CN108623793A - A kind of polyester polyol and preparation method thereof of low hydroxyl value - Google Patents
A kind of polyester polyol and preparation method thereof of low hydroxyl value Download PDFInfo
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- CN108623793A CN108623793A CN201810399712.3A CN201810399712A CN108623793A CN 108623793 A CN108623793 A CN 108623793A CN 201810399712 A CN201810399712 A CN 201810399712A CN 108623793 A CN108623793 A CN 108623793A
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- Prior art keywords
- acid
- polyester polyol
- hydroxyl value
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- value
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
- C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
- C08G18/425—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids the polyols containing one or two ether groups
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
This application involves a kind of polyester polyol and preparation method thereof of low hydroxyl value.The present processes include in an inert atmosphere that under agitation, mixed aromatic dicarboxylic acids or acid anhydrides, dihydric alcohol and catalyst react 46 hours at a temperature of 100 170 DEG C.170 240 DEG C are then raised temperature to, persistently leads to inert gas and reacts 57 hours.Inert gas is closed, segmentation is evacuated to negative pressure, reacts 34 hours, until product reaches predetermined acid value to get to the polyester polyol.The polyester polyol of low hydroxyl value is prepared using the dihydric alcohol and aromatic dicarboxilic acid or acid anhydrides of one-component for the present processes.Convenient for continuous production, obtained product quality consistency is good.In preparation process without using aliphatic acid and without adding entrainer, the volatile byproducts for reacting generation are few, are good for the environment.
Description
Technical field
This application involves polyester polyol technical fields.Specifically, this application involves a kind of polyester polyols of low hydroxyl value
Alcohol and preparation method thereof.
Background technology
Since polyurethane has excellent intensity, elasticity, wear-resistant row, it is widely used in adhesive, foam, elasticity
The multiple fields such as body, coating.Wherein, polyester polyol is to produce one of the core material of polyester polyurethane.Polyester polyol
Typically by binary/polybasic carboxylic acid (may include acid anhydrides or ester) and binary/polyol condensating (or transesterification) or by lactone with it is more
First alcohol is polymerized.According to the difference of synthesis material, polyester polyol can show different excellent properties.
Currently, the synthesis of polyester polyol mainly uses batch process, by raw polyol and a variety of polyacids, including fat
Acid and aromatic acid, are added in reaction kettle by a certain percentage, heating, stirring, and are passed through nitrogen and take the water that reaction generates out of,
The polyester polyol of low molecular weight is generated in kettle；It then heats up and gradually reduces system vacuum degree, water that reaction is generated and small
Molecule reactant/product steams.
However, on the one hand, in process of production, wider aliphatic acid of molecular weight distribution itself and/or itself and polyalcohol are given birth to
At small molecule be unfavorable for the consistency of the stability and product quality that generate, and obtained multicomponent polyester polyol is as anti-
Answer intensity and the caking property of the polyurethane adhesive of object preparation not high.On the other hand, entrainer need to be added in preparation process, and
Water and small molecule reaction object/product of generation steam together, generate a large amount of harmful wastes, are unfavorable for environmental protection.
Therefore, it is necessary to provide a kind of polyester polyol of low hydroxyl value newly and preparation method thereof to solve the above problems.
Invention content
This application involves a kind of preparation methods of the polyester polyol of low hydroxyl value, to solve above-mentioned skill in the prior art
Art problem.Specifically, the present processes are included in nitrogen atmosphere, under agitation, mixed aromatic dicarboxylic acids
Or acid anhydrides, dihydric alcohol and catalyst, it is reacted 4-6 hours at a temperature of 100-170 DEG C.170-240 DEG C is then raised temperature to, is held
Continuous logical inert gas reacts 5-7 hours.Inert gas is closed, segmentation is evacuated to negative pressure, reacts 3-4 hours, pre- until reaching
Determine acid value, obtains the polyester polyol.The fragrance two of the dihydric alcohol and one-component of one-component is used only in the present processes
The polyester polyol of low hydroxyl value is prepared in carboxylic acid or acid anhydrides.Convenient for continuous production, obtained product quality consistency is good.It is making
For standby process without using aliphatic acid and without adding entrainer, the volatile byproducts for reacting generation are few, are good for the environment.
The purpose of the application also reside in provide a kind of one-component prepared using the above method, low hydroxyl value polyester polyols
Alcohol.
To achieve the goals above, the application provides following technical proposals.
In the first aspect, the application provides a kind of method for the polyester polyol preparing low hydroxyl value, the method includes
Following step：
(1) in an inert atmosphere, under agitation, mixed aromatic dicarboxylic acids or acid anhydrides, dihydric alcohol and catalysis
Agent is reacted 4-6 hours at a temperature of 100-170 DEG C；
(2) it is warming up to 170-240 DEG C, persistently leads to inert gas and reacts 5-7 hours；And
(3) inert gas is closed, segmentation is evacuated to negative pressure, reacts 3-4 hours, until reaching predetermined acid value, obtains institute
Polyester polyol is stated,
Aliphatic acid is not used wherein.
In a kind of embodiment of first aspect, the predetermined acid value is less than or equal to 5.0mgKOH/g.
In a kind of embodiment of first aspect, the aromatic binary carboxylic acid or acid anhydrides include phthalic anhydride.
In a kind of embodiment of first aspect, the dihydric alcohol includes diethylene glycol (DEG).
In a kind of embodiment of first aspect, mole of the aromatic series dicarboxyl carboxylic acid or acid anhydrides and the dihydric alcohol
Than for (0.8-1.15)：1.
In a kind of embodiment of first aspect, entrainer is not used in the method, in embodiment without limiting
In, the entrainer is selected from benzene,toluene,xylene, chlorobenzene and dichloromethane.
In a kind of embodiment of first aspect, the catalyst be at least one or more of titanium system, antimony system, germanium system,
Tin system and W-Sn deposits and combinations thereof.
In a kind of embodiment of first aspect, the catalyst includes alkyl titanate, sulfuric acid, p-methyl benzenesulfonic acid,
One or more of stannous oxide, aluminium oxide or molecular sieve.
In the second aspect of the application, the application provides a kind of low hydroxyl prepared by method as described in relation to the first aspect
The polyester polyol of value.
In a kind of embodiment of second aspect, the polyester polyol has following properties：At 25 DEG C, viscosity is
50000-80000mPas, hydroxyl value 40-50mgKOH/g, acid value are less than or equal to 5.0mgKOH/g.
Compared with prior art, the advantageous effect of the application is that (1) uses the dihydric alcohol of one-component and fragrant dicarboxyl
The polyester polyol of low hydroxyl value is prepared in acid or acid anhydrides, is convenient for continuous production, obtained product quality consistency good；(2)
The intensity for the polyurethane adhesive that the polyester polyol of the low hydroxyl value arrived is prepared as reactant is high, and caking property is good；And (3) exist
For preparation process without using aliphatic acid and without adding entrainer, the volatile byproducts for reacting generation are few, are good for the environment.
Specific implementation mode
This application involves a kind of preparation methods of the polyester polyol of low hydroxyl value, and the low hydroxyl prepared using the above method
The polyester polyol of value.
Unless otherwise indicated, from context cues or belong to the convention of the prior art, otherwise number all in the application
It is all based on weight with percentage, and test and characterizing method used is all synchronous with the submission date of the application.It is being applicable in
In the case of, any patent, patent application or disclosure involved in the application are fully incorporated in this as reference, and its
Patent families of equal value are also introduced into as reference, disclosed by these special documents about the synthetic technology in this field, product
With the definition of fabrication design, polymer, comonomer, initiator or catalyst etc..If the specific art disclosed in the prior art
Defining for language is inconsistent with any definition provided herein, then term provided herein of being subject to defines.
Digital scope in the application is approximation, therefore unless otherwise stated, it may include the number other than range
Value.Numberical range include with the increased all numerical value from lower limiting value to upper limit value of 1 unit, condition be any lower value with
There are the intervals of at least two unit between arbitrary high value.For example, if compositional, physics or other property (such as molecules
Amount, melt index (MI) etc.) it is 100 to 1000, it is meant that clearly list all single numbers, such as 100,101,102 etc., with
And all subranges, such as 100 to 166,155 to 170,198 to 200 etc..For comprising less than 1 numerical value or comprising big
In the range of 1 score (such as 1.1,1.5 etc.), then suitably regard 1 unit as 0.0001,0.001,0.01 or 0.1.
For including the range of the units less than 10 (such as 1 to 5), usually regarding 1 unit as 0.1., these are only intended to table
The specific example of the content reached, and all possible combination of the numerical value between cited minimum and peak is all recognized
In this application for clear record.
About chemical compound in use, unless explicitly stated otherwise, otherwise odd number includes all isomeric forms, otherwise also
So (for example, " hexane " either individually or collectively includes whole isomers of hexane).In addition, unless explicitly stated otherwise, otherwise using
"one", the noun that "an" or "the" are described also includes its plural form.
Term "comprising", " comprising ", " having " and their derivative are not excluded for any other component, step or mistake
The presence of journey, and whether disclose in this application with these other components, step or process unrelated.To eliminate any query,
Unless expressly stated, otherwise all in the application to use term "comprising", " comprising ", or the composition of " having " can include to appoint
What additional additive, auxiliary material or compound.On the contrary, in addition to necessary to operating characteristics those, term " substantially by ...
Composition " excludes any other component, step or process except the hereinafter described range of any term.Term " by ...
Composition " does not include any component, step or the process for not specifically describing or listing.Unless expressly stated, otherwise term "or" refers to
The separate member listed or any combination thereof.
Term defines
As used herein, term " fatty acid " " refers to the aliphatic hydrocarbon chain for the length that one end contains there are one carboxyl, is to have
The general formula of machine object, linear saturated fatty acids is CnH(2n+1)COOH。
As used herein, term " aromatic series " refers in hydrocarbon molecules at least containing there are one the benzene with delocalized bond
Ring has the family of the peculiar property different from open chain compound or alicyclic (claiming armaticity, aromaticity).
As used herein, term " entrainer " refers to one or two components for being used in azeotropic distillation and feeding and generates altogether
The third addO-on therapy of boiling object is referred to as " entrainer ".Azeotropic mixture is formed by either to remove from tower top or remove from bottom of tower.
As used herein, term " hydroxyl value " refers to the amount of the substance of the hydroxyl group in 100g resins.And usually industry
Upper hydroxyl value refer to the hydroxyl in hydroxyl value (Hydroxyl value) 1g samples comparable potassium hydroxide (KOH) milligram
Number, is indicated with mgKOH/g.
As used herein, term " low hydroxyl value " can be regarded as hydroxyl value in polyester polyol industry and be less than or equal to
300mgKOH/g。
In the first aspect, the application provides a kind of method for the polyester polyol preparing low hydroxyl value, the method includes
Following step：(1) in an inert atmosphere, under agitation, mixed aromatic dicarboxylic acids or acid anhydrides, dihydric alcohol and catalysis
Agent is reacted 4-6 hours at a temperature of 100-170 DEG C；(2) it is warming up to 170-240 DEG C, it is small persistently to lead to inert gas reaction 5-7
When；And (3) close inert gas, segmentation is evacuated to negative pressure, reacts 3-4 hours, until reaching predetermined acid value, obtains described
Polyester polyol, wherein not using aliphatic acid.
Inventor it was surprisingly found that in the preparation method of the application, by using one-component dihydric alcohol and
The polyester polyol of low hydroxyl value is prepared in aromatic dicarboxilic acid or acid anhydrides.Without using the wider aliphatic acid of molecular weight dispersion, it is convenient for
Continuous production, obtained product quality consistency are good.And the polyester polyol of obtained low hydroxyl value is gathered as prepared by reactant
The intensity of urethane adhesive is high, and caking property is good.
In one embodiment, the predetermined acid value is less than or equal to 5.0mgKOH/g.
In one embodiment, system vacuum degree is reduced to more than or equal to -0.02MPa.Those skilled in the art can
To understand, term " vacuum degree is greater than or equal to -0.02MPa " means that the vacuum degree of reaction kettle when vacuum dehydration is -0.02MPa, -
0.03MPa ... -0.1MPa etc..
In one embodiment, the aromatic binary carboxylic acid or acid anhydrides are phthalic anhydride.
In one embodiment, the dihydric alcohol can be any dihydric alcohol.In a specific embodiment, described two
First alcohol can be one in ethylene glycol, propylene glycol, butanediol, diethylene glycol (DEG) (diglycol), triethylene glycol and dipropylene glycol
Kind is several.In a preferred embodiment, the dihydric alcohol is diethylene glycol (DEG).
In one embodiment, the molar ratio of the aromatic binary carboxylic acid or acid anhydrides and the dihydric alcohol is (0.8-
1.15)：1.In a preferred embodiment, the molar ratio of the aromatic dicarboxylic acid or acid anhydrides and the dihydric alcohol is
(1-1.125)：1.
In a kind of embodiment of first aspect, entrainer is not used in the method, in embodiment without limiting
In, the entrainer is selected from benzene,toluene,xylene, chlorobenzene and dichloromethane.Aliphatic acid is not used in preparation process, then low boiling
Point small molecule is less, and so there is no need to add for removing water and the entrainer of small molecule so that and the volatile byproducts for reacting generation are few,
It is good for the environment.
In the second aspect of the application, the application provides a kind of low hydroxyl prepared by method as described in relation to the first aspect
It is worth polyester polyol.In a specific embodiment, the polyester polyol has following properties：At 25 DEG C, viscosity is
50000-80000mPas, hydroxyl value 40-50mgKOH/g, acid value are less than or equal to 5.0mgKOH/g.
Embodiment
Below in conjunction with embodiments herein, clear and complete description is carried out to the technical solution of the application.Such as nothing
It illustrates, reagent used and raw material can all be bought by commercial sources.
Embodiment
The present embodiment is related to the method for synthesizing polyester polyalcohol.
First, 950~1000kg phthalic anhydrides are added in a kettle, 850~900kg diethylene glycol (DEG)s and 5kg's
Butyl titanate (PLSCONFM catalyst and addition).Logical nitrogen, stirring are reacted 5 hours at a temperature of 100-170 DEG C.
Then, it is gradually heating to 170-240 DEG C, is kept for 6 hours at 230-240 DEG C, and increase nitrogen flow during this period,
It then carries out segmentation to vacuumize, the vacuum degree of device is made to be down to 0~-0.09MPa, react 3-4 hours, until acid value is less than or waits
In 5.0mgKOH/g.After acid value is up to standard, the polyester polyol according to embodiment 1 is obtained.
After testing, ester composition according to the embodiment has following properties：At 25 DEG C, viscosity is 50000-
80000mPas, hydroxyl value 40-50mgKOH/g, acid value are less than or equal to 5.0mgKOH/g.
In addition, low hydroxyl value polyester polyol according to the embodiment is prepared polyurethane adhesive as reactant, find
The polyurethane adhesive intensity arrived is high, and cohesive force is good.
The above-mentioned description to embodiment is that this Shen can be understood and applied for the ease of those skilled in the art
Please.Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein
General Principle is applied in other embodiments without paying performing creative labour.Therefore, the application is not limited to implementation here
Example, those skilled in the art make according to herein disclosed content in the case where not departing from the application scope and spirit
It improves and changes within all scope of the present application.
Claims (10)
1. a kind of method of polyester polyol that making low hydroxyl value, the method includes following step：
(1) in an inert atmosphere, under agitation, mixed aromatic dicarboxylic acids or acid anhydrides, dihydric alcohol and catalyst,
It is reacted 4-6 hours at a temperature of 100-170 DEG C；
(2) it is warming up to 170-240 DEG C, persistently leads to inert gas and reacts 5-7 hours；And
(3) inert gas is closed, segmentation is evacuated to negative pressure, reacts 3-4 hours, until reaching predetermined acid value, obtains described poly-
Ester polyol,
Aliphatic acid is not used wherein.
2. the method as described in claim 1, which is characterized in that the predetermined acid value is less than or equal to 5.0mgKOH/g.
3. the method as described in claim 1, which is characterized in that the aromatic binary carboxylic acid or acid anhydrides include phthalic acid
Acid anhydride.
4. the method as described in claim 1, which is characterized in that the dihydric alcohol includes diethylene glycol (DEG).
5. the method as described in claim 1, which is characterized in that the aromatic binary carboxylic acid or acid anhydrides and the dihydric alcohol
Molar ratio is (0.8-1.15)：1.
6. the method as described in claim 1, which is characterized in that do not use entrainer in the method, the entrainer is selected from
Benzene,toluene,xylene, chlorobenzene and dichloromethane.
7. the method as described in any one of claim 1-5, which is characterized in that the catalyst is at least one or more of titanium
System, antimony system, germanium system, tin system and W-Sn deposits and combinations thereof.
8. the method for claim 7, which is characterized in that the catalyst includes alkyl titanate, p-methyl benzenesulfonic acid, oxygen
Change one or more of stannous, aluminium oxide or molecular sieve.
9. a kind of polyester polyol of low hydroxyl value, which is characterized in that the polyester polyol by preparing as described in claim 1
Method is made.
10. polyester polyol as claimed in claim 9, which is characterized in that the polyester polyol has following properties：At 25 DEG C
When viscosity be 50000-80000mPas, hydroxyl value 40-50mgKOH/g, acid value be less than or equal to 5.0mgKOH/g.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810399712.3A CN108623793A (en) | 2018-04-28 | 2018-04-28 | A kind of polyester polyol and preparation method thereof of low hydroxyl value |
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| CN201810399712.3A CN108623793A (en) | 2018-04-28 | 2018-04-28 | A kind of polyester polyol and preparation method thereof of low hydroxyl value |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108822285A (en) * | 2018-07-11 | 2018-11-16 | 广东美涂士建材股份有限公司 | The low thinning of the low hydroxyl of high-solid lower-viscosity is than alkyd resin and its preparation method and application |
| CN111394044A (en) * | 2020-04-16 | 2020-07-10 | 上海炼升化工股份有限公司 | Fast-curing high-temperature-resistant adhesive and preparation method thereof |
| CN111454685A (en) * | 2020-04-16 | 2020-07-28 | 上海炼升化工股份有限公司 | High-temperature-resistant adhesive and preparation method thereof |
| CN111533891A (en) * | 2020-04-16 | 2020-08-14 | 上海炼升化工股份有限公司 | Polyester polyol for high-temperature-resistant adhesive and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108822285A (en) * | 2018-07-11 | 2018-11-16 | 广东美涂士建材股份有限公司 | The low thinning of the low hydroxyl of high-solid lower-viscosity is than alkyd resin and its preparation method and application |
| CN108822285B (en) * | 2018-07-11 | 2020-12-25 | 广东美涂士建材股份有限公司 | Alkyd resin with high solid content, low viscosity, low hydroxyl content and low dilution ratio as well as preparation method and application thereof |
| CN111394044A (en) * | 2020-04-16 | 2020-07-10 | 上海炼升化工股份有限公司 | Fast-curing high-temperature-resistant adhesive and preparation method thereof |
| CN111454685A (en) * | 2020-04-16 | 2020-07-28 | 上海炼升化工股份有限公司 | High-temperature-resistant adhesive and preparation method thereof |
| CN111533891A (en) * | 2020-04-16 | 2020-08-14 | 上海炼升化工股份有限公司 | Polyester polyol for high-temperature-resistant adhesive and preparation method thereof |
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