CN108424510A - The preparation method of polyester polyol for adhesive for laminated film - Google Patents
The preparation method of polyester polyol for adhesive for laminated film Download PDFInfo
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- CN108424510A CN108424510A CN201810241380.6A CN201810241380A CN108424510A CN 108424510 A CN108424510 A CN 108424510A CN 201810241380 A CN201810241380 A CN 201810241380A CN 108424510 A CN108424510 A CN 108424510A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
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- Polyesters Or Polycarbonates (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The preparation method of polyester polyol for adhesive for laminated film, the primary aromatic binary carboxylic acid 25.0~35.0% that feeds intake, small molecule dihydric alcohol 25.0~40.0%, it puts into reaction kettle, temperature programming promotes esterification, after acid value drops to 10~30mgKOH/g, then cool down and carries out secondary batching, secondary batching aliphatic dicarboxylic acid 25.0~40.0%, small molecule dihydric alcohol 5.0~15.0%, heating carries out esterification water outlet again, and butyl titanate or stannous octoate catalyst is added, control temperature programming and program vacuum, obtain the target polyesters polyol product not only containing phenyl ring aromatic hydrocarbons but also containing aliphatic hydrocarbon；And be the bifunctionality polyalcohol of primary hydroxyl sealing end, there is higher reactivity with isocyanate group.It is the polyurethane adhesive that main soft segment is polymerized by the polyester polyol, is suitble to the bonding of the resistance to cooking disinfection food packaging laminated film of high temperature resistant requirement.
Description
Technical field
The present invention relates to polyester polyol technologies of preparing, in particular for the system of the polyester polyol of adhesive for laminated film
Preparation Method.
Background technology
Polyester polyol is the alkyd polyester polyalcohol made of dicarboxylic acids and small molecule polyol polycondensation.Common two
First carboxylic acid has adipic acid, azelaic acid, decanedioic acid, succinic acid, phthalic anhydride, M-phthalic acid, terephthalic acid (TPA) etc., commonly uses
Small molecule polyol have ethylene glycol, 1,2- propylene glycol, 1,4- butanediols, 1,6-HD, diethylene glycol, neopentyl glycol, first
Base propylene glycol, trimethylolpropane, glycerine etc..It is wide in variety due to dicarboxylic acids and small molecule polyol, so combinatorial compound
Polyester polyol molecule structure it is varied, polyester polyol product specification is also various with regard to type.It is former with straight-chain even carbon
The small molecule polyol of son such as 1,4- butanediols, ethylene glycol, 1,6-HD and the polyester polyol crystallization of adipic acid synthesis
Property is higher, is mainly used for the high polyurethane adhesive of requirement initial adhesive strength, elastomer, PU resins etc.；With with side group and ehter bond
The polyester polyol that small molecule polyol is synthesized with adipic acid has preferable flexibility and cryogenic property；Neopentyl glycol structure
The polyurethane of polyester polyol synthesis has excellent alkali resistance and hydrolytic resistance；With the such as long-chains fat such as azelaic acid, decanedioic acid
The polyurethane of polyester polyol synthesis prepared by fat acid has excellent stability to hydrolysis resistance；Aromatic polyester polyol contains
The polyester polyol that phthalic anhydride, M-phthalic acid, terephthalic acid (TPA) of benzene ring structure etc. are synthesized with small molecule polyol,
The better heat resistance of polyurethane product and corrosion resistance can be assigned.
The preparation of polyester polyol generally uses batch process to produce：Production equipment mainly has reaction kettle, fractionator condenser, cold
Condenser, vacuum system, heating and cooling system and control system etc., reaction process are broadly divided into esterification and ester exchange reaction two
A stage.Small molecule polyol and carboxylic acid are successively added in reaction kettle first when production and melted, nitrogen is passed through, in 140~
150 DEG C of reactions generate low molecule polyester and condensation water, condensation water gradually steam, and maintain the suitable water speed that goes out, control fractionation cold
Condenser top temperature prevents a large amount of vapor from taking a large amount of small molecule polyol out of fractionator condenser within 105 DEG C, gradually will
Temperature in the kettle is increased to 180~190 DEG C and holds warm a period of time, then is gradually warming up to 210~230 DEG C, when acid value drops to
After 35mgKOH/g or less, it is discharged basic stopping, esterification is difficult to carry out, and esterification stage terminates substantially；It opens at this time true
Empty set is united, and gradually reduces vacuum degree to 1000~5000Pa, instead by excessive dihydric alcohol and a small amount of low molecule polyester, aldehyde and ketone pair
Product is answered to be steamed together with the residual water that reaction generates.Ester exchange reaction mainly occurs for this stage, generates new ester and newly more
First alcohol, while also a small amount of condensation water generates.Sample detection acid value, hydroxyl value or viscosity in the process, when acid value is in 0.5mgKOH/g
Below, after hydroxyl value or viscosity make it, you can breaking vacuum, be cooled to 120 DEG C or less go out kettle packaging, as polyester is more
First alcohol finished product.
The polyester polyol of different cultivars is since type is different or preparation process is different, and property is also different, for poly-
The important several indexs of ester polyol are：Hydroxyl value, acid value, moisture, viscosity, molecular weight, density and coloration etc..Polyester is more
First alcohol is mainly for the production of polyurethane products, such as polyurethane elastomer, polyurethane adhesive, polyurethane coating, polyurethane oil
Ink, polyurethane leather resin, polyurethane coating resin, polyurethane foam etc..Polyester polyurethane product contains because of its intramolecular
More ester group, amino isopolarity group, cohesive strength and strong adhesive force have higher intensity, abrasion resistance, heat resistance, resistance to
Oily solvent resistance etc..
The advantage and disadvantage that any type film has it intrinsic only can just obtain the Film laminated of various characteristics together
High performance composite material, laminated film make food flexible packing have it is easy to carry, it is easy storage, high temperature resistant boil sterilization and
The advantages that ensureing food hygiene, is favored by people, in all parts of the country successive in order to meet the needs to increase substantially to flexible package
Laminated film production line is introduced, the development of production laminating glue stick is promoted.The production method of laminated film is mainly
Compound and dry laminating is squeezed out, dry laminating is that different films are bonded together through compounding machine with adhesive, used in
Adhesive is all polyurethane adhesive, can be made meet heat-resisting, cold-resistant, oil resistant, acidproof, drug-resistant, choke, it is transparent, wear-resisting with
And the package compound film of the performance requirements such as being folded without breaking.This laminated film includes that polyester film, polypropylene film, nylon are thin
Film, aluminum foil film etc..
The performance of laminated film has the glue additionally depended on outside the Pass different Film laminateds together in addition to the film with selection
Stick performance, and to polyurethane adhesive performance play a decisive role it is main be exactly polyester polyol structure and characteristic.
In the prior art, polyurethane adhesive refer in strand containing carbamate groups (- NHCOO-) or
The adhesive of isocyanate group (- NCO).Polyurethane adhesive is divided into polyisocyanates and polyurethane two major classes.Polyisocyanates
Contain isocyano group (- NCO) and carbamate groups (- NH-COO-) in strand, therefore polyurethane adhesive shows the work of height
Property and polarity.With the base material containing active hydrogen, such as foam, plastics, timber, leather, fabric, paper, ceramics porous material, with
And the material of any surface finish such as metal, glass, rubber, plastics has excellent chemical adhesive power.No matter which kind of polyurethane gluing
Agent is all isocyanate groups in system in system or the outer substance containing active hydrogen of system reacts, and generates poly- ammonia
Ester group or polyureas, so that system intensity greatly improves and realize the purpose of bonding.
The document of polyester polyol in relation to laminated film polyurethane adhesive or adhesive for laminated film discloses less.
Jiangsu Hua Da new material Co., Ltd discloses a kind of high in the patent application of application number 201710113242.5
The preparation method of quality polyester polyol, it includes the following steps：(a) add in rectifying column, churned mechanically reaction kettle
Enter dicarboxylic acids and dihydric alcohol, is gradually warming up to 180~200 DEG C under inert gas atmosphere and carries out esterification dehydration, and control
The temperature of rectifying column tower top processed is 95~110 DEG C；(b) catalyst is added into reaction kettle, with the speed liter of 5~10 DEG C/30min
Temperature is performed under reduced pressure polycondensation reaction to 220~250 DEG C；The reduced pressure is with 0.005~0.015MPa
Speed from 0.01MPa be incremented to 0.1MPa and every time be incremented by after kept for 0.5~1 hour, the quality of the catalyst is institute
State the 0.005~0.05% of dicarboxylic acids and dihydric alcohol gross mass.To guarantee system technique and product molecular weight distribution,
The stabilization of hydroxyl value, acid value, chromatic number.
Coating material tomorrow Co., Ltd of Zhongshan city discloses one in the patent application of application number 201710186684.2
Kind polyurethane macromolecule polyester polyol formula and its synthetic method, including following component：Decanedioic acid, ethanedioic acid and 1,2-
The molar ratio of propylene glycol, 1,6- hexylene glycols, 1,5-PD, neopentyl glycol, wherein alcohol and acid is 1.95.Its synthetic method is such as
Under：A carries out proportioning mixing by above-mentioned formula；B reacts in reaction kettle, in a kettle, stirs and heats heating, in taking the photograph
165 DEG C of family name starts to be discharged, and is warming up to 240 DEG C, then the isothermal reaction 5h at 240 DEG C again at this time, until acid value is less than in mixture
5mgKOH/g；C, vacuum distillation gradually reduce vacuum degree to 20KPa, detect the acid value in mixture, acid value in a kettle
Until being less than 1mgKOH/g, continue to reduce vacuum degree to -100KPa, and react 2.5h, then detect its relative molecular weight, opposite point
Son amount is qualification in 10000-15000.
Zhongshan University discloses a kind of composite membrane with solvent-free poly- in the patent application of application number 200910037754.3
Urethane adhesive, is made of component A and B component, and component A is end-OH polyester polyol, and B component is end NCO- polyurethane prepolymers
Body；A, B component is by functional group's molar ratio NCO/OH=1.2~1.9: 1.0.The composite membrane polyurethane adhesive of the present invention, nothing
Solvent must be used, it is safe.Due to introducing dimeric dibasic acid, low water absorbable, low in hydrolysis high impact strength are shown, it is special to some
It is difficult to the base material for bonding, adhering to, shows good caking property.By the design of ingredient and molecular structure to adhesive, change
The adhesive strength of laminated film has been apt to it, T peel strengths reach 3.8N/15MM or more after compound 3~5 days between plastic film, mould
Material reaches 4.2N/15MM or more with aluminizer.
It is thin that Jiaxing Hexin Chemical Industrial Co., Ltd discloses a kind of PVC in 200910095580.6 patent application of application number
Film dry type is compound to use double-component environmental-protection type polyurethane adhesive, including host agent and curing agent.Host agent is a kind of base polyurethane prepolymer for use as,
Raw material and its mass percent are：Oligomer polyol 5~30%, small molecule polyol or amine 0~20%, polyisocyanates 2
~20%, catalyst 0~0.05%, diluent 50~80%；The main performance index of host agent is：Viscosity 500~
20000mPa.s/25 DEG C, solid content 20~50%.Curing agent is closed by pre-polymerization method with polyol by polyisocyanates
At the base polyurethane prepolymer for use as of terminal isocyanate group, isocyanate group content is 10%~15%, and solid content is 75 ± 3%.It will
Suitable host agent, curing agent and diluent mix, you can are used for the dry-lamination process of PVC film and other materials, have
Very high initial adhesive strength, stablize after peel strength and tearing load, and plasticizer-resistant effect is notable.
Invention content
The object of the present invention is to provide the preparation methods of the polyester polyol for adhesive for laminated film.
The purpose of the present invention will be realized by following technical measures：By weight percentage, aromatic binary carboxylic acid
25.0~35.0%, small molecule dihydric alcohol 25.0~40.0% puts into above-mentioned raw materials in reaction kettle, and 5~20L/ of logical nitrogen
Min is begun to warm up, and one section of temperature programming holds temperature to 180~190 DEG C, at a temperature of this 1~3 hour；It is arranged in 2~4 hours later
210~230 DEG C are to slowly warm up to, temperature is held at a temperature of this 2~4 hours；Esterification water outlet mainly occurs in above procedure, pays attention to
Heating rate and overhead temperature are controlled within 100~105 DEG C, to prevent small molecular alcohol excessive loss.210~230 DEG C
During holding temperature, with the progress of esterification, system acid value is gradually reduced, sampling detecting acid number, when acid value reaches 10~
After 30mgKOH/g, then it can start to cool down, 150~160 DEG C be cooled to, subsequently into the secondary batching stage of reaction.Secondary batching
Amount, by weight percentage, aliphatic dicarboxylic acid 25.0~40.0%, small molecule dihydric alcohol 5.0~15.0%, by above-mentioned original
In material input reaction kettle, 5~20L/min of nitrogen is kept, is begun to warm up, one section of temperature programming is to 140~150 DEG C, at a temperature of this
Hold temperature 1~3 hour；Then it designs in 2~4 hours and is to slowly warm up to 210~230 DEG C, temperature is held at a temperature of this 2~4 hours；More than
Esterification water outlet mainly occurs in the process, pays attention to controlling heating rate and overhead temperature within 100~105 DEG C,
To prevent small molecular alcohol excessive loss；With the progress of esterification, system acid value is gradually reduced, sampling detecting acid number, when acid value reaches
To after 20~40mgKOH/g, then it can enter the vacuum program phase, and the butyl titanate or stannous octoate of 10~100ppm is added
Pressure in kettle is gradually evacuated to relative vacuum about -0.098MPa (25torr) by catalyst from normal pressure in 3~5 hours；Vacuum degree reaches
When to -0.095~-0.098MPa, nitrogen vacuum breaker then can be used after meeting product standard in sample detection acid value, viscosity or hydroxyl value
And 120 DEG C are cooled to hereinafter, blowing or packaging, obtain target polyesters polyol product；Raw materials used dicarboxylic acids mainly has oneself
Diacid, M-phthalic acid, phthalic anhydride, decanedioic acid, azelaic acid etc., small molecule dihydric alcohol refer to ethylene glycol, Isosorbide-5-Nitrae-fourth two
Alcohol, diglycol, neopentyl glycol, 3- methyl-1s, 5- pentanediols, hexylene glycol etc. are one such or a variety of；Final product
Standard, which is acid value, can control in 0.70mgKOH/g or less, coloration 100APHA or less, moisture 300ppm hereinafter, and hydroxyl value and viscous
It spends after reaching desired value, as qualified products.
Especially, by weight percentage, by M-phthalic acid (IPA) 27.42%, (water removes liquid neopentyl glycol NPG
It 29.57% is added in reaction kettle outside), and 5~20L/min of logical nitrogen, starts to stir and heat, one section of temperature programming to 180~
190 DEG C, temperature is held at a temperature of this 1~3 hour；It is arranged in 2~4 hours later and is to slowly warm up to 210~230 DEG C, holds at a temperature of this
Temperature 2~4 hours.Esterification water outlet mainly occurs in above procedure, notices that controlling heating rate and overhead temperature exists
Within 100~105 DEG C, to prevent small molecular alcohol excessive loss.During 210~230 DEG C are held temperature, with the progress of esterification,
System acid value is gradually reduced, sampling detecting acid number, after acid value reaches 10~30mgKOH/g, then can be started to cool down, be cooled to 150
~160 DEG C, subsequently into the secondary batching stage of reaction.Second of inventory, by weight percentage, by decanedioic acid (SBA)
33.38%, diethylene glycol (DEG) 9.62% is added in reaction kettle, keeps 5~20L/min of nitrogen, continues to heat, one section of program
140~150 DEG C are warming up to, temperature is held at a temperature of this 1~3 hour；Then it designs in 2~4 hours and is to slowly warm up to 210~230 DEG C,
Temperature is held at a temperature of this 2~4 hours.Esterification water outlet mainly occurs in above procedure, pays attention to controlling heating rate and destilling tower
Tower top temperature is within 100~105 DEG C, to prevent small molecular alcohol excessive loss.With the progress of esterification, system acid value is gradual
Decline, sampling detecting acid number, after acid value reaches 20~40mgKOH/g, then can enter the vacuum program phase, and be added 100ppm's
Butyl titanate or stannous octoate catalyst, pressure in kettle is gradually evacuated to from normal pressure in 3~5 hours relative vacuum about-
0.098MPa(25torr).Sample detection in processing procedure, when acid value≤0.70mgKOH/g of polyester polyol, hydroxyl value 53.0~
When 59.0mgKOH/g, moisture≤300ppm, coloration≤100APHA, then product qualification is judged to.Reaction kettle is broken with nitrogen
Vacuum simultaneously cools to 120 DEG C hereinafter, blowing is packed.Obtain the polyester polyol of number-average molecular weight 2000.
Especially, by weight percentage, by phthalic anhydride (PA) 26.28%, (water removes liquid neopentyl glycol NPG
It 31.79% is added in reaction kettle outside), and 5~20L/min of logical nitrogen, starts to stir and heat, one section of temperature programming to 180~
190 DEG C, temperature is held at a temperature of this 1~3 hour；It is arranged in 2~4 hours later and is to slowly warm up to 210~230 DEG C, holds at a temperature of this
Temperature 2~4 hours.Esterification water outlet mainly occurs in above procedure, notices that controlling heating rate and overhead temperature exists
Within 100~105 DEG C, to prevent small molecular alcohol excessive loss.During 210~230 DEG C are held temperature, with the progress of esterification,
System acid value is gradually reduced, sampling detecting acid number, after acid value reaches 10~30mgKOH/g, then can be started to cool down, be cooled to 150
~160 DEG C, subsequently into the secondary batching stage of reaction.Second of inventory, by weight percentage, by decanedioic acid (SBA)
35.88%, ethylene glycol (EG) 6.04% is added in reaction kettle, keeps 5~20L/min of nitrogen, continues to heat, one section of temperature programming
Temperature is held to 140~150 DEG C, at a temperature of this 1~3 hour；Then it designs in 2~4 hours and is to slowly warm up to 210~230 DEG C, this temperature
Temperature is held under degree 2~4 hours.Esterification water outlet mainly occurs in above procedure, pays attention to controlling heating rate and overhead
Temperature is within 100~105 DEG C, to prevent small molecular alcohol excessive loss.With the progress of esterification, under system acid value is gradual
Drop, sampling detecting acid number can then enter the vacuum program phase, and the titanium of 100ppm is added after acid value reaches 20~40mgKOH/g
Sour four butyl esters or stannous octoate catalyst, pressure in kettle is gradually evacuated to from normal pressure in 3~5 hours relative vacuum about-
0.098MPa(25torr).Sample detection in processing procedure, when acid value≤0.70mgKOH/g of polyester polyol, hydroxyl value 53.0~
When 59.0mgKOH/g, moisture≤300ppm, coloration≤100APHA, then product qualification is judged to.Reaction kettle is broken with nitrogen
Vacuum simultaneously cools to 120 DEG C hereinafter, blowing is packed.Obtain the polyester polyol of number-average molecular weight 2000.
Especially, by weight percentage, by M-phthalic acid (IPA) 27.42%, 3- methyl-1s, 5- pentanediols (MPD)
33.55% is added in reaction kettle, and 5~20L/min of logical nitrogen, starts to stir and heat, one section of temperature programming to 180~190
DEG C, temperature is held at a temperature of this 1~3 hour；It is arranged in 2~4 hours later and is to slowly warm up to 210~230 DEG C, temperature 2 is held at a temperature of this
~4 hours.Esterification water outlet mainly occurs in above procedure, pays attention to controlling heating rate and overhead temperature 100
Within~105 DEG C, to prevent small molecular alcohol excessive loss.During 210~230 DEG C are held temperature, with the progress of esterification, system
Acid value is gradually reduced, sampling detecting acid number, after acid value reaches 10~30mgKOH/g, then can be started to cool down, be cooled to 150~160
DEG C, subsequently into the secondary batching stage of reaction.Second of inventory, by weight percentage, by decanedioic acid (SBA) 33.39%,
Ethylene glycol (EG) 5.63% is added in reaction kettle, keeps 5~20L/min of nitrogen, continues to heat, and one section of temperature programming to 140~
150 DEG C, temperature is held at a temperature of this 1~3 hour；Then it designs in 2~4 hours and is to slowly warm up to 210~230 DEG C, hold at a temperature of this
Temperature 2~4 hours.Esterification water outlet mainly occurs in above procedure, notices that controlling heating rate and overhead temperature exists
Within 100~105 DEG C, to prevent small molecular alcohol excessive loss.With the progress of esterification, system acid value is gradually reduced, sampling
Acid value is surveyed, after acid value reaches 20~40mgKOH/g, then can enter the vacuum program phase, and four fourth of metatitanic acid of 100ppm is added
Pressure in kettle is gradually evacuated to relative vacuum about -0.098MPa by ester or stannous octoate catalyst from normal pressure in 3~5 hours
(25torr).Sample detection in processing procedure, acid value≤0.70mgKOH/g, 42.0~48.0mgKOH/ of hydroxyl value when polyester polyol
G, when moisture≤300ppm, coloration≤100APHA, then it is judged to product qualification.By reaction kettle nitrogen vacuum breaker and cool down
To 120 DEG C hereinafter, blowing is packed.Obtain the polyester polyol of number-average molecular weight 2500.
Especially, by weight percentage, by M-phthalic acid (IPA) 31.61%, (water removes liquid neopentyl glycol NPG
It 34.09% is added in reaction kettle outside), and 5~20L/min of logical nitrogen, starts to stir and heat, one section of temperature programming to 180~
190 DEG C, temperature is held at a temperature of this 1~3 hour；It is arranged in 2~4 hours later and is to slowly warm up to 210~230 DEG C, holds at a temperature of this
Temperature 2~4 hours.Esterification water outlet mainly occurs in above procedure, notices that controlling heating rate and overhead temperature exists
Within 100~105 DEG C, to prevent small molecular alcohol excessive loss.During 210~230 DEG C are held temperature, with the progress of esterification,
System acid value is gradually reduced, sampling detecting acid number, after acid value reaches 10~30mgKOH/g, then can be started to cool down, be cooled to 150
~160 DEG C, subsequently into the secondary batching stage of reaction.Second of inventory, by weight percentage, by adipic acid (AA)
27.80%, ethylene glycol (EG) 6.49% is added in reaction kettle, keeps 5~20L/min of nitrogen, continues to heat, one section of temperature programming
Temperature is held to 140~150 DEG C, at a temperature of this 1~3 hour；Then it designs in 2~4 hours and is to slowly warm up to 210~230 DEG C, this temperature
Temperature is held under degree 2~4 hours.Esterification water outlet mainly occurs in above procedure, pays attention to controlling heating rate and overhead
Temperature is within 100~105 DEG C, to prevent small molecular alcohol excessive loss.With the progress of esterification, under system acid value is gradual
Drop, sampling detecting acid number can then enter the vacuum program phase, and the titanium of 100ppm is added after acid value reaches 20~40mgKOH/g
Sour four butyl esters or stannous octoate catalyst, pressure in kettle is gradually evacuated to from normal pressure in 3~5 hours relative vacuum about-
0.098MPa(25torr).Sample detection in processing procedure, when acid value≤0.70mgKOH/g of polyester polyol, hydroxyl value 35.0~
When 39.0mgKOH/g, moisture≤300ppm, coloration≤100APHA, then product qualification is judged to.Reaction kettle is broken with nitrogen
Vacuum simultaneously cools to 120 DEG C hereinafter, blowing is packed.Obtain the polyester polyol of number-average molecular weight 3000.
Especially, by weight percentage, by M-phthalic acid (IPA) 27.42%, (water removes liquid neopentyl glycol NPG
It 29.57% is added in reaction kettle outside), and 5~20L/min of logical nitrogen, starts to stir and heat, one section of temperature programming to 180~
190 DEG C, temperature is held at a temperature of this 1~3 hour；It is arranged in 2~4 hours later and is to slowly warm up to 210~230 DEG C, holds at a temperature of this
Temperature 2~4 hours.Esterification water outlet mainly occurs in above procedure, notices that controlling heating rate and overhead temperature exists
Within 100~105 DEG C, to prevent small molecular alcohol excessive loss.During 210~230 DEG C are held temperature, with the progress of esterification,
System acid value is gradually reduced, sampling detecting acid number, after acid value reaches 10~30mgKOH/g, then can be started to cool down, be cooled to 150
~160 DEG C, subsequently into the secondary batching stage of reaction.Second of inventory, by weight percentage, by decanedioic acid (SBA)
33.38%, diethylene glycol (EG) 9.62% is added in reaction kettle, keeps 5~20L/min of nitrogen, continues to heat, one section of program liter
Temperature holds temperature to 140~150 DEG C, at a temperature of this 1~3 hour；Then it designs in 2~4 hours and is to slowly warm up to 210~230 DEG C, this
At a temperature of hold temperature 2~4 hours.Esterification water outlet mainly occurs in above procedure, pays attention to controlling heating rate and destilling tower tower
Temperature is pushed up within 100~105 DEG C, to prevent small molecular alcohol excessive loss.With the progress of esterification, under system acid value is gradual
Drop, sampling detecting acid number can then enter the vacuum program phase, and the titanium of 100ppm is added after acid value reaches 20~40mgKOH/g
Sour four butyl esters or stannous octoate catalyst, pressure in kettle is gradually evacuated to from normal pressure in 3~5 hours relative vacuum about-
0.098MPa(25torr).Sample detection in processing procedure, as acid value≤0.70mgKOH/g of polyester polyol, hydroxyl value 35.0~
39.0mgKOH/g, moisture≤300ppm when coloration≤100APHA, are then judged to product qualification.Reaction kettle is broken with nitrogen
Vacuum simultaneously cools to 120 DEG C hereinafter, blowing is packed.Obtain the polyester polyol of number-average molecular weight 3000.
Especially, the polyester polyol of preparation is the bifunctionality polyalcohol of primary hydroxyl sealing end, and number-average molecular weight is 1000
Between~4000, phenyl ring aromatic hydrocarbons was not only contained but also had contained aliphatic hydrocarbon, or contained side group.
Especially, the polyester polyol of preparation aggregates into polyurethane adhesive with isocyanates and small molecule chain extender.
Advantages of the present invention and effect：Target polyesters polyol product is obtained not only to have contained phenyl ring aromatic hydrocarbons but also contained aliphatic hydrocarbon,
Side group can also be contained, be all the bifunctionality polyalcohol of primary hydroxyl sealing end, there is higher reactivity with isocyanate group.
The polyurethane adhesive being polymerized by the polyester polyol and isocyanates and small molecule chain extender etc. is pasted for various films
Close, not only have excellent adhesive strength, ageing-resistant, odorlessness, and heat-resisting, cold-resistant, oil resistant, acidproof, drug-resistant, choke,
The function admirables such as transparent, wear-resisting and being folded without breaking, transparency, bin stability and wetability are good, freeze-thawing resistant, rate of drying compared with
Soon, viscosity is low good economy, there is good machining property, and first viscous effect is particularly evident after compound, is especially suitable for
The bonding for the resistance to cooking disinfection food packaging laminated film that high temperature resistant requires.
Description of the drawings
Fig. 1 is preparation method flow Program heating step schematic diagram in the present invention.
Fig. 2 is that preparation method flow Program vacuum step illustrates table in the present invention.
Fig. 3 is the polyester polyol product formula component table of comparisons by weight percentage in embodiment 1 to 5.
Specific implementation mode
The principle of the invention is, by weight percentage, aromatic binary carboxylic acid 25.0~35.0%, small molecule dihydric alcohol
25.0~40.0%, above-mentioned raw materials are put into reaction kettle, and 5~20L/min of logical nitrogen, is begun to warm up, one section of temperature programming
Temperature is held to 180~190 DEG C, at a temperature of this 1~3 hour；It is arranged in 2~4 hours later and is to slowly warm up to 210~230 DEG C, this temperature
Temperature is held under degree 2~4 hours.Esterification water outlet mainly occurs in above procedure, pays attention to controlling heating rate and overhead
Temperature is within 100~105 DEG C, to prevent small molecular alcohol excessive loss.During 210~230 DEG C are held temperature, with esterification
It carries out, system acid value is gradually reduced, and sampling detecting acid number can then start to cool down after acid value reaches 10~30mgKOH/g, cooling
To 150~160 DEG C, subsequently into the secondary batching stage of reaction.Secondary batching amount, by weight percentage, binary aliphatic carboxylic
Acid 25.0~40.0%, small molecule dihydric alcohol 5.0~15.0% put into above-mentioned raw materials in reaction kettle, keep 5~20L/ of nitrogen
Min is begun to warm up, and one section of temperature programming holds temperature to 140~150 DEG C, at a temperature of this 1~3 hour；Then it designs in 2~4 hours
210~230 DEG C are to slowly warm up to, temperature is held at a temperature of this 2~4 hours.Esterification water outlet mainly occurs in above procedure, pays attention to
Heating rate and overhead temperature are controlled within 100~105 DEG C, to prevent small molecular alcohol excessive loss.As esterification is anti-
The progress answered, system acid value are gradually reduced, sampling detecting acid number, after acid value reaches 20~40mgKOH/g, then can enter vacuum journey
The sequence stage, and the butyl titanate or stannous octoate catalyst of 10~100ppm is added, by pressure in kettle from normal in 3~5 hours
Pressure is gradually evacuated to relative vacuum about -0.098MPa (25torr).When vacuum degree reaches -0.095~-0.098MPa, sample detection
Acid value, viscosity or hydroxyl value then can be used nitrogen vacuum breaker after meeting product standard and be cooled to 120 DEG C hereinafter, blowing or packaging, obtain
To target polyesters polyol product.
The raw materials used in the present invention dicarboxylic acids mainly has adipic acid, M-phthalic acid, phthalic anhydride, decanedioic acid, nonyl
Diacid etc., small molecule dihydric alcohol are primarily referred to as ethylene glycol, 1,4-butanediol, diglycol, neopentyl glycol, 3- methyl-1s,
5- pentanediols, hexylene glycol etc. are one such or a variety of.Final product standard be acid value can control 0.70mgKOH/g or less,
Coloration 100APHA or less, moisture 300ppm hereinafter, and after hydroxyl value and viscosity reaches desired value, as qualified products.
Program heating step of the present invention such as attached drawing 1, program vacuum step such as attached drawing 2.
The invention will be further described with reference to the accompanying drawings and examples.Percentage by weight in embodiment 1 to embodiment 5
It is more as shown in Fig. 3 than meter polyester polyol product formula component.
Embodiment 1：By weight percentage, by M-phthalic acid (IPA) 27.42%, (water removes liquid neopentyl glycol NPG
It 29.57% is added in reaction kettle outside), and 5~20L/min of logical nitrogen, starts to stir and heat, one section of temperature programming to 180~
190 DEG C, temperature is held at a temperature of this 1~3 hour；It is arranged in 2~4 hours later and is to slowly warm up to 210~230 DEG C, holds at a temperature of this
Temperature 2~4 hours.Esterification water outlet mainly occurs in above procedure, notices that controlling heating rate and overhead temperature exists
Within 100~105 DEG C, to prevent small molecular alcohol excessive loss.During 210~230 DEG C are held temperature, with the progress of esterification,
System acid value is gradually reduced, sampling detecting acid number, after acid value reaches 10~30mgKOH/g, then can be started to cool down, be cooled to 150
~160 DEG C, subsequently into the secondary batching stage of reaction.Second of inventory, by weight percentage, by decanedioic acid (SBA)
33.38%, diethylene glycol (DEG) 9.62% is added in reaction kettle, keeps 5~20L/min of nitrogen, continues to heat, one section of program
140~150 DEG C are warming up to, temperature is held at a temperature of this 1~3 hour；Then it designs in 2~4 hours and is to slowly warm up to 210~230 DEG C,
Temperature is held at a temperature of this 2~4 hours.Esterification water outlet mainly occurs in above procedure, pays attention to controlling heating rate and destilling tower
Tower top temperature is within 100~105 DEG C, to prevent small molecular alcohol excessive loss.With the progress of esterification, system acid value is gradual
Decline, sampling detecting acid number, after acid value reaches 20~40mgKOH/g, then can enter the vacuum program phase, and be added 100ppm's
Butyl titanate or stannous octoate catalyst, pressure in kettle is gradually evacuated to from normal pressure in 3~5 hours relative vacuum about-
0.098MPa(25torr).Sample detection in processing procedure, when acid value≤0.70mgKOH/g of polyester polyol, hydroxyl value 53.0~
When 59.0mgKOH/g, moisture≤300ppm, coloration≤100APHA, then product qualification is judged to.Reaction kettle is broken with nitrogen
Vacuum simultaneously cools to 120 DEG C hereinafter, blowing is packed.Obtain the polyester polyol PE-8820A of number-average molecular weight 2000.
Embodiment 2：By weight percentage, by phthalic anhydride (PA) 26.28%, (water removes liquid neopentyl glycol NPG
It 31.79% is added in reaction kettle outside), and 5~20L/min of logical nitrogen, starts to stir and heat, one section of temperature programming to 180~
190 DEG C, temperature is held at a temperature of this 1~3 hour；It is arranged in 2~4 hours later and is to slowly warm up to 210~230 DEG C, holds at a temperature of this
Temperature 2~4 hours.Esterification water outlet mainly occurs in above procedure, notices that controlling heating rate and overhead temperature exists
Within 100~105 DEG C, to prevent small molecular alcohol excessive loss.During 210~230 DEG C are held temperature, with the progress of esterification,
System acid value is gradually reduced, sampling detecting acid number, after acid value reaches 10~30mgKOH/g, then can be started to cool down, be cooled to 150
~160 DEG C, subsequently into the secondary batching stage of reaction.Second of inventory, by weight percentage, by decanedioic acid (SBA)
35.88%, ethylene glycol (EG) 6.04% is added in reaction kettle, keeps 5~20L/min of nitrogen, continues to heat, one section of temperature programming
Temperature is held to 140~150 DEG C, at a temperature of this 1~3 hour；Then it designs in 2~4 hours and is to slowly warm up to 210~230 DEG C, this temperature
Temperature is held under degree 2~4 hours.Esterification water outlet mainly occurs in above procedure, pays attention to controlling heating rate and overhead
Temperature is within 100~105 DEG C, to prevent small molecular alcohol excessive loss.With the progress of esterification, under system acid value is gradual
Drop, sampling detecting acid number can then enter the vacuum program phase, and the titanium of 100ppm is added after acid value reaches 20~40mgKOH/g
Sour four butyl esters or stannous octoate catalyst, pressure in kettle is gradually evacuated to from normal pressure in 3~5 hours relative vacuum about-
0.098MPa(25torr).Sample detection in processing procedure, when acid value≤0.70mgKOH/g of polyester polyol, hydroxyl value 53.0~
When 59.0mgKOH/g, moisture≤300ppm, coloration≤100APHA, then product qualification is judged to.Reaction kettle is broken with nitrogen
Vacuum simultaneously cools to 120 DEG C hereinafter, blowing is packed.Obtain the polyester polyol PE-8820B of number-average molecular weight 2000.
Embodiment 3：By weight percentage, by M-phthalic acid (IPA) 27.42%, 3- methyl-1s, 5- pentanediols
(MPD) it 33.55% is added in reaction kettle, and 5~20L/min of logical nitrogen, starts to stir and heat, one section of temperature programming to 180
~190 DEG C, temperature is held at a temperature of this 1~3 hour；It is arranged in 2~4 hours later and is to slowly warm up to 210~230 DEG C, at a temperature of this
Hold temperature 2~4 hours.Esterification water outlet mainly occurs in above procedure, pays attention to controlling heating rate and overhead temperature
Within 100~105 DEG C, to prevent small molecular alcohol excessive loss.During 210~230 DEG C are held temperature, with esterification into
Row, system acid value are gradually reduced, and sampling detecting acid number can then start to cool down, cool to after acid value reaches 10~30mgKOH/g
150~160 DEG C, subsequently into the secondary batching stage of reaction.Second of inventory, by weight percentage, by decanedioic acid (SBA)
33.39%, ethylene glycol (EG) 5.63% is added in reaction kettle, keeps 5~20L/min of nitrogen, continues to heat, one section of temperature programming
Temperature is held to 140~150 DEG C, at a temperature of this 1~3 hour；Then it designs in 2~4 hours and is to slowly warm up to 210~230 DEG C, this temperature
Temperature is held under degree 2~4 hours.Esterification water outlet mainly occurs in above procedure, pays attention to controlling heating rate and overhead
Temperature is within 100~105 DEG C, to prevent small molecular alcohol excessive loss.With the progress of esterification, under system acid value is gradual
Drop, sampling detecting acid number can then enter the vacuum program phase, and the titanium of 100ppm is added after acid value reaches 20~40mgKOH/g
Sour four butyl esters or stannous octoate catalyst, pressure in kettle is gradually evacuated to from normal pressure in 3~5 hours relative vacuum about-
0.098MPa(25torr).Sample detection in processing procedure, when acid value≤0.70mgKOH/g of polyester polyol, hydroxyl value 42.0~
When 48.0mgKOH/g, moisture≤300ppm, coloration≤100APHA, then product qualification is judged to.Reaction kettle is broken with nitrogen
Vacuum simultaneously cools to 120 DEG C hereinafter, blowing is packed.Obtain the polyester polyol PE-8825A of number-average molecular weight 2500.
Embodiment 4：By weight percentage, by M-phthalic acid (IPA) 31.61%, (water removes liquid neopentyl glycol NPG
It 34.09% is added in reaction kettle outside), and 5~20L/min of logical nitrogen, starts to stir and heat, one section of temperature programming to 180~
190 DEG C, temperature is held at a temperature of this 1~3 hour；It is arranged in 2~4 hours later and is to slowly warm up to 210~230 DEG C, holds at a temperature of this
Temperature 2~4 hours.Esterification water outlet mainly occurs in above procedure, notices that controlling heating rate and overhead temperature exists
Within 100~105 DEG C, to prevent small molecular alcohol excessive loss.During 210~230 DEG C are held temperature, with the progress of esterification,
System acid value is gradually reduced, sampling detecting acid number, after acid value reaches 10~30mgKOH/g, then can be started to cool down, be cooled to 150
~160 DEG C, subsequently into the secondary batching stage of reaction.Second of inventory, by weight percentage, by adipic acid (AA)
27.80%, ethylene glycol (EG) 6.49% is added in reaction kettle, keeps 5~20L/min of nitrogen, continues to heat, one section of temperature programming
Temperature is held to 140~150 DEG C, at a temperature of this 1~3 hour；Then it designs in 2~4 hours and is to slowly warm up to 210~230 DEG C, this temperature
Temperature is held under degree 2~4 hours.Esterification water outlet mainly occurs in above procedure, pays attention to controlling heating rate and overhead
Temperature is within 100~105 DEG C, to prevent small molecular alcohol excessive loss.With the progress of esterification, under system acid value is gradual
Drop, sampling detecting acid number can then enter the vacuum program phase, and the titanium of 100ppm is added after acid value reaches 20~40mgKOH/g
Sour four butyl esters or stannous octoate catalyst, pressure in kettle is gradually evacuated to from normal pressure in 3~5 hours relative vacuum about-
0.098MPa(25torr).Sample detection in processing procedure, when acid value≤0.70mgKOH/g of polyester polyol, hydroxyl value 35.0~
When 39.0mgKOH/g, moisture≤300ppm, coloration≤100APHA, then product qualification is judged to.Reaction kettle is broken with nitrogen
Vacuum simultaneously cools to 120 DEG C hereinafter, blowing is packed.Obtain the polyester polyol PE-8830A of number-average molecular weight 3000.
Embodiment 5：By weight percentage, by M-phthalic acid (IPA) 27.42%, (water removes liquid neopentyl glycol NPG
It 29.57% is added in reaction kettle outside), and 5~20L/min of logical nitrogen, starts to stir and heat, one section of temperature programming to 180~
190 DEG C, temperature is held at a temperature of this 1~3 hour；It is arranged in 2~4 hours later and is to slowly warm up to 210~230 DEG C, holds at a temperature of this
Temperature 2~4 hours.Esterification water outlet mainly occurs in above procedure, notices that controlling heating rate and overhead temperature exists
Within 100~105 DEG C, to prevent small molecular alcohol excessive loss.During 210~230 DEG C are held temperature, with the progress of esterification,
System acid value is gradually reduced, sampling detecting acid number, after acid value reaches 10~30mgKOH/g, then can be started to cool down, be cooled to 150
~160 DEG C, subsequently into the secondary batching stage of reaction.Second of inventory, by weight percentage, by decanedioic acid (SBA)
33.38%, diethylene glycol (EG) 9.62% is added in reaction kettle, keeps 5~20L/min of nitrogen, continues to heat, one section of program liter
Temperature holds temperature to 140~150 DEG C, at a temperature of this 1~3 hour；Then it designs in 2~4 hours and is to slowly warm up to 210~230 DEG C, this
At a temperature of hold temperature 2~4 hours.Esterification water outlet mainly occurs in above procedure, pays attention to controlling heating rate and destilling tower tower
Temperature is pushed up within 100~105 DEG C, to prevent small molecular alcohol excessive loss.With the progress of esterification, under system acid value is gradual
Drop, sampling detecting acid number can then enter the vacuum program phase, and the titanium of 100ppm is added after acid value reaches 20~40mgKOH/g
Sour four butyl esters or stannous octoate catalyst, pressure in kettle is gradually evacuated to from normal pressure in 3~5 hours relative vacuum about-
0.098MPa(25torr).Sample detection in processing procedure, as acid value≤0.70mgKOH/g of polyester polyol, hydroxyl value 35.0~
39.0mgKOH/g, moisture≤300ppm when coloration≤100APHA, are then judged to product qualification.Reaction kettle is broken with nitrogen
Vacuum simultaneously cools to 120 DEG C hereinafter, blowing is packed.Obtain the polyester polyol PE-8830B of number-average molecular weight 3000.
Polyester polyol prepared by the present invention is the bifunctionality polyalcohol of primary hydroxyl sealing end, number-average molecular weight 1000~
Between 4000, not only contained phenyl ring aromatic hydrocarbons but also contained aliphatic hydrocarbon, side group can also be contained, be mainly used for adhesive for laminated film, this
Kind laminated film includes polyester film, polypropylene film, nylon film, aluminum foil film etc., is used for food flexible packing.
Claims (9)
1. the preparation method of the polyester polyol for adhesive for laminated film, which is characterized in that by weight percentage, fragrance
Race's dicarboxylic acids 25.0~35.0%, small molecule dihydric alcohol 25.0~40.0% put into above-mentioned raw materials in reaction kettle, and logical nitrogen
5~20L/min of gas, begins to warm up, and one section of temperature programming holds temperature to 180~190 DEG C, at a temperature of this 1~3 hour；2 are arranged later
It is to slowly warm up to 210~230 DEG C in~4 hours, temperature is held at a temperature of this 2~4 hours；Esterification mainly occurs in above procedure
Water outlet pays attention to controlling heating rate and overhead temperature within 100~105 DEG C, to prevent small molecular alcohol excessive loss；
During 210~230 DEG C are held temperature, with the progress of esterification, system acid value is gradually reduced, sampling detecting acid number, when acid value reaches
To after 10~30mgKOH/g, then it can start to cool down, 150~160 DEG C be cooled to, subsequently into the secondary batching stage of reaction；It is secondary
Inventory, by weight percentage, aliphatic dicarboxylic acid 25.0~40.0%, small molecule dihydric alcohol 5.0~15.0% will be upper
It states in raw material input reaction kettle, keeps 5~20L/min of nitrogen, begin to warm up, one section of temperature programming is to 140~150 DEG C, this temperature
Temperature is held under degree 1~3 hour；Then it designs in 2~4 hours and is to slowly warm up to 210~230 DEG C, temperature is held at a temperature of this 2~4 hours；
Mainly occur in above procedure esterification water outlet, pays attention to control heating rate and overhead temperature 100~105 DEG C with
It is interior, to prevent small molecular alcohol excessive loss；With the progress of esterification, system acid value is gradually reduced, and sampling detecting acid number works as acid value
It after reaching 20~40mgKOH/g, then can enter the vacuum program phase, and butyl titanate or the octanoic acid Asia of 10~100ppm is added
Pressure in kettle is gradually evacuated to relative vacuum about -0.098MPa (25torr) by tin catalyst from normal pressure in 3~5 hours；Vacuum degree
When reaching -0.095~-0.098MPa, sample detection acid value, viscosity or hydroxyl value then can be used nitrogen broken true after meeting product standard
Sky is simultaneously cooled to 120 DEG C hereinafter, blowing or packaging, obtain target polyesters polyol product；Raw materials used dicarboxylic acids mainly has
Adipic acid, M-phthalic acid, phthalic anhydride, decanedioic acid, azelaic acid etc., small molecule dihydric alcohol refer to ethylene glycol, Isosorbide-5-Nitrae-fourth
Glycol, diglycol, neopentyl glycol, 3- methyl-1s, 5- pentanediols, hexylene glycol etc. are one such or a variety of；Finally produce
Product standard is acid value control in 0.70mgKOH/g or less, coloration 100APHA or less, moisture 300ppm hereinafter, and hydroxyl value and viscous
It spends after reaching desired value, as qualified products.
2. the preparation method for the polyester polyol of adhesive for laminated film as described in claim 1, which is characterized in that with
Reaction is added in M-phthalic acid (IPA) 27.42%, liquid neopentyl glycol NPG (except water) 29.57% by percent by weight
In kettle, and logical 5~20L/min of nitrogen, start to stir and heat, one section of temperature programming holds temperature 1 to 180~190 DEG C, at a temperature of this
~3 hours；It is arranged in 2~4 hours later and is to slowly warm up to 210~230 DEG C, temperature is held at a temperature of this 2~4 hours；Above procedure
In mainly occur esterification water outlet, pays attention to control heating rate and overhead temperature within 100~105 DEG C, to prevent
Small molecular alcohol excessive loss；During 210~230 DEG C are held temperature, with the progress of esterification, system acid value is gradually reduced, takes
Sample surveys acid value can then start to cool down, 150~160 DEG C be cooled to, subsequently into secondary after acid value reaches 10~30mgKOH/g
Feed intake the stage of reaction；Second of inventory, by weight percentage, by decanedioic acid (SBA) 33.38%, diethylene glycol (DEG)
9.62% is added in reaction kettle, keeps 5~20L/min of nitrogen, continues to heat, and one section of temperature programming is to 140~150 DEG C, this temperature
Temperature is held under degree 1~3 hour；Then it designs in 2~4 hours and is to slowly warm up to 210~230 DEG C, temperature is held at a temperature of this 2~4 hours；
Mainly occur in above procedure esterification water outlet, pays attention to control heating rate and overhead temperature 100~105 DEG C with
It is interior, to prevent small molecular alcohol excessive loss；With the progress of esterification, system acid value is gradually reduced, and sampling detecting acid number works as acid value
After reaching 20~40mgKOH/g, then it can enter the vacuum program phase, and the butyl titanate of 100ppm is added or stannous octoate is urged
Pressure in kettle is gradually evacuated to relative vacuum about -0.098MPa (25torr) by agent from normal pressure in 3~5 hours；It is sampled in processing procedure
Detection, when acid value≤0.70mgKOH/g of polyester polyol, 53.0~59.0mgKOH/g of hydroxyl value, moisture≤300ppm,
When coloration≤100APHA, then product qualification is judged to；By reaction kettle nitrogen vacuum breaker and 120 DEG C are cooled to hereinafter, blowing packet
Dress；Obtain the polyester polyol of number-average molecular weight 2000.
3. the preparation method for the polyester polyol of adhesive for laminated film as described in claim 1, which is characterized in that with
Reaction is added in phthalic anhydride (PA) 26.28%, liquid neopentyl glycol NPG (except water) 31.79% by percent by weight
In kettle, and logical 5~20L/min of nitrogen, start to stir and heat, one section of temperature programming holds temperature 1 to 180~190 DEG C, at a temperature of this
~3 hours；It is arranged in 2~4 hours later and is to slowly warm up to 210~230 DEG C, temperature is held at a temperature of this 2~4 hours；Above procedure
In mainly occur esterification water outlet, pays attention to control heating rate and overhead temperature within 100~105 DEG C, to prevent
Small molecular alcohol excessive loss；During 210~230 DEG C are held temperature, with the progress of esterification, system acid value is gradually reduced, takes
Sample surveys acid value can then start to cool down, 150~160 DEG C be cooled to, subsequently into secondary after acid value reaches 10~30mgKOH/g
Feed intake the stage of reaction；Second of inventory, by weight percentage, by decanedioic acid (SBA) 35.88%, ethylene glycol (EG)
6.04% is added in reaction kettle, keeps 5~20L/min of nitrogen, continues to heat, and one section of temperature programming is to 140~150 DEG C, this temperature
Temperature is held under degree 1~3 hour；Then it designs in 2~4 hours and is to slowly warm up to 210~230 DEG C, temperature is held at a temperature of this 2~4 hours；
Mainly occur in above procedure esterification water outlet, pays attention to control heating rate and overhead temperature 100~105 DEG C with
It is interior, to prevent small molecular alcohol excessive loss；With the progress of esterification, system acid value is gradually reduced, and sampling detecting acid number works as acid value
After reaching 20~40mgKOH/g, then it can enter the vacuum program phase, and the butyl titanate of 100ppm is added or stannous octoate is urged
Pressure in kettle is gradually evacuated to relative vacuum about -0.098MPa (25torr) by agent from normal pressure in 3~5 hours；It is sampled in processing procedure
Detection, when acid value≤0.70mgKOH/g of polyester polyol, 53.0~59.0mgKOH/g of hydroxyl value, moisture≤300ppm,
When coloration≤100APHA, then product qualification is judged to；By reaction kettle nitrogen vacuum breaker and 120 DEG C are cooled to hereinafter, blowing packet
Dress.Obtain the polyester polyol of number-average molecular weight 2000.
4. the preparation method for the polyester polyol of adhesive for laminated film as described in claim 1, which is characterized in that with
Percent by weight, by M-phthalic acid (IPA) 27.42%, 3- methyl-1s, reaction kettle is added in 5- pentanediols (MPD) 33.55%
In, and logical 5~20L/min of nitrogen starts to stir and heat, one section of temperature programming held to 180~190 DEG C, at a temperature of this temperature 1~
3 hours；It is arranged in 2~4 hours later and is to slowly warm up to 210~230 DEG C, temperature is held at a temperature of this 2~4 hours；In above procedure
It is main that esterification water outlet occurs, pay attention to controlling heating rate and overhead temperature within 100~105 DEG C, to prevent small
Molecule alcohol excessive loss；During 210~230 DEG C are held temperature, with the progress of esterification, system acid value is gradually reduced, sampling
Surveying acid value can then start to cool down, 150~160 DEG C be cooled to, subsequently into secondary throwing after acid value reaches 10~30mgKOH/g
Expect the stage of reaction；Second of inventory, by weight percentage, by decanedioic acid (SBA) 33.39%, ethylene glycol (EG) 5.63%
It is added in reaction kettle, keeps 5~20L/min of nitrogen, continue to heat, one section of temperature programming is held to 140~150 DEG C, at a temperature of this
Temperature 1~3 hour；Then it designs in 2~4 hours and is to slowly warm up to 210~230 DEG C, temperature is held at a temperature of this 2~4 hours；The above mistake
Esterification water outlet mainly occurs in journey, pays attention to controlling heating rate and overhead temperature within 100~105 DEG C, with
Anti- small molecular alcohol excessive loss；With the progress of esterification, system acid value is gradually reduced, sampling detecting acid number, when acid value reaches
It after 20~40mgKOH/g, then can enter the vacuum program phase, and butyl titanate or the stannous octoate catalysis of 100ppm is added
Pressure in kettle is gradually evacuated to relative vacuum about -0.098MPa (25torr) by agent from normal pressure in 3~5 hours；Inspection is sampled in processing procedure
It surveys, when acid value≤0.70mgKOH/g of polyester polyol, 42.0~48.0mgKOH/g of hydroxyl value, moisture≤300ppm, color
When degree≤100APHA, then product qualification is judged to；By reaction kettle nitrogen vacuum breaker and 120 DEG C are cooled to hereinafter, blowing is packed.
Obtain the polyester polyol of number-average molecular weight 2500.
5. the preparation method for the polyester polyol of adhesive for laminated film as described in claim 1, which is characterized in that with
Reaction is added in M-phthalic acid (IPA) 31.61%, liquid neopentyl glycol NPG (except water) 34.09% by percent by weight
In kettle, and logical 5~20L/min of nitrogen, start to stir and heat, one section of temperature programming holds temperature 1 to 180~190 DEG C, at a temperature of this
~3 hours；It is arranged in 2~4 hours later and is to slowly warm up to 210~230 DEG C, temperature is held at a temperature of this 2~4 hours；Above procedure
In mainly occur esterification water outlet, pays attention to control heating rate and overhead temperature within 100~105 DEG C, to prevent
Small molecular alcohol excessive loss；During 210~230 DEG C are held temperature, with the progress of esterification, system acid value is gradually reduced, takes
Sample surveys acid value can then start to cool down, 150~160 DEG C be cooled to, subsequently into secondary after acid value reaches 10~30mgKOH/g
Feed intake the stage of reaction；Second of inventory, by weight percentage, by adipic acid (AA) 27.80%, ethylene glycol (EG) 6.49%
It is added in reaction kettle, keeps 5~20L/min of nitrogen, continue to heat, one section of temperature programming is held to 140~150 DEG C, at a temperature of this
Temperature 1~3 hour；Then it designs in 2~4 hours and is to slowly warm up to 210~230 DEG C, temperature is held at a temperature of this 2~4 hours；The above mistake
Esterification water outlet mainly occurs in journey, pays attention to controlling heating rate and overhead temperature within 100~105 DEG C, with
Anti- small molecular alcohol excessive loss；With the progress of esterification, system acid value is gradually reduced, sampling detecting acid number, when acid value reaches
It after 20~40mgKOH/g, then can enter the vacuum program phase, and butyl titanate or the stannous octoate catalysis of 100ppm is added
Pressure in kettle is gradually evacuated to relative vacuum about -0.098MPa (25torr) by agent from normal pressure in 3~5 hours；Inspection is sampled in processing procedure
It surveys, when acid value≤0.70mgKOH/g of polyester polyol, 35.0~39.0mgKOH/g of hydroxyl value, moisture≤300ppm, color
When degree≤100APHA, then product qualification is judged to；By reaction kettle nitrogen vacuum breaker and 120 DEG C are cooled to hereinafter, blowing is packed.
Obtain the polyester polyol of number-average molecular weight 3000.
6. the preparation method for the polyester polyol of adhesive for laminated film as described in claim 1, which is characterized in that with
Reaction is added in M-phthalic acid (IPA) 27.42%, liquid neopentyl glycol NPG (except water) 29.57% by percent by weight
In kettle, and logical 5~20L/min of nitrogen, start to stir and heat, one section of temperature programming holds temperature 1 to 180~190 DEG C, at a temperature of this
~3 hours；It is arranged in 2~4 hours later and is to slowly warm up to 210~230 DEG C, temperature is held at a temperature of this 2~4 hours；Above procedure
In mainly occur esterification water outlet, pays attention to control heating rate and overhead temperature within 100~105 DEG C, to prevent
Small molecular alcohol excessive loss；During 210~230 DEG C are held temperature, with the progress of esterification, system acid value is gradually reduced, takes
Sample surveys acid value can then start to cool down, 150~160 DEG C be cooled to, subsequently into secondary after acid value reaches 10~30mgKOH/g
Feed intake the stage of reaction；Second of inventory, by weight percentage, by decanedioic acid (SBA) 33.38%, diethylene glycol (EG)
9.62% is added in reaction kettle, keeps 5~20L/min of nitrogen, continues to heat, and one section of temperature programming is to 140~150 DEG C, this temperature
Temperature is held under degree 1~3 hour；Then it designs in 2~4 hours and is to slowly warm up to 210~230 DEG C, temperature is held at a temperature of this 2~4 hours；
Mainly occur in above procedure esterification water outlet, pays attention to control heating rate and overhead temperature 100~105 DEG C with
It is interior, to prevent small molecular alcohol excessive loss；With the progress of esterification, system acid value is gradually reduced, and sampling detecting acid number works as acid value
After reaching 20~40mgKOH/g, then it can enter the vacuum program phase, and the butyl titanate of 100ppm is added or stannous octoate is urged
Pressure in kettle is gradually evacuated to relative vacuum about -0.098MPa (25torr) by agent from normal pressure in 3~5 hours；It is sampled in processing procedure
Detection, as acid value≤0.70mgKOH/g of polyester polyol, 35.0~39.0mgKOH/g of hydroxyl value, moisture≤300ppm,
When coloration≤100APHA, then product qualification is judged to；By reaction kettle nitrogen vacuum breaker and 120 DEG C are cooled to hereinafter, blowing packet
Dress；Obtain the polyester polyol of number-average molecular weight 3000.
7. the preparation method for the polyester polyol of adhesive for laminated film as described in claim 1, which is characterized in that system
Standby polyester polyol is the bifunctionality polyalcohol of primary hydroxyl sealing end, and number-average molecular weight both contained between 1000~4000
Phenyl ring aromatic hydrocarbons contains aliphatic hydrocarbon again, or contains side group.
8. the preparation method for the polyester polyol of adhesive for laminated film as described in claim 1, which is characterized in that system
Standby polyester polyol aggregates into polyurethane adhesive with isocyanates and small molecule chain extender.
9. the preparation method as described in claim 1 for meeting the polyester polyol of film glue, which is characterized in that system
Standby technique is carried out in two steps, and the first step is the esterification of aromatic binary carboxylic acid and small molecule dihydric alcohol, esterification degree
To 10~30mgKOH/g of acid value, then cools down and carry out second step；Second step is mainly aliphatic dicarboxylic acid and small molecule two
The esterification of first alcohol, and butyl titanate or stannous octoate catalyst is added, temperature programming and program vacuum are controlled, into traveling
The esterification and ester exchange reaction of one step, obtain target polyesters polyol product.
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| CN110699029A (en) * | 2019-08-18 | 2020-01-17 | 上海回天新材料有限公司 | Adhesive for handholding |
| CN111057512A (en) * | 2019-12-30 | 2020-04-24 | 北京华腾新材料股份有限公司 | Bi-component polyurethane adhesive for steam-resistant aluminum-plastic composite and preparation method thereof |
| CN111320960A (en) * | 2020-03-17 | 2020-06-23 | 北京华腾新材料股份有限公司 | Low-viscosity high-temperature-resistant single-component solvent-free polyurethane adhesive and preparation method thereof |
| CN111533891A (en) * | 2020-04-16 | 2020-08-14 | 上海炼升化工股份有限公司 | Polyester polyol for high-temperature-resistant adhesive and preparation method thereof |
| CN111533890A (en) * | 2020-04-16 | 2020-08-14 | 上海炼升化工股份有限公司 | PTA (pure terephthalic acid) modified alkyd polyester polyol and preparation method thereof |
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| CN115044020A (en) * | 2021-10-25 | 2022-09-13 | 上海联景高分子材料有限公司 | Application of polyester polyol in adhesive for food packaging |
| CN115073715A (en) * | 2021-10-22 | 2022-09-20 | 上海联景高分子材料有限公司 | Polyester polyol for adhesive, and preparation method and application thereof |
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| CN110699029A (en) * | 2019-08-18 | 2020-01-17 | 上海回天新材料有限公司 | Adhesive for handholding |
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| CN111320960A (en) * | 2020-03-17 | 2020-06-23 | 北京华腾新材料股份有限公司 | Low-viscosity high-temperature-resistant single-component solvent-free polyurethane adhesive and preparation method thereof |
| CN111533891A (en) * | 2020-04-16 | 2020-08-14 | 上海炼升化工股份有限公司 | Polyester polyol for high-temperature-resistant adhesive and preparation method thereof |
| CN111533890A (en) * | 2020-04-16 | 2020-08-14 | 上海炼升化工股份有限公司 | PTA (pure terephthalic acid) modified alkyd 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 |
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| CN115044020A (en) * | 2021-10-25 | 2022-09-13 | 上海联景高分子材料有限公司 | Application of polyester polyol in adhesive for food packaging |
| CN115044020B (en) * | 2021-10-25 | 2023-11-03 | 上海联景高分子材料有限公司 | Application of polyester polyol in adhesive for food packaging |
| CN114437326A (en) * | 2021-12-27 | 2022-05-06 | 山东一诺威聚氨酯股份有限公司 | Polyol component of flexible bi-component polyurethane adhesive for flexible packaging composite film and preparation method and application thereof |
| CN115521749A (en) * | 2022-10-17 | 2022-12-27 | 山东逸飞新材料有限公司 | Bi-component solvent-free steaming-resistant polyurethane composite adhesive and preparation method thereof |
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