has the characteristics of environmentally friendly, efficient, less toxic and permanent；The structural flame retardant polyester polyalcohol long-term use of production will not reduce fire resistance, and low in raw material price, relative cost more dominant, have higher cost performance.
Description
Technical field
The invention belongs to polyurethane product technical field, and in particular to a kind of production method of hard bubble PEPA.
Background technology
RPUF, abbreviation hard polyurethane foam, its dosage in polyurethane product are only second to polyurethane
Soft bubble.Hard polyurethane foam is mostly hole-closing structure, has that insulation effect is good, in light weight, specific strength is big, the excellent spy such as easy for construction
Property, while also there is sound insulation, shockproof, electric insulation, heat-resisting, cold-resistant, solvent resistant, it is widely used in the casing of refrigerator, refrigerator-freezer
The heat-insulating materials such as heat insulation layer, freezer, refrigerator car, building, storage tank and pipe insulation material, on a small quantity for nonadiabatic occasion, such as
Imitation wood material, packaging material etc..In general, the hard polyurethane foam compared with low-density is mainly used as heat-insulated (insulation) material, it is highly denser
The hard polyurethane foam of degree can be used as structural material (imitation wood material).
Common hard polyurethane foam, oxygen index (OI) is typically in 16-18 or so, it is impossible to meets to build fire-retardant requirement, therefore increases
The anti-flammability for adding foam is particularly important.Excellent flame retardancy is developed, while foam items physical and mechanical properties reaches former bubble
The requirement of foam, it is significant in the large-scale application of building trade for polyurethane foam.Experimental study shows, gathers
The foam of ester polyol, especially structure containing aroma type PEPA synthesis, its resistance to gentle fire resistance are substantially better than polyethers
Polyalcohol.The polyol starting material that foreign countries are used for the hard polyurethane foams of building field mainly uses polyester polyol, wherein
Product using benzoic anhydride polyester polyol as representative has formed a large family.China to benzoic anhydride polyester polyol research starting compared with
It is evening, less to the combination property and Study of flame retardancy of the product.
Flame-proof polyol refers to the polyalcohol containing ignition-proof element or fire-retardant group, Ke Yifen in molecular backbone or side chain
For phosphorus system, halogen system, compound and heteroaromatic class flame-proof polyol etc..As people increasingly pay attention to the resistance of polyurethane heat insulation material
Performance is fired, the research of flame-proof polyol turns into a kind of trend.Due to organic molecule additive flame retardant exist it is easy to migrate, fire-retardant
The shortcomings of performance is not lasting and destroys foam mechanical property, is extremely difficult to require in use.Flame-proof polyol is applied to poly- ammonia
Can reach lasting flame retardant effect in ester foam, including phosphate, phosphite ester, phosphoramidate, halogen, melamine,
Polyimides, oxazolidone, polyurea polylol and contain the polyalcohols such as the heterocycle structures such as phenyl ring, isocyanurate ring.
Most of PEPA on the market is mostly addition type, on the basis of original conventional polyester polyalcohol,
A large amount of phosphorous, nitrogenous or halogen fire retardants are added to improve the anti-flammability of polyester, but the flame retardant polyester polyalcohol of addition type is big
More anti-flammabilitys are unstable, and anti-flammability can not be lasting, sometimes due to heartburn phenomenon occurs greatly in addition.
The content of the invention
For overcome the deficiencies in the prior art, the present invention provides a kind of production method of hard bubble PEPA, has ring
The characteristics of protecting, be efficient, less toxic and permanent；The structural flame retardant polyester polyalcohol long-term use of production will not reduce fire resistance,
And low in raw material price, relative cost more dominant, there is higher cost performance.
Hard bubble of the present invention with PEPA be melamine and dicarboxylic acids or anhydride reaction is modified,
Polycondensation reaction is carried out under catalyst action with small molecule polyol and dicarboxylic acids or acid anhydrides to be made.
Wherein：
The mass fraction of melamine and dicarboxylic acids or acid anhydrides is as follows：Melamine 15-30 parts, dicarboxylic acids or acid anhydrides
70-85 parts.
Dicarboxylic acids or acid anhydrides are one or two kinds of in phthalic anhydride, terephthalic acid (TPA) or M-phthalic acid.
Small molecule polyol be ethylene glycol, diethylene glycol (DEG), triethylene glycol, neopentyl glycol, glycerine or pentaerythrite in one kind or
It is a variety of.
Melamine and dicarboxylic acids or anhydride reaction be modified the intermediate of generation, small molecule polyol, dicarboxylic acids or
The mass fraction of acid anhydrides and catalyst is as follows：Intermediate 10-20 parts, small molecule polyol 40-60 parts, dicarboxylic acids or acid anhydrides
20-50 parts, catalyst 0.01-0.02 parts.
Catalyst is one kind in organic titanium class or organic tin.
Organic tin is preferably T-9 and T-12, and organic titanium class catalyst is preferably tetrabutyl titanate and isopropyl titanate.
T-9 and T-12 manufacturer is air Chemical Co., Ltd..
The production method of hard bubble PEPA of the present invention, comprises the following steps：
(1) melamine and dicarboxylic acids or acid anhydrides are added in reactor, are heated to 260-270 DEG C, dehydration, melting is instead
2-3 hours are answered, cool to 100-120 DEG C, obtain intermediate；
(2) small molecule polyol and dicarboxylic acids or acid anhydrides are added, material temperature is increased to 160-170 DEG C, is incubated two hours,
Then post-processed.
As a preferable technical scheme, the production method of hard bubble PEPA of the present invention, including with
Lower step：
(1) melamine and binary acid or acid anhydrides are added in reactor first, are heated to 260-270 DEG C, decompression is de-
The water of dereaction generation, frit reaction 2-3 hours, then cools to 100-120 DEG C, obtains intermediate；
(2) small molecule polyol and dicarboxylic acids or acid anhydrides of setting quantity are added, material temperature is then increased to 160-170
Between DEG C, start water outlet, be incubated two hours, between material temperature then is slowly raised into 225-230 DEG C, during which control reflux column temperature
Between 97-103 DEG C, two hours then are incubated, then is progressively vacuumized, sampling and testing acid number, until acid number drops to 2.0mg
During KOH/g, stopping is vacuumized and cooled, and is dropped to less than 90 DEG C and is produced PEPA.
This method production hard bubble with PEPA be used in hard polyurethane foam in, hydroxyl value 200-500mg KOH/g it
Between, acid number is less than 2.0mg KOH/g.
PEPA described in the invention, it is reaction-type flame-retarding mechanism, physics does not add any fire retardant, is reacting
It is middle to introduce fire-retardant preferable polyamide structure, it is a kind of structural flame retardant polyester polyalcohol of function admirable.By the polyester polyols
Hard polyurethane foam made of alcohol, not only foamy body is good, abscess is fine and smooth, and has very high oxygen index (OI).
Compared with prior art, the invention has the advantages that：
(1) preparation method of reaction-type flame-retarding PEPA of the present invention, overcomes the shortcomings of additive flame retardant polyester, has
The characteristics of environmentally friendly, efficient, less toxic, permanent, more and more important effect is played in polyurethane flame-proof research.
(2) ignition-proof element nitrogen is imported in polyalcohol at the same time or separately by chemically reacting, joined as a kind of reacted constituent
It is small to Effect of Materials performance with reaction, being attached in polyurethane matrix for its stabilization, polyurethane is contained flame-retardant composition in itself,
It will not be separated out in long-term use of process and reduce fire resistance.
(3) due to the low in raw material price used, relative cost more dominant, there is higher cost performance, in market
On be welcomed by customers very much.
Embodiment
The invention will be further described with reference to embodiments.
Embodiment 1
(1) 15 parts of melamines and 85 parts of terephthalic acid (TPA)s are added in reactor first, are heated between 260 DEG C,
The water of reaction generation is sloughed in decompression, frit reaction 2.5 hours, intermediate 1 is obtained between then cooling to 110 DEG C.
(2) by 1,35 portions of diethylene glycol (DEG)s of intermediate in 10 parts, 15 parts of glycerine, 40 parts of phthalic anhydrides, 0.01 part of T-9 is successively
It is added in reactor, material temperature is then increased to 170 DEG C, start water outlet, is incubated two hours, is then slowly raised to material temperature
230, during which control reflux column temperature to be then incubated two hours at 100 ± 3 DEG C, progressively vacuumizing, sampling and testing acid number, directly
When dropping to 2.0mg KOH/g to acid number, stopping is vacuumized and cooled, and drops to barrelling at 90 DEG C.
Embodiment 2
(1) 20 parts of melamines and 80 parts of phthalic anhydrides are added in reactor first, be heated to 265 DEG C it
Between, the water of reaction generation is sloughed in decompression, frit reaction 3 hours, intermediate 2 is obtained between then cooling to 105 DEG C.
(2) by 2,35 portions of diethylene glycol (DEG)s of intermediate in 15 parts, 10 parts of glycerine, 5 parts of triethylene glycols, 40 parts of terephthalic acid (TPA)s, 0.015
Part isopropyl titanate is added sequentially in reactor, between material temperature then is increased into 165 DEG C, is started water outlet, is incubated two hours,
Then material temperature is slowly raised to 230 DEG C, during which controls reflux column temperature to be then incubated two hours at 100 ± 3 DEG C, progressively taking out
Vacuum, sampling and testing acid number, when acid number drops to 2.0mg KOH/g, stopping is vacuumized and cooled, and drops at 90 DEG C barrelling i.e.
Can.
Embodiment 3
(1) 20 parts of melamines and 80 parts of phthalic anhydrides are added in reactor first, are heated to 270 DEG C, subtract
The water of pressure-off dereaction generation, frit reaction 3 hours, then cools to 110 DEG C and obtains intermediate 3.
(2) by 3,30 portions of diethylene glycol (DEG)s of intermediate in 20 parts, 10 parts of ethylene glycol, 5 parts of pentaerythrites, 35 parts of terephthalic acid (TPA)s,
0.02 part of T-12 is added sequentially in reactor, and material temperature then is increased into 160 DEG C, starts water outlet, is incubated two hours, then will
Material temperature is slowly raised to 230 DEG C, during which controls reflux column temperature to be then incubated two hours at 100 ± 3 DEG C, progressively vacuumizing, taking
Sample tests acid number, and when acid number drops to 2.0mg KOH/g, stopping is vacuumized and cooled, and drops to barrelling under 90 degree.
Embodiment 4
(1) 15 parts of melamines and 85 parts of M-phthalic acids are added in reactor first, are heated to 270 DEG C, decompression
The water of reaction generation is sloughed, frit reaction 2 hours, intermediate 4 is obtained between then cooling to 120 DEG C.
(2) by 4,30 portions of diethylene glycol (DEG)s of intermediate in 10 parts, 20 parts of ethylene glycol, 5 parts of glycerine, 10 parts of phthalic anhydrides, 25
Part terephthalic acid (TPA), 0.02 part of tetrabutyl titanate are added sequentially in reactor, material temperature then are increased into 170 DEG C, starts
Water, two hours are incubated, material temperature is then slowly raised to 230 DEG C, during which control reflux column temperature to be then incubated two at 100 ± 3 DEG C
Hour, progressively vacuumizing, sampling and testing acid number, when acid number drops to 2.0mg KOH/g, stopping is vacuumized and cooled, and is dropped
To 90 degree of lower barrellings.
Claims (10)
- A kind of 1. production method of hard bubble PEPA, it is characterised in that：Step is as follows：(1) by melamine and dicarboxylic acids or anhydride reaction is modified obtains intermediate；(2) polycondensation reaction is carried out with small molecule polyol and dicarboxylic acids or acid anhydrides under catalyst action to be made.
- 2. the production method of hard bubble PEPA according to claim 1, it is characterised in that：In step (1), trimerization When cyanamide is modified with dicarboxylic acids or anhydride reaction, material quality number is as follows：Melamine 15-30 parts, dicarboxylic acids or acid Acid anhydride 70-85 parts.
- 3. the production method of hard bubble PEPA according to claim 1, it is characterised in that：Step (1) and step (2) in, dicarboxylic acids or acid anhydrides are one or two kinds of in phthalic anhydride, terephthalic acid (TPA) or M-phthalic acid.
- 4. the production method of hard bubble PEPA according to claim 1, it is characterised in that：Small molecule polyol is One or more in ethylene glycol, diethylene glycol (DEG), triethylene glycol, neopentyl glycol, glycerine or pentaerythrite.
- 5. the production method of hard bubble PEPA according to claim 1, it is characterised in that：It is middle in step (2) The mass fraction of body, small molecule polyol, dicarboxylic acids or acid anhydrides and catalyst is as follows：Intermediate 10-20 parts, small molecule are polynary Alcohol 40-60 parts, dicarboxylic acids or acid anhydrides 20-50 parts, catalyst 0.01-0.02 parts.
- 6. the production method of hard bubble PEPA according to claim 1, it is characterised in that：Catalyst is organic titanium One kind in class or organic tin.
- 7. the production method of hard bubble PEPA according to claim 1, it is characterised in that：Organic tin is T-9 And T-12, organic titanium class catalyst are tetrabutyl titanate and isopropyl titanate.
- 8. the production method of hard bubble PEPA according to claim 1, it is characterised in that：Comprise the following steps：(1) melamine and dicarboxylic acids or acid anhydrides are added in reactor, are heated to 260-270 DEG C, are dehydrated, frit reaction 2- 3 hours, 100-120 DEG C is cooled to, obtains intermediate；(2) small molecule polyol and dicarboxylic acids or acid anhydrides are added in intermediate, material temperature is increased to 160-170 DEG C, insulation Two hours, then post-processed.
- 9. the production method of hard bubble PEPA according to claim 8, it is characterised in that：Described in step (2) Post processing be insulation 2-3 hours after, material temperature is then raised to 225-230 DEG C, during which control reflux column temperature at 97-103 DEG C Between, 2-3 hours are incubated, vacuumizes, sampling and testing acid number, when acid number drops to 1.0-2.0mg KOH/g, stops vacuumizing And cool, temperature, which is dropped at 90 DEG C, produces hard bubble PEPA.
- 10. according to the production method of any described hard bubble PEPAs of claim 1-9, it is characterised in that：This method For the hard bubble hydroxyl value of polyester polyol of production between 200-500mg KOH/g, acid number is less than 2.0mg KOH/g.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711049574.8A CN107602831B (en) | 2017-10-31 | 2017-10-31 | Production method of polyester polyol for hard foam |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711049574.8A CN107602831B (en) | 2017-10-31 | 2017-10-31 | Production method of polyester polyol for hard foam |
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| CN107602831A true CN107602831A (en) | 2018-01-19 |
| CN107602831B CN107602831B (en) | 2020-02-14 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4180475A1 (en) | 2021-11-10 | 2023-05-17 | Norchem Limited | Process for producing a triazine ring containing compound, addition product, triazine ring containing polyol, use of the addition product, use of the triazine ring containing polyol and pu/pir foam obtained by using the triazine ring containing polyol |
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| US20110236671A1 (en) * | 2008-11-06 | 2011-09-29 | Bayer Material Science Ag | Method for producing polyester polyols having low amounts of dioxane waste |
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| CN106243335A (en) * | 2016-08-01 | 2016-12-21 | 常州聚博节能科技有限公司 | Inorganic hybridization PEPA etherified melamine polyimide resin and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20110236671A1 (en) * | 2008-11-06 | 2011-09-29 | Bayer Material Science Ag | Method for producing polyester polyols having low amounts of dioxane waste |
| CN102718957A (en) * | 2012-06-27 | 2012-10-10 | 淄博德信联邦化学工业有限公司 | Aromatic polyester polyol for preparing polyurethane foam and preparation method thereof |
| CN103642009A (en) * | 2013-12-09 | 2014-03-19 | 山东一诺威聚氨酯股份有限公司 | Polyester polyol as well as preparation method and application thereof |
| CN105367774A (en) * | 2015-11-19 | 2016-03-02 | 滕州市科米特新材料有限责任公司 | Nitrogen heterocyclic castor oil-based polyester polyol and preparation method and use thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4180475A1 (en) | 2021-11-10 | 2023-05-17 | Norchem Limited | Process for producing a triazine ring containing compound, addition product, triazine ring containing polyol, use of the addition product, use of the triazine ring containing polyol and pu/pir foam obtained by using the triazine ring containing polyol |
| WO2023083442A1 (en) | 2021-11-10 | 2023-05-19 | Norchem Limited | Process for producing a triazine ring containing compound, addition product, triazine ring containing polyol, use of the addition product, use of the triazine ring containing polyol and pu/pir foam obtained by using the triazine ring containing polyol |
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| CN107602831B (en) | 2020-02-14 |
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