CN103012757A - Preparation method of poly(butylene succinate) - Google Patents
Preparation method of poly(butylene succinate) Download PDFInfo
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- CN103012757A CN103012757A CN 201210493333 CN201210493333A CN103012757A CN 103012757 A CN103012757 A CN 103012757A CN 201210493333 CN201210493333 CN 201210493333 CN 201210493333 A CN201210493333 A CN 201210493333A CN 103012757 A CN103012757 A CN 103012757A
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- succinic acid
- butyleneglycol
- preparation
- butylene succinate
- polycondensation
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Abstract
The invention discloses a preparation method of poly(butylene succinate) The method comprises the following preparation steps of: (1) pre-polycondensation: putting butanediol and succinic acid into a reaction kettle; adding a catalyst with presence of nitrogen; stirring at 100-120r/m; increasing the temperature until the succinic acid is completely melted; starting esterifying the butanediol and the succinic acid for 1-2h, and collecting water generated from the esterification by a water collecting device, to obtain a hydroxyl-terminated pre-polycondensate; and (2) vacuum polycondensation: vacuumizing the reaction kettle; keeping the vacuum degree below 12mmHg; meanwhile, raising the temperature of the reaction kettle to 210-230 DEG C; and adding a chain extender, stirring for 1.5-3h, melting and extruding with the presence of the nitrogen, to obtain a product, and detecting the product. The preparation method disclosed by the invention, adopting the fractional pre-polycondensation and vacuum polycondensation in two kettles, can directly polymerize to obtain the poly(butylene succinate) (PBS) with molecular weight above 10000-130000; in comparison with the conventional chain extension method, the chain extension step is saved by the direct polycondensation, so that the production process is simplified; and meanwhile, the material loss and equipment input in the production process are reduced, and the material production cost is lowered.
Description
Technical field
The invention belongs to polymeric material field, especially a kind of preparation method of poly butylene succinate.
Background technology
Poly butylene succinate (hereinafter to be referred as PBS) is good Biodegradable Polymers, and PBS can be used as refuse bag, packing bag, bottle for cosmetics, various plastic cards, baby diaper, agricultural materials and slow releasing carrier of medication matrix etc.; Also have other to relate to the various plastics of environment protection, such as building greening net, film etc.Can be used for the fields such as packing, tableware, bottle for cosmetics and drug bottle, disposable medical article, agricultural film, agricultural chemicals and slow-release fertilizer material, biological medical polymer material.
But the PBS relative molecular mass that Succinic Acid and butyleneglycol polycondensation obtain is lower, and have very large problem man-hour in actual adding: can not carry out forming process with techniques such as curtain coating, blowings, the use limitation of PBS is strong.Report with method synthetic macromolecule amount (more than the 100000) PBS of direct polymerization seldom sees in the document, and the PBS number-average molecular weight that most document, patent are mentioned does not yet have analogous products to occur at 5-8 ten thousand at home.
And the molecular weight of some products abroad (for example Bionolle) reached 100,000 or more than, this high molecular often by post-synthesis phase chain extension, with the preparation high molecular polymkeric substance.But comparatively effectively chainextender concentrates on isocyano series basically, these chainextenders itself are poisonous or hypertoxic, make thus the sanitation performance of PBS degradative plastics be not suitable with the Food Contact requirement, greatly limited the application of PBS in fields such as medical packaging, food product pack.
Through retrieval, find two pieces of patent documentations relevant with the application:
1. publication number is that the Chinese patent of CN1424339 discloses a kind of method for preparing poly butylene succinate, the method for preparing poly butylene succinate take butyleneglycol and Succinic Acid as monomer.Succinic Acid and butyleneglycol are placed reaction unit, wherein, the mole ratio of Succinic Acid and butyleneglycol is 1～3: 1, be to carry out normal pressure esterification reaction under 150～200 ℃ in temperature, then be 200～280 ℃ in temperature, and in the presence of catalyzer, be decompressed to 10～100Pa polycondensation and obtain poly butylene succinate; Wherein, the consumption of catalyzer is 0.01%～5% of Succinic Acid mole number.
2. publication number is that the Chinese patent of CN102775590A discloses a kind of poly butylene succinate, to form with Succinic Acid, butyleneglycol and cyclic diols copolymerization, comprise Succinic Acid residue, butyleneglycol residue and cyclic diols residue, wherein, by mole% meter, the butyleneglycol residue accounts for the 90-98% of dibasic alcohol total amount; The cyclic diols residue accounts for the 2-10% of dibasic alcohol total amount.Its preparation method comprise the steps: with Succinic Acid and butyleneglycol and cyclic diols under catalyst action in 200-230 ℃ of reaction, direct esterification obtains carboxylate; Then add stablizer, under 220-250 ℃, carry out prepolymerization reaction, get prepolymer; With prepolymer under 235-250 ℃ temperature, control reaction system vacuum tightness is down to gradually less than 150Pa, carries out polycondensation; After polycondensation finishes, in reactant, add the carbodiimide compounds, mixed 2-15 minute, make.
Through contrast, above-mentioned patent documentation and teachings herein have more different.
Summary of the invention
The object of the invention is to overcome the prior art weak point, provide that a kind of technique is simple, production safety and do not contain the preparation method of the poly butylene succinate of toxic substance.
The present invention solves its technical problem and takes following technical scheme to realize:
A kind of preparation method of poly butylene succinate, its preparation process is:
⑴ precondensation: butyleneglycol and Succinic Acid are put into reactor, the molar ratio of alcohol to acid of butyleneglycol and Succinic Acid is 1. 05, under nitrogen protection, put into catalyzer, the total input amount mol ratio of catalyzer and butyleneglycol and Succinic Acid is and 0.03:1, stir, rotating speed is 100-120 r/m, heat up, temperature of reaction kettle remains on 140～160 ℃, to the complete melting of Succinic Acid, butyleneglycol and Succinic Acid begin esterification, the water that produces when collecting esterification by water collecting device, esterification 1 ~ 2h obtains the terminal hydroxy group prepolycondensate of butyleneglycol and Succinic Acid;
⑵ vacuum polycondensation: reactor is vacuumized; vacuum keep is to 12mmHg; simultaneously temperature of reaction kettle is elevated between 210～230 ℃, adds chainextender, the total input amount mol ratio of chainextender and butyleneglycol and Succinic Acid is 0.001～.01:1; stir; rotating speed is 200～300r/m, and stopped reaction behind 1.5 ~ 3h melt extrudes the reactor interpolymer under nitrogen protection; obtain product, detect.
And the described catalyzer of step ⑴ is selected from any one of tetraisopropoxy titanium, toluenesulphonic acids, tetrabutyl titanate, antimonous oxide and rare-earth oxidation agent.
And the described chainextender of step ⑵ is any one of stannous octoate or two (the 2 – oxazoline) chainextenders of 2,2 ′ –.
A kind of poly butylene succinate, the preparation method by above-mentioned poly butylene succinate obtains, and 100000-150000 between its molecular weight area, and tensile strength is that 36 MPa, extension at break degree are 301%.
Advantage of the present invention and positively effect are:
1, the present invention adopts precondensation and vacuum polycondensation two still step-by-step polymerizations, but direct polymerization obtains molecular weight at 00000 ~ 150000 PBS, compare with traditional chain extension method, economized the chain extending reaction step by direct polymerization, simplified production technique, simultaneously also reduce material loss and equipment investment in the production process, reduced the material produce cost.
2, the prepared PBS of the present invention does not contain any chainextender, sanitation performance is good, owing to be that direct polymerization obtains, do not contain any isocyanic ester chainextender, sanitation performance be improved significantly, the national standard requirement of composite contact food makes it to be applicable to fully the strict fields of hygienic requirements such as food, medicine, makeup fully.
Embodiment
The invention will be further described below by specific embodiment, and following examples are descriptive, is not determinate, can not limit protection scope of the present invention with this.
A kind of preparation method of poly butylene succinate, its preparation process is:
⑴ ⑴ precondensation: butyleneglycol and Succinic Acid are put into reactor, the molar ratio of alcohol to acid of butyleneglycol and Succinic Acid is 1. 05, under nitrogen protection, put into catalyzer, the total input amount mol ratio of catalyzer and butyleneglycol and Succinic Acid is and 0.03:1, stir, rotating speed is 100-120 r/m, heat up, temperature of reaction kettle remains on 140～160 ℃, to the complete melting of Succinic Acid, butyleneglycol and Succinic Acid begin esterification, the water that produces when collecting esterification by water collecting device, esterification 1 ~ 2h obtains the terminal hydroxy group prepolycondensate of butyleneglycol and Succinic Acid;
⑵ vacuum polycondensation: reactor is vacuumized; vacuum keep is to 12mmHg; temperature of reaction kettle is elevated between 210～230 ℃ simultaneously; add chainextender, the total input amount mol ratio of chainextender and butyleneglycol and Succinic Acid is 0.001～.01:1, stirs; rotating speed is 200～300r/m; 1.5 stopped reaction behind the ~ 3h melt extrudes the reactor interpolymer under nitrogen protection, obtain product.
Embodiment
A kind of preparation method of poly butylene succinate, required reactant and weight thereof are respectively:
Its preparation process is:
⑴ precondensation: butyleneglycol and Succinic Acid are put into reactor, the molar ratio of alcohol to acid of butyleneglycol and Succinic Acid is 1. 05, puts into tetraisopropoxy titanium under nitrogen protection, stirs, rotating speed is 100-120 r/m, heat up, temperature of reaction kettle remains on 140～160 ℃, to the complete melting of Succinic Acid, butyleneglycol and Succinic Acid begin esterification, the water that produces when collecting esterification by water collecting device, esterification 1 ~ 2h obtains the terminal hydroxy group prepolycondensate of butyleneglycol and Succinic Acid;
⑵ vacuum polycondensation: reactor is vacuumized; vacuum keep is to 12mmHg; temperature of reaction kettle is elevated between 210～230 ℃ simultaneously; add stannous octoate; stir, rotating speed is 200～300r/m, stopped reaction behind 1.5 ~ 3h; the reactor interpolymer is melt extruded under nitrogen protection, obtain poly butylene succinate.
After testing, the poly butylene succinate molecular weight that obtains by the present invention is 100000 ~ 150000, and all the other parameters see the following form.
Other physical and mechanical properties of test agent detects table in the PBS material
| Project | Unit | Performance | Standard | Remarks |
| Relative density | g/cm 3 | 1.25～1.27 | GB/T?1033.1-2008 | 25℃ |
| Fusing point | ℃ | 116 | ------ | Use the DSC Instrument measuring |
| Melt flow rate (MFR) | g/10min | 2.6 | GB/T?3682-2000 | 190℃,2.16?kg |
| Tensile strength | MPa | 36 | GB/T?1040.3-2006 | Speed: 50mm/min |
| Elongation at break | % | 301 | GB/T?1040.3-2006 | Speed: 50mm/min |
| Shock strength | kJ/m 2 | 10 | GB/T?1043-2000 | Breach |
Claims (4)
1. the preparation method of a poly butylene succinate, it is characterized in that: its preparation process is:
⑴ precondensation: butyleneglycol and Succinic Acid are put into reactor, the molar ratio of alcohol to acid of butyleneglycol and Succinic Acid is 1. 05, under nitrogen protection, put into catalyzer, the total input amount mol ratio of catalyzer and butyleneglycol and Succinic Acid is and 0.03:1, stir, rotating speed is 100-120 r/m, heat up, temperature of reaction kettle remains on 140～160 ℃, to the complete melting of Succinic Acid, butyleneglycol and Succinic Acid begin esterification, the water that produces when collecting esterification by water collecting device, esterification 1 ~ 2h obtains the terminal hydroxy group prepolycondensate of butyleneglycol and Succinic Acid;
⑵ vacuum polycondensation: reactor is vacuumized; vacuum keep is to 12mmHg; simultaneously temperature of reaction kettle is elevated between 210～230 ℃, adds chainextender, the total input amount mol ratio of chainextender and butyleneglycol and Succinic Acid is 0.001～.01:1; stir; rotating speed is 200～300r/m, and stopped reaction behind 1.5 ~ 3h melt extrudes the reactor interpolymer under nitrogen protection; obtain product, detect.
2. the preparation method of poly butylene succinate according to claim 1, it is characterized in that: the described catalyzer of step ⑴ is selected from any one of tetraisopropoxy titanium, toluenesulphonic acids, tetrabutyl titanate, antimonous oxide and rare-earth oxidation agent.
3. the preparation method of poly butylene succinate according to claim 1 is characterized in that: the described chainextender of step ⑵ is any one of stannous octoate or two (the 2 – oxazoline) chainextenders of 2,2 ′ –.
4. poly butylene succinate, it is characterized in that: the preparation method by any described poly butylene succinate of claim of claim 1 ~ 3 obtains, 100000-150000 between its molecular weight area, and tensile strength is that 36 MPa, extension at break degree are 301%.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103408736A (en) * | 2013-08-08 | 2013-11-27 | 山东汇盈新材料科技有限公司 | Preparation method of high-molecular-weight biodegradable polyester |
| CN104761707A (en) * | 2015-04-14 | 2015-07-08 | 江苏钟腾化工有限公司 | Preparation method of polybutylene succinate |
| CN107057049A (en) * | 2017-05-09 | 2017-08-18 | 天津科技大学 | Phosphorous PBS fire proofings and phosphorous polyurethane and preparation method |
| CN108047436A (en) * | 2017-12-19 | 2018-05-18 | 青岛科技大学 | A kind of efficient poly butylene succinate chain extension method |
| CN110204687A (en) * | 2019-05-20 | 2019-09-06 | 华南理工大学 | A kind of thermally conductive poly butylene succinate ionomer and its preparation method and application |
| CN112724007A (en) * | 2020-12-17 | 2021-04-30 | 中国成达工程有限公司 | System and method for producing succinic acid and PBS (Poly Butylene succinate) by using natural gas |
| CN112920386A (en) * | 2021-01-29 | 2021-06-08 | 临朐齐力催化剂有限公司 | Production and preparation method of PBS (poly butylenes succinate) for degradable product |
| CN114507338A (en) * | 2022-03-02 | 2022-05-17 | 万华化学集团股份有限公司 | Preparation method of poly (butylene succinate) with low cyclic by-product |
-
2012
- 2012-11-27 CN CN 201210493333 patent/CN103012757A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103408736B (en) * | 2013-08-08 | 2015-12-09 | 山东汇盈新材料科技有限公司 | The preparation method of high-molecular-weighbiodegradable biodegradable polyester |
| CN103408736A (en) * | 2013-08-08 | 2013-11-27 | 山东汇盈新材料科技有限公司 | Preparation method of high-molecular-weight biodegradable polyester |
| CN104761707A (en) * | 2015-04-14 | 2015-07-08 | 江苏钟腾化工有限公司 | Preparation method of polybutylene succinate |
| CN104761707B (en) * | 2015-04-14 | 2016-08-31 | 江苏钟腾化工有限公司 | A kind of preparation method of poly butylene succinate |
| CN107057049A (en) * | 2017-05-09 | 2017-08-18 | 天津科技大学 | Phosphorous PBS fire proofings and phosphorous polyurethane and preparation method |
| CN108047436B (en) * | 2017-12-19 | 2019-11-12 | 青岛科技大学 | A kind of poly butylene succinate chain extension method |
| CN108047436A (en) * | 2017-12-19 | 2018-05-18 | 青岛科技大学 | A kind of efficient poly butylene succinate chain extension method |
| CN110204687A (en) * | 2019-05-20 | 2019-09-06 | 华南理工大学 | A kind of thermally conductive poly butylene succinate ionomer and its preparation method and application |
| CN112724007A (en) * | 2020-12-17 | 2021-04-30 | 中国成达工程有限公司 | System and method for producing succinic acid and PBS (Poly Butylene succinate) by using natural gas |
| CN112724007B (en) * | 2020-12-17 | 2023-07-18 | 中国成达工程有限公司 | System and method for producing succinic acid and PBS (Poly Butylene succinate) by using natural gas |
| CN112920386A (en) * | 2021-01-29 | 2021-06-08 | 临朐齐力催化剂有限公司 | Production and preparation method of PBS (poly butylenes succinate) for degradable product |
| CN114507338A (en) * | 2022-03-02 | 2022-05-17 | 万华化学集团股份有限公司 | Preparation method of poly (butylene succinate) with low cyclic by-product |
| CN114507338B (en) * | 2022-03-02 | 2024-04-09 | 万华化学集团股份有限公司 | Preparation method of polybutylene succinate with low cyclic byproducts |
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Application publication date: 20130403 |