CN103214659B - High molecular weight bio-based poly(butylene succinate) synthesis method - Google Patents
High molecular weight bio-based poly(butylene succinate) synthesis method Download PDFInfo
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- CN103214659B CN103214659B CN201310097087.4A CN201310097087A CN103214659B CN 103214659 B CN103214659 B CN 103214659B CN 201310097087 A CN201310097087 A CN 201310097087A CN 103214659 B CN103214659 B CN 103214659B
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Abstract
The invention belongs to the technical field of fully biodegradable aliphatic copolyester preparation, and particularly relates to a high molecular weight bio-based poly(butylene succinate) synthesis method. According to the method, bio-based succinic acid and 1,4-butanediol are used as polymerization monomers, and the high molecular weight bio-based poly(butylene succinate) is synthesized by esterification polycondensation in the presence of a high-efficient composite catalyst and a stabilizer, wherein the high-efficient composite catalyst is a mixture of Ti/Si organic esters and metal oxides or salts; and the stabilizer is carbodiimide or a self-polymerization polymer thereof. The method improves the catalytic efficiency and polycondensation reaction rate, reduces degradation and other side reactions and terminal carboxyl groups of the product in the presence of the stabilizer, meets the requirements of the degradation aging rate of the product, optimizes the product color, provides good conditions for product subsequent modification processing and extends the application field.
Description
Technical field
The invention belongs to the aliphatic copolyester preparing technical field of complete biodegradable, be specifically related to a kind of high molecular biological poly succinic acid-butanediol ester synthetic method.
Background technology
Due to the non-biodegradable of conventional plastic, its goods have also been with more and more Heavy environmental pollution problem to people's life, industrial production while bringing facility and interests, degradable plastics is the important channel addressed this problem.Being polymerized with petroleum succinic acid, butyleneglycol the poly butylene succinate (PBS) obtained is a kind of typical biodegradable plastic, and conventional plastic can be replaced to be widely used in the every field of human lives, and by a large amount of development & production.
Due to the exhaustion day by day of petroleum resources, obtain succinic acid by Biological resources fermentation and produce PBS to substitute present petroleum base PBS, be the new direction of degradative plastics industry development, its follow-up modification fabricated product makes bio-based PBS have more vast potential for future development as a kind of green plastic.
Also there is series of problems in the poly butylene succinate of current employing bio-based succinic acid synthesis, due to the catalyzer difference adopted, have that catalytic efficiency is low, the polycondensation time is long, reaction is unstable, and the follow-up product caused divides quantum not high, product degradation and the problem such as shade deviation, mechanical property be not up to standard.
Summary of the invention
The object of this invention is to provide a kind of with bio-based succinic acid and 1,4 butyleneglycols are polymerization single polymerization monomer, under efficient composite catalyst and stablizer exist, by esterifying polycondensation synthesising biological based high molecular amount, low terminal carboxy content, coloury biological poly succinic acid-butanediol ester.
High molecular biological poly succinic acid-butanediol ester synthetic method of the present invention, with bio-based succinic acid and 1,4 butyleneglycols are polymerization single polymerization monomer, under efficient composite catalyst and stablizer exist, by esterifying polycondensation synthesis high molecular biological poly succinic acid-butanediol ester; Described efficient composite catalyst is titanium/silicon organosilane ester and the mixture of metal oxide or corresponding salt; Described stablizer is carbodiimide or carbodiimide autohemagglutination polymkeric substance.
In described titanium/silicon organosilane ester, the mol ratio of titanium/silicon is 1 ~ 10:1, and wherein titanium organic ester is one or more in butyl (tetra) titanate, isopropyl titanate, tetraethyl titanate, two trolamine di-isopropyl titanic acid ester, the different monooctyl ester of metatitanic acid four, titanium potassium oxalate(T.P.O.), titanium ethylene glycolate or butyleneglycol titanium; Silicon organic ester is methyl silicate or tetraethoxy.
Described metal oxide or corresponding salt are the one in calcium, magnesium, aluminium, titanium, zinc, germanium, the oxide compound of cerium or its corresponding salt.
The consumption of described efficient composite catalyst is 0.1 ~ 0.5% of theoretical product quality, and metal oxide or corresponding salt consumption are 0.01% ~ 0.05% of theoretical product quality.
Described stablizer is N, one in N'-DIC, dicyclohexylcarbodiimide, 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride or its corresponding autohemagglutination polymkeric substance, preferred carbodiimide autohemagglutination polymkeric substance, consumption is 0.01 ~ 0.05% of theoretical product quality.
Described high molecular biological poly succinic acid-butanediol ester synthetic method comprises the steps: bio-based succinic acid and 1,4-butyleneglycol is placed in reaction vessel for 1:1 ~ 2 in molar ratio, be warmed up to 150 ~ 190 DEG C, first carry out the reaction of constant temperature normal pressure esterification, 2 ~ 3 hours time, then negative pressure esterification is carried out at 60 ~ 80Kpa, time 15 ~ 30min; The polycondensation of final high temperature negative pressure, adopts efficient composite catalyst, with carbodiimide or carbodiimide autohemagglutination polymkeric substance for stablizer, temperature controls at 220 ~ 260 DEG C, pressure-controlling is in 10 ~ 50pa, and in 2 ~ 5 hours reaction times, polycondensation obtains high molecular biological poly succinic acid-butanediol ester.
Described is warmed up in 150 ~ 190 DEG C of processes, and temperature rise rate is 15 ~ 20 DEG C/min.
The molecular weight 9 × 10 of described high molecular biological poly succinic acid-butanediol ester
4~ 15 × 10
4, tensile strength is 30 ~ 45MPa, and elongation at break is 300 ~ 500%.
Beneficial effect of the present invention is as follows:
The present invention adopts composite catalyst, improves catalytic efficiency, improves polycondensation speed, under stablizer participates in, reduces the side reactions such as degraded, can improve molecular weight of product within a short period of time, molecular weight 9 × 10
4~ 15 × 10
4; Improve mechanical performance index, tensile strength is 30 ~ 45MPa, and elongation at break is 300 ~ 500%; With carbodiimide or its autohemagglutination polymkeric substance for stablizer, reduce the end carboxyl of product, meet the degraded rate of ageing requirement of product; And optimize product color, for the successive modified processing of product provides good condition, extend Application Areas.
Embodiment
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1
120g bio-based succinic acid, 100g butyleneglycol are placed in 500ml reactor (acid alcohol mol ratio 1:1.1), and stir, rapid temperature increases, 15 DEG C/min carries out normal pressure esterification, isothermal reaction 3 hours under temperature is the condition of 160 DEG C.Then negative pressure esterification is carried out under 80Kpa, time 25min; Be warming up to 220 DEG C again, add composite catalyst 0.4g tetrabutyl titanate/methyl silicate (titanium/silicon mol ratio 5:1) and 0.02g titanium dioxide, 0.05g stablizer gathers N, N'-DIC, be decompressed to 50Pa and carry out polycondensation, react 5 hours, the poly butylene succinate molecular weight obtained is 9.6 × 10
4, tensile strength is 34.5MPa, and elongation at break is 343%, L value 75.9, b value 2.4, acid number 15.2mol/t.
Embodiment 2
150g bio-based succinic acid, 150g butyleneglycol are placed in 500ml reactor (acid alcohol mol ratio 1:1.3), and stir, rapid temperature increases, 20 DEG C/min carries out normal pressure esterification, isothermal reaction 2 hours under temperature is the condition of 180 DEG C.Then negative pressure esterification is carried out under 70Kpa, time 30min; Be warming up to 240 DEG C again, add the two trolamine di-isopropyl titanic acid ester/methyl silicate (titanium/silicon mol ratio 4:1) of composite catalyst 0.6g and 0.03g magnesium oxide, 0.06g stablizer gathers dicyclohexylcarbodiimide, be decompressed to 20Pa and carry out polycondensation, react 3 hours, the poly butylene succinate molecular weight obtained is 14.9 × 10
4, tensile strength is 40.8MPa, and elongation at break is 407%, L value 80.1, b value 4, acid number 18mol/t.
Embodiment 3
118g bio-based succinic acid, 180g butyleneglycol are placed in 500ml reactor (acid alcohol mol ratio 1:2), and stir, rapid temperature increases, 20 DEG C/min carries out normal pressure esterification, isothermal reaction 2 hours under temperature is the condition of 190 DEG C.Then negative pressure esterification is carried out under 80Kpa, time 30min; Be warming up to 260 DEG C again, add the different monooctyl ester/tetraethoxy of composite catalyst 0.5g metatitanic acid four (titanium/silicon mol ratio 5:1) and 0.06g tetravalence cerous sulfate, add 0.03g stablizer 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride, be decompressed to 15Pa and carry out polycondensation, react 2.5 hours, the poly butylene succinate molecular weight obtained is 12 × 10
4, tensile strength is 38MPa, and elongation at break is 398%, L value 77, b value 1.2, acid number 10mol/t.
Embodiment 4
118g bio-based succinic acid, 135g butyleneglycol are placed in 500ml reactor (acid alcohol mol ratio 1:1.5), and stir, rapid temperature increases, 15 DEG C/min carries out normal pressure esterification, isothermal reaction 2.5 hours under temperature is the condition of 180 DEG C.Then negative pressure esterification is carried out under 60Kpa, time 20min; Be warming up to 250 DEG C again, add composite catalyst 0.3g isopropyl titanate/methyl silicate (titanium/silicon mol ratio 8:1) and 0.05g aluminum acetate, add 0.06g stablizer and gather dicyclohexylcarbodiimide, be decompressed to 20Pa and carry out polycondensation, react 4 hours, the poly butylene succinate molecular weight obtained is 13 × 10
4, tensile strength is 33MPa, and elongation at break is 452%, L value 75, b value 1.5, acid number 13.5mol/t.
Claims (7)
1. a high molecular biological poly succinic acid-butanediol ester synthetic method, is characterized in that: with bio-based succinic acid and Isosorbide-5-Nitrae butyleneglycol for polymerization single polymerization monomer, by esterifying polycondensation synthesis high molecular biological poly succinic acid-butanediol ester; During polycondensation, add efficient composite catalyst and stablizer; Described efficient composite catalyst is titanium/silicon organosilane ester and the mixture of metal oxide or corresponding salt; Described stablizer is carbodiimide or carbodiimide autohemagglutination polymkeric substance; Described metal oxide or corresponding salt are the one in calcium, magnesium, aluminium, titanium, zinc, germanium, the oxide compound of cerium or its corresponding salt.
2. high molecular biological poly succinic acid-butanediol ester synthetic method according to claim 1, it is characterized in that: in described titanium/silicon organosilane ester, the mol ratio of titanium/silicon is 1 ~ 10:1, and wherein titanium organic ester is one or more in butyl (tetra) titanate, isopropyl titanate, tetraethyl titanate, two trolamine di-isopropyl titanic acid ester, the different monooctyl ester of metatitanic acid four, titanium potassium oxalate(T.P.O.), titanium ethylene glycolate or butyleneglycol titanium; Silicon organic ester is methyl silicate or tetraethoxy.
3. high molecular biological poly succinic acid-butanediol ester synthetic method according to claim 2, it is characterized in that: the consumption of described efficient composite catalyst is 0.1 ~ 0.5% of theoretical product quality, metal oxide or corresponding salt consumption are 0.01% ~ 0.05% of theoretical product quality.
4. high molecular biological poly succinic acid-butanediol ester synthetic method according to claim 3, it is characterized in that: described stablizer is N, one in N'-DIC, dicyclohexylcarbodiimide, 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride or its corresponding autohemagglutination polymkeric substance, consumption is 0.01 ~ 0.05% of theoretical product quality.
5. high molecular biological poly succinic acid-butanediol ester synthetic method according to claim 4, it is characterized in that comprising the steps: bio-based succinic acid and 1,4-butyleneglycol is placed in reaction vessel for 1:1 ~ 2 in molar ratio, be warmed up to 150 ~ 190 DEG C, first carry out the reaction of constant temperature normal pressure esterification, 2 ~ 3 hours time, then carry out negative pressure esterification at 60 ~ 80Kpa, time 15 ~ 30min; The polycondensation of final high temperature negative pressure, adopts efficient composite catalyst, with carbodiimide or carbodiimide autohemagglutination polymkeric substance for stablizer, temperature controls at 220 ~ 260 DEG C, pressure-controlling is in 10 ~ 50pa, and in 2 ~ 5 hours reaction times, polycondensation obtains high molecular biological poly succinic acid-butanediol ester.
6. high molecular biological poly succinic acid-butanediol ester synthetic method according to claim 5, is characterized in that: be warmed up in 150 ~ 190 DEG C of processes, temperature rise rate is 15 ~ 20 DEG C/min.
7. high molecular biological poly succinic acid-butanediol ester synthetic method according to claim 5, is characterized in that: the molecular weight 9 × 10 of described high molecular biological poly succinic acid-butanediol ester
4~ 15 × 10
4, tensile strength is 30 ~ 45MPa, and elongation at break is 300 ~ 500%.
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| CN104877121B (en) * | 2015-04-29 | 2016-08-10 | 苏州市湘园特种精细化工有限公司 | A kind of aliphatic polyester is combined preparation method and the application of catalyst |
| CN104829820B (en) * | 2015-05-12 | 2017-01-04 | 苏州市湘园特种精细化工有限公司 | The preparation method of a kind of high molecular polymerization catalyst and application |
| CN110041516B (en) * | 2019-05-10 | 2019-12-03 | 淄博成达塑化有限公司 | The preparation method of permanent seal cooling poly butylene succinate |
| 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 |
| CN114163626B (en) * | 2021-12-10 | 2023-05-05 | 中化学科学技术研究有限公司 | Polymerization catalyst, preparation method thereof and application thereof in preparation of polybutylene succinate |
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| CN101671435A (en) * | 2008-09-08 | 2010-03-17 | 上海华明高技术（集团）有限公司 | Catalyst for preparing polybutylene succinate and copolyesters thereof and preparation method thereof |
| CN102775590A (en) * | 2012-08-15 | 2012-11-14 | 金发科技股份有限公司 | Poly(butylene succinate) and preparation method thereof |
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| CN101671435A (en) * | 2008-09-08 | 2010-03-17 | 上海华明高技术（集团）有限公司 | Catalyst for preparing polybutylene succinate and copolyesters thereof and preparation method thereof |
| CN102775590A (en) * | 2012-08-15 | 2012-11-14 | 金发科技股份有限公司 | Poly(butylene succinate) and preparation method thereof |
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