CN104262596B - A kind of high-functionality polyester polyol and preparation method thereof - Google Patents
A kind of high-functionality polyester polyol and preparation method thereof Download PDFInfo
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- CN104262596B CN104262596B CN201410488556.XA CN201410488556A CN104262596B CN 104262596 B CN104262596 B CN 104262596B CN 201410488556 A CN201410488556 A CN 201410488556A CN 104262596 B CN104262596 B CN 104262596B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
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Abstract
The invention discloses a kind of high-functionality polyester polyol and preparation method thereof, described high-functionality polyester polyol is by 900～1200 mass parts polyester alcoholysis liquid, 900 mass parts phthalic anhydrides, 400～600 mass parts binary of fatty acids, 800～1000 mass parts dihydroxylic alcohols, 550～900 mass parts polyalcohols, 0.3～0.5 mass parts esterification catalyst, through esterification and remove moisture, again through polycondensation, the most prepared；This high-functionality polyester polyol average functionality is 2.4～2.5, viscosity is≤10000 mPa S(25 DEG C), hydroxyl value 300～350 mgKOH/g, acid number be≤1 mgKOH/g, and do not crystallize after storing 3 months under the conditions of 2 DEG C.PEPA of the present invention can be widely applied to the fields such as polyurethane rigid foam board, polyurethane elastomer and adhesive for polyurethane.
Description
Technical field
The invention belongs to organic high molecular compound and preparation thereof, relate to a kind of high-functionality polyester polyol and preparation thereof
Method.High-functionality polyester polyol prepared by present invention polyester (polyester waste material), it is adaptable to polyurethane rigid foam board,
The field such as polyurethane elastomer and adhesive for polyurethane.
Background technology
PEPA is widely used in the fields such as polyurethane rigid foam board, polyurethane elastomer and adhesive for polyurethane,
The production method of its classics is to be formed with dihydroxylic alcohols (polyalcohol) condensation by binary acid (acid anhydrides).Along with poly-to benzene
Naphthalate (being called for short PET) is widely used in preparing fabric, beverage bottle and packaging material and produces a large amount of
Pet waste, recent domestic begin with these pet wastes be raw material produce PEPA, reach abundant
Utilize all available resources to reduce the purpose of its environmental pollution.Main method has: CN1148058A is open
A kind of method using polyester waste material to produce PEPA, it uses diethylene glycol (DEG), triethylene glycol, glycerine and three ethanol
The mixing alcoholysis agent such as amine carries out alcoholysis, relatively low (the average sense of the method gained polyester polyol functionality to polyester waste material
Degree 2.2), viscosity higher (20 DEG C, 20000mPa S), and product be easier to crystallization；US4720571 uses diethylene glycol (DEG)
And dipropylene glycol carries out alcoholysis as mixing alcoholysis agent to polyester waste material, although the method products therefrom is difficult to crystallization,
But its degree of functionality relatively low (average functionality 2.0), acid number higher (3.4～3.8mgKOH/g)；US5360900 uses
Diethylene glycol (DEG) carries out alcoholysis to polyester waste material, by adding the polynary glucosides such as glucoside, glucoside polyalcohol to increase
The degree of functionality of PEPA, although the method products therefrom be difficult to crystallization, degree of functionality higher (average functionality 2.4～
2.5), but products therefrom viscosity is relatively big (25 DEG C, 30000mPa S).Prior art uses polyester (polyester waste material) system
Standby PEPA, is primarily present following shortcoming:
(1) alcoholysis reaction used catalyst is single and amount is compared with big (addition is more than the 0.2% of the total inventory of alcoholysis reaction),
Follow-up reaction and downstream application will be had undesirable effect by this: on the one hand alcoholysis catalysts has extremely strong ester exchange and urges
Change effect, easily increase the condensation degree of dissolved of subsequent reactions, cause PEPA viscosity excessive thus affect product and use,
On the other hand alcoholysis catalysts the most easily accelerates the decomposition (mechanism is similar with alcoholysis) of polyurethane foam, thus causes
Foam thermal stability declines, and affects its anti-flammability；
(2) PEPA easily crystallizes: whether ethylene glycol terephthalate or terephthalic acid (TPA) one contracting diethyl two
Alcohol ester, its molecular structure all has the symmetry of height, is therefore produced many by polyester (polyester waste material) alcoholysis liquid
Unit's alcohol the most easily crystallizes, typically, and aromatic hydrocarbons PEPA (particularly terephthaldehyde's acid type) and ring
The physical blowing agents such as pentane have poor compatibility, and PEPA crystallization will increase the weight of the effect above, even occur
The lamination of white material, this will make the inspiration degradation of foam, and the foam structure and the density that finally affect foam are equal
One property, and presently disclosed alcoholysis polyester (polyester waste material) is produced in the method for PEPA, lacks effectively suppression
The way of PEPA crystallization；
(3) PEPA generally existing defects in terms of degree of functionality: a. because of degree of functionality too low (average functionality 2.0～
2.2), easily cause polyurethane foam dimensional stability to decline；Although b. degree of functionality higher (average functionality 2.4～2.5),
But viscosity is relatively big (25 DEG C, 20000～30000mPa S), easily reduce the PEPA mobility when foaming, shadow
Ring its foaming effect.
Summary of the invention
The purpose of the present invention is intended to overcome above-mentioned deficiency of the prior art, it is provided that a kind of high-functionality polyester polyol and
Its preparation method.Using high-functionality polyester polyol of the present invention, the mechanical mechanics property of the polyurethane plate of preparation is excellent
In using universal PEPA and reaching or be better than PPG gained foam board.
Present disclosure is: a kind of high-functionality polyester polyol, it is characterized in that: gathered by 900～1200 mass parts
Ester alcoholysis liquid, 900 mass parts phthalic anhydrides, 400～600 mass parts binary of fatty acids, 800～1000 mass parts
Dihydroxylic alcohols, 550～900 mass parts polyalcohols, 0.3～0.5 mass parts esterification catalyst, through esterification and remove water
Point, then through polycondensation, i.e. prepare high-functionality polyester polyol；
The preparation method of described polyester alcoholysis liquid is: by 1000 mass parts polyester material, 1000 mass parts alcoholysis agent and 1.2～
1.6 mass parts alcoholysis catalysts put into be had in the reactor A of rectifying column, is passed through nitrogen, stir and be warming up to 225～
235 DEG C (particularly preferred 235 DEG C), constant temperature 20 minutes (making polyester material be completely dissolved) of stirring, (the slowest) heats up
To 240～250 DEG C (particularly preferred 240 DEG C), carry out constant temperature 6～8 hours alcoholysis reactions under nitrogen protection, when instead
The ethylene glycol amount answering the rectifying column of device A to be removed reaches 48～50 mass parts and reactant viscosity reaches at 25 DEG C
After 1000～1500mPa S, stop reaction, be cooled to 160 DEG C, filter (removing impurity) with diatomite, filtrate
It is prepared polyester alcoholysis liquid；
Described polyester material is the section of pet resin (being called for short PET), reclaims film, recovery
One or more co-grinding material in section, recycled plastic bottle and the material that is recycled and packaged, this material
Inherent viscosity is 0.55～0.85dl/g (i.e. η=0.55～0.85dl/g)；
Described alcoholysis agent be in diethylene glycol (DEG), triethylene glycol, tetraethylene glycol, glycerine and pentaerythrite one or both with
On mixture；
Described alcoholysis catalysts be zinc acetate, dibutyl tin laurate, Mono-n-butyltin, antimony oxide, with
And the mixture of two or more in tetrabutyl titanate；
Described binary of fatty acids is any one in succinic acid, glutaric acid, adipic acid, azelaic acid, decanedioic acid；
Described dihydroxylic alcohols is one or both in ethylene glycol, 1,2-propane diols, 1,3 butylene glycol, neopentyl glycol etc.；
Described polyalcohol is one or both the mixture in glycerine, trimethylolpropane；
Described esterification catalyst is zinc acetate, tetrabutyl titanate, tetraisopropyl titanate, Mono-n-butyltin, dibutyl
Any one in tin oxide and stannous chloride etc..
In present disclosure: the average functionality of described high-functionality polyester polyol is 2.4～2.5, viscosity is 25 DEG C
Under≤10000mPa S, hydroxyl value 300～350mgKOH/g, acid number be≤1mgKOH/g, and store up under the conditions of 2 DEG C
Do not crystallize after depositing 3 months.
In present disclosure: described alcoholysis agent is preferably one or both mixed of diethylene glycol (DEG), triethylene glycol, glycerine
Compound.
In present disclosure: described alcoholysis catalysts is preferably the mixture of zinc acetate and tetrabutyl titanate.
In present disclosure: described binary of fatty acids is preferably adipic acid.
Another content of the present invention is: the preparation method of a kind of high-functionality polyester polyol, it is characterized in that step is as follows:
A, prepare polyester alcoholysis liquid: by 1000 mass parts polyester material, 1000 mass parts alcoholysis agent and 1.2～1.6 mass
Part alcoholysis catalysts puts in the reactor A having rectifying column, is passed through nitrogen, stirs and is warming up to 225～235 DEG C of (spies
The most preferably 235 DEG C), constant temperature 20 minutes (making polyester material be completely dissolved) of stirring, (the slowest) is warming up to 240～250 DEG C
(particularly preferred 240 DEG C), carry out constant temperature 6～8 hours alcoholysis reactions, under nitrogen protection when the rectifying of reactor A
The ethylene glycol amount that post is removed reaches 48～50 mass parts and reactant viscosity reaches 1000～1500mPa S at 25 DEG C
Afterwards, stopping reaction, be cooled to 160 DEG C, filter (removing impurity) with diatomite, filtrate is prepared polyesterols
Solve liquid；
Described polyester material is the section of pet resin (being called for short PET), reclaims film, recovery
One or more co-grinding material in section, recycled plastic bottle and the material that is recycled and packaged, this material
Inherent viscosity is 0.55～0.85dl/g (i.e. η=0.55～0.85dl/g)；
Described alcoholysis agent be in diethylene glycol (DEG), triethylene glycol, tetraethylene glycol, glycerine and pentaerythrite one or both with
On mixture；
Described alcoholysis catalysts be zinc acetate, dibutyl tin laurate, Mono-n-butyltin, antimony oxide, with
And the mixture of two or more in tetrabutyl titanate；
B, dispensing: by 900～1200 mass parts polyester alcoholysis liquid, 900 mass parts phthalic anhydrides, 400～600
Mass parts binary of fatty acids, 800～1000 mass parts dihydroxylic alcohols, 550～900 mass parts polyalcohols, 0.3～0.5 mass
The quality proportioning of part esterification catalyst takes each component raw material；
Described binary of fatty acids is any one in succinic acid, glutaric acid, adipic acid, azelaic acid, decanedioic acid；
Described dihydroxylic alcohols is one or both in ethylene glycol, 1,2-propane diols, 1,3 butylene glycol, neopentyl glycol etc.；
Described polyalcohol is one or both the mixture in glycerine, trimethylolpropane；
Described esterification catalyst is zinc acetate, tetrabutyl titanate, tetraisopropyl titanate, Mono-n-butyltin, dibutyl
Any one in tin oxide and stannous chloride etc..
C, prepare high-functionality polyester polyol: component raw material each described in step b is put into the reactor of rectifying column
In B, being passed through nitrogen, stirring heats up, and the rectifying column head temperature (all the time) controlling reactor B is maintained at 100 DEG C
Within, when in reactor B, temperature reaches 145～155 DEG C, insulation carries out (and removing when esterification 1～2 is little
The water generated), insulation reaction terminates the rectifying column head temperature of post-reactor B when being reduced to less than 70 DEG C, with every 20
Minute heat up 5 DEG C speed, when making the temperature in reactor B reach 160 DEG C, insulation reaction 1 hour, then, with
Within every 20 minutes, heat up 5 DEG C speed, when making the temperature in reactor B reach 180 DEG C, insulation reaction is after 1 hour,
Again with within every 20 minutes, heat up 5 DEG C speed, make the temperature in reactor B reach 200 DEG C time, insulation reaction 1 hour
After, then it being warming up to 220～230 DEG C, insulation reaction 1 hour with every 20 minutes speed of 5 DEG C of heating up, insulation reaction is tied
When after bundle, the rectifying column head temperature of reaction mass acid number≤10mgKOH/g and reactor B is down to less than 70 DEG C, stop
Heating, stops when reaction mass temperature is down to 200 DEG C being passed through nitrogen and being slowly evacuated to-0.070～-0.085
MPa, as acid number≤1mgKOH/g, stops reaction, cooling, i.e. prepares high-functionality polyester polyol product.
In another content of the present invention: alcoholysis agent described in step a be preferably diethylene glycol (DEG), triethylene glycol, the one of glycerine
Plant or the mixture of two kinds.
In another content of the present invention: alcoholysis catalysts described in step a is preferably zinc acetate and tetrabutyl titanate
Mixture.
In another content of the present invention: binary of fatty acids described in step b is preferably adipic acid.
In another content of the present invention: the average functionality of described prepared high-functionality polyester polyol is 2.4～2.5,
Viscosity is at 25 DEG C≤10000mPa S, hydroxyl value 300～350mgKOH/g, acid number be≤1mgKOH/g, and at 2 DEG C
Under the conditions of store after 3 months and do not crystallize.
Described not crystallizing refers to be placed under conditions of 2 DEG C by this high-functionality polyester polyol, after 3 months
Employing visually observes, and this high-functionality polyester polyol still can keep clear, and macroscopic muddiness does not occur
Phenomenon.Crystallization because of PEPA mainly affects the compatibility of itself and polyurethane physical blowing agent, and severe patient can cause
Lamination occurs after PEPA and physical blowing agent are miscible, and finally affects the inspiration performance of foam, cause gathering
The abscess of urethane foam is thick, density homogeneity declines.
Compared with prior art, the present invention has features and a beneficial effect:
(1) present invention is by improving glycolysis temperature (240 DEG C) and effective catalyst compounding (zinc acetate and the positive fourth of metatitanic acid
Ester) method, with reduce alcoholysis catalysts usage amount (consumption be only the total inventory of alcoholysis reaction 0.02%～
0.04%), through the alcoholysis of 6～8 hours, the viscosity of reactant can be reduced to 1500mPa S (25 DEG C) and below, be better than
The alcoholysis effect (25 DEG C, viscosity is at more than 2000mPa S) of single heavy dose of catalyst under low temperature.Additionally, this
Bright using rectifying column removed ethylene glycol amount and reactant viscosity as alcoholysis reaction terminal point determining index, simple to operate, produce
Thing batch is stable；
(2) the inventive method is by introducing alcoholysis by compounds such as binary acid (acid anhydrides), branched chain dihydric alcohol, polyalcohols
In polyester (polyester waste material) liquid structure, can effectively destroy ethylene glycol terephthalate and terephthalic acid (TPA) one contracts two
The molecule regularity of glycol ester, to reach the prepared non crystallized purpose of PEPA.Particularly 1,2-the third two
The addition of the branched chain dihydric alcohol such as alcohol, neopentyl glycol, owing to it expands the intermolecular distance of PEPA, more can promote
The execution of molecule regularity, it is ensured that the amorphism of PEPA；
(3) the inventive method is by introducing polyester polyols by binary LCFAs such as adipic acid, azelaic acid, decanedioic acid
Alcohol backbone structure, enhances the pliability of its molecular structure, effectively reduces product viscosity.With do not introduce above-mentioned binary
The high-functionality polyester polyol formula system of LCFA compares, the binary long-chain fat that the inventive method prepares
The high-functionality polyester polyol of fat acid, its viscosity is reduced to 10000 by 25000～30000mPa S (25 DEG C)
MPa S (25 DEG C) is below；
(4) the inventive method is by carrying out arranging in pairs or groups to improve the sense of PEPA by glycerine and trimethylolpropane
Degree, generally, prior art uses merely the glycerine secondary hydroxyl to promote the degree of functionality of PEPA, on its molecular structure
Base has relatively low activity in polycondensation process, it is ensured that PEPA has relatively low viscosity, but this structure is the most serious
(primary hydroxyl is the 3 of secondary hydroxyl with the reactivity of isocyanates to have impact on the reactivity of PEPA and isocyanates
Times), cause wire drawing and de-glutinous time lag, even occur that foam sends out the phenomenon that shortcake is difficult to solidify.The present invention is by by three
Hydroxymethyl-propane and glycerine carry out a certain degree of collocation, on the one hand can effectively promote polyester polyol functionality, another
Aspect is ensureing (25 DEG C ,≤10000mPa S) in the case of polyester polyol product has relatively low viscosity, itself and isocyanide
The gel reaction activity of acid esters is barely affected；
(5) technique of the inventive method synthesis high-functionality polyester polyol is simple, it is easy to industrialized production, whole mistake
In journey, contamination-free produces, and meets environmental requirement, easily operates, practical.
Detailed description of the invention
The invention will be further described for example given below plan, but is not to be construed as scope
Restriction, some nonessential improvement that the present invention is made by person skilled in art according to the content of the invention described above
And adjustment, still fall within protection scope of the present invention.
Part I prepares polyester alcoholysis liquid
Embodiment 1-1:
By polyester slice (η=0.85dl/g) 1000, diethylene glycol (DEG) 1000, zinc acetate 0.8, tetrabutyl titanate
0.8 puts into reactor A, is passed through nitrogen, stirs and be warming up to 235 DEG C, and constant temperature stirring makes polyester slice in 20 minutes
It is completely dissolved, is to slowly warm up to 240 DEG C afterwards, carry out 6 hours alcoholysis reactions of constant temperature under nitrogen protection, work as reactor
The ethylene glycol amount that the rectifying column of A is removed reach 48 and reactant viscosity reach at 25 DEG C 1100～1200mPa S it
After, stop reaction, be cooled to 160 DEG C, use diatomite impurity screening, i.e. obtain polyester alcoholysis liquid.
Embodiment 1-2:
By recycled PET film powder (η=0.73dl/g) 1000, diethylene glycol (DEG) 1000, zinc acetate 0.6, titanium
Acid N-butyl 0.6 puts into reactor A, is passed through nitrogen, stirs and be warming up to 240 DEG C, and constant temperature stirring makes for 20 minutes
Recycled PET film is completely dissolved, and is to slowly warm up to 240 DEG C afterwards, carries out constant temperature alcoholysis in 8 hours under nitrogen protection
Reaction, the ethylene glycol amount removed when the rectifying column of reactor A reach 50 and reactant viscosity reach
After 25 DEG C 1100～1200mPa S, it is cooled to 160 DEG C, uses diatomite impurity screening, obtain polyester alcoholysis liquid.
Embodiment 1-3:
Cut into slices (η=0.55dl/g) 1000 by Pillar recovery, glycerine 1000, the positive fourth of zinc acetate 0.7, metatitanic acid
Ester 0.6 puts into reactor A, is passed through nitrogen, stirs and is warming up to 235 DEG C, and constant temperature stirring makes recovery gather for 20 minutes
Ester section is completely dissolved, and is to slowly warm up to 245 DEG C afterwards, carries out 7 hours alcoholysis reactions of constant temperature under nitrogen protection, when
The ethylene glycol amount that the rectifying column of reactor A is removed reach 49 and reactant viscosity reach at 25 DEG C 1100～1200
After mPa S, it is cooled to 160 DEG C, uses diatomite impurity screening, obtain polyester alcoholysis liquid.
Embodiment 1-4:
By polyester slice (η=0.82dl/g) 1000, diethylene glycol (DEG) 500, glycerine 500, zinc acetate 0.7,
Tetrabutyl titanate 0.8 puts into reactor A, is passed through nitrogen, stirs and is warming up to 225 DEG C, and constant temperature stirs 20 minutes
Make polyester slice be completely dissolved, be to slowly warm up to 245 DEG C afterwards, carry out 6 hours alcoholysis reactions of constant temperature under nitrogen protection,
The ethylene glycol amount removed when the rectifying column of reactor A reach 48 and reactant viscosity reach 25 DEG C 1400～1500
After mPa S, stop reaction, be cooled to 160 DEG C, use diatomite impurity screening, i.e. obtain polyester alcoholysis liquid.
Embodiment 1-5:
By recycled PET film powder (η=0.73dl/g) 1000, diethylene glycol (DEG) 500, glycerine 500, acetic acid
Zinc 0.6, tetrabutyl titanate 0.8 put into reactor A, are passed through nitrogen, stir and are warming up to 227 DEG C, and constant temperature stirs
Mix 20 minutes and make recycled PET film be completely dissolved, be to slowly warm up to 250 DEG C afterwards, carry out constant temperature under nitrogen protection
8 hours alcoholysis reactions, the ethylene glycol amount removed when the rectifying column of reactor A reach 50 and reactant viscosity reach
After 25 DEG C 1400～1500mPa S, it is cooled to 160 DEG C, uses diatomite impurity screening, obtain polyester alcoholysis liquid.
Embodiment 1-6:
Cut into slices (η=0.59dl/g) 1000 by Pillar recovery, diethylene glycol (DEG) 500, glycerine 500, zinc acetate 0.6
, dibutyl tin laurate 0.2, antimony oxide 0.7 put into reactor A, be passed through nitrogen, stir and rise
Temperature is to 231 DEG C, and constant temperature stirring makes Pillar recovery section be completely dissolved for 20 minutes, is to slowly warm up to 246 DEG C afterwards,
Carrying out 7 hours alcoholysis reactions of constant temperature under nitrogen protection, the ethylene glycol amount removed when the rectifying column of reactor A reaches 49
And reactant viscosity reaches at 25 DEG C, after 1400～1500mPa S, to be cooled to 160 DEG C, diatomite is used to filter
Impurity, obtains polyester alcoholysis liquid.
Embodiment 1-7:
By polyester slice (η=0.82dl/g) 1000, diethylene glycol (DEG) 300, triethylene glycol 200, glycerine 500,
Zinc acetate 0.5, tetrabutyl titanate 0.8 put into reactor A, are passed through nitrogen, stir and are warming up to 230 DEG C, permanent
Temperature stirring makes polyester slice be completely dissolved in 20 minutes, is to slowly warm up to 250 DEG C afterwards, carries out constant temperature under nitrogen protection
6 hours alcoholysis reactions, the ethylene glycol amount removed when the rectifying column of reactor A reach 48 and reactant viscosity reach
After 25 DEG C 1300～1400mPa S, stop reaction, be cooled to 160 DEG C, use diatomite impurity screening, i.e. obtain
Polyester alcoholysis liquid.
Embodiment 1-8:
By recycled PET film powder (η=0.74dl/g) 1000, diethylene glycol (DEG) 300, triethylene glycol 200, sweet
Oil 500, dibutyl tin laurate 0.2, antimony oxide 0.5, tetrabutyl titanate 0.6 put into reaction
Device A, is passed through nitrogen, stirs and is warming up to 225 DEG C, and constant temperature stirring makes recycled PET film be completely dissolved for 20 minutes,
It is to slowly warm up to 242 DEG C afterwards, carries out 8 hours alcoholysis reactions of constant temperature under nitrogen protection, when the rectifying of reactor A
The ethylene glycol amount that post is removed reaches 50 and after reactant viscosity reaches 25 DEG C 1300～1400mPa S, is cooled to
160 DEG C, diatomite impurity screening is used i.e. to obtain polyester alcoholysis liquid.
Embodiment 1-9:
Cut into slices (η=0.58dl/g) 1000 by Pillar recovery, diethylene glycol (DEG) 300, triethylene glycol 200, glycerine 500
, antimony oxide 0.3, tetrabutyl titanate 1.0 put into reactor A, are passed through nitrogen, stir and are warming up to 228 DEG C,
Constant temperature stirring makes Pillar recovery section be completely dissolved for 20 minutes, is to slowly warm up to 248 DEG C afterwards, enters under nitrogen protection
7 hours alcoholysis reactions of row constant temperature, the ethylene glycol amount removed when the rectifying column of reactor A reach 49 and reactant glue
After degree reaches 25 DEG C 1300～1400mPa S, it is cooled to 160 DEG C, uses diatomite impurity screening i.e. to obtain polyesterols
Solve liquid.
Embodiment 1-10:
Cut into slices (η=0.59dl/g) 1000 by Pillar recovery, diethylene glycol (DEG) 500, glycerine 285, pentaerythrite
215, zinc acetate 0.7, Mono-n-butyltin 0.7 put into reactor A, are passed through nitrogen, stir and are warming up to
235 DEG C, constant temperature stirring makes Pillar recovery section be completely dissolved for 20 minutes, is to slowly warm up to 250 DEG C afterwards, at nitrogen
Carry out 7 hours alcoholysis reactions of constant temperature under protection, the ethylene glycol amount removed when the rectifying column of reactor A reach 49 and
After reactant viscosity reaches 25 DEG C 1400～1500mPa S, it is cooled to 160 DEG C, uses diatomite impurity screening i.e.
Obtain polyester alcoholysis liquid.
Part II prepares high-functionality polyester polyol
Embodiment 2-1:
Get the raw materials ready: polyester alcoholysis liquid 1200 prepared by embodiment 1-1, phthalic anhydride 900, adipic acid 450
, ethylene glycol 495,1,2-propane diols 405, glycerine 360, trimethylolpropane 540 and monobutyl oxygen
Change tin 0.3.
Preparation technology: put in reactor B by the material of above-mentioned formula, is passed through nitrogen, and stirring heats up, and controls anti-
Within the rectifying column head temperature answering device B remains at 100 DEG C, when in reactor B, temperature reaches 150 DEG C,
Insulation carries out esterification 1.5 hours and removes the water of generation, and insulation terminates the rectifying column head temperature of post-reactor B
It is 65 DEG C, with the speed of intensification in every 20 minutes 5 DEG C after this, when making the temperature in reactor B reach 160 DEG C, protects
Temperature is after 1 hour, with the speed of intensification in every 20 minutes 5 DEG C, when making the temperature in reactor B reach 180 DEG C, insulation
After 1 hour, with the speed of intensification in every 20 minutes 5 DEG C, when making the temperature in reactor B reach 200 DEG C, it is incubated 1
After hour, then being warming up to 225 DEG C with the speed of intensification in every 20 minutes 5 DEG C, then be incubated 1 hour, insulation is anti-after terminating
Answering thing acid number is 9.0mgKOH/g, and rectifying capital temperature is 60 DEG C, stops heating, when reaction mass temperature is down to 200 DEG C
Time stop being passed through nitrogen, and be slowly evacuated to-0.08MPa, as acid number≤1mgKOH/g, stop reaction, cooling,
I.e. obtain polyester polyol product.The indices of test PEPA: acid number 0.85mgKOH/g, hydroxyl value 335
MgKOH/g, viscosity 7078mPa S (25 DEG C), average functionality 2.42.
Embodiment 2-2:
Get the raw materials ready: alcoholysis liquid 950 prepared by embodiment 1-2, phthalic anhydride 900, adipic acid 450,
Ethylene glycol 495, neopentyl glycol 550, glycerine 337, trimethylolpropane 490 and Mono-n-butyltin
0.35㎏。
Preparation technology and other parameters are all identical with embodiment 2-1, the indices of test PEPA: acid number 0.96
MgKOH/g, hydroxyl value 302mgKOH/g, viscosity 8263mPa S (25 DEG C), average functionality 2.50.
Embodiment 2-3:
Get the raw materials ready: alcoholysis liquid 1000 prepared by embodiment 1-3, phthalic anhydride 900, adipic acid 450,
Ethylene glycol 495,1,2-PD 405, glycerine 345, trimethylolpropane 500 and Mono-n-butyltin
0.4㎏。
Preparation technology: put in reactor B by the material of above-mentioned formula, is passed through nitrogen, and stirring heats up, and controls anti-
Within the rectifying column head temperature answering device B remains at 100 DEG C, when in reactor B, temperature reaches 145 DEG C,
Insulation carries out esterification 2 hours and removes the water of generation, and insulation terminates the rectifying column head temperature of post-reactor B and is
68 DEG C, with the speed of intensification in every 20 minutes 5 DEG C, when making the temperature in reactor B reach 160 DEG C, insulation after this
After 1 hour, with the speed of intensification in every 20 minutes 5 DEG C, when making the temperature in reactor B reach 180 DEG C, it is incubated 1
After hour, with the speed of intensification in every 20 minutes 5 DEG C, when making the temperature in reactor B reach 200 DEG C, insulation 1 is little
Shi Hou, then it is warming up to 220 DEG C with the speed of intensification in every 20 minutes 5 DEG C, then it is incubated 1 hour, insulation is reacted after terminating
Thing acid number is 9.8mgKOH/g, and rectifying capital temperature is 68 DEG C, stops heating, when reaction mass temperature is down to 200 DEG C
Time stop being passed through nitrogen, and be slowly evacuated to-0.08MPa, whole polycondensation reaction need to be carried out 4 hours, when acid number≤1
MgKOH/g, stops reaction, cooling, i.e. obtains polyester polyol product.The indices of test PEPA:
Acid number 0.87mgKOH/g, hydroxyl value 321mgKOH/g, viscosity 7634mPa S (25 DEG C), average functionality 2.45.
Embodiment 2-4:
Get the raw materials ready: alcoholysis liquid 950 prepared by embodiment 1-4, phthalic anhydride 900, succinic acid 400,
Ethylene glycol 500,1,3-BDO 480, glycerine 100, trimethylolpropane 490 and Mono-n-butyltin
0.35㎏.Its preparation technology and other parameters are all identical with embodiment 2-3, the indices of test PEPA:
Acid number 0.93mgKOH/g, hydroxyl value 311mgKOH/g, viscosity 7958mPa S (25 DEG C), average functionality 2.48.
Embodiment 2-5:
Get the raw materials ready: alcoholysis liquid 1050 prepared by embodiment 1-5, phthalic anhydride 900, adipic acid 450,
Ethylene glycol 550, neopentyl glycol 650, glycerine 95, trimethylolpropane 500 and Mono-n-butyltin 0.45
㎏。
Preparation technology: put in reactor B by the material of above-mentioned formula, is passed through nitrogen, and stirring heats up, and controls anti-
Within the rectifying column head temperature answering device B remains at 100 DEG C, when in reactor B, temperature reaches 155 DEG C,
Insulation carries out esterification 1 hour and removes the water of generation, and insulation terminates the rectifying column head temperature of post-reactor B and is
59 DEG C, with the speed of intensification in every 20 minutes 5 DEG C, when making the temperature in reactor B reach 160 DEG C, insulation after this
After 1 hour, with the speed of intensification in every 20 minutes 5 DEG C, when making the temperature in reactor B reach 180 DEG C, it is incubated 1
After hour, with the speed of intensification in every 20 minutes 5 DEG C, when making the temperature in reactor B reach 200 DEG C, insulation 1 is little
Shi Hou, then it is warming up to 230 DEG C with the speed of intensification in every 20 minutes 5 DEG C, then it is incubated 1 hour, insulation is reacted after terminating
Thing acid number is 8.8mgKOH/g, and rectifying capital temperature is 56 DEG C, stops heating, when reaction mass temperature is down to 200 DEG C
Time stop being passed through nitrogen, and be slowly evacuated to-0.08MPa, whole polycondensation reaction need to be carried out 3 hours, when acid number≤1
MgKOH/g, stops reaction, cooling, i.e. obtains polyester polyol product.The indices of test PEPA:
Acid number 0.86mgKOH/g, hydroxyl value 325mgKOH/g, viscosity 7558mPa S (25 DEG C), average functionality 2.46.
Embodiment 2-6:
Get the raw materials ready: alcoholysis liquid 1150 prepared by embodiment 1-6, phthalic anhydride 900, glutaric acid 420,
Ethylene glycol 500,1,3-BDO 600, glycerine 70, trimethylolpropane 540 and zinc acetate 0.5.
Preparation technology and other parameters are all identical with embodiment 2-5, the indices of test PEPA: acid number 0.84
MgKOH/g, hydroxyl value 338mgKOH/g, viscosity 7008mPa S (25 DEG C), average functionality 2.42.
Embodiment 2-7:
Get the raw materials ready: alcoholysis liquid 980 prepared by embodiment 1-7, phthalic anhydride 900, azelaic acid 560,
Ethylene glycol 495,1,2-PD 405, glycerine 100, trimethylolpropane 490 and stannous chloride 0.3
㎏。
Preparation technology: put in reactor B by the material of above-mentioned formula, is passed through nitrogen, and stirring heats up, and controls anti-
Within the rectifying column head temperature answering device B remains at 100 DEG C, when in reactor B, temperature reaches 152 DEG C,
Insulation carries out esterification 1 hour and removes the water of generation, and insulation terminates the rectifying column head temperature of post-reactor B and is
60 DEG C, with the speed of intensification in every 20 minutes 5 DEG C, when making the temperature in reactor B reach 160 DEG C, insulation after this
After 1 hour, with the speed of intensification in every 20 minutes 5 DEG C, when making the temperature in reactor B reach 180 DEG C, it is incubated 1
After hour, with the speed of intensification in every 20 minutes 5 DEG C, when making the temperature in reactor B reach 200 DEG C, insulation 1 is little
Shi Hou, then it is warming up to 230 DEG C with the speed of intensification in every 20 minutes 5 DEG C, then it is incubated 1 hour, insulation is reacted after terminating
Thing acid number is 8.4mgKOH/g, and rectifying capital temperature is 54 DEG C, stops heating, when reaction mass temperature is down to 200 DEG C
Time stop being passed through nitrogen, and be slowly evacuated to-0.08MPa, whole polycondensation reaction need to be carried out 4 hours, when acid number≤1
MgKOH/g, stops reaction, cooling, i.e. obtains polyester polyol product.The indices of test PEPA:
Acid number 0.92mgKOH/g, hydroxyl value 302mgKOH/g, viscosity 7238mPa S (25 DEG C), average functionality 2.41.
Embodiment 2-8:
Get the raw materials ready: alcoholysis liquid 1000 prepared by embodiment 1-8, phthalic anhydride 900, decanedioic acid 600,
Ethylene glycol 495, neopentyl glycol 550, glycerine 95, trimethylolpropane 500 and tetrabutyl titanate 0.35
㎏。
Preparation technology and other parameters are all identical with embodiment 2-7, the indices of test PEPA: acid number 0.88
MgKOH/g, hydroxyl value 315mgKOH/g, viscosity 6894mPa S (25 DEG C).
Embodiment 2-9:
Get the raw materials ready: alcoholysis liquid 1200 prepared by embodiment 1-9, phthalic anhydride 900, adipic acid 450,
Ethylene glycol 495,1,3-PD 405, glycerine 70, trimethylolpropane 540 and Dibutyltin oxide
0.4㎏。
Preparation technology: put in reactor B by the material of above-mentioned formula, is passed through nitrogen, and stirring heats up, and controls anti-
Within the rectifying column head temperature answering device B remains at 100 DEG C, when in reactor B, temperature reaches 152 DEG C,
Insulation carries out esterification 1 hour and removes the water of generation, and insulation terminates the rectifying column head temperature of post-reactor B and is
60 DEG C, with the speed of intensification in every 20 minutes 5 DEG C, when making the temperature in reactor B reach 160 DEG C, insulation after this
After 1 hour, with the speed of intensification in every 20 minutes 5 DEG C, when making the temperature in reactor B reach 180 DEG C, it is incubated 1
After hour, with the speed of intensification in every 20 minutes 5 DEG C, when making the temperature in reactor B reach 200 DEG C, insulation 1 is little
Shi Hou, then it is warming up to 230 DEG C with the speed of intensification in every 20 minutes 5 DEG C, then it is incubated 1 hour, insulation is reacted after terminating
Thing acid number is 8.4mgKOH/g, and rectifying capital temperature is 54 DEG C, stops heating, when reaction mass temperature is down to 200 DEG C
Time stop being passed through nitrogen, and be slowly evacuated to-0.08MPa, whole polycondensation reaction need to be carried out 4 hours, when acid number≤1
MgKOH/g, stops reaction, cooling, i.e. obtains polyester polyol product.The indices of test PEPA:
Acid number 0.82mgKOH/g, hydroxyl value 327mgKOH/g, viscosity 6484mPa S (25 DEG C), average functionality 2.40.
Embodiment 2-10:
Get the raw materials ready: alcoholysis liquid 900 prepared by embodiment 1-10, phthalic anhydride 900, succinic acid 400,
Ethylene glycol 450,1,2-PD 350, glycerine 200, trimethylolpropane 350 and tetraisopropyl titanate
0.45㎏。
Preparation technology and other parameters are all identical with embodiment 2-9, the indices of test PEPA: acid number 0.87
MgKOH/g, hydroxyl value 320mgKOH/g, viscosity 7769mPa S (25 DEG C), average functionality 2.46.
Part III prepares the Application Example of high-strength polyurethane rigid foam
Embodiment 3-1:
Take PEPA prepared by 100 embodiments 2-1,2～3 water, 2.5～3.5 foam stabilizers, 0.6～0.8
Catalyst (stannous octoate compounds with triethanolamine), high-speed stirred mixes, and adds 105 isocyanates afterwards
And high-speed stirred 25s～30s, above-mentioned high-speed stirred rotating speed need >=3000r/min, compound is fallen rapidly after terminating by stirring
Entering in 70 DEG C of aluminium-making moulds, and cure 4 hours at 100 DEG C, the demoulding can be prepared by high-strength polyurethane rigid foam.
Embodiment 3-2:
Take PEPA prepared by 100 embodiments 2-2, remaining material quality number and foam preparation step with should
Identical by embodiment 1.
Embodiment 3-3:
Take PEPA prepared by 100 embodiments 2-3, remaining material quality number and foam preparation step with should
Identical by embodiment 1.
Embodiment 3-4:
Take PEPA prepared by 100 embodiments 2-4, remaining material quality number and foam preparation step with should
Identical by embodiment 1.
Embodiment 3-5:
Take PEPA prepared by 100 embodiments 2-5, remaining material quality number and foam preparation step with should
Identical by embodiment 1.
Embodiment 3-6:
Take PEPA prepared by 100 embodiments 2-6, remaining material quality number and foam preparation step with should
Identical by embodiment 1.
Embodiment 3-7:
Take PEPA prepared by 100 embodiments 2-7, remaining material quality number and foam preparation step with should
Identical by embodiment 1.
Embodiment 3-8:
Take PEPA prepared by 100 embodiments 2-8, remaining material quality number and foam preparation step with should
Identical by embodiment 1.
Embodiment 3-9:
Take PEPA prepared by 100 embodiments 2-9, remaining material quality number and foam preparation step with should
Identical by embodiment 1.
Embodiment 3-10:
Take PEPA prepared by 100 embodiments 2-10, remaining material quality number and foam preparation step with should
Identical by embodiment 1.
Comparative example 1:
Taking 100 PEPAs (trade mark 3152), 2～3 water, 2.0～2.5 foam stabilizers, 0.6～0.8 urges
Agent (stannous octoate compounds with triethanolamine), 105 isocyanates, foam preparation step and Application Example 1 phase
With.
Comparative example 2:
Taking 100 PEPAs (trade mark 2352), 2～3 water, 2.0～2.5 foam stabilizers, 0.6～0.8 urges
Agent (stannous octoate compounds with triethanolamine), 105 isocyanates, foam preparation step and Application Example 1 phase
With.
Comparative example 3:
Taking 100 PEPAs (trade mark 1752), 2～3 water, 2.0～2.5 foam stabilizers, 0.6～0.8 urges
Agent (stannous octoate compounds with triethanolamine), 105 isocyanates, foam preparation step and Application Example 1 phase
With.
Comparative example 4
Taking 100 PPGs (trade mark 4110), 2～3 water, 2.0～2.5 foam stabilizers, 0.4～0.6 urges
Agent (stannous octoate compounds with triethanolamine), 105 isocyanates, foam preparation step and Application Example 1 phase
With.
Comparative example 5:
Taking 100 PPGs (trade mark 635), 2～3 water, 2.0～2.5 foam stabilizers, 0.4～0.6 urges
Agent (stannous octoate compounds with triethanolamine), 105 isocyanates, foam preparation step and Application Example 1 phase
With.
Comparative example 6:
Taking 100 PPGs (trade mark 450), 2～3 water, 2.0～2.5 foam stabilizers, 0.4～0.6 urges
Agent (stannous octoate compounds with triethanolamine), 105 isocyanates, foam preparation step and Application Example 1 phase
With.
Application Example and the performance test value such as following table of the polyurethane foamed material obtained by comparative example:
Application Example and the mechanical performance table of the made hard polyurethane foam material of comparative example
Note: what comparative example 1～3 was taken is all the PEPA that current hard polyurethane foam is conventional, and its average functionality is equal
Being 2.0, what comparative example 4～6 was taken is all the PPG that current hard polyurethane foam is conventional, and its average functionality exists
4.0 left and right.
As can be seen from the above table: utilize polyurethane foam prepared by PEPA of the present invention size changing rate,
Bending strength and three mechanical mechanics property test aspects of compressive strength, its all technical is superior to use universal
The test data of PEPA, and reach or be better than using the test data of PPG.
Embodiment 4:
A kind of high-functionality polyester polyol, by 900 mass parts polyester alcoholysis liquid, 900 mass parts phthalic anhydrides,
400 mass parts binary of fatty acids, 800 mass parts dihydroxylic alcohols, 550 mass parts polyalcohols, 0.3 mass parts esterification catalyst,
Through esterification and remove moisture, then through polycondensation, i.e. prepare high-functionality polyester polyol；
The preparation method of described polyester alcoholysis liquid is: by 1000 mass parts polyester material, 1000 mass parts alcoholysis agent and 1.2
Mass parts alcoholysis catalysts puts in the reactor A having rectifying column, is passed through nitrogen, stirs and be warming up to 225 DEG C, permanent
Temperature stirring makes polyester material be completely dissolved for 20 minutes, is to slowly warm up to 240240 DEG C afterwards, carries out constant temperature under nitrogen protection
6 hours alcoholysis reactions, the ethylene glycol amount removed when the rectifying column of reactor A reaches 48 mass parts and reactant viscosity
Reach at 25 DEG C after 1000～1500mPa S, stop reaction, be cooled to 160 DEG C, filter with diatomite and (remove
Impurity), filtrate is prepared polyester alcoholysis liquid.
Embodiment 5:
A kind of high-functionality polyester polyol, by 1200 mass parts polyester alcoholysis liquid, 900 mass parts phthalic anhydrides,
600 mass parts binary of fatty acids, 1000 mass parts dihydroxylic alcohols, 900 mass parts polyalcohols, 0.5 mass parts catalyzing esterification
Agent, through esterification and remove moisture, then through polycondensation, i.e. prepares high-functionality polyester polyol；
The preparation method of described polyester alcoholysis liquid is: by 1200 mass parts polyester material, 1200 mass parts alcoholysis agent and 1.6
Mass parts alcoholysis catalysts puts in the reactor A having rectifying column, is passed through nitrogen, stirs and be warming up to 230 DEG C, permanent
Temperature stirring makes polyester material be completely dissolved for 20 minutes, is to slowly warm up to 250 DEG C afterwards, carries out constant temperature 8 under nitrogen protection
Hour alcoholysis reaction, the ethylene glycol amount removed when the rectifying column of reactor A reaches 50 mass parts and reactant viscosity reaches
At 25 DEG C after 1000～1500mPa S, stop reaction, be cooled to 160 DEG C, filter with diatomite and (remove miscellaneous
Matter), filtrate is prepared polyester alcoholysis liquid.
Embodiment 6:
A kind of high-functionality polyester polyol, by 1050 mass parts polyester alcoholysis liquid, 900 mass parts phthalic anhydrides,
500 mass parts binary of fatty acids, 900 mass parts dihydroxylic alcohols, 720 mass parts polyalcohols, 0.4 mass parts esterification catalyst,
Through esterification and remove moisture, then through polycondensation, i.e. prepare high-functionality polyester polyol；
The preparation method of described polyester alcoholysis liquid is: by 1000 mass parts polyester material, 1000 mass parts alcoholysis agent and 1.4
Mass parts alcoholysis catalysts puts in the reactor A having rectifying column, is passed through nitrogen, stirs and be warming up to 235 DEG C, permanent
Temperature stirring makes polyester material be completely dissolved for 20 minutes, is to slowly warm up to 240 DEG C afterwards, carries out constant temperature 7 under nitrogen protection
Hour alcoholysis reaction, the ethylene glycol amount removed when the rectifying column of reactor A reaches 49 mass parts and reactant viscosity reaches
At 25 DEG C after 1000～1500mPa S, stop reaction, be cooled to 160 DEG C, filter with diatomite and (remove miscellaneous
Matter), filtrate is prepared polyester alcoholysis liquid.
Embodiment 7:
A kind of preparation method of high-functionality polyester polyol, step is as follows:
A, prepare polyester alcoholysis liquid: by 1000 mass parts polyester material, 1000 mass parts alcoholysis agent and 1.2 mass parts alcohol
Solve catalyst to put in the reactor A having rectifying column, be passed through nitrogen, stir and be warming up to 225 DEG C, constant temperature stirring 20
Minute make polyester material be completely dissolved, be to slowly warm up to 245 DEG C afterwards, carry out constant temperature alcoholysis in 6 hours under nitrogen protection anti-
Should, the ethylene glycol amount removed when the rectifying column of reactor A reaches 48 mass parts and reactant viscosity reaches at 25 DEG C
After 1000～1500mPa S, stop reaction, be cooled to 160 DEG C, filter (removing impurity) with diatomite, filtrate
It is prepared polyester alcoholysis liquid；
B, dispensing: by 900 mass parts polyester alcoholysis liquid, 900 mass parts phthalic anhydrides, 400 mass parts binary
Aliphatic acid, 800 mass parts dihydroxylic alcohols, 550 mass parts polyalcohols, the quality proportioning of 0.3 mass parts esterification catalyst take
Each component raw material；
C, prepare high-functionality polyester polyol: component raw material each described in step b is put into the reactor of rectifying column
In B, being passed through nitrogen, stirring heats up, and the rectifying column head temperature (all the time) controlling reactor B is maintained at 100 DEG C
Within, when in reactor B, temperature reaches 145 DEG C, insulation carry out esterification 1 little time and remove the water of generation,
Insulation reaction terminates the rectifying column head temperature of post-reactor B when being reduced to less than 70 DEG C, heats up 5 DEG C with every 20 minutes
Speed, when making the temperature in reactor B reach 160 DEG C, insulation reaction 1 hour, then, rose with every 20 minutes
The speed of temperature 5 DEG C, when making the temperature in reactor B reach 180 DEG C, insulation reaction is after 1 hour, then with every 20 points
Clock heat up 5 DEG C speed, when making the temperature in reactor B reach 200 DEG C, insulation reaction is after 1 hour, then with often
The speed of 5 DEG C of heating up for 20 minutes is warming up to 220 DEG C, insulation reaction 1 hour, and insulation reaction terminates rear reaction mass acid number
When the rectifying column head temperature of≤10mgKOH/g and reactor B is down to less than 70 DEG C, stops heating, work as reaction mass
Stop when temperature is down to 200 DEG C being passed through nitrogen and being slowly evacuated to-0.070～-0.085MPa, when acid number≤1
MgKOH/g, stops reaction, cooling, i.e. prepares high-functionality polyester polyol product.
Embodiment 8:
A kind of preparation method of high-functionality polyester polyol, step is as follows:
A, prepare polyester alcoholysis liquid: by 1000 mass parts polyester material, 1000 mass parts alcoholysis agent and 1.6 mass parts alcohol
Solve catalyst to put in the reactor A having rectifying column, be passed through nitrogen, stir and be warming up to 230 DEG C, constant temperature stirring 20
Minute make polyester material be completely dissolved, be to slowly warm up to 250 DEG C afterwards, carry out constant temperature alcoholysis in 8 hours under nitrogen protection anti-
Should, the ethylene glycol amount removed when the rectifying column of reactor A reaches 50 mass parts and reactant viscosity reaches at 25 DEG C
After 1000～1500mPa S, stop reaction, be cooled to 160 DEG C, filter (removing impurity) with diatomite, filtrate
It is prepared polyester alcoholysis liquid；
B, dispensing: by 1200 mass parts polyester alcoholysis liquid, 900 mass parts phthalic anhydrides, 600 mass parts binary
Aliphatic acid, 1000 mass parts dihydroxylic alcohols, 900 mass parts polyalcohols, the quality proportioning of 0.5 mass parts esterification catalyst take
Each component raw material；
C, prepare high-functionality polyester polyol: component raw material each described in step b is put into the reactor of rectifying column
In B, being passed through nitrogen, stirring heats up, and the rectifying column head temperature (all the time) controlling reactor B is maintained at 100 DEG C
Within, when in reactor B, temperature reaches 155 DEG C, insulation carry out esterification 2 little time and remove the water of generation,
Insulation reaction terminates the rectifying column head temperature of post-reactor B when being reduced to less than 70 DEG C, heats up 5 DEG C with every 20 minutes
Speed, when making the temperature in reactor B reach 160 DEG C, insulation reaction 1 hour, then, rose with every 20 minutes
The speed of temperature 5 DEG C, when making the temperature in reactor B reach 180 DEG C, insulation reaction is after 1 hour, then with every 20 points
Clock heat up 5 DEG C speed, when making the temperature in reactor B reach 200 DEG C, insulation reaction is after 1 hour, then with often
The speed of 5 DEG C of heating up for 20 minutes is warming up to 230 DEG C, insulation reaction 1 hour, and insulation reaction terminates rear reaction mass acid number
When the rectifying column head temperature of≤10mgKOH/g and reactor B is down to less than 70 DEG C, stops heating, work as reaction mass
Stop when temperature is down to 200 DEG C being passed through nitrogen and being slowly evacuated to-0.070～-0.085MPa, when acid number≤1
MgKOH/g, stops reaction, cooling, i.e. prepares high-functionality polyester polyol product.
Embodiment 9:
A kind of preparation method of high-functionality polyester polyol, step is as follows:
A, prepare polyester alcoholysis liquid: by 1000 mass parts polyester material, 1000 mass parts alcoholysis agent and 1.4 mass parts alcohol
Solve catalyst to put in the reactor A having rectifying column, be passed through nitrogen, stir and be warming up to 235 DEG C, constant temperature stirring 20
Minute make polyester material be completely dissolved, be to slowly warm up to 240 afterwards, carry out 7 hours alcoholysis reactions of constant temperature under nitrogen protection,
The ethylene glycol amount removed when the rectifying column of reactor A reaches 49 mass parts and reactant viscosity reaches at 25 DEG C
After 1000～1500mPa S, stop reaction, be cooled to 160 DEG C, filter (removing impurity) with diatomite, filtrate
It is prepared polyester alcoholysis liquid；
B, dispensing: by 1100 mass parts polyester alcoholysis liquid, 900 mass parts phthalic anhydrides, 500 mass parts binary
Aliphatic acid, 900 mass parts dihydroxylic alcohols, 730 mass parts polyalcohols, the quality proportioning of 0.4 mass parts esterification catalyst take
Each component raw material；
C, prepare high-functionality polyester polyol: component raw material each described in step b is put into the reactor of rectifying column
In B, be passed through nitrogen, stirring heat up, and the rectifying column head temperature controlling reactor B remain at 100 DEG C with
In, when in reactor B, temperature reaches 150 DEG C, insulation carry out that esterification 1.5 is little (and to be removed the water of generation, protect
When the rectifying column head temperature of temperature reaction end post-reactor B is reduced to less than 70 DEG C, heated up 5 DEG C with every 20 minutes
Speed, when making the temperature in reactor B reach 160 DEG C, insulation reaction 1 hour, then, heated up with every 20 minutes
The speed of 5 DEG C, when making the temperature in reactor B reach 180 DEG C, insulation reaction is after 1 hour, then with every 20 minutes
Heat up 5 DEG C speed, when making the temperature in reactor B reach 200 DEG C, insulation reaction is after 1 hour, then with every 20
The speed of 5 DEG C of minute heating up is warming up to 225 DEG C, insulation reaction 1 hour, and insulation reaction terminates rear reaction mass acid number≤10
When the rectifying column head temperature of mgKOH/g and reactor B is down to less than 70 DEG C, stop heating, when reactant material temperature
Stop when degree is down to 200 DEG C being passed through nitrogen and being slowly evacuated to-0.070～-0.085MPa, when acid number≤1
MgKOH/g, stops reaction, cooling, i.e. prepares high-functionality polyester polyol product.
In above-described embodiment 4～9: described polyester material is cutting of pet resin (being called for short PET)
One or more mixing in sheet, recovery film, recovery section, recycled plastic bottle and the material that is recycled and packaged
Comminuting matter, the inherent viscosity of this material can be 0.55～0.85dl/g (i.e. η=0.55～0.85dl/g)；
In above-described embodiment 4～9: described alcoholysis agent can be diethylene glycol (DEG), triethylene glycol, tetraethylene glycol, glycerine, Yi Jiji
One or more mixture in penta tetrol；Be preferably diethylene glycol (DEG), triethylene glycol, glycerine one or both
Mixture.
In above-described embodiment 4～9: described alcoholysis catalysts can be zinc acetate, dibutyl tin laurate, monobutyl
Two or more mixture in tin oxide, antimony oxide and tetrabutyl titanate；It is preferably acetic acid
Zinc and the mixture of tetrabutyl titanate.
In above-described embodiment 4～9: described binary of fatty acids can be succinic acid, glutaric acid, adipic acid, azelaic acid,
Any one in decanedioic acid；It is preferably adipic acid.
In above-described embodiment 4～9: described dihydroxylic alcohols can be ethylene glycol, 1,2-propane diols, 1,3 butylene glycol, new penta 2
One or both in alcohol etc.；
In above-described embodiment 4～9: described polyalcohol is one or both the mixture in glycerine, trimethylolpropane；
In above-described embodiment 4～9: described esterification catalyst can be zinc acetate, tetrabutyl titanate, tetraisopropyl titanate,
Any one in Mono-n-butyltin, Dibutyltin oxide and stannous chloride etc..
In above-described embodiment 4～9: the average functionality of described high-functionality polyester polyol is 2.4～2.5, viscosity is
At 25 DEG C≤10000mPa S, hydroxyl value 300～350mgKOH/g, acid number be≤1mgKOH/g, and 2 DEG C of conditions
Lower storage did not crystallized after 3 months.
Described not crystallizing refers to be placed under conditions of 2 DEG C by this high-functionality polyester polyol, after 3 months
Employing visually observes, and this high-functionality polyester polyol still can keep clear, and macroscopic muddiness does not occur
Phenomenon.Crystallization because of PEPA mainly affects the compatibility of itself and polyurethane physical blowing agent, and severe patient can cause
Lamination occurs after PEPA and physical blowing agent are miscible, and finally affects the inspiration performance of foam, cause gathering
The abscess of urethane foam is thick, density homogeneity declines.
In above-described embodiment: in the percentage used, indicate the most especially, be quality (weight) percentage
Example；In the ratio used, indicate the most especially, be quality (weight) ratio；Described quality (weight) part
Can be all gram or kilogram.
In above-described embodiment: technological parameter (temperature, time, pressure, concentration etc.) and each component in each step are used
Numerical quantities etc. are scope, and any point is the most applicable.
The technology contents being not specifically delineated in present invention and above-described embodiment is compared with technology, and described raw material are
Commercially available prod.
The invention is not restricted to above-described embodiment, described in present invention, all can implement and have described good result.
Claims (9)
1. a high-functionality polyester polyol, it is characterized in that: by 900～1200 mass parts polyester alcoholysis liquid, 900 mass parts phthalic anhydrides, 400～600 mass parts binary of fatty acids, 800～1000 mass parts dihydroxylic alcohols, 550～900 mass parts polyalcohols, 0.3～0.5 mass parts esterification catalyst, through esterification and remove moisture, again through polycondensation, i.e. prepare high-functionality polyester polyol；
The average functionality of described high-functionality polyester polyol is 2.4～2.5, viscosity be at 25 DEG C≤10000 mPa s, hydroxyl value 300～350 mgKOH/g, acid number be≤1 mgKOH/g, and do not crystallize after storing 3 months under the conditions of 2 DEG C；
The preparation method of described polyester alcoholysis liquid is: by 1000 mass parts polyester material, 1000 mass parts alcoholysis agent and 1.2～1.6 mass parts alcoholysis catalysts put in the reactor A having rectifying column, it is passed through nitrogen, stir and be warming up to 225～235 DEG C, constant temperature stirs 20 minutes, it is warming up to 240～250 DEG C, carry out constant temperature 6～8 hours alcoholysis reactions under nitrogen protection, the ethylene glycol amount removed when the rectifying column of reactor A reaches 48～50 mass parts and reactant viscosity reaches at 25 DEG C after 1000～1500 mPa s, stop reaction, it is cooled to 160 DEG C, filter with diatomite, filtrate is prepared polyester alcoholysis liquid；
Described polyester material is the section of pet resin, reclaims one or more co-grinding material in film, recovery section, recycled plastic bottle and the material that is recycled and packaged, and the inherent viscosity of this material is 0.55～0.85 dl/g；
Described alcoholysis agent is one or more the mixture in diethylene glycol (DEG), triethylene glycol, tetraethylene glycol, glycerine and pentaerythrite；
Described alcoholysis catalysts is two or more the mixture in zinc acetate, dibutyl tin laurate, Mono-n-butyltin, antimony oxide and tetrabutyl titanate；
Described binary of fatty acids is any one in succinic acid, glutaric acid, adipic acid, azelaic acid, decanedioic acid；
Described dihydroxylic alcohols is one or both in ethylene glycol, 1,2-propane diols, 1,3 butylene glycol, neopentyl glycol；
Described polyalcohol is one or both the mixture in glycerine, trimethylolpropane；
Described esterification catalyst is any one in zinc acetate, tetrabutyl titanate, tetraisopropyl titanate, Mono-n-butyltin, Dibutyltin oxide and stannous chloride.
2. the high-functionality polyester polyol as described in claim 1, is characterized in that: described alcoholysis agent is one or both mixture of diethylene glycol (DEG), triethylene glycol, glycerine.
3. the high-functionality polyester polyol as described in claim 1, is characterized in that: described alcoholysis catalysts is the mixture of zinc acetate and tetrabutyl titanate.
4. the high-functionality polyester polyol as described in claim 1, is characterized in that: described binary of fatty acids is adipic acid.
5. a preparation method for high-functionality polyester polyol, is characterized in that step is as follows:
A, prepare polyester alcoholysis liquid: by 1000 mass parts polyester material, 1000 mass parts alcoholysis agent and 1.2～1.6 mass parts alcoholysis catalysts put in the reactor A having rectifying column, it is passed through nitrogen, stir and be warming up to 225～235 DEG C, constant temperature stirs 20 minutes, it is warming up to 240～250 DEG C, carry out constant temperature 6～8 hours alcoholysis reactions under nitrogen protection, the ethylene glycol amount removed when the rectifying column of reactor A reaches 48～50 mass parts and reactant viscosity reaches at 25 DEG C after 1000～1500 mPa s, stop reaction, it is cooled to 160 DEG C, filter with diatomite, filtrate is prepared polyester alcoholysis liquid；
Described polyester material is the section of pet resin, reclaims one or more co-grinding material in film, recovery section, recycled plastic bottle and the material that is recycled and packaged, and the inherent viscosity of this material is 0.55～0.85 dl/g；
Described alcoholysis agent is one or more the mixture in diethylene glycol (DEG), triethylene glycol, tetraethylene glycol, glycerine and pentaerythrite；
Described alcoholysis catalysts is two or more the mixture in zinc acetate, dibutyl tin laurate, Mono-n-butyltin, antimony oxide and tetrabutyl titanate；
B, dispensing: by 900～1200 mass parts polyester alcoholysis liquid, 900 mass parts phthalic anhydrides, 400～600 mass parts binary of fatty acids, 800～1000 mass parts dihydroxylic alcohols, 550～900 mass parts polyalcohols, 0.3～0.5 the quality proportioning of mass parts esterification catalyst take each component raw material；
Described binary of fatty acids is any one in succinic acid, glutaric acid, adipic acid, azelaic acid, decanedioic acid；
Described dihydroxylic alcohols is one or both in ethylene glycol, 1,2-propane diols, 1,3 butylene glycol, neopentyl glycol；
Described polyalcohol is one or both the mixture in glycerine, trimethylolpropane；
Described esterification catalyst is any one in zinc acetate, tetrabutyl titanate, tetraisopropyl titanate, Mono-n-butyltin, Dibutyltin oxide and stannous chloride；
nullc、Prepare high-functionality polyester polyol: component raw material each described in step b put in the reactor B of rectifying column，It is passed through nitrogen，Stirring heats up，And within the rectifying column head temperature controlling reactor B is maintained at 100 DEG C，When in reactor B, temperature reaches 145～155 DEG C、Insulation carries out esterification 1～2 hours，Insulation reaction terminates the rectifying column head temperature of post-reactor B when being reduced to less than 70 DEG C，Speed with intensification in every 20 minutes 5 DEG C、When making the temperature in reactor B reach 160 DEG C、Insulation reaction 1 hour，Then，Speed with intensification in every 20 minutes 5 DEG C、When making the temperature in reactor B reach 180 DEG C、After insulation reaction 1 hour，Again with the speed of intensification in every 20 minutes 5 DEG C、When making the temperature in reactor B reach 200 DEG C、After insulation reaction 1 hour，It is warming up to 220～230 DEG C again with the speed of intensification in every 20 minutes 5 DEG C、Insulation reaction 1 hour，Insulation reaction terminates the rectifying column head temperature of rear reaction mass acid number≤10 mgKOH/g and reactor B when being down to less than 70 DEG C，Stop heating，Stop when reaction mass temperature is down to 200 DEG C being passed through nitrogen、And slowly it is evacuated to-0.070～-0.085 MPa，As acid number≤1 mgKOH/g，Stop reaction，Cooling，I.e. prepare high-functionality polyester polyol product.
6. the preparation method of high-functionality polyester polyol as described in claim 5, is characterized in that: alcoholysis agent described in step a is one or both mixture of diethylene glycol (DEG), triethylene glycol, glycerine.
7. the preparation method of high-functionality polyester polyol as described in claim 5, is characterized in that: alcoholysis catalysts described in step a is the mixture of zinc acetate and tetrabutyl titanate.
8. the preparation method of high-functionality polyester polyol as described in claim 5, is characterized in that: binary of fatty acids described in step b is adipic acid.
9. the preparation method of high-functionality polyester polyol as described in claim 5, it is characterized in that: the average functionality of described prepared high-functionality polyester polyol is 2.4～2.5, viscosity be at 25 DEG C≤10000 mPa s, hydroxyl value 300～350 mgKOH/g, acid number be≤1 mgKOH/g, and do not crystallize after storing 3 months under the conditions of 2 DEG C.
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| CN105056992A (en) * | 2015-08-11 | 2015-11-18 | 永悦科技股份有限公司 | Catalyst for alcoholysis of PET and process adopting catalyst for alcoholysis of PET |
| CN105693995B (en) * | 2016-04-22 | 2018-08-03 | 福建华普化学有限公司 | The method for making polyurethane resin and artificial leather through wet process using waste PET bottle |
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| CN109320679B (en) * | 2018-09-30 | 2020-12-15 | 山东一诺威新材料有限公司 | Environment-friendly combined polyether for high-self-adhesion stainless steel freezer cabinet, preparation method and application |
| CN110643011B (en) * | 2019-08-02 | 2022-02-08 | 上海炼升化工股份有限公司 | High-strength polyurethane foam composition, polyurethane foam and synthesis method thereof |
| CN110563935B (en) * | 2019-08-02 | 2021-08-24 | 上海炼升化工股份有限公司 | High-functionality polyester polyol and preparation method thereof |
| CN111533891B (en) * | 2020-04-16 | 2023-01-13 | 上海炼升化工股份有限公司 | Polyester polyol for high-temperature-resistant adhesive and preparation method thereof |
| CN114716656B (en) * | 2022-04-21 | 2023-11-17 | 江西百盛精细化学品有限公司 | High-toughness high-bonding-strength polyester polyol resin |
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