CN107383353A - A kind of preparation method of silane-modified polyester prepolyer - Google Patents

A kind of preparation method of silane-modified polyester prepolyer Download PDF

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Publication number
CN107383353A
CN107383353A CN201710770055.4A CN201710770055A CN107383353A CN 107383353 A CN107383353 A CN 107383353A CN 201710770055 A CN201710770055 A CN 201710770055A CN 107383353 A CN107383353 A CN 107383353A
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polyester
diol
silane
catalyst
preparation
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CN201710770055.4A
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Inventor
曾正好
蓝庆东
段伟情
吕斌
金峰
徐鸿
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ZHEJIANG DAOMING OPTOELECTRONICS TECHNOLOGY Co Ltd
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ZHEJIANG DAOMING OPTOELECTRONICS TECHNOLOGY Co Ltd
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Priority to CN201710770055.4A priority Critical patent/CN107383353A/en
Publication of CN107383353A publication Critical patent/CN107383353A/en
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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
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/916—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G63/183—Terephthalic acids
    • 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
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
    • 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
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
    • C08G63/86—Germanium, antimony, or compounds thereof
    • C08G63/866—Antimony or compounds thereof
    • 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
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • C09J167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Abstract

The invention discloses a kind of preparation method of silane-modified polyester prepolyer, comprise the following steps：（1）Take in terephthalic acid (TPA), M-phthalic acid, ethylene glycol, neopentyl glycol, decanedioic acid, the first catalyst input synthesis reactor and slowly heated up；（2）Open stirring, control the rate of output water, then temperature reaction, until reaction without distillate, obtain for oligomer；（3）Low vacuumize process is carried out, releases distillate；（4）Carry out pumping high vacuum processing；（5）Cooling, obtains polyester-diol；（6）It is qualified to determine whether；（7）Ethyl acetate is added to be stirred；（8）The second catalyst is added, isocyanato alkoxy silanes compound is slowly added dropwise and stirs；（9）Desolventizing processing is carried out, obtains silane-modified polyester prepolyer.Silane-modified polyester prepolyer produced by the present invention has excellent high and low temperature resistance, pliability, moisture-proof, wetting levelability.

Description

A kind of preparation method of silane-modified polyester prepolyer
Technical field
The present invention relates to aluminum-plastic composite membrane adhesive field, more particularly to a kind of preparation of silane-modified polyester prepolyer Method.
Background technology
Soft package lithium battery battery since the advent of the world, because its characteristic such as more frivolous, safer has obtained swift and violent development, lithium electricity A part of the pond aluminum-plastic composite membrane as soft package lithium battery, have for raising battery energy density, light and thin degree important Influence.
Lithium battery is generally three-decker with aluminum-plastic composite membrane, i.e. outer layer/aluminium foil/internal layer.In dry-lamination process, respectively It is integral by adhesive bonding between layer, is typically bonded between outer layer and aluminium foil layer using two component polyurethane.It is wherein double Part polyurethane generally use PEPA is as host, and modified isocyanate is as curing agent, because its bonding force is by force and first Viscosity is good, thus occupies leading position in dry type is compound.But dual-component polyurethane is very sensitive to aqueous vapor, easily with air Aqueous vapor reaction generation carbon dioxide, cause it is compound after aluminum-plastic composite membrane finished product in have bubble, cause its yields decline, and The curing dose of actual participation reaction is reduced, and causes proportioning inaccurate, so as to influence the performance of product.Further, since Soft Roll lithium is electric When pond is applied to the electrical source of power of vehicle, more harsh compared with energy storage, consumable electronic product of its use environment are therefore, right Lifting the applicability under high and low temperature environment and durability improvement turns into the important subject of dynamic lithium battery aluminum-plastic composite membrane One of.
The content of the invention
The present invention is directed to the adhesive selected in existing aluminum-plastic composite membrane field in recombination process to aqueous vapor sensitivity, and Not high-low temperature resistant, the defects of obtained aluminum-plastic composite membrane unstable product quality, there is provided a kind of new silane-modified polyester is pre- The preparation method of polymers.
A kind of preparation method of silane-modified polyester prepolyer, described preparation method comprise the following steps：
Each raw material is in parts by mass in following step；
（1）Take 34 ~ 48 parts terephthalic acid (TPA), 8.5 ~ 12 parts of M-phthalic acid, 10 ~ 16 parts of ethylene glycol, 17 ~ 26 parts new Pentanediol, 7.5 ~ 24 parts of decanedioic acid, the first catalyst of above raw material gross mass 0.01% ~ 0.5% are put into polyester synthesis kettle, Drying nitrogen is passed through, is slowly heated up；
（2）Work as step（1）After obtained mixture melting, stirring is opened, reaction temperature is controlled at 130 DEG C ~ 160 DEG C, controlled out Water speed rate, insulation reaction to water yield reach the 50% ~ 70% of theoretical water yield, 210 DEG C ~ 220 DEG C are then heated to, in this temperature Lower reaction 1h ~ 8h, until reaction without distillate, obtain for oligomer；
（3）By step（2）In obtained oligomer carry out low vacuumize process, vacuum rises to -0.05Mpa in 1 ~ 3h, then Continue to keep to stop after this vacuum state 0.5h ~ 3h it is low vacuumize, release distillate；
（4）By step（3）The middle reactor stopped after low vacuumize carries out pumping high vacuum processing, in 1h ~ 3h vacuum rise to- 0.095Mpa, now kettle temperature control continue to keep pumping high vacuum state 1h ~ 6h at 210 DEG C ~ 240 DEG C；
（5）Work as step（4）After reaction terminates, kettle temperature is dropped to less than 100 DEG C under the protection of nitrogen, obtains polyester-diol；
（6）Determination step（5）Acid number, hydroxyl value, number-average molecular weight and the glass transition temperature of obtained polyester-diol simultaneously judge whether It is qualified；
（7）Work as step（6）In polyester-diol when being judged as qualified, nitrogen is passed through into polyester synthesis kettle, adds polyester-diol 0.25 ~ 1 times of ethyl acetate of quality, it is stirred after polyester-diol dissolving；
（8）The second catalyst is added, kettle temperature is heated to 60 DEG C ~ 100 DEG C, and isocyanato alkoxy silanes chemical combination is slowly added dropwise Thing, after dripping, continue to stir；
（9）Work as step（8）The hydroxyl value of middle reactant terminates to react when no longer reducing, and then carries out desolventizing processing：First normal pressure liter Temperature controls cut discharge rate, distillate is poured out when flowing out without cut goes out, then carries out vacuumize process to 80 ~ 100 DEG C, Ensure slowly to improve vacuum on the premise of not slug to -0.095Mpa, and by temperature control at 100 DEG C, until without distillate After continue to vacuumize 0.5h, then advertise lower releasing vacuum state in nitrogen, that is, obtain silane-modified polyester prepolyer.
Step（1）In, add terephthalic acid (TPA), M-phthalic acid can lift the chemical-resistant of final product, moisture-proof Gas, ethylene glycol, neopentyl glycol, decanedioic acid can lift the pliability of final product, the first catalyst energy by cooperating Enough reduce reaction temperature, shorten the reaction time, so as to reduce the possibility of final product xanthochromia, risen under the protection of nitrogen Temperature and follow-up reaction can further reduce the possibility of final product xanthochromia, reduce shadow of the external environment to reaction system Ring, ensure the quality and stability of product.
Step（2）In, it is stirred again after mixture melting, the uniformity of subsequent reactions can be ensured, is started instead firm At once, the concentration of each reactant is higher, now controls in the range of 130 DEG C ~ 160 DEG C reaction temperature and controls out water speed Rate, the steady progress of reaction can be ensured, hereafter because the concentration of each reactant is comparatively decreased, cause reaction rate Slow down, now carry out heating and can speed up intermolecular collision, accelerate the progress of reaction, so as to ensure the reaction speed entirely reacted Rate.When reaction is without distillate, show that product reaches certain degree of polymerization, low molecule content in reactant is reduced so as to reach Purpose, prevent follow-up low oligomer when vacuumizing to be extracted, reduce significant loss.
Step（3）（4）In, take the water for reacting generation out of reaction system by way of vacuumizing, promote reaction to continue Carry out, further improve the degree of polymerization, wherein first carrying out low vacuumize process can prevent when just starting to vacuumize because of suction mistake Material is caused to be gone out greatly, so as to can progressively be pulled water out in low vacuumizing phase, at the end of low vacuumize, oligomer The degree of polymerization is of a relatively high, and on the one hand the degree of polymerization of oligomer can further be lifted by now carrying out pumping high vacuum processing again, separately On the one hand some of which low molecule can be released.After low vacuumize process and pumping high vacuum processing terminate, pass through Step（5）Cooling method can just obtain polyester-diol.
Pass through step（6）Judgement, the polyester-diol that can ensure to obtain reaches written standards, so as to ensure subsequent reactions Be smoothed out and the quality of final product.
Step（7）In, nitrogen can protect reaction system, reduce influence of the external environment to reaction.Ethyl acetate plays The effect of solvent, polyester-diol is dissolved into ethyl acetate, so as to ensure being normally carried out for subsequent reactions.
Step（8）In, add isocyanato alkoxy silanes compound and in step（8）Reaction condition under carry out it is anti- Should, it is modified so as to add isocyanato alkoxy silanes compound into polyester-diol.
Step（9）In, first no longer reduced using hydroxyl value and be used as step（8）The standard that middle reaction terminates, then carries out desolventizing Processing, so as to by step（8）In product separated from solvent, wherein temperature is warming up into 80 ~ 100 DEG C can allow step （8）Solvent boiling in product, consequently facilitating by step（8）Most of solvent and unreacted isocyanate group alkane in product TMOS compound is separated.When flowing out without cut goes out, then by vacuumizing mode by step（8）It is remaining molten in product Agent is extracted out, so as to ensure the purity of obtained silane-modified polyester prepolyer.
By containing Si-O-Si keys in silane-modified polyester prepolyer made from above step, the bond energys of Si-O-Si keys compared with It is high so that adhesive made from the silane-modified polyester prepolyer obtained by the present invention has（1）：Excellent resistant of high or low temperature Can, the aluminum-plastic composite membrane that can prevent from obtaining xanthochromia under high temperature applicationss；（2）Preferable pliability, it is more beneficial for plastic-aluminum combined The scouring depth of film；（3）Preferable moisture-proof, the adhesive for preventing from obtaining make plastic-aluminum combined under the heavier occasion of moisture with water reaction There are bubble or white dot in film finished product；（4）Preferably wetting levelability：So that can on film substrate after adhesive coating Rapid dispersion, so as to lift coating efficiency, so as to get aluminum-plastic composite membrane product quality it is also of a relatively high.What the present invention obtained Silane-modified polyester prepolyer, in addition to it can assign bonding force enough between outer membrane and metal foil layer, more focus on Its long-term resistant of high or low temperature and wet-hot aging performance is improved, to avoid the outer layer during long-term use from being layered, ftracture The problems such as.
Preferably, a kind of preparation method of silane-modified polyester prepolyer described above, first catalyst are Titanium series catalyst or antimony-based catalyst.
This two classes catalyst more meets the needs of modern industrial production, can effectively accelerate reaction speed, greatly contract In the short reaction time, reduce the generation of side reaction.
Preferably, a kind of preparation method of silane-modified polyester prepolyer described above, first catalyst is used Measure as step（1）The 0.1 ~ 0.5% of middle above raw material gross mass, the Titanium series catalyst are butyl titanate, the antimony system catalysis Agent is the composition of antimony acetate or antimony glycol or both.
From above species material as catalyst on the one hand be because its cost it is relatively low, can mass produce, accord with The needs of modern industrial production are closed, on the other hand can effectively accelerate reaction speed, greatly shorten the reaction time, are reduced The generation of side reaction.
Preferably, a kind of preparation method of silane-modified polyester prepolyer described above, the step（6）In, when The hydroxyl value of obtained polyester-diol is 25mgKOH/g ~ 60mgKOH/g, acid number is 0.01mgKOH/g ~ 2mgKOH/g, the equal molecule of number Measure as 2000g/mol ~ 4000g/mol, glass transition temperature be judged as when being -30 DEG C ~ 10 DEG C it is qualified.
When polyester-diol hydroxyl value, acid number, number-average molecular weight, glass transition temperature in the above range when, can ensure to obtain Silane-modified polyester prepolyer made from adhesive there is suitable viscosity, levelability, so as to ensure the quality of adhesive.
Preferably, a kind of preparation method of silane-modified polyester prepolyer described above, the step（8）In it is different The general structure of cyanic acid base alkoxysilane compound containing trialkylsilyl group in molecular structure is as follows:
In formula, R1Be carbon number be 1 ~ 20 alkylidene, R2、R3、R4Represent carbon number be 1 ~ 20 alkoxy or alkyl and R2、R3、R4In at least one be alkoxy, R2、R3、R4It is same to each other or different to each other.
The isocyanato alkoxy silanes compound acquisition difficulty of formula above is relatively low, so as to reduce production cost, Meet the needs of modern industrial production.
Preferably, a kind of preparation method of silane-modified polyester prepolyer described above, the R1For propylidene, institute State R2、R3、R4It is all methoxy or ethoxy.
R1、R2、R3、R4Select that for above group, reactivity can be lifted, easier polyester-diol can be carried out Modification.
Preferably, a kind of preparation method of silane-modified polyester prepolyer described above, the step（8）In it is different The input amount of cyanic acid base alkoxysilane compound containing trialkylsilyl group in molecular structure determines by the hydroxyl value of polyester-diol, wherein isocyanato alkoxy silanes chemical combination The mol ratio of NCO bases and OH bases in polyester-diol is 1 in thing:1~2:1.
Within this range, it can ensure that the OH bases reaction in polyester-diol is complete, so as to lift raw material availability, reduce life Produce cost.
Preferably, a kind of preparation method of silane-modified polyester prepolyer described above, the second described catalyst It is the 0.01% ~ 0.5% of polyester-diol and silane gross mass for organic tin catalyst and dosage.
The organic tin catalyst of input above dosage can effectively facilitate the reaction of isocyanate group and hydroxyl, reduce secondary anti- The generation answered.
Preferably, a kind of preparation method of silane-modified polyester prepolyer described above, the organic tin catalysis Agent dosage is the 0.1% ~ 0.5% of polyester-diol and isocyanato alkoxy silanes compound gross mass, the organic tin catalysis Agent is dibutyl tin laurate.
Dibutyl tin laurate has higher reactivity, can further improve the reaction of isocyanate group and hydroxyl Speed, reduce the generation of side reaction.
Embodiment
The present invention is described in further detail with reference to embodiment, but they are not the limits to the present invention System：
Embodiment 1
A kind of preparation method of silane-modified polyester prepolyer, described preparation method comprise the following steps：
Each raw material is in parts by mass in following step；
（1）Take 41 parts terephthalic acid (TPA), 10.25 parts of M-phthalic acid, 13 parts of ethylene glycol, 21.5 parts of neopentyl glycol, In 15.75 parts of decanedioic acid, the first catalyst input polyester synthesis kettle of above raw material gross mass 0.1%, drying nitrogen is passed through, Slowly heated up；
（2）Work as step（1）After obtained mixture melting, stirring is opened, reaction temperature is controlled at 145 DEG C, controls the rate of output water, Insulation reaction to water yield reaches the 60% of theoretical water yield, then heats to 215 DEG C, reacts 4.5h at this temperature, until anti- Should without distillate, obtain for oligomer；
（3）By step（2）In obtained oligomer carry out low vacuumize process, vacuum rises to -0.05Mpa, Ran Houji in 2h Continuation of insurance hold stop after this vacuum state 1.75h it is low vacuumize, release distillate；
（4）By step（3）The middle reactor stopped after low vacuumize carries out pumping high vacuum processing, in 2h vacuum rise to- 0.095Mpa, now kettle temperature control continue to keep pumping high vacuum state 3.5h at 225 DEG C；
（5）Work as step（4）After reaction terminates, kettle temperature is dropped to less than 100 DEG C under the protection of nitrogen, obtains polyester-diol；
（6）Determination step（5）Acid number, hydroxyl value, number-average molecular weight and the glass transition temperature of obtained polyester-diol simultaneously judge whether It is qualified；
（7）Work as step（6）In polyester-diol when being judged as qualified, nitrogen is passed through into polyester synthesis kettle, adds polyester-diol 0.625 times of ethyl acetate of quality, it is stirred after polyester-diol dissolving；
（8）The second catalyst is added, kettle temperature is heated to 80 DEG C, and isocyanato alkoxy silanes compound is slowly added dropwise, is dripped After adding, continue to stir；
（9）Work as step（8）The hydroxyl value of middle reactant terminates to react when no longer reducing, and then carries out desolventizing processing：First normal pressure liter Temperature controls cut discharge rate, distillate is poured out when flowing out without cut goes out, then carries out vacuumize process, is being ensured to 90 DEG C Vacuum is not improved on the premise of slug slowly to -0.095Mpa, and by temperature control at 100 DEG C, until follow-up without distillate It is continuous to vacuumize 0.5h, lower releasing vacuum state then is advertised in nitrogen, that is, obtains silane-modified polyester prepolyer.
Preferably, first catalyst is Titanium series catalyst or antimony-based catalyst.
Preferably, the Titanium series catalyst is butyl titanate, the antimony-based catalyst is antimony acetate or antimony glycol Or both composition.
Preferably, the step（6）In, when the hydroxyl value of obtained polyester-diol is 38mgKOH/g, acid number is It is qualified that 1mgKOH/g, number-average molecular weight 3000g/mol, glass transition temperature are judged as when being -10 DEG C.
Preferably, the step（8）In isocyanato alkoxy silanes compound general structure it is as follows:
In formula, R1Be carbon number be 1 ~ 20 alkylidene, R2、R3、R4Represent carbon number be 1 ~ 20 alkoxy or alkyl and R2、R3、R4In at least one be alkoxy, R2、R3、R4It is same to each other or different to each other.
Preferably, the R1For propylidene, the R2、R3、R4It is all methoxyl group.
Preferably, the step（8）In isocyanato alkoxy silanes compound input amount by polyester-diol Hydroxyl value determines that the mol ratio of NCO bases and OH bases in polyester-diol is 1.5 wherein in isocyanato alkoxy silanes compound:1.
Preferably, the second described catalyst is organic tin catalyst, its dosage is polyester-diol and the total matter of silane The 0.1% of amount.
Preferably, the organic tin catalyst is dibutyl tin laurate.
Embodiment 2
A kind of preparation method of silane-modified polyester prepolyer, described preparation method comprise the following steps：
Each raw material is in parts by mass in following step；
（1）Take 48 parts terephthalic acid (TPA), 8.5 parts of M-phthalic acid, 15 parts of ethylene glycol, 17 parts of neopentyl glycol, 8 parts Decanedioic acid, the first catalyst of above raw material gross mass 0.3% are put into polyester synthesis kettle, are passed through drying nitrogen, are slowly risen Temperature；
（2）Work as step（1）After obtained mixture melting, stirring is opened, reaction temperature is controlled at 160 DEG C, controls the rate of output water, Insulation reaction to water yield reaches the 50% of theoretical water yield, then heats to 210 DEG C, reacts 3h at this temperature, until reaction Without distillate, obtain for oligomer；
（3）By step（2）In obtained oligomer carry out low vacuumize process, vacuum rises to -0.05Mpa, Ran Houji in 1h Continuation of insurance hold stop after this vacuum state 1.75h it is low vacuumize, release distillate；
（4）By step（3）The middle reactor stopped after low vacuumize carries out pumping high vacuum processing, in 3h vacuum rise to- 0.095Mpa, now kettle temperature control continue to keep pumping high vacuum state 1h at 210 DEG C；
（5）Work as step（4）After reaction terminates, kettle temperature is dropped to less than 100 DEG C under the protection of nitrogen, obtains polyester-diol；
（6）Determination step（5）Acid number, hydroxyl value, number-average molecular weight and the glass transition temperature of obtained polyester-diol simultaneously judge whether It is qualified；
（7）Work as step（6）In polyester-diol when being judged as qualified, nitrogen is passed through into polyester synthesis kettle, adds polyester-diol 0.5 times of ethyl acetate of quality, it is stirred after polyester-diol dissolving；
（8）The second catalyst is added, kettle temperature is heated to 60 DEG C, and isocyanato alkoxy silanes compound is slowly added dropwise, is dripped After adding, continue to stir；
（9）Work as step（8）The hydroxyl value of middle reactant terminates to react when no longer reducing, and then carries out desolventizing processing：First normal pressure liter Temperature controls cut discharge rate, distillate is poured out when flowing out without cut goes out, then carries out vacuumize process, is being ensured to 80 DEG C Vacuum is not improved on the premise of slug slowly to -0.095Mpa, and by temperature control at 100 DEG C, until follow-up without distillate It is continuous to vacuumize 0.5h, lower releasing vacuum state then is advertised in nitrogen, that is, obtains silane-modified polyester prepolyer.
Preferably, first catalyst is Titanium series catalyst or antimony-based catalyst.
Preferably, the Titanium series catalyst is butyl titanate, the antimony-based catalyst is antimony acetate or antimony glycol Or both composition.
Preferably, the step（6）In, when the hydroxyl value of obtained polyester-diol is 32mgKOH/g, acid number is It is qualified that 0.5mgKOH/g, number-average molecular weight 3400g/mol, glass transition temperature are judged as when being 5 DEG C.
Preferably, the step（8）In isocyanato alkoxy silanes compound general structure it is as follows:
In formula, R1Be carbon number be 1 ~ 20 alkylidene, R2、R3、R4Represent carbon number be 1 ~ 20 alkoxy or alkyl and R2、R3、R4In at least one be alkoxy, R2、R3、R4It is same to each other or different to each other.
Preferably, the R1For propylidene, the R2、R3、R4It is all ethyoxyl.
Preferably, the step（8）In isocyanato alkoxy silanes compound input amount by polyester-diol Hydroxyl value determines that the mol ratio of NCO bases and OH bases in polyester-diol is 1.5 wherein in isocyanato alkoxy silanes compound:1.
Preferably, the second described catalyst is organic tin catalyst, its dosage is polyester-diol and the total matter of silane The 0.3% of amount.
Preferably, the organic tin catalyst is dibutyl tin laurate.
Embodiment 3
A kind of preparation method of silane-modified polyester prepolyer, described preparation method comprise the following steps：
Each raw material is in parts by mass in following step；
（1）Take 34 parts terephthalic acid (TPA), 12 parts of M-phthalic acid, 10 parts of ethylene glycol, 18 parts of neopentyl glycol, 7.5 parts Decanedioic acid, above raw material gross mass 0.2% the first catalyst input polyester synthesis kettle in, be passed through drying nitrogen, carry out slow Heating；
（2）Work as step（1）After obtained mixture melting, stirring is opened, reaction temperature is controlled at 130 DEG C, controls the rate of output water, Insulation reaction to water yield reaches the 70% of theoretical water yield, then heats to 210 DEG C, reacts 1h at this temperature, until reaction Without distillate, obtain for oligomer；
（3）By step（2）In obtained oligomer carry out low vacuumize process, vacuum rises to -0.05Mpa, Ran Houji in 1h Continuation of insurance hold stop after this vacuum state 2h it is low vacuumize, release distillate；
（4）By step（3）The middle reactor stopped after low vacuumize carries out pumping high vacuum processing, in 1h vacuum rise to- 0.095Mpa, now kettle temperature control continue to keep pumping high vacuum state 1h at 240 DEG C；
（5）Work as step（4）After reaction terminates, kettle temperature is dropped to less than 100 DEG C under the protection of nitrogen, obtains polyester-diol；
（6）Determination step（5）Acid number, hydroxyl value, number-average molecular weight and the glass transition temperature of obtained polyester-diol simultaneously judge whether It is qualified；
（7）Work as step（6）In polyester-diol when being judged as qualified, nitrogen is passed through into polyester synthesis kettle, adds polyester-diol 0.625 times of ethyl acetate of quality, it is stirred after polyester-diol dissolving；
（8）The second catalyst is added, kettle temperature is heated to 60 DEG C, and isocyanato alkoxy silanes compound is slowly added dropwise, is dripped After adding, continue to stir；
（9）Work as step（8）The hydroxyl value of middle reactant terminates to react when no longer reducing, and then carries out desolventizing processing：First normal pressure liter Temperature controls cut discharge rate, distillate is poured out when flowing out without cut goes out, then carries out vacuumize process, is being ensured to 80 DEG C Vacuum is not improved on the premise of slug slowly to -0.095Mpa, and by temperature control at 100 DEG C, until follow-up without distillate It is continuous to vacuumize 0.5h, lower releasing vacuum state then is advertised in nitrogen, that is, obtains silane-modified polyester prepolyer.
Preferably, first catalyst is Titanium series catalyst or antimony-based catalyst.
Preferably, the Titanium series catalyst is butyl titanate, the antimony-based catalyst is antimony acetate or antimony glycol Or both composition.
Preferably, the step（6）In, when the hydroxyl value of obtained polyester-diol is 28mgKOH/g, acid number is It is qualified that 2mgKOH/g, number-average molecular weight 3800g/mol, glass transition temperature are judged as when being -5 DEG C.
Preferably, the step（8）In isocyanato alkoxy silanes compound general structure it is as follows:
In formula, R1Be carbon number be 1 ~ 20 alkylidene, R2、R3、R4Represent carbon number be 1 ~ 20 alkoxy or alkyl and R2、R3、R4In at least one be alkoxy, R2、R3、R4It is same to each other or different to each other.
Preferably, the R1For propylidene, the R2、R3、R4It is all ethyoxyl.
Preferably, the step（8）In isocyanato alkoxy silanes compound input amount by polyester-diol Hydroxyl value determines that the mol ratio of NCO bases and OH bases in polyester-diol is 1.7 wherein in isocyanato alkoxy silanes compound:1.
Preferably, the second described catalyst is organic tin catalyst, its dosage is polyester-diol and the total matter of silane The 0.3% of amount.
Preferably, the organic tin catalyst is dibutyl tin laurate.
Embodiment 4
A kind of preparation method of silane-modified polyester prepolyer, described preparation method comprise the following steps：
Each raw material is in parts by mass in following step；
（1）Take 41 parts terephthalic acid (TPA), 8.5 parts of M-phthalic acid, 16 parts of ethylene glycol, 17 parts of neopentyl glycol, 16 parts Decanedioic acid, above raw material gross mass 0.01% the first catalyst input polyester synthesis kettle in, be passed through drying nitrogen, delayed Slow heating；
（2）Work as step（1）After obtained mixture melting, stirring is opened, reaction temperature is controlled at 150 DEG C, controls the rate of output water, Insulation reaction to water yield reaches the 50% of theoretical water yield, then heats to 220 DEG C, reacts 1h at this temperature, until reaction Without distillate, obtain for oligomer；
（3）By step（2）In obtained oligomer carry out low vacuumize process, vacuum rises to -0.05Mpa, Ran Houji in 1h Continuation of insurance hold stop after this vacuum state 0.5h it is low vacuumize, release distillate；
（4）By step（3）The middle reactor stopped after low vacuumize carries out pumping high vacuum processing, in 1h vacuum rise to- 0.095Mpa, now kettle temperature control continue to keep pumping high vacuum state 6h at 210 DEG C；
（5）Work as step（4）After reaction terminates, kettle temperature is dropped to less than 100 DEG C under the protection of nitrogen, obtains polyester-diol；
（6）Determination step（5）Acid number, hydroxyl value, number-average molecular weight and the glass transition temperature of obtained polyester-diol simultaneously judge whether It is qualified；
（7）Work as step（6）In polyester-diol when being judged as qualified, nitrogen is passed through into polyester synthesis kettle, adds polyester-diol 0.25 times of ethyl acetate of quality, it is stirred after polyester-diol dissolving；
（8）The second catalyst is added, kettle temperature is heated to 60 DEG C, and isocyanato alkoxy silanes compound is slowly added dropwise, is dripped After adding, continue to stir；
（9）Work as step（8）The hydroxyl value of middle reactant terminates to react when no longer reducing, and then carries out desolventizing processing：First normal pressure liter Temperature controls cut discharge rate, distillate is poured out when flowing out without cut goes out, then carries out vacuumize process, is being ensured to 80 DEG C Vacuum is not improved on the premise of slug slowly to -0.095Mpa, and by temperature control at 100 DEG C, until follow-up without distillate It is continuous to vacuumize 0.5h, lower releasing vacuum state then is advertised in nitrogen, that is, obtains silane-modified polyester prepolyer.
Preferably, first catalyst is Titanium series catalyst or antimony-based catalyst.
Preferably, the Titanium series catalyst is butyl titanate, the antimony-based catalyst is antimony acetate or antimony glycol Or both composition.
Preferably, the step（6）In, when the hydroxyl value of obtained polyester-diol is 60mgKOH/g, acid number is It is qualified that 0.01mgKOH/g, number-average molecular weight 2000g/mol, glass transition temperature are judged as when being -30 DEG C.
Preferably, the step（8）In isocyanato alkoxy silanes compound general structure it is as follows:
In formula, R1Be carbon number be 1 ~ 20 alkylidene, R2、R3、R4Represent carbon number be 1 ~ 20 alkoxy or alkyl and R2、R3、R4In at least one be alkoxy, R2、R3、R4It is same to each other or different to each other.
Preferably, the R1For propylidene, the R2、R3、R4It is all ethyoxyl.
Preferably, the step（8）In isocyanato alkoxy silanes compound input amount by polyester-diol Hydroxyl value determines that the mol ratio of NCO bases and OH bases in polyester-diol is 2 wherein in isocyanato alkoxy silanes compound:1.
Preferably, the second described catalyst is organic tin catalyst, its dosage is polyester-diol and the total matter of silane The 0.01% of amount.
Preferably, the organic tin catalyst is dibutyl tin laurate.
Embodiment 5
A kind of preparation method of silane-modified polyester prepolyer, described preparation method comprise the following steps：
Each raw material is in parts by mass in following step；
（1）Take 34 parts terephthalic acid (TPA), 8.5 parts of M-phthalic acid, 10 parts of ethylene glycol, 26 parts of neopentyl glycol, 24 parts Decanedioic acid, above raw material gross mass 0.01% the first catalyst input polyester synthesis kettle in, be passed through drying nitrogen, delayed Slow heating；
（2）Work as step（1）After obtained mixture melting, stirring is opened, reaction temperature is controlled at 130 DEG C, controls the rate of output water, Insulation reaction to water yield reaches the 50% of theoretical water yield, then heats to 210 DEG C, reacts 8h at this temperature, until reaction Without distillate, obtain for oligomer；
（3）By step（2）In obtained oligomer carry out low vacuumize process, vacuum rises to -0.05Mpa, Ran Houji in 1h Continuation of insurance hold stop after this vacuum state 0.5h it is low vacuumize, release distillate；
（4）By step（3）The middle reactor stopped after low vacuumize carries out pumping high vacuum processing, in 1h vacuum rise to- 0.095Mpa, now kettle temperature control continue to keep pumping high vacuum state 1h at 210 DEG C；
（5）Work as step（4）After reaction terminates, kettle temperature is dropped to less than 100 DEG C under the protection of nitrogen, obtains polyester-diol；
（6）Determination step（5）Acid number, hydroxyl value, number-average molecular weight and the glass transition temperature of obtained polyester-diol simultaneously judge whether It is qualified；
（7）Work as step（6）In polyester-diol when being judged as qualified, nitrogen is passed through into polyester synthesis kettle, adds polyester-diol 1 times of ethyl acetate of quality, it is stirred after polyester-diol dissolving；
（8）The second catalyst is added, kettle temperature is heated to 60 DEG C, and isocyanato alkoxy silanes compound is slowly added dropwise, is dripped After adding, continue to stir；
（9）Work as step（8）The hydroxyl value of middle reactant terminates to react when no longer reducing, and then carries out desolventizing processing：First normal pressure liter Temperature controls cut discharge rate, distillate is poured out when flowing out without cut goes out, then carries out vacuumize process, is being ensured to 80 DEG C Vacuum is not improved on the premise of slug slowly to -0.095Mpa, and by temperature control at 100 DEG C, until follow-up without distillate It is continuous to vacuumize 0.5h, lower releasing vacuum state then is advertised in nitrogen, that is, obtains silane-modified polyester prepolyer.
Preferably, first catalyst is Titanium series catalyst or antimony-based catalyst.
Preferably, the Titanium series catalyst is butyl titanate, the antimony-based catalyst is antimony acetate or antimony glycol Or both composition.
Preferably, the step（6）In, when the hydroxyl value of obtained polyester-diol is 46mgKOH/g, acid number is It is qualified that 0.01mgKOH/g, number-average molecular weight 2600g/mol, glass transition temperature are judged as when being -20 DEG C.
Preferably, the step（8）In isocyanato alkoxy silanes compound general structure it is as follows:
In formula, R1Be carbon number be 1 ~ 20 alkylidene, R2、R3、R4Represent carbon number be 1 ~ 20 alkoxy or alkyl and R2、R3、R4In at least one be alkoxy, R2、R3、R4It is same to each other or different to each other.
Preferably, the R1For propylidene, the R2、R3、R4It is all ethyoxyl.
Preferably, the step（8）In isocyanato alkoxy silanes compound input amount by polyester-diol Hydroxyl value determines that the mol ratio of NCO bases and OH bases in polyester-diol is 1 wherein in isocyanato alkoxy silanes compound:1.
Preferably, the second described catalyst is organic tin catalyst, its dosage is polyester-diol and the total matter of silane The 0.2% of amount.
Preferably, the organic tin catalyst is dibutyl tin laurate.
Embodiment 6
A kind of preparation method of silane-modified polyester prepolyer, described preparation method comprise the following steps：
Each raw material is in parts by mass in following step；
（1）Take 48 parts terephthalic acid (TPA), 12 parts of M-phthalic acid, 16 parts of ethylene glycol, 17 parts of neopentyl glycol, 8 parts Decanedioic acid, the first catalyst of above raw material gross mass 0.01% are put into polyester synthesis kettle, are passed through drying nitrogen, are carried out slow Heating；
（2）Work as step（1）After obtained mixture melting, stirring is opened, reaction temperature is controlled at 160 DEG C, controls the rate of output water, Insulation reaction to water yield reaches the 50% of theoretical water yield, then heats to 210 DEG C, reacts 1h at this temperature, until reaction Without distillate, obtain for oligomer；
（3）By step（2）In obtained oligomer carry out low vacuumize process, vacuum rises to -0.05Mpa, Ran Houji in 3h Continuation of insurance hold stop after this vacuum state 3h it is low vacuumize, release distillate；
（4）By step（3）The middle reactor stopped after low vacuumize carries out pumping high vacuum processing, in 1h vacuum rise to- 0.095Mpa, now kettle temperature control continue to keep pumping high vacuum state 1h at 210 DEG C；
（5）Work as step（4）After reaction terminates, kettle temperature is dropped to less than 100 DEG C under the protection of nitrogen, obtains polyester-diol；
（6）Determination step（5）Acid number, hydroxyl value, number-average molecular weight and the glass transition temperature of obtained polyester-diol simultaneously judge whether It is qualified；
（7）Work as step（6）In polyester-diol when being judged as qualified, nitrogen is passed through into polyester synthesis kettle, adds polyester-diol 0.625 times of ethyl acetate of quality, it is stirred after polyester-diol dissolving；
（8）The second catalyst is added, kettle temperature is heated to 100 DEG C, and isocyanato alkoxy silanes compound is slowly added dropwise, is dripped After adding, continue to stir；
（9）Work as step（8）The hydroxyl value of middle reactant terminates to react when no longer reducing, and then carries out desolventizing processing：First normal pressure is protected Temperature is held at 100 DEG C, cut discharge rate is controlled, distillate is poured out when flowing out without cut goes out, then carries out vacuumize process, Ensure slowly to improve vacuum on the premise of not slug to -0.095Mpa, and by temperature control at 100 DEG C, until without distillate After continue to vacuumize 0.5h, then advertise lower releasing vacuum state in nitrogen, that is, obtain silane-modified polyester prepolyer.
Preferably, first catalyst is Titanium series catalyst or antimony-based catalyst.
Preferably, the Titanium series catalyst is butyl titanate, the antimony-based catalyst is antimony acetate or antimony glycol Or both composition.
Preferably, the step（6）In, when the hydroxyl value of obtained polyester-diol is 42.5mgKOH/g, acid number is It is qualified that 2mgKOH/g, number-average molecular weight 3200g/mol, glass transition temperature are judged as when being -10 DEG C.
Preferably, the step（8）In isocyanato alkoxy silanes compound general structure it is as follows:
In formula, R1Be carbon number be 1 ~ 20 alkylidene, R2、R3、R4Represent carbon number be 1 ~ 20 alkoxy or alkyl and R2、R3、R4In at least one be alkoxy, R2、R3、R4It is same to each other or different to each other.
Preferably, the R1For propylidene, the R2、R3、R4It is all ethyoxyl.
Preferably, the step（8）In isocyanato alkoxy silanes compound input amount by polyester-diol Hydroxyl value determines that the mol ratio of NCO bases and OH bases in polyester-diol is 1 wherein in isocyanato alkoxy silanes compound:1.
Preferably, the second described catalyst is organic tin catalyst, its dosage is polyester-diol and the total matter of silane The 0.3% of amount.
Preferably, the organic tin catalyst is dibutyl tin laurate.
Embodiment 7
A kind of preparation method of silane-modified polyester prepolyer, described preparation method comprise the following steps：
Each raw material is in parts by mass in following step；
（1）Take 34 parts terephthalic acid (TPA), 8.5 parts of M-phthalic acid, 10 parts of ethylene glycol, 17 parts of neopentyl glycol, 7.5 parts Decanedioic acid, above raw material gross mass 0.5% the first catalyst input polyester synthesis kettle in, be passed through drying nitrogen, carry out slow Heating；
（2）Work as step（1）After obtained mixture melting, stirring is opened, reaction temperature is controlled at 130 DEG C, controls the rate of output water, Insulation reaction to water yield reaches the 50% of theoretical water yield, then heats to 210 DEG C, reacts 3h at this temperature, until reaction Without distillate, obtain for oligomer；
（3）By step（2）In obtained oligomer carry out low vacuumize process, vacuum rises to -0.05Mpa, Ran Houji in 1h Continuation of insurance hold stop after this vacuum state 3h it is low vacuumize, release distillate；
（4）By step（3）The middle reactor stopped after low vacuumize carries out pumping high vacuum processing, in 1h vacuum rise to- 0.095Mpa, now kettle temperature control continue to keep pumping high vacuum state 1h at 210 DEG C；
（5）Work as step（4）After reaction terminates, kettle temperature is dropped to less than 100 DEG C under the protection of nitrogen, obtains polyester-diol；
（6）Determination step（5）Acid number, hydroxyl value, number-average molecular weight and the glass transition temperature of obtained polyester-diol simultaneously judge whether It is qualified；
（7）Work as step（6）In polyester-diol when being judged as qualified, nitrogen is passed through into polyester synthesis kettle, adds polyester-diol 0.25 times of ethyl acetate of quality, it is stirred after polyester-diol dissolving；
（8）The second catalyst is added, kettle temperature is heated to 60 DEG C, and isocyanato alkoxy silanes compound is slowly added dropwise, is dripped After adding, continue to stir；
（9）Work as step（8）The hydroxyl value of middle reactant terminates to react when no longer reducing, and then carries out desolventizing processing：First normal pressure liter Temperature controls cut discharge rate, distillate is poured out when flowing out without cut goes out, then carries out vacuumize process, is being ensured to 100 DEG C Vacuum is not improved on the premise of slug slowly to -0.095Mpa, and by temperature control at 100 DEG C, until follow-up without distillate It is continuous to vacuumize 0.5h, lower releasing vacuum state then is advertised in nitrogen, that is, obtains silane-modified polyester prepolyer.
Preferably, first catalyst is Titanium series catalyst or antimony-based catalyst.
Preferably, the Titanium series catalyst is butyl titanate, the antimony-based catalyst is antimony acetate or antimony glycol Or both composition.
Preferably, the step（6）In, when the hydroxyl value of obtained polyester-diol is 47mgKOH/g, acid number is It is qualified that 0.01mgKOH/g, number-average molecular weight 2500g/mol, glass transition temperature are judged as when being -30 DEG C.
Preferably, the step（8）In isocyanato alkoxy silanes compound general structure it is as follows:
In formula, R1Be carbon number be 1 ~ 20 alkylidene, R2、R3、R4Represent carbon number be 1 ~ 20 alkoxy or alkyl and R2、R3、R4In at least one be alkoxy, R2、R3、R4It is same to each other or different to each other.
Preferably, the R1For propylidene, the R2、R3、R4It is all ethyoxyl.
Preferably, the step（8）In isocyanato alkoxy silanes compound input amount by polyester-diol Hydroxyl value determines that the mol ratio of NCO bases and OH bases in polyester-diol is 2 wherein in isocyanato alkoxy silanes compound:1.
Preferably, the second described catalyst is organic tin catalyst, its dosage is polyester-diol and the total matter of silane The 0.1% of amount.
Preferably, the organic tin catalyst is dibutyl tin laurate.
Embodiment 8
A kind of preparation method of silane-modified polyester prepolyer, described preparation method comprise the following steps：
Each raw material is in parts by mass in following step；
（1）Take 34 parts terephthalic acid (TPA), 10.25 parts of M-phthalic acid, 10 parts of ethylene glycol, 17 parts of neopentyl glycol, 8 parts Decanedioic acid, above raw material gross mass 0.3% the first catalyst input polyester synthesis kettle in, be passed through drying nitrogen, carry out slow Heating；
（2）Work as step（1）After obtained mixture melting, stirring is opened, reaction temperature is controlled at 130 DEG C, controls the rate of output water, Insulation reaction to water yield reaches the 50% of theoretical water yield, then heats to 210 DEG C, reacts 4.5h at this temperature, until anti- Should without distillate, obtain for oligomer；
（3）By step（2）In obtained oligomer carry out low vacuumize process, vacuum rises to -0.05Mpa, Ran Houji in 1h Continuation of insurance hold stop after this vacuum state 3h it is low vacuumize, release distillate；
（4）By step（3）The middle reactor stopped after low vacuumize carries out pumping high vacuum processing, in 1h vacuum rise to- 0.095Mpa, now kettle temperature control continue to keep pumping high vacuum state 4h at 210 DEG C；
（5）Work as step（4）After reaction terminates, kettle temperature is dropped to less than 100 DEG C under the protection of nitrogen, obtains polyester-diol；
（6）Determination step（5）Acid number, hydroxyl value, number-average molecular weight and the glass transition temperature of obtained polyester-diol simultaneously judge whether It is qualified；
（7）Work as step（6）In polyester-diol when being judged as qualified, nitrogen is passed through into polyester synthesis kettle, adds polyester-diol 1 times of ethyl acetate of quality, it is stirred after polyester-diol dissolving；
（8）The second catalyst is added, kettle temperature is heated to 60 DEG C, and isocyanato alkoxy silanes compound is slowly added dropwise, is dripped After adding, continue to stir；
（9）Work as step（8）The hydroxyl value of middle reactant terminates to react when no longer reducing, and then carries out desolventizing processing：First normal pressure liter Temperature controls cut discharge rate, distillate is poured out when flowing out without cut goes out, then carries out vacuumize process, is being ensured to 80 DEG C Vacuum is not improved on the premise of slug slowly to -0.095Mpa, and by temperature control at 100 DEG C, until follow-up without distillate It is continuous to vacuumize 0.5h, lower releasing vacuum state then is advertised in nitrogen, that is, obtains silane-modified polyester prepolyer.
Preferably, first catalyst is Titanium series catalyst or antimony-based catalyst.
Preferably, the Titanium series catalyst is butyl titanate, the antimony-based catalyst is antimony acetate or antimony glycol Or both composition.
Preferably, the step（6）In, when the hydroxyl value of obtained polyester-diol is 25mgKOH/g, acid number is It is qualified that 0.01mgKOH/g, number-average molecular weight 4000g/mol, glass transition temperature are judged as when being 10 DEG C.
Preferably, the step（8）In isocyanato alkoxy silanes compound general structure it is as follows:
In formula, R1Be carbon number be 1 ~ 20 alkylidene, R2、R3、R4Represent carbon number be 1 ~ 20 alkoxy or alkyl and R2、R3、R4In at least one be alkoxy, R2、R3、R4It is same to each other or different to each other.
Preferably, the R1For propylidene, the R2、R3、R4It is all methoxyl group.
Preferably, the step（8）In isocyanato alkoxy silanes compound input amount by polyester-diol Hydroxyl value determines that the mol ratio of NCO bases and OH bases in polyester-diol is 2 wherein in isocyanato alkoxy silanes compound:1.
Preferably, the second described catalyst is organic tin catalyst, its dosage is polyester-diol and the total matter of silane The 0.5% of amount.
Preferably, the organic tin catalyst is dibutyl tin laurate.
Embodiment 9
A kind of preparation method of silane-modified polyester prepolyer, described preparation method comprise the following steps：
Each raw material is in parts by mass in following step；
（1）Take 48 parts terephthalic acid (TPA), 12 parts of M-phthalic acid, 16 parts of ethylene glycol, 26 parts of neopentyl glycol, 22 parts Decanedioic acid, the first catalyst of above raw material gross mass 0.5% are put into polyester synthesis kettle, are passed through drying nitrogen, are slowly risen Temperature；
（2）Work as step（1）After obtained mixture melting, stirring is opened, reaction temperature is controlled at 160 DEG C, controls the rate of output water, Insulation reaction to water yield reaches the 70% of theoretical water yield, then heats to 220 DEG C, reacts 8h at this temperature, until reaction Without distillate, obtain for oligomer；
（3）By step（2）In obtained oligomer carry out low vacuumize process, vacuum rises to -0.05Mpa, Ran Houji in 3h Continuation of insurance hold stop after this vacuum state 3h it is low vacuumize, release distillate；
（4）By step（3）The middle reactor stopped after low vacuumize carries out pumping high vacuum processing, in 3h vacuum rise to- 0.095Mpa, now kettle temperature control continue to keep pumping high vacuum state 6h at 240 DEG C；
（5）Work as step（4）After reaction terminates, kettle temperature is dropped to less than 100 DEG C under the protection of nitrogen, obtains polyester-diol；
（6）Determination step（5）Acid number, hydroxyl value, number-average molecular weight and the glass transition temperature of obtained polyester-diol simultaneously judge whether It is qualified；
（7）Work as step（6）In polyester-diol when being judged as qualified, nitrogen is passed through into polyester synthesis kettle, adds polyester-diol 1 times of ethyl acetate of quality, it is stirred after polyester-diol dissolving；
（8）The second catalyst is added, kettle temperature is heated to 80 DEG C, and isocyanato alkoxy silanes compound is slowly added dropwise, is dripped After adding, continue to stir；
（9）Work as step（8）The hydroxyl value of middle reactant terminates to react when no longer reducing, and then carries out desolventizing processing：First normal pressure liter Temperature controls cut discharge rate, distillate is poured out when flowing out without cut goes out, then carries out vacuumize process, is being ensured to 100 DEG C Vacuum is not improved on the premise of slug slowly to -0.095Mpa, and by temperature control at 100 DEG C, until follow-up without distillate It is continuous to vacuumize 0.5h, lower releasing vacuum state then is advertised in nitrogen, that is, obtains silane-modified polyester prepolyer.
Preferably, first catalyst is Titanium series catalyst or antimony-based catalyst.
Preferably, the Titanium series catalyst is butyl titanate, the antimony-based catalyst is antimony acetate or antimony glycol Or both composition.
Preferably, the step（6）In, when the hydroxyl value of obtained polyester-diol is 37mgKOH/g, acid number is It is qualified that 0.01mgKOH/g, number-average molecular weight 3000g/mol, glass transition temperature are judged as when being -10 DEG C.
Preferably, the step（8）In isocyanato alkoxy silanes compound general structure it is as follows:
In formula, R1Be carbon number be 1 ~ 20 alkylidene, R2、R3、R4Represent carbon number be 1 ~ 20 alkoxy or alkyl and R2、R3、R4In at least one be alkoxy, R2、R3、R4It is same to each other or different to each other.
Preferably, the R1For propylidene, the R2、R3、R4It is all methoxyl group.
Preferably, the step（8）In isocyanato alkoxy silanes compound input amount by polyester-diol Hydroxyl value determines that the mol ratio of NCO bases and OH bases in polyester-diol is 2 wherein in isocyanato alkoxy silanes compound:1.
Preferably, the second described catalyst is organic tin catalyst, its dosage is polyester-diol and the total matter of silane The 0.5% of amount.
Preferably, the organic tin catalyst is dibutyl tin laurate.
In a word, presently preferred embodiments of the present invention is the foregoing is only, all scopes according to the present patent application patent are made equal Deng change and modification, it should all belong to covering scope of the invention.

Claims (9)

1. a kind of preparation method of silane-modified polyester prepolyer, it is characterised in that described preparation method comprises the following steps：
Each raw material is in parts by mass in following step；
（1）Take 34 ~ 48 parts terephthalic acid (TPA), 8.5 ~ 12 parts of M-phthalic acid, 10 ~ 16 parts of ethylene glycol, 17 ~ 26 parts new Pentanediol, 7.5 ~ 24 parts of decanedioic acid, the first catalyst of above raw material gross mass 0.01% ~ 0.5% are put into polyester synthesis kettle, Drying nitrogen is passed through, is slowly heated up；
（2）Work as step（1）After obtained mixture melting, stirring is opened, reaction temperature is controlled at 130 DEG C ~ 160 DEG C, controlled out Water speed rate, insulation reaction to water yield reach the 50% ~ 70% of theoretical water yield, 210 DEG C ~ 220 DEG C are then heated to, in this temperature Lower reaction 1h ~ 8h, until reaction without distillate, obtain for oligomer；
（3）By step（2）In obtained oligomer carry out low vacuumize process, vacuum rises to -0.05Mpa in 1 ~ 3h, then Continue to keep to stop after this vacuum state 0.5h ~ 3h it is low vacuumize, release distillate；
（4）By step（3）The middle reactor stopped after low vacuumize carries out pumping high vacuum processing, in 1h ~ 3h vacuum rise to- 0.095Mpa, now kettle temperature control continue to keep pumping high vacuum state 1h ~ 6h at 210 DEG C ~ 240 DEG C；
（5）Work as step（4）After reaction terminates, kettle temperature is dropped to less than 100 DEG C under the protection of nitrogen, obtains polyester-diol；
（6）Determination step（5）Acid number, hydroxyl value, number-average molecular weight and the glass transition temperature of obtained polyester-diol simultaneously judge whether It is qualified；
（7）Work as step（6）In polyester-diol when being judged as qualified, nitrogen is passed through into polyester synthesis kettle, adds polyester-diol 0.25 ~ 1 times of ethyl acetate of quality, it is stirred after polyester-diol dissolving；
（8）The second catalyst is added, kettle temperature is heated to 60 DEG C ~ 100 DEG C, and isocyanato alkoxy silanes chemical combination is slowly added dropwise Thing, after dripping, continue to stir；
（9）Work as step（8）The hydroxyl value of middle reactant terminates to react when no longer reducing, and then carries out desolventizing processing：First normal pressure liter Temperature controls cut discharge rate, distillate is poured out when flowing out without cut goes out, then carries out vacuumize process to 80 ~ 100 DEG C, Ensure slowly to improve vacuum on the premise of not slug to -0.095Mpa, and by temperature control at 100 DEG C, until without distillate After continue to vacuumize 0.5h, then advertise lower releasing vacuum state in nitrogen, that is, obtain silane-modified polyester prepolyer.
A kind of 2. preparation method of silane-modified polyester prepolyer according to claim 1, it is characterised in that：Described first Catalyst is Titanium series catalyst or antimony-based catalyst.
A kind of 3. preparation method of silane-modified polyester prepolyer according to claim 2, it is characterised in that：Described first Catalyst amount is step（1）The 0.1 ~ 0.5% of middle above raw material gross mass, the Titanium series catalyst is butyl titanate, described Antimony-based catalyst is the composition of antimony acetate or antimony glycol or both.
A kind of 4. preparation method of silane-modified polyester prepolyer according to claim 1, it is characterised in that：The step （6）In, when the hydroxyl value of obtained polyester-diol is 25mgKOH/g ~ 60mgKOH/g, acid number be 0.01mgKOH/g ~ 2mgKOH/g, It is qualified to be judged as when number-average molecular weight is 2000g/mol ~ 4000g/mol, glass transition temperature is -30 DEG C ~ 10 DEG C.
A kind of 5. preparation method of silane-modified polyester prepolyer according to claim 1, it is characterised in that：The step （8）In isocyanato alkoxy silanes compound general structure it is as follows:
C:\Users\fanghj\AppData\Local\Temp\WeChat Files\bd517f13911a3e2ca6f4fbd4dbf628c.png
In formula, R1Be carbon number be 1 ~ 20 alkylidene, R2、R3、R4Represent carbon number be 1 ~ 20 alkoxy or alkyl and R2、R3、R4In at least one be alkoxy, R2、R3、R4It is same to each other or different to each other.
A kind of 6. preparation method of silane-modified polyester prepolyer according to claim 5, it is characterised in that：The R1For Propylidene, the R2、R3、R4It is all methoxy or ethoxy.
A kind of 7. preparation method of silane-modified polyester prepolyer according to claim 5, it is characterised in that：The step （8）In the input amount of isocyanato alkoxy silanes compound determined by the hydroxyl value of polyester-diol, wherein isocyanate group alcoxyl The mol ratio of NCO bases and OH bases in polyester-diol is 1 in base silane compound:1~2:1.
A kind of 8. preparation method of silane-modified polyester prepolyer according to claim 1, it is characterised in that：Described Two catalyst are organic tin catalyst and dosage is the 0.01% ~ 0.5% of polyester-diol and silane gross mass.
A kind of 9. preparation method of silane-modified polyester prepolyer according to claim 1, it is characterised in that：It is described organic Tin catalyst dosage is the 0.1% ~ 0.5% of polyester-diol and isocyanato alkoxy silanes compound gross mass, described organic Tin catalyst is dibutyl tin laurate.
CN201710770055.4A 2017-08-31 2017-08-31 A kind of preparation method of silane-modified polyester prepolyer Pending CN107383353A (en)

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CN111170440A (en) * 2020-01-14 2020-05-19 南京大学盐城环保技术与工程研究院 High-salinity wastewater advanced oxidation method, industrial waste salt recycling method and equipment
CN111471302A (en) * 2020-04-24 2020-07-31 江阴市明达胶辊有限公司 Double-liquid type liquid rubber for liquid silicone rubber roller and preparation method thereof
CN115584233A (en) * 2022-02-22 2023-01-10 浙江星华反光材料有限公司 Preparation process and application of high-toughness polyurethane adhesive
CN115612083A (en) * 2022-02-22 2023-01-17 浙江星华反光材料有限公司 Silane modified polyester prepolymer and preparation method thereof
CN115678478A (en) * 2022-02-22 2023-02-03 浙江星华反光材料有限公司 Elastic single-component moisture-curing adhesive and application thereof

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CN106701003A (en) * 2016-11-18 2017-05-24 北京高盟新材料股份有限公司 Composite adhesive for aluminum plastic flexible package of liquid food and preparation method of composite adhesive

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CN102458386A (en) * 2009-06-23 2012-05-16 拜耳医药股份有限公司 Pharmaceutical composition for emergency contraception
CN106701003A (en) * 2016-11-18 2017-05-24 北京高盟新材料股份有限公司 Composite adhesive for aluminum plastic flexible package of liquid food and preparation method of composite adhesive

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111170440A (en) * 2020-01-14 2020-05-19 南京大学盐城环保技术与工程研究院 High-salinity wastewater advanced oxidation method, industrial waste salt recycling method and equipment
CN111471302A (en) * 2020-04-24 2020-07-31 江阴市明达胶辊有限公司 Double-liquid type liquid rubber for liquid silicone rubber roller and preparation method thereof
CN115584233A (en) * 2022-02-22 2023-01-10 浙江星华反光材料有限公司 Preparation process and application of high-toughness polyurethane adhesive
CN115612083A (en) * 2022-02-22 2023-01-17 浙江星华反光材料有限公司 Silane modified polyester prepolymer and preparation method thereof
CN115678478A (en) * 2022-02-22 2023-02-03 浙江星华反光材料有限公司 Elastic single-component moisture-curing adhesive and application thereof
CN115584233B (en) * 2022-02-22 2024-02-27 浙江星华反光材料有限公司 Preparation process and application of high-toughness polyurethane adhesive
CN115678478B (en) * 2022-02-22 2024-04-30 浙江星华反光材料有限公司 Elastic single-component moisture-curing adhesive and application thereof

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Application publication date: 20171124