CN105504238A - Preparation method of monobutyl ether alcohol terminated polyester plasticizer - Google Patents
Preparation method of monobutyl ether alcohol terminated polyester plasticizer Download PDFInfo
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- CN105504238A CN105504238A CN201610016534.2A CN201610016534A CN105504238A CN 105504238 A CN105504238 A CN 105504238A CN 201610016534 A CN201610016534 A CN 201610016534A CN 105504238 A CN105504238 A CN 105504238A
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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
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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
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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
- C08G63/46—Polyesters chemically modified by esterification
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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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- Polymers & Plastics (AREA)
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- General Chemical & Material Sciences (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a preparation method of a monobutyl ether alcohol terminated polyester plasticizer in the field of polymer material additives. The preparation method mainly comprises the following steps that under the action of a water-carrying agent and a catalyst, an excessive amount of dicarboxylic acid and dihydric alcohol are subjected to condensation polymerization, and a terminal carboxyl group polyester is obtained; monobutyl ether alcohol is added into the reaction product, and esterification reaction termination is conducted; vacuum distillation is conducted, the water-carrying agent and an excessive amount of unreacted monobutyl ether alcohol are steamed out, and the monobutyl ether alcohol terminated polyester is obtained. The monobutyl ether alcohol terminated polyester plasticizer obtained through the preparation method has the advantages that low volatility of the polyester plasticizer is achieved, heat resistance is good, the low temperature flexibility is good, the durability and oil extraction resistance are achieved, the compatibility and flexibility of the monobutyl ether alcohol are achieved, the adjustability of viscosity is achieved, and the nontoxic and environment-friendly type plasticizer is suitable for polymer materials such as plastics, rubber and adhesives.
Description
Technical field
The present invention relates to the preparation method of a kind of polyester plasticizer in polymer materials additive agent field, particularly a kind of preparation method of polyester plasticizer of monobutyl ether alcohol end-blocking.
Background technology
Softening agent is a kind of important additives joined in the materials such as plastics, rubber, tackiness agent, coating and ink, is intended to the soffening increasing polymer materials, improves its processing characteristics, reduce its second-order transition temperature, improve its snappiness and ductility etc.Softening agent product in the market mainly based on phthalate, as dibutyl phthalate, dihexyl phthalate, dioctyl phthalate (DOP), diisononyl phthalate etc.This kind of softening agent due to cost low, good combination property, is thus widely applied.But because this kind of phthalic ester plasticizer is low-molecular weight compound, volatile, easily move, and there is certain toxicity mostly, particularly there is potential carinogenicity.Forbid the use of this kind of softening agent in toy for children, medical treatment product and food product pack etc. in the world.Therefore, the asepsis environment-protecting softening agent of high, the resistance to migration of exploitation plasticizing efficiency, resistant to extraction becomes inexorable trend.
Be developed a large amount of non-phthalate monomeric ester class softening agent, as Octyl adipate (DOA), dioctyl sebacate (DOS) and azelate class, this kind of softening agent has good resistance to low temperature, the winter hardiness of goods can be improved significantly, but poor with the consistency of polyvinyl chloride (PVC), can only use as secondary softening agent." fine chemistry industry " periodical calendar year 2001 18 is interim, and ' in the synthesis of Non-toxic Plasticizer Tributyl Acetylcitrate ' one literary composition, introduction thionamic acid two-step approach catalyzes and synthesizes tributyl acetylcitrate (ATBC), ATBC has the advantages such as consistency is good, plasticization effect is strong as primary plasticizer, and is non-toxic product by U.S. food Drug Administration (FDA) certification.But ATBC is as a kind of small molecules softening agent, there is resistance to migration difference equally, easily by the feature of extracting, be mated the plastics poor durability of use.China Patent Publication No. CN1618847A, publication date on May 25th, 2005, invention and created name is a kind of diester softening agent and manufacture method thereof, this application case discloses and obtains softening agent by hexanodioic acid and ether alcohol through esterification and have that consistency is good, volatilization loss is little, be not easily drawn out of the feature washed away, and has positive effect for the low-temperature flexibility improving polymer materials.But this kind of softening agent still belongs to low molecular weight monomers ester class, and poor durability, easily moves, and high temperature is volatile.
Relative monomer ester plasticizer, polyester plasticizer is a kind of high molecular weight plasticizer, has that volatility is little, transport property is little, oil resistant and resistance to suds are extracted out, are the good thermotolerance of performance and weather resistance softening agent.Polyester plasticizer uses relatively more extensive, a development class non-toxic, environmental friendly softening agent faster at present.Chinese patent CN1411479A, publication date is on April 16th, 2003, invention and created name is by the polyester of isomeric nonanols end-blocking, its preparation method and the purposes as softening agent thereof, diprotic acid, dibasic alcohol and nonyl alcohol is adopted single stage method to get off to prepare the polyester of nonyl alcohol end-blocking in metal catalyst effect in literary composition.Prepared by this invention
Polyester there is higher flexibility and stability, but nonyl alcohol structure and plastic molecules consistency not good, and molecular weight of polyesters prepared by this preparation method is not high, and plasticization effect is not good.
Summary of the invention
Object of the present invention will overcome the deficiencies in the prior art exactly, provides a kind of preparation method of polyester plasticizer of monobutyl ether alcohol end-blocking.The polyester plasticizer viscosity prepared is adjustable, and having the advantages such as consistency is good, resistant to extraction, volatility are little, good heat resistance, is a kind of nontoxic, environment-friendlyplasticizer plasticizer that can be suitable for the polymer materialss such as plastics, rubber, tackiness agent.
Realizing technical scheme of the present invention is that excessive diprotic acid and dibasic alcohol are first under catalyzer and water entrainer exist, terminal carboxyl polyester is obtained through polycondensation, then esterification end-blocking is carried out with monobutyl ether alcohol, finally extract water entrainer and excessive monobutyl ether alcohol out, namely obtain a kind of polyester plasticizer of monobutyl ether alcohol end-blocking.
A preparation method for the polyester plasticizer of monobutyl ether alcohol end-blocking, its preparation method comprises the following steps:
(1) di-carboxylic acid and dibasic alcohol are added in esterifying kettle by the mol ratio of 1.1 ~ 1.4:1, add water entrainer and catalyzer respectively by 1 ~ 10%, 0.05 ~ 0.5% of di-carboxylic acid and dibasic alcohol total mass simultaneously, under temperature of reaction 140 DEG C ~ 220 DEG C and agitation condition, carry out the polycondensation of 6 ~ 9 hours, obtain terminal carboxyl polyester;
(2) upwards walk in the product of gained and add monobutyl ether alcohol by the mol ratio of dibasic alcohol and monobutyl ether alcohol 1:0.3 ~ 1, under 160 DEG C ~ 220 DEG C and agitation condition, proceed the esterification of 4 ~ 8 hours, end-blocking is carried out to terminal carboxyl polyester;
(3) when the acid number of the product of step (2) gained is less than 1mgKOH/g, first below 180 DEG C and vacuum tightness 2000Pa, extract water entrainer out, then below 210 DEG C and vacuum tightness 500Pa, extract excessive unreacted monobutyl ether alcohol out, filter, namely the polyester of monobutyl ether alcohol end-blocking is obtained
Described di-carboxylic acid is the one in succinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, sebacic acid,
Described dibasic alcohol is the one in glycol ether, triglycol, Tetraglycol 99, Macrogol 200, Liquid Macrogol and poly(oxyethylene glycol) 400,
Described monobutyl ether alcohol is the one in ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, propylene glycol monobutyl ether, Dipropylene glycol mono-n-butyl Ether, Tri(propylene glycol)butyl ether,mixture of isomers,
Described catalyzer is the one in tin protochloride, stannous oxalate, stannous octoate, Mono-n-butyltin, Dibutyltin oxide,
Described water entrainer is the one in sherwood oil, toluene and dimethylbenzene.
Owing to adopting above technical scheme, the polyester plasticizer obtained by preparation method of the present invention has the following advantages:
(1) adopt the two-step reaction mode of esterification after first polycondensation, can control the structure of synthesized polyester well, the polyester after monobutyl ether alcohol end-blocking has satisfactory stability, overcomes the shortcoming of polyester plasticizer poor stability.
(2) polyester has more advantages as softening agent, as resistant to extraction, resistance to migration, low-temperature flexibility due to the characteristic of high molecular
Property is good, high temperature resistant etc., but also there is the shortcoming of the low and poor compatibility of plasticizing efficiency; The small molecules softener that monobutyl ether alcohol is inherently good and softening agent, have good consistency.Utilize the polyester of the involutory one-tenth of monobutyl ether alcohol to carry out end-blocking, effectively both advantages got up, the polyester synthesizing the monobutyl ether alcohol end-blocking obtained both had remained the advantage of polyester plasticizer, obtained good improvement again in plasticizing efficiency and consistency.
(3) structure and the viscosity of synthesizing the polyester plasticizer of the monobutyl ether alcohol end-blocking obtained have adjustability, by selecting the diprotic acid of different structure, dibasic alcohol and monobutyl ether alcohol and controlling the molar feed ratio of diprotic acid and dibasic alcohol, the polyester of different structure and viscosity can be obtained, and then the polyester plasticizer of monobutyl ether alcohol end-blocking is obtained with monobutyl ether alcohol end-blocking, thus improve its scope of application, the plasticising demand of the polymer materialss such as plastics, rubber, tackiness agent can be met.
Embodiment
Embodiment 1 takes 236.2g succinic acid, 231.1g triglycol, 2.34g stannous octoate and 37.4g toluene respectively and joins in the esterifying kettle of 1L, logical N
2protection, stir and heat up, timing is started when toluene band water starts backflow, by the temperature of recycling effluent rise to 220 DEG C gradually, reaction 8h, to no longer water outlet, then 222.2g triethylene glycol monobutyl ether is added, 220 DEG C are risen to gradually by temperature during recycling effluent, continue reaction 6h, sampling detecting acid number, when to record acid number be 0.8mgKOH/g, be cooled to 180 DEG C, first toluene is extracted out at below vacuum tightness 2000Pa, then 210 DEG C are warming up to, excessive responseless triethylene glycol monobutyl ether is gone out in below vacuum tightness 500Pa underpressure distillation, finally cool, filter, obtain light amber liquid, be poly-(succinic acid triglycol) ester plasticizer that triethylene glycol monobutyl is ether capped, at 25 DEG C, recording viscosity is 450cps, the key technical indexes of final gained polyester is as shown in table 1.
Embodiment 2 takes 250g hexanodioic acid, 129.7g glycol ether, 0.38g Dibutyltin oxide and 4g sherwood oil respectively and joins in the esterifying kettle of 1L, logical N
2protection, stir and heat up, timing is started when sherwood oil band water starts backflow, by the temperature of recycling effluent rise to 220 DEG C gradually, reaction 6h, to no longer water outlet, then 198.2g diethylene glycol monobutyl ether is added, 220 DEG C are risen to gradually by temperature during recycling effluent, continue reaction 7h, sampling detecting acid number, when to record acid number be 0.9mgKOH/g, be cooled to 180 DEG C, first sherwood oil is extracted out at below vacuum tightness 2000Pa, then 210 DEG C are warming up to, excessive responseless diethylene glycol monobutyl ether is gone out in below vacuum tightness 500Pa underpressure distillation, finally cool, filter, obtain light amber liquid, be poly-(hexanodioic acid glycol ether) ester plasticizer of diethylene glycol monobutyl ether end-blocking, at 25 DEG C, recording viscosity is 210cps, the key technical indexes of final gained polyester is as shown in table 1.
Embodiment 3 takes 260g pentanedioic acid, 347.5g Tetraglycol 99,0.3g Mono-n-butyltin and 9.1g sherwood oil respectively and joins in the esterifying kettle of 1L, logical N
2protection, stirs and heats up, and starts timing when sherwood oil band water starts backflow; by the temperature of recycling effluent rise to 220 DEG C gradually, reaction 9h, to no longer water outlet; then add 102.1g Dipropylene glycol mono-n-butyl Ether, rise to 220 DEG C gradually by temperature during recycling effluent, continue reaction 5h; sampling detecting acid number; when to record acid number be 0.7mgKOH/g, be cooled to 180 DEG C, first extract sherwood oil out at below vacuum tightness 2000Pa; then be warming up to 210 DEG C, vacuum tightness 500Pa with
Lower underpressure distillation goes out excessive responseless Dipropylene glycol mono-n-butyl Ether, finally cool, filter, obtain light amber liquid, be poly-(pentanedioic acid Tetraglycol 99) ester plasticizer of Dipropylene glycol mono-n-butyl Ether end-blocking, at 25 DEG C, recording viscosity is 6840cps, and the key technical indexes of final gained polyester is as shown in table 1.
Embodiment 4 takes 230g pimelic acid, 239.3g Macrogol 200,0.94g tin protochloride and 46.9g dimethylbenzene respectively and joins in the esterifying kettle of 1L, logical N
2protection, stir and heat up, timing is started when dimethylbenzene band water starts backflow, by the temperature of recycling effluent rise to 220 DEG C gradually, reaction 8h, to no longer water outlet, then 178.3g Tri(propylene glycol)butyl ether,mixture of isomers is added, 220 DEG C are risen to gradually by temperature during recycling effluent, continue reaction 5h, sampling detecting acid number, when to record acid number be 0.8mgKOH/g, be cooled to 180 DEG C, first to extract dimethylbenzene out under vacuum tightness 2000Pa, then 210 DEG C are warming up to, excessive responseless Tri(propylene glycol)butyl ether,mixture of isomers is gone out in below vacuum tightness 500Pa underpressure distillation, finally cool, filter, obtain light amber liquid, be poly-(pimelic acid polyoxyethylene glycol) ester plasticizer (Macrogol 200) of Tri(propylene glycol)butyl ether,mixture of isomers end-blocking, at 25 DEG C, recording viscosity is 2370cps, the key technical indexes of final gained polyester is as shown in table 1.
Embodiment 5 takes 240g sebacic acid, 309.6g Liquid Macrogol, 0.82g stannous oxalate and 33g toluene respectively and joins in the esterifying kettle of 1L, logical N
2protection, stir and heat up, timing is started when toluene band water starts backflow, by the temperature of recycling effluent rise to 220 DEG C gradually, reaction 9h, to no longer water outlet, then 81.9g propylene glycol monobutyl ether is added, 220 DEG C are risen to gradually by temperature during recycling effluent, continue reaction 4h, sampling detecting acid number, when to record acid number be 0.9mgKOH/g, be cooled to 180 DEG C, first toluene is extracted out at below vacuum tightness 2000Pa, then 210 DEG C are warming up to, excessive responseless propylene glycol monobutyl ether is gone out in below vacuum tightness 500Pa underpressure distillation, finally cool, filter, obtain light amber liquid, be poly-(sebacic acid polyoxyethylene glycol) ester plasticizer (Liquid Macrogol) that propyleneglycol monobutyl is ether capped, at 25 DEG C, recording viscosity is 4960cps, the key technical indexes of final gained polyester is as shown in table 1.
Embodiment 6 takes 220g suberic acid, 459.3g poly(oxyethylene glycol) 400,1.36g Mono-n-butyltin and 54.3g dimethylbenzene respectively and joins in the esterifying kettle of 1L, logical N
2protection, stir and heat up, timing is started when dimethylbenzene band water starts backflow, by the temperature of recycling effluent rise to 220 DEG C gradually, reaction 9h, to no longer water outlet, then 81.9g ethylene glycol monobutyl ether is added, 220 DEG C are risen to gradually by temperature during recycling effluent, continue reaction 5h, sampling detecting acid number, when to record acid number be 0.75mgKOH/g, be cooled to 180 DEG C, first dimethylbenzene is extracted out at below vacuum tightness 2000Pa, then 210 DEG C are warming up to, excessive responseless ethylene glycol monobutyl ether is gone out in below vacuum tightness 500Pa underpressure distillation, finally cool, filter, obtain light amber liquid, be poly-(suberic acid polyoxyethylene glycol) ester plasticizer (poly(oxyethylene glycol) 400) of ethylene glycol monobutyl ether end-blocking, at 25 DEG C, recording viscosity is 6740cps, the key technical indexes of final gained polyester is as shown in table 1.
Embodiment 7 takes 240g hexanodioic acid, 139.4g glycol ether, 0.38g Mono-n-butyltin and 5.7g sherwood oil respectively and joins in the esterifying kettle of 1L, logical N
2protection, stir and heat up, timing is started when sherwood oil band water starts backflow, by the temperature of recycling effluent rise to 220 DEG C gradually, reaction 6h, to no longer water outlet, then 127.9g diethylene glycol monobutyl ether is added, 220 DEG C are risen to gradually by temperature during recycling effluent, continue reaction 7h, sampling detecting acid number, when to record acid number be 0.65mgKOH/g, be cooled to 180 DEG C, first sherwood oil is extracted out under vacuum tightness 2000Pa, then 210 DEG C are warming up to, under vacuum tightness 500Pa, underpressure distillation goes out excessive responseless diethylene glycol monobutyl ether, finally cool, filter, obtain light amber liquid, be poly-(hexanodioic acid glycol ether) ester plasticizer of diethylene glycol monobutyl ether end-blocking, at 25 DEG C, recording viscosity is 1240cps, the key technical indexes of final gained polyester is as shown in table 1.
Embodiment 8 takes 250g pimelic acid, 173.6g triglycol, 1.27g stannous oxalate and 38.1g toluene respectively and joins in the esterifying kettle of 1L, logical N
2protection, stir and heat up, timing is started when toluene band water starts backflow, by the temperature of recycling effluent rise to 220 DEG C gradually, reaction 9h, to no longer water outlet, then 122.3g propylene glycol monobutyl ether is added, 220 DEG C are risen to gradually by temperature during recycling effluent, continue reaction 8h, sampling detecting acid number, when to record acid number be 0.95mgKOH/g, be cooled to 180 DEG C, first toluene is extracted out at below vacuum tightness 2000Pa, then 210 DEG C are warming up to, excessive responseless propylene glycol monobutyl ether is gone out in below vacuum tightness 500Pa underpressure distillation, finally cool, filter, obtain light amber liquid, be poly-(pimelic acid triglycol) ester plasticizer that propyleneglycol monobutyl is ether capped, at 25 DEG C, recording viscosity is 520cps, the key technical indexes of gained polyester is as shown in table 1.
As shown in Table 1, by controlling the molar ratio of diprotic acid and dibasic alcohol, and carry out end-blocking with monobutyl ether alcohol, the viscosity of the polyester of the monobutyl ether alcohol end-blocking obtained can regulate, and the acid number of the polyester obtained is lower, illustrates that end-blocking is more complete.
Table 2 is that poly-(hexanodioic acid glycol ether) ester plasticizer of diethylene glycol monobutyl ether end-blocking prepared in embodiment 7 contrasts for the middle part the performance test results of polyvinyl chloride (PVC) with dioctyl phthalate (DOP) (DOP).The polyester that the present invention obtains as can be seen from the table has good plasticization effect to PVC, and temperature limit of brittleness, volume resistance and shore hardness all comparatively small molecules plasticizer DOP will be got well.
Poly-(hexanodioic acid glycol ether) ester plasticizer addition of the diethylene glycol monobutyl ether end-blocking of table 3 synthesized by softening agent TP95 and embodiment 2 is 15%(weight part) time effect comparison to paracril (NBR).As can be seen from Table 3 the present invention synthesis polyester and TP95 small molecules softening agent, all better with the consistency of NBR, normality performance is substantially close, but thermotolerance and oil-proofness aspect are obviously better than TP95, mainly because although the molecular weight of polyesters of the 2-in-1 one-tenth of embodiment is relatively low, Comparatively speaking much higher with small molecules TP95, be difficult to volatilization, resistance to oil extraction is good, thus in thermotolerance and resistance to oil extraction, is better than small molecules softening agent TP95.
Poly-(pentanedioic acid Tetraglycol 99) ester plasticizer of the Dipropylene glycol mono-n-butyl Ether end-blocking that table 4 synthesizes for embodiment 3 is used for the effect (100 parts of solid contents are add 26 parts of polyester in the PVAc emulsion of 55%) of PVAc emulsion, the polyester of high molecular and PVAc have good consistency as can be seen from the table, and volatility is little, resistant to extraction is good.
In a word, the present invention is by controlling the mol ratio of diprotic acid and dibasic alcohol, and carry out end-blocking with monobutyl ether alcohol, the polyester of different viscosity can be obtained, meet the different demands of plastics, rubber and tackiness agent, the advantage such as have that consistency is good, plasticizing efficiency is high, volatility is little, good heat resistance, resistance to oil extraction, low temperature flexibility are good is a kind of nontoxic, environment-friendlyplasticizer plasticizer.
Table 1
Table 2
Table 3
Table 4
Claims (6)
1. a preparation method for the polyester plasticizer of monobutyl ether alcohol end-blocking, is characterized in that, it be by di-carboxylic acid, dibasic alcohol and monobutyl ether alcohol under water entrainer and catalysts conditions, form through polycondensation and esterification, specifically comprise the following steps:
(1) di-carboxylic acid and dibasic alcohol are added in esterifying kettle by the mol ratio of 1.1 ~ 1.4:1, add water entrainer and catalyzer respectively by 1 ~ 10%, 0.05 ~ 0.5% of di-carboxylic acid and dibasic alcohol total mass simultaneously, under temperature of reaction 140 DEG C ~ 220 DEG C and agitation condition, carry out the polycondensation of 6 ~ 9 hours, obtain terminal carboxyl polyester;
(2) upwards walk in the product of gained and add monobutyl ether alcohol by the mol ratio of dibasic alcohol and monobutyl ether alcohol 1:0.3 ~ 1, under 160 DEG C ~ 220 DEG C and agitation condition, proceed the esterification of 4 ~ 8 hours, end-blocking is carried out to terminal carboxyl polyester;
(3) when the acid number of the product of step (2) gained is less than 1mgKOH/g, first below 180 DEG C and vacuum tightness 2000Pa, extract water entrainer out, below 210 DEG C and vacuum tightness 500Pa, extract excessive unreacted monobutyl ether alcohol again out, filter, namely obtain the polyester of monobutyl ether alcohol end-blocking.
2. the preparation method of the polyester plasticizer of a kind of monobutyl ether alcohol end-blocking according to claim 1, is characterized in that: described di-carboxylic acid is the one in succinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, sebacic acid.
3. the preparation method of the polyester plasticizer of a kind of monobutyl ether alcohol end-blocking according to claim 1, is characterized in that: described dibasic alcohol is the one in glycol ether, triglycol, Tetraglycol 99, Macrogol 200, Liquid Macrogol and poly(oxyethylene glycol) 400.
4. the preparation method of the polyester plasticizer of a kind of monobutyl ether alcohol end-blocking according to claim 1, is characterized in that: described monobutyl ether alcohol is the one in ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, propylene glycol monobutyl ether, Dipropylene glycol mono-n-butyl Ether, Tri(propylene glycol)butyl ether,mixture of isomers.
5. the preparation method of the polyester plasticizer of a kind of monobutyl ether alcohol end-blocking according to claim 1, is characterized in that: described catalyzer is the one in tin protochloride, stannous oxalate, stannous octoate, Mono-n-butyltin, Dibutyltin oxide.
6. the preparation method of the polyester plasticizer of a kind of monobutyl ether alcohol end-blocking according to claim 1, is characterized in that: described water entrainer is the one in sherwood oil, toluene and dimethylbenzene.
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| CN107722348A (en) * | 2017-10-26 | 2018-02-23 | 中国科学院长春应用化学研究所 | A kind of nylon acid ether-ester plasticizers and preparation method thereof |
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| CN112142961A (en) * | 2020-09-28 | 2020-12-29 | 美瑞新材料股份有限公司 | Tackifying additive and application thereof in aspect of woodworking glue |
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| CN107022067A (en) * | 2017-04-26 | 2017-08-08 | 中国科学院长春应用化学研究所 | A kind of isobide base polyether ester, its preparation method and application |
| CN107722348A (en) * | 2017-10-26 | 2018-02-23 | 中国科学院长春应用化学研究所 | A kind of nylon acid ether-ester plasticizers and preparation method thereof |
| CN110078902A (en) * | 2019-05-24 | 2019-08-02 | 镇江巨杰新材料技术研发中心(有限合伙) | A kind of synthetic method of polyglycol ester plasticizer |
| CN110078902B (en) * | 2019-05-24 | 2021-09-24 | 镇江巨杰新材料技术研发中心(有限合伙) | Method for synthesizing glycol polyester plasticizer |
| CN112142961A (en) * | 2020-09-28 | 2020-12-29 | 美瑞新材料股份有限公司 | Tackifying additive and application thereof in aspect of woodworking glue |
| CN112142961B (en) * | 2020-09-28 | 2022-06-10 | 美瑞新材料股份有限公司 | Tackifying additive and application thereof in aspect of woodworking glue |
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