CN107236119A - A kind of elastic PBT industrial continuous preparation method - Google Patents
A kind of elastic PBT industrial continuous preparation method Download PDFInfo
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- CN107236119A CN107236119A CN201610182338.2A CN201610182338A CN107236119A CN 107236119 A CN107236119 A CN 107236119A CN 201610182338 A CN201610182338 A CN 201610182338A CN 107236119 A CN107236119 A CN 107236119A
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- esterification
- pbt
- elastic
- antioxidant
- preshrunk
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- 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
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention relates to a kind of elastic PBT industrial continuous preparation method, this method is with terephthalic acid (TPA), 1,4 butanediols and PolyTHF are raw material, according to the process route of PTA continuous esterification methods, carry out industrializing continuous production elasticity PBT on conventional PBT continuous devices.The product as made from the inventive method, inherent viscosity is up to 0.800 1.300 dL/g, and physical performance index shows product elasticity enhancing, and elongation at break has reached after more than 250%, spinning elastic recovery rate up to more than 48%；The products application is in spinning field, many advantages, such as obtained final products have good processability, elasticity is good, soft, dyeability is good.
Description
Technical field
The present invention relates to elastic PBT preparation method, belong to polyester, elastomer synthesis processing technique field.
Background technology
Polybutylene terephthalate (PBT) (PBT) is a kind of good polyester product of combination property, extensively should
For industries such as fiber, engineering plastics, optical cables.PBT, which is applied to elastomer, can produce denim, wool
The products such as shirt, but there are still elastic not enough, partially hard etc. weakness of feel, have impact on the further of application market
Expand.
Thus, people attempt to introduce polyethers or aliphatic polyester soft segment in PBT synthesis segments, and production contains
PBT polyester hard section (there is provided intensity for crystalline phase) and polyethers or aliphatic polyester soft segment (continuous segment) it is embedding
Section linear copolymers.Such product is referred to as thermoplastic polyester elastomer (referred to as TPEE) or modified
PBT products, it contains the rigidity, polarity and crystallinity of PBT hard sections, make it have prominent intensity and
Preferable heat-resisting quantity, creep resistant, solvent resistance and impact resistance；Polyethers or aliphatic polyester soft segment
Low Tg and saturability, then make it have excellent lower temperature resistance and ageing resistance.Using such production
The elastomer of product production, the characteristics of possessing original PBT products easy processing more has elastic high, good hand touch concurrently
The advantages of, it is a kind of raw material of new elastomer.
All the time, domestic and international enterprise generally produces such product using batch process, and Very few companies are used
Continuous polymerization technique is produced, and the synthetic method of batch process has two classes：Ester-interchange method and direct esterification.At present
It is industrial many using ester-interchange method Batch Process, i.e., with dimethyl terephthalate (DMT) (DMT), polyethers or fat
Fat adoption ester and BDO (BD) are raw material, are produced using tetrabutyltin as catalyst, product
Engineering plastics, film applications are mainly used in, rarely the report applied to elastomer.For direct ester
Change method, a kind of " method for preparing conjugated polyether ester elastomer " of JinFa Science Co., Ltd's application is (specially
201210517640.0) profit number is related to a kind of method for preparing conjugated polyether ester elastomer, and raw material is aromatic series two
First acid, polyether Glycols and small molecule dihydric alcohol, soft segment ratio are 20-65%, and fusing point is 180-215 DEG C,
Elongation at break, which is more than in 300%, preparation process, adds hindered phenolic antioxidant, but the patent is not specific
Ground discloses how methods described is applied to industrialized production.
The content of the invention
It is an object of the invention to overcome the shortcomings of prior art, the industry of elastic PBT a kind of is proposed even
Continuousization preparation method, meets the demand of downstream fiber user, expands PBT application field.
The purpose of the present invention is achieved through the following technical solutions：
A kind of elastic PBT industrial continuous preparation method, this method is with terephthalic acid (TPA), BDO
It is raw material with PolyTHF, according to the process route of PTA continuous esterification methods, in conventional PBT serializations
Device, follows the steps below continuous production：
(1) raw material slurrying in slurry tank：Terephthalic acid (TPA), 1,4- butanediols are according to mol ratio 1:(1.0~
2.0) it is configured to slurry；PolyTHF is according to product quality 5~30% in slurry tank, esterification Fu or preshrunk
Any one or more position is added in Fu；
(2) slurry is continuously introduced into esterification Fu and carries out esterification：Esterification temperature is 220~250 DEG C, pressure
For 40~100kPa, the reaction time is 1~3hr, and catalyst butyl titanate content is 50~120ppm；
(3) material esterification yield is continuously introduced into preshrunk Fu after reaching 95% in esterification Fu：The material in preshrunk kettle
Esterification is further completed, while carrying out prepolymerization reaction, preshrunk reaction temperature is 230~260 DEG C, pressure
Power is 1~5kPa, and the reaction time is 0.5~3hr；
(4) product property viscosity reaches final minification Fu is continuously introduced into after 0.25dL/g in preshrunk kettle, continues to complete
Polycondensation reaction obtains product：Final minification reaction temperature is 230~260 DEG C, and pressure is 10~500kPa, reaction
Time is 1~3hr.
Further, additive is added in the elastic PBT preparation process, and, point of addition is slurry
Any position in make-up tank, esterification Fu, preshrunk Fu.
Further, the additive is phosphorus-containing stabilizers, antioxidant, defoamer, light stabilizer.
Preferably, the phosphorus-containing stabilizers be trimethyl phosphate, triethyl phosphate, triphenyl phosphate in one kind or
It is a variety of.The antioxidant is antioxidant 1222, antioxidant 1012, antioxidant 168, anti-oxidant
One or more in agent 1010, BHT.The defoamer is silicone emulsion, high-carbon alcohol fatty acid ester is answered
Compound, polyoxyethylene polyoxypropylene pentaerythrite ether, polypropylene glycerol aether, the one of dimethyl silicone polymer
Plant or a variety of.The light stabilizer be 770,944,292,783, UV 9, UV 326,
The one or more of UV 531.
The prominent substantive distinguishing features of the present invention and marked improvement are mainly reflected in following several respects：
1st, the present invention produces thermoplastic according to PTA continuous esterification methods using conventional PBT industrial production devices
Property polyester elastomer, reduce production equipment cost, so as to reduce production cost.
2nd, the product performance viscosity of the inventive method production can be in 0.800-1.300dL/g scopes, physical property
Index shows product elasticity enhancing, and elongation at break has reached that elastic recovery rate reaches after more than 250%, spinning
More than 48%.
3rd, product produced by the invention can be applied to have specific characteristics the elastomer field of requirement, and with plus
The advantages of work performance is good, elasticity is good, soft, dyeability is good.
4th, product produced by the invention can also be applied to the film applications of particular/special requirement.
Embodiment
The present invention is with terephthalic acid (TPA) (PTA), 1,4- butanediols (BDO) and PolyTHF
(PTMEG) it is raw material, according to the process route of PTA continuous esterification methods, continuously disguises in conventional PBT
Put, highly elastic material is produced after gathering through esterification, preshrunk, final minification.The present invention's comprises the following steps that：
(1) raw material slurrying in slurry tank：Terephthalic acid (TPA), 1,4- butanediols are according to mol ratio 1:(1.0~
2.0) it is configured to slurry；In addition, raw material PolyTHF (PTMEG) is according to the 5~30% of product quality
Any one or more position is added in slurry tank, esterification Fu or preshrunk Fu；
(2) slurry is continuously introduced into esterification Fu and carries out esterification：Esterification temperature is 220~250 DEG C, pressure
For 40~100kPa, the reaction time is 1~3hr, and catalyst butyl titanate content is 50~120ppm；
(3) material esterification yield is continuously introduced into preshrunk Fu after reaching 95% in esterification Fu：The material in preshrunk kettle
Esterification is further completed, while carrying out prepolymerization reaction, preshrunk reaction temperature is 230~260 DEG C, pressure
Power is 1~5kPa, and the reaction time is 0.5~3hr；
(4) product property viscosity reaches final minification Fu is continuously introduced into after 0.25dL/g in preshrunk kettle, continues to complete
Polycondensation reaction obtains product：Final minification reaction temperature is 230~260 DEG C, and pressure is 10~500kPa, reaction
Time is 1~3hr.
In addition, added with the addition such as phosphorus-containing stabilizers, antioxidant, defoamer in above-mentioned building-up process
Agent, additive point of addition is any position in slurry preparation groove, esterification Fu, preshrunk Fu.Wherein, contain
Phosphorus stabilizer agent mainly has the one or more in trimethyl phosphate, triethyl phosphate, triphenyl phosphate；Antioxygen
Agent mainly uses antioxidant 1222, antioxidant 1012, antioxidant 168, antioxidant
1010th, the one or more in BHT (2,6 di tert butyl 4 methyl phenol)；Defoamer is emulsification silicon
Oil, the fatty acid ester compounded thing of higher alcohols, polyoxyethylene polyoxypropylene pentaerythrite ether, polyoxypropylene glyceryl
The one or more of ether, dimethyl silicone polymer.Light stabilizer be 770,944,292,783, it is ultraviolet
UV9, UV 326, the one or more of UV 531.
PBT product performances viscosity produced by the invention can be adjusted according to customer demand, and inherent viscosity is in 0.800-
1.300dL/g.Moreover, the quality index of product of the present invention is as shown in table 1.
Table 1：Elasticity PBT quality index of the invention
Meanwhile, elastic PBT produced by the invention quality is compared with routine PBT with advantages below：
1. dyeability：More easy dyeing；
2. feel：Elastic PBT is more soft；
3. resilience：Elastic PBT ＞ routine PBT (being shown in Table 2)；
4. feel elasticity recovery：Elastic PBT ＞ routine PBT (being shown in Table 2).
Table 2：Elasticity PBT is compared with routine PBT by the present invention
With reference to specific embodiment, the present invention will be described, for embodiment be only to product of the present invention
Or method makees generality illustration, help to more fully understand the present invention, but be not limiting upon the scope of the invention.
Experimental method described in following embodiments, is conventional method unless otherwise specified；The material, such as without
Specified otherwise, is commercially obtained.
Embodiment 1
Liquid phase polymerization device produce load is 60 ton days.1,4- butanediols, terephthalic acid (TPA) are prepared into slurry and mixed
Compound, catalyst butyl titanate is added in reaction kettle of the esterification by finite concentration.Esterification reaction temperature
220~250 DEG C or so, Stress control is controlled 95% in 30~60kPa or so, esterification yield.Precondensation is anti-
Should, temperature control is at 230~260 DEG C or so, and reaction pressure controls 0.5~10kPa or so, inherent viscosity
Control is in 0.25dL/g.The control of final minification Fu reaction temperatures at 230~260 DEG C or so, Stress control 50~
500Pa or so.Final products, sampling are made in the material feeding Granulation Equipments granulation that whole batch condensation polymerization reactor comes out
Measure：Inherent viscosity is 0.990dL/g, and content of carboxyl end group is 22mol/t, and fusing point is 224 DEG C, and fracture is stretched
Long rate is 150%.
Embodiment 2
Liquid phase polymerization device produce load is 45 ton days.1,4- butanediols, terephthalic acid (TPA), PolyTHF
Slurry mix is prepared into, PolyTHF ratio is mass ratio 10% in product.Defoamer is mixed with BDO
Close uniform rear add and be esterified Fu, stabilizer, antioxidant, light stabilizer press 1:1 ratio is mixed with BDO
Preshrunk reactor is added to after uniform.Catalyst butyl titanate is added to reaction kettle of the esterification by finite concentration
In.220~250 DEG C or so of esterification reaction temperature, Stress control is in 40~100kPa or so, esterification yield control
System is 95.5%.Prepolymerization reaction, temperature control at 230~260 DEG C or so, reaction pressure control 0.5~
10kPa or so, inherent viscosity is controlled in 0.27dL/g.Final minification Fu reaction temperatures are controlled on 230~260 DEG C of left sides
The right side, Stress control is in 10~500Pa or so.The material feeding Granulation Equipments granulation that whole batch condensation polymerization reactor comes out
Final products are made, sampling is measured：Inherent viscosity is 1.045dL/g, and content of carboxyl end group is 28mol/t, is melted
Point is 218 DEG C, and elongation at break is 350%.
Embodiment 3
Liquid phase polymerization device produce load is 40 ton days.1,4- butanediols, terephthalic acid (TPA), PolyTHF
Slurry mix is prepared into, PolyTHF ratio is mass ratio 20% in product.Defoamer, stabilizer,
Antioxidant, light stabilizer add esterification Fu after being well mixed with BDO.Catalyst butyl titanate presses one
Determine concentration to be added in reaction kettle of the esterification.220~250 DEG C or so of esterification reaction temperature, Stress control exists
40~100kPa or so, esterification yield is controlled 96%.Prepolymerization reaction, temperature control is at 230~260 DEG C
Left and right, reaction pressure controls 0.5~10kPa or so, and inherent viscosity is controlled in 0.26dL/g.Final minification Fu is anti-
Answer temperature control at 230~260 DEG C or so, Stress control is in 10~500Pa or so.Whole batch condensation polymerization reactor goes out
Final products are made in the material feeding Granulation Equipments granulation come, and sampling is measured：Inherent viscosity is 1.160dL/g,
Content of carboxyl end group is 30mol/t, and fusing point is 203 DEG C, and elongation at break is 420%.
Embodiment 4
Liquid phase polymerization device produce load is 40 ton days.1,4- butanediols, terephthalic acid (TPA), PolyTHF
Slurry mix is prepared into, PolyTHF ratio is mass ratio 30% in product.Defoamer, stabilizer,
Antioxidant, light stabilizer add esterification Fu after being well mixed with BDO.Catalyst butyl titanate presses one
Determine concentration to be added in reaction kettle of the esterification.225~245 DEG C or so of esterification reaction temperature, Stress control exists
40~100kPa or so, esterification yield is controlled 95.5%.Prepolymerization reaction, temperature control is at 230~260 DEG C
Left and right, reaction pressure controls 0.5~10kPa or so, and inherent viscosity is controlled in 0.25dL/g.Final minification is poly- anti-
Final products are made in the material feeding Granulation Equipments granulation for answering kettle to come out, and sampling is measured：Inherent viscosity is
1.058dL/g, content of carboxyl end group is 30mol/t, and fusing point is 192 DEG C, and elongation at break is 450%.
Claims (7)
1. a kind of elastic PBT industrial continuous preparation method, it is characterised in that：This method, according to the process route of PTA continuous esterification methods, in conventional PBT continuous devices, follows the steps below continuous production using terephthalic acid (TPA), BDO and PolyTHF as raw material：
（1）Raw material slurrying in slurry tank：Terephthalic acid (TPA), 1,4- butanediols are according to mol ratio 1:(1.0~2.0) are configured to slurry；PolyTHF according to product quality 5~30% in slurry tank, esterification Fu or preshrunk Fu any one or more position add；
（2）Slurry is continuously introduced into esterification Fu and carries out esterification：Esterification temperature is 220~250 DEG C, and pressure is 40~100 kPa, and the reaction time is 1~3
Hr, catalyst butyl titanate content is 50~120ppm；
（3）Material esterification yield is continuously introduced into preshrunk Fu after reaching 95% in esterification Fu：Material further completes esterification in preshrunk kettle, while carrying out prepolymerization reaction, preshrunk reaction temperature is 230~260 DEG C, and pressure is 1~5 kPa, and the reaction time is 0.5~3 hr；
（4）Product property viscosity, which reaches, in preshrunk kettle is continuously introduced into final minification Fu after 0.25dL/g, continue to complete polycondensation reaction and obtain product：Final minification reaction temperature is 230~260 DEG C, and pressure is 10~500kPa, and the reaction time is 1~3 hr.
2. a kind of elastic PBT according to claim 1 industrial continuous preparation method, it is characterised in that：Additive is added with the elastic PBT preparation process, the point of addition of additive is any position in slurry preparation groove, esterification Fu, preshrunk Fu.
3. a kind of elastic PBT according to claim 2 industrial continuous preparation method, it is characterised in that：The additive is the one or more in phosphorus-containing stabilizers, antioxidant, defoamer, light stabilizer.
4. a kind of elastic PBT according to claim 3 industrial continuous preparation method, it is characterised in that：The phosphorus-containing stabilizers are the one or more in trimethyl phosphate, triethyl phosphate, triphenyl phosphate.
5. a kind of elastic PBT according to claim 3 industrial continuous preparation method, it is characterised in that：The antioxidant is the one or more in antioxidant 1222, antioxidant 1012, antioxidant 168, antioxidant 1010, BHT.
6. a kind of elastic PBT according to claim 3 industrial continuous preparation method, it is characterised in that：The defoamer is silicone emulsion, the fatty acid ester compounded thing of higher alcohols, polyoxyethylene polyoxypropylene pentaerythrite ether, polypropylene glycerol aether, the one or more of dimethyl silicone polymer.
7. a kind of elastic PBT according to claim 3 industrial continuous preparation method, it is characterised in that：The light stabilizer be 770,944,292,783, UV 9, UV 326, the one or more of UV 531.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107955992A (en) * | 2017-10-19 | 2018-04-24 | 无锡市兴盛新材料科技有限公司 | A kind of short fine and its fused mass directly spinning preparation methods of high-quality PBT |
| CN113461921A (en) * | 2021-07-19 | 2021-10-01 | 新疆维格瑞生物科技有限公司 | Low-melting-point thermoplastic polyester elastomer and preparation method thereof |
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| CN107955992A (en) * | 2017-10-19 | 2018-04-24 | 无锡市兴盛新材料科技有限公司 | A kind of short fine and its fused mass directly spinning preparation methods of high-quality PBT |
| CN113461921A (en) * | 2021-07-19 | 2021-10-01 | 新疆维格瑞生物科技有限公司 | Low-melting-point thermoplastic polyester elastomer and preparation method thereof |
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Application publication date: 20171010 |