CN109824877A

CN109824877A - A method of using PTA residue synthesizing environment-friendly polyester polyol

Info

Publication number: CN109824877A
Application number: CN201910077507.XA
Authority: CN
Inventors: 董绍华
Original assignee: Lian Sheng Chemical Inc Shanghai
Current assignee: Lian Sheng Chemical Inc Shanghai
Priority date: 2019-01-28
Filing date: 2019-01-28
Publication date: 2019-05-31
Anticipated expiration: 2039-01-28
Also published as: CN109824877B

Abstract

This application involves a kind of methods using PTA residue synthesizing environment-friendly polyester polyol, it is the following steps are included: S1: at the first temperature, make PTA residue, unsaturated unary fatty acid, the first predetermined amount of time of inorganic acid, catalyst and polyol reaction, obtains the first reaction mixture；S2: making the first reaction mixture keep the temperature the second predetermined amount of time at the second temperature, obtains the environmentally friendly polyester polyol after the reaction was completed.The beneficial effects of the present application are as follows increasing inorganic acid during using PTA residue to synthesize polyester polyol initiatively as additive, significantly shorten the filtration time in subsequent technique, and heavy metal catalyst valuable in PTA residue can be recycled, the cost of preparation polyester polyol is reduced indirectly.

Description

A method of using PTA residue synthesizing environment-friendly polyester polyol

Technical field

This application involves organic syntheses and chemical industrial waste object utilization technology field.Specifically, this application involves one The method that kind uses PTA residue synthesizing environment-friendly polyester polyol.

Background technique

Such as group norms " T/SPUIA000001-2018 " defined that Shanghai City polyurethane industrial association issues, essence is to benzene Dioctyl phthalate (PTA) residue (residues resulting in pure terephthalic acid fabrication) refers to life The residue generated during p-phthalic acid (PTA) oxidation and purification two is produced, main component has terephthalic acid (TPA), to first Yl benzoic acid, M-phthalic acid and benzoic acid etc..90% in these components of PTA residue all has recycling value.

China is PTA big producer, annual to produce at least 40,000,000 tons of PTA, and will be generated by producing PTA per ton by about 5 kilograms PTA residue, it is annual to produce at least 200,000 tons of PTA residues.Therefore, the recycling PTA residue of the task is very arduous.Recycling at present Chemical method using PTA residue mainly includes that esterification process prepares plasticizer, methanol esterification synthesis first ester type compound and second two Alcohol esterification prepares unsaturated-resin and prepares active carbon etc. using PTA residue.

In addition, synthesizing polyester polyol using PTA residue as polyacid material is another for recycling PTA residue Important directions.It can be used as by the Aromatic Polyester Polyols that PTA residue synthesizes and prepare urethane raw, have a wide range of applications With considerable economic benefit.But it will use the heavy metals such as cobalt, manganese in PTA production process as catalyst, these heavy metals Catalyst also remains in PTA residue, brings certain obstacle to the recycling of PTA residue.

For this purpose, this field, which is continuously needed, develops a kind of use PTA that can decrease or even eliminate heavy metal catalyst influence The method of residue synthesizing environment-friendly polyester polyol.

Summary of the invention

It include remaining heavy metal catalyst, such as cobalt or manganese etc. in PTA residue.On the one hand, these heavy metal catalysts It is expensive but effectively to be recycled because of included in PTA residue, cause precious resources to waste.On the other hand, exist When using PTA residue synthetic polymer, these heavy metal catalysts or their ion are easy to be not easy with organic acid formation The metallic soap of water, this brings larger difficulty to subsequent filtering technique, causes filtration time too long, and significantly shorten filtering and set Standby service life.In addition, during producing PTA, in order to carry out scale removal to pipeline, it usually needs with highly basic such as hydrogen-oxygen Change sodium and washs pipeline.When using PTA residue synthetic polymer, the cation in highly basic also will form metallic soap, increase filtering Difficulty.

The application's is designed to provide a kind of use PTA residue that can decrease or even eliminate heavy metal catalyst influence The method of synthesizing environment-friendly polyester polyol, to solve above-mentioned technical problem in the prior art.Specifically, the side of the application Method increases inorganic acid as additive during using PTA residue to synthesize polyester polyol initiatively.Inorganic acid can be with Metallic soaps not soluble in water various in PTA residue are converted into soluble easily in water or reaction system inorganic acid salt, this is unexpected Ground shortens synthesized polyester polyol consumed time in subsequent filter, can also recycle these valuable huge sum of moneys simultaneously Belong to.

To achieve the goals above, the application provides following technical proposals.

In the first aspect, the application provides a kind of method using PTA residue synthesizing environment-friendly polyester polyol, feature It is, the described method comprises the following steps:

S1: at the first temperature, make PTA residue, unsaturated unary fatty acid, inorganic acid, catalyst and polyol reaction First predetermined amount of time obtains the first reaction mixture；

S2: making the first reaction mixture keep the temperature the second predetermined amount of time at the second temperature, obtains after the reaction was completed described Environmentally friendly polyester polyol.

In a kind of embodiment of first aspect, the method also includes before step S1 at 170 DEG C to formation The raw material of first reaction mixture is dehydrated.

In a kind of embodiment of first aspect, the method also includes making environmentally friendly polyester polyol upon step s 2 Third predetermined amount of time is kept under vacuum conditions.

In a kind of embodiment of first aspect, the unsaturation unary fatty acid is oleic acid.

In a kind of embodiment of first aspect, the inorganic acid is boric acid.

In a kind of embodiment of first aspect, the polyalcohol is the mixture of glycerine and diethylene glycol (DEG).

In a kind of embodiment of first aspect, at least part of the diethylene glycol (DEG) is substandard goods diethylene glycol (DEG).

In a kind of embodiment of first aspect, the catalyst includes butyl titanate, zinc acetate or two laurels One or more of sour dibutyl tin.

In a kind of embodiment of first aspect, first predetermined amount of time is 4-6 hours.

In a kind of embodiment of first aspect, second predetermined amount of time is 5-8 hours.

In a kind of embodiment of first aspect, first temperature is 190-220 DEG C.

In a kind of embodiment of first aspect, the second temperature is 220-230 DEG C.

Compared with prior art, the beneficial effects of the present application are as follows synthesizing polyester polyols using PTA residue initiatively Increase inorganic acid during alcohol as additive, significantly shortens the filtration time in subsequent technique, and recyclable PTA residue The heavy metal catalyst of middle preciousness reduces the cost of preparation polyester polyol indirectly.

Specific embodiment

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 where, 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, about the synthetic technology in this field, product disclosed by these special documents 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 limit value to upper limit value of 1 unit, condition be any lower value with There are the intervals of at least two unit between any 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 the numerical value less than 1 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 the range comprising 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.Numberical range in the application particularly provides various comonomers in acrylate copolymer In content, content of the various components in photoetching compositions, temperature and these components when acrylic ester synthesizing it is each Kind feature and property.

About chemical compound in use, unless explicitly stated otherwise, otherwise odd number includes all isomeric forms, otherwise also So (for example, whole isomers that " hexane " either individually or collectively includes 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 in the application it is all use term "comprising"s, " comprising ", or " having " composition may include 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 Separate member listed or any combination thereof.

It in a specific embodiment, can be in step S2 when unstable under reaction condition of the catalyst in step S1 Middle addition catalyst.

In a specific embodiment, first predetermined amount of time is 4-6 hours.Those skilled in the art can basis Actual needs adjusts the length of the first predetermined amount of time.

In a specific embodiment, second predetermined amount of time is 5-8 hours.Similarly, those skilled in the art Member can adjust the length of the second predetermined amount of time according to indexs such as the acid values of actual requirement.In a specific embodiment, should The acid value index in stage is less than or equal to 10mgKOH/g.

In a specific embodiment, first temperature is 190-220 DEG C.In a specific embodiment, institute Stating the first temperature is 190 DEG C, 195 DEG C, 200 DEG C, 205 DEG C, 210 DEG C or 220 DEG C.In a specific embodiment, the rank Section heating rate be preferably 10-20 DEG C/h, may be, for example, 10 DEG C/h, 11 DEG C/h, 12 DEG C/h, 13 DEG C/ Hour, 14 DEG C/h, 15 DEG C/h, 16 DEG C/h, 17 DEG C/h, 18 DEG C/h, 19 DEG C/h or 20 DEG C/small When.

In a specific embodiment, the second temperature is 220-230 DEG C.In a specific embodiment, institute State second temperature be 220 DEG C, 221 DEG C, 222 DEG C, 223 DEG C, 224 DEG C, 225 DEG C, 226 DEG C, 227 DEG C, 228 DEG C, 229 DEG C or 230℃.In a specific embodiment, the heating rate in the stage is preferably 10-20 DEG C/h, may be, for example, 10 DEG C/ Hour, 11 DEG C/h, 12 DEG C/h, 13 DEG C/h, 14 DEG C/h, 15 DEG C/h, 16 DEG C/h, 17 DEG C/h, 18 DEG C/h, 19 DEG C/h or 20 DEG C/h.

In a specific embodiment, the method also includes before step S1 at 170 DEG C it is anti-to forming first The raw material of mixture is answered to be dehydrated.

Carrying out dehydration to raw material may include removing the moisture in raw material components being vacuumized to reaction unit.

In a specific embodiment, the method also includes making environmentally friendly polyester polyol in vacuum upon step s 2 Third predetermined amount of time is kept under state.

In one embodiment, when carrying out vacuum dehydration, the vacuum degree is 0 to -0.09MPa.Those skilled in the art Member is appreciated that term " vacuum degree 0-0.09MPa " means that the vacuum degree of reaction kettle when vacuum dehydration is -0.02MPa, - 0.03MPa ... -0.09MPa etc..

In a specific embodiment, third predetermined amount of time can be 1-2 hours, may be, for example, 1 hour, 1.5 hours, Or 2 hours.Keeping the period length of vacuum state can be used for the acid value of reaction product polyester polyol, viscosity and hydroxyl value etc. Index adjusting is optimized to required numberical range.After indices are up to standard, reaction product polyester polyol is cooled down, is filtered, It discharges and is packed.

In one embodiment, p-phthalic acid's residue is the PTA residue from oil of SPC.Although below The central scope and spirit of the application, but this field are described in embodiment using the PTA residue from oil of SPC as example Technical staff is appreciated that the present processes are applied equally to the PTA residue of other different components.

In a specific embodiment, the unsaturated unary fatty acid is oleic acid.

It is in the field of business pioneering of inventor that inorganic acid is added during synthesizing polyester polyol.In a kind of specific implementation In mode, the type of inorganic acid used is not particularly limited herein, if its organic metal soap can be converted into it is soluble easily in water Inorganic salts.In a kind of particularly preferred embodiment, the inorganic acid is boric acid.Boric acid can use PTA residue The metallic soap that water is insoluble in PTA residue is converted into inorganic salts soluble easily in water during synthesis polyester polyol.In addition, The organic carboxyl acid and excessive boric acid thus generated can carboxylate corresponding with polyol reaction generation and borate, obtain environmental protection Polyester polyol, without generating additional spent acid waste water.

In a specific embodiment, the dosage of inorganic acid is not particularly limited.In a specific embodiment, with It is counted on the basis of molal quantity, inorganic acid is excessive for the total amounts such as heavy metal catalyst, metallic soap in PTA residue. In a specific embodiment, counted on the basis of quality, the dosage of inorganic acid account for all raw material components total weights be less than or Equal to 5%.For example, in a specific embodiment, being counted on the basis of quality, it is total that the dosage of inorganic acid accounts for all raw material components 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 3.5%, 4.0%, 4.5% or the 5.0% of weight.

In a specific embodiment, the polyalcohol is the mixture of glycerine and diethylene glycol (DEG).

In a specific embodiment, at least part of the diethylene glycol (DEG) is substandard goods diethylene glycol (DEG).

As described herein to use, term " substandard goods diethylene glycol (DEG) " is the mixture of diethylene glycol (DEG), triethylene glycol and water.Using weight as base Quasi- meter, substandard goods diethylene glycol (DEG) includes the water of the diethylene glycol (DEG) of 70-80%, the triethylene glycol of 15-20% and 5-10%.

In a specific embodiment, catalyst used is not particularly limited.In a preferred embodiment, The catalyst includes one or more of butyl titanate, zinc acetate or dibutyl tin dilaurate.A kind of specific In embodiment, the dosage of the catalyst is not particularly limited.In a preferred embodiment, on the basis of weight Meter, the dosage of the catalyst account for all raw material components total weights be less than or equal to 5%.For example, in a kind of specific embodiment party In formula, counted on the basis of quality, the dosage of catalyst account for all raw material components total weights 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 3.5%, 4.0%, 4.5% or 5.0%.

It is stated on the basis of meeting this field Conventional wisdom, above-mentioned various optimum conditions carry out any combination, obtain this hair Bright preferred embodiment.

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.

In the following embodiments, PTA residue used is the PTA residue from oil of SPC.

Viscosity is according to the regulation of national standard " the 7th part of 12008.7 plastics polyether polyol of GB/T: the measurement of viscosity " It is measured.

Hydroxyl value is surveyed according to the regulation of professional standard " measurement of HG/T 2709-1995-T polyester polyol middle hydroxyl value " It is fixed.

Acid value is measured according to the regulation of professional standard " measurement of acid value in HG/T 2708-1995 polyester polyol ".

Color is measured according to the regulation of national standard " GB/T 1722-1992 first method iron cobalt colorimetric method ".

Moisture is according to national standard " survey of the GB/T 22313-2008 plastics for the polyalcohol water content of polyurethane production Regulation calmly " is measured.

Embodiment 1

The present embodiment is related to the method for synthesizing environment-friendly polyester polyol LPS-360.

Firstly, 5 tons of PTA residue (oil of SPC), 3 tons of diethylene glycol (DEG), 2 tons of diethylene glycol (DEG) pair are added in a kettle Product, 1.3 tons of glycerine, 1 ton of oleic acid and 5kg boric acid.By above-mentioned reaction mass, normal pressure is dehydrated 2 hours at 170 DEG C.It is de- After water is completed, with 15 DEG C/h of heating rate, the temperature of reaction system is increased to 190 DEG C, and keep the temperature at such a temperature 6 hours, obtain the first reaction mixture.

Then, the catalyst butyl titanate of 5kg is added, and into reaction kettle with 10 DEG C/h of heating rate, it will be anti- It answers the temperature of system to be increased to 230 DEG C, keeps the temperature 5 hours, when detecting that the acid value of reaction product is less than 10mgKOH/g, under One stage of reaction.

Next, keeping reaction system 2 hours under the vacuum degree of -0.09MPa.Detect that the acid value of reaction product is small When 2.5mgKOH/g, 150 DEG C are cooled to hereinafter, and being 10 square metres using filter area with 5000kg/ hours flux The filter of CT-10 model filters 2 hours, and per hour for 12 cubic metres, discharging packaging obtains environmental protection to the flow of filtrate discharging pump Polyester polyol finished product.

The environmentally friendly polyester of the present embodiment is detected according to every national standard, professional standard or group norms as described above Polyalcohol, measuring viscosity at its 25 DEG C is 3000mPas, hydroxyl value 380mgKOH/g, acid value 1.5mgKOH/g, color (iron-cobalt) is No. 11, and moisture weight content is 0.1%.

Acid value, viscosity, hydroxyl value and the coloration of the environmentally friendly polyester polyol of the present embodiment meet Shanghai City polyurethane industrial association Requirement in the group norms " T/SPUIA000001-2018 " that can be issued to I type polyester polyol physicochemical property.

Embodiment 2

Firstly, 5 tons of PTA residue (oil of SPC), 3 tons of diethylene glycol (DEG), 2 tons of diethylene glycol (DEG) pair are added in a kettle Product, 1.3 tons of glycerine, 1 ton of oleic acid, the catalyst acetic acid zinc of 25kg and the boric acid of 15kg.By above-mentioned reaction mass 170 Normal pressure is dehydrated 2 hours at DEG C.After dehydration is completed, with 20 DEG C/h of heating rate, the temperature of reaction system is increased to 200 DEG C, and 5 hours are kept the temperature at such a temperature, obtain the first reaction mixture.

Then, with 10 DEG C/h of heating rate, the temperature of reaction system is increased to 230 DEG C, keeps the temperature 7 hours, detection To reaction product acid value be less than 10mgKOH/g when, into next stage of reaction.

Next, keeping reaction system 2 hours under the vacuum degree of -0.09MPa.Detect that the acid value of reaction product is small When 2.5mgKOH/g, 150 DEG C are cooled to hereinafter, and being 10 square metres using filter area with 6000kg/ hours flux The filter of CT-10 model filters 2 hours, and per hour for 12 cubic metres, the heavy metal in filtrate can for the flow of filtrate discharging pump It is recycled by way of adding sodium carbonate, discharging packaging obtains environmentally friendly polyester polyol finished product.

The environmentally friendly polyester of the present embodiment is detected according to every national standard, professional standard or group norms as described above Polyalcohol, measuring viscosity at its 25 DEG C is 3000mPas, hydroxyl value 350mgKOH/g, acid value 1.3mgKOH/g, color (iron-cobalt) is No. 11, and moisture weight content is 0.1%.

Embodiment 3

Firstly, 5 tons of PTA residue (oil of SPC), 3 tons of diethylene glycol (DEG), 2 tons of diethylene glycol (DEG) pair are added in a kettle Product, 1.3 tons of glycerine, 1 ton of oleic acid, the catalyst dibutyltin dilaurylate of 5kg and the boric acid of 35kg.By above-mentioned reaction Material normal pressure at 170 DEG C is dehydrated 2 hours.After dehydration is completed, with 20 DEG C/h of heating rate, by the temperature of reaction system Degree is increased to 210 DEG C, and keeps the temperature 5 hours at such a temperature, obtains the first reaction mixture.

Then, with 10 DEG C/h of heating rate, the temperature of reaction system is increased to 225 DEG C, keeps the temperature 8 hours, detection To reaction product acid value be less than 10mgKOH/g when, into next stage of reaction.

Next, keeping reaction system 2 hours under the vacuum degree of -0.09MPa.Detect that the acid value of reaction product is small When 2.5mgKOH/g, 150 DEG C are cooled to hereinafter, and being 10 square metres using filter area with 5000kg/ hours flux The filter of CT-10 model filters 2 hours, and per hour for 12 cubic metres, the heavy metal in filtrate can for the flow of filtrate discharging pump It is recycled by way of adding sodium carbonate, discharging packaging obtains environmentally friendly polyester polyol finished product.

The environmentally friendly polyester of the present embodiment is detected according to every national standard, professional standard or group norms as described above Polyalcohol, measuring viscosity at its 25 DEG C is 3600mPas, hydroxyl value 400mgKOH/g, acid value 2.0mgKOH/g, color (iron-cobalt) is No. 11, and moisture weight content is 0.1%.

Embodiment 4

The present embodiment is related to the method for synthesizing environment-friendly polyester polyol LPS-410.

Firstly, 5 tons of PTA residue (oil of SPC), 5 tons of diethylene glycol (DEG), 1.3 tons of glycerine, 1 are added in a kettle The oleic acid of ton and the boric acid of 45kg.By above-mentioned reaction mass, normal pressure is dehydrated 2 hours at 170 DEG C.After dehydration is completed, with 20 DEG C/h heating rate, the temperature of reaction system is increased to 210 DEG C, and at such a temperature keep the temperature 5 hours, obtain first Reaction mixture.

Then, the catalyst butyl titanate of 5kg is added, and into reaction kettle with 10 DEG C/h of heating rate, it will be anti- It answers the temperature of system to be increased to 220 DEG C, keeps the temperature 8 hours, when detecting that the acid value of reaction product is less than 10mgKOH/g, under One stage of reaction.

Next, keeping reaction system 2 hours under the vacuum degree of -0.09MPa.Detect that the acid value of reaction product is small When 2.5mgKOH/g, 150 DEG C are cooled to hereinafter, and small using the filter filtering 2 of XX model with 5000kg/ hours flux When, per hour for 12 cubic metres, the heavy metal in filtrate can be carried out the flow of filtrate discharging pump by way of adding sodium carbonate Recycling, discharging packaging obtains environmentally friendly polyester polyol finished product.

The environmentally friendly polyester of the present embodiment is detected according to every national standard, professional standard or group norms as described above Polyalcohol, measuring viscosity at its 25 DEG C is 2900mPas, hydroxyl value 420mgKOH/g, acid value 1.0mgKOH/g, color (iron-cobalt) is No. 9, and moisture weight content is 0.1%.

Acid value, viscosity, hydroxyl value and the coloration of the environmentally friendly polyester polyol of the present embodiment meet Shanghai City polyurethane industrial association Requirement in the group norms " T/SPUIA000001-2018 " that can be issued to II type polyester polyol physicochemical property.

Embodiment 5

Firstly, 5 tons of PTA residue (oil of SPC), 5 tons of diethylene glycol (DEG), 1.3 tons of glycerine, 1 are added in a kettle Oleic acid, the catalyst acetic acid zinc of 25kg and the boric acid of 5kg of ton.By above-mentioned reaction mass, normal pressure is dehydrated 2 hours at 170 DEG C. After dehydration is completed, with 15 DEG C/h of heating rate, the temperature of reaction system is increased to 190 DEG C, and protect at such a temperature Temperature 6 hours, obtains the first reaction mixture.

Then, with 10 DEG C/h of heating rate, the temperature of reaction system is increased to 220 DEG C, keeps the temperature 8 hours, detection To reaction product acid value be less than 10mgKOH/g when, into next stage of reaction.

Next, keeping reaction system 2 hours under the vacuum degree of -0.09MPa.Detect that the acid value of reaction product is small When 2.5mgKOH/g, 150 DEG C are cooled to hereinafter, and being 10 square metres using filter area with 7000kg/ hours flux The filter of CT-10 model filters 2 hours, and per hour for 12 cubic metres, the heavy metal in filtrate can for the flow of filtrate discharging pump It is recycled by way of adding sodium carbonate, discharging packaging obtains environmentally friendly polyester polyol finished product.

The environmentally friendly polyester of the present embodiment is detected according to every national standard, professional standard or group norms as described above Polyalcohol, measuring viscosity at its 25 DEG C is 3000mPas, hydroxyl value 400mgKOH/g, acid value 1.0mgKOH/g, color (iron-cobalt) is No. 7, and moisture weight content is 0.1%.

Embodiment 6

Firstly, 5 tons of PTA residue (oil of SPC), 5 tons of diethylene glycol (DEG), 1.3 tons of glycerine, 1 are added in a kettle Oleic acid, the catalyst dibutyltin dilaurylate of 5kg and the boric acid of 25kg of ton.By above-mentioned reaction mass at 170 DEG C normal pressure Dehydration 2 hours.After dehydration is completed, with 15 DEG C/h of heating rate, the temperature of reaction system is increased to 190 DEG C, and 6 hours are kept the temperature at this temperature, obtains the first reaction mixture.

The environmentally friendly polyester of the present embodiment is detected according to every national standard, professional standard or group norms as described above Polyalcohol, measuring viscosity at its 25 DEG C is 2900mPas, hydroxyl value 405mgKOH/g, acid value 1.0mgKOH/g, color (iron-cobalt) is No. 9, and moisture weight content is 0.1%.

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 creative labor.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 modifies within all scope of the present application.

Claims

1. a kind of method using PTA residue synthesizing environment-friendly polyester polyol, which is characterized in that the method includes following steps It is rapid:

S2: making the first reaction mixture keep the temperature the second predetermined amount of time at the second temperature, obtains the environmental protection after the reaction was completed Polyester polyol.

2. using the method for PTA residue synthesizing environment-friendly polyester polyol as described in claim 1, which is characterized in that the side Method further includes being dehydrated at 170 DEG C to the raw material for forming the first reaction mixture before step S1.

3. using the method for PTA residue synthesizing environment-friendly polyester polyol as described in claim 1, which is characterized in that the side Method further includes that environmentally friendly polyester polyol is made to keep third predetermined amount of time under vacuum conditions upon step s 2.

4. the method as claimed in any one of claims 1-3 using PTA residue synthesizing environment-friendly polyester polyol, feature exist In the unsaturation unary fatty acid is oleic acid.

5. the method as claimed in any one of claims 1-3 using PTA residue synthesizing environment-friendly polyester polyol, feature exist In the inorganic acid is boric acid.

6. the method as claimed in any one of claims 1-3 using PTA residue synthesizing environment-friendly polyester polyol, feature exist In the polyalcohol is the mixture of glycerine and diethylene glycol (DEG).

7. using the method for PTA residue synthesizing environment-friendly polyester polyol as claimed in claim 6, which is characterized in that described two At least part of glycol is substandard goods diethylene glycol (DEG).

8. the method as claimed in any one of claims 1-3 using PTA residue synthesizing environment-friendly polyester polyol, feature exist In the catalyst includes one or more of butyl titanate, zinc acetate or dibutyl tin dilaurate.

9. the method as claimed in any one of claims 1-3 using PTA residue synthesizing environment-friendly polyester polyol, feature exist In first predetermined amount of time is 4-6 hours；

And/or second predetermined amount of time is 5-8 hours.

10. the method as claimed in any one of claims 1-3 using PTA residue synthesizing environment-friendly polyester polyol, feature It is, first temperature is 190-220 DEG C；

And/or the second temperature is 220-230 DEG C.