CN103450641A - Polybutylene succinate/graphene oxide composite material and preparation method thereof - Google Patents
Polybutylene succinate/graphene oxide composite material and preparation method thereof Download PDFInfo
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- CN103450641A CN103450641A CN201210174306XA CN201210174306A CN103450641A CN 103450641 A CN103450641 A CN 103450641A CN 201210174306X A CN201210174306X A CN 201210174306XA CN 201210174306 A CN201210174306 A CN 201210174306A CN 103450641 A CN103450641 A CN 103450641A
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Abstract
The invention discloses a polybutylene succinate/graphene oxide composite material which comprises polybutylene succinate and graphene oxide, the size of the graphene oxide dispersion phase is 5-50 nm, and the weight part ratio of polybutylene succinate to graphene oxide is 100:0.1-10. The invention also discloses a preparation method of the polybutylene succinate/graphene oxide composite material. The preparation method comprises the steps: dispersing graphene oxide in water to obtain a graphene oxide dispersion liquid; mixing the graphene oxide dispersion liquid with butanedioic acid and butanediol, stirring, and carrying out an esterification reaction; and then employing a titanium catalyst, and carrying out a polycondensation reaction to obtain the polybutylene succinate/graphene oxide composite material. The obtained polybutylene succinate/graphene oxide composite material has excellent heat resistance performance, toughness and mechanical properties.
Description
Technical field
The invention belongs to polymeric material field, relate to particularly a kind of poly butylene succinate/stannic oxide/graphene nano matrix material and preparation method thereof.
Background technology
Poly butylene succinate (PBS), also claim polybutylene succinate or poly-succsinic acid fourth diester, contains the ester bond of facile hydrolysis in its main chain, and main chain is submissive, a kind of half crystalline thermoplastic resin with completely biodegradable energy, 114 ℃ of fusing points, degree of crystallinity is between 40 ~ 60%.Its performance, can be directly as plastic working between polyethylene and polypropylene.It has good processing characteristics, can on common equipment, carry out forming process, also can carry out the forming process such as injection moulding, blowing, blown film, plastic uptake, lamination, foaming, spinning.Poly butylene succinate has good biodegradable performance, can be used as full Biodegradable material, be applied to the aspects such as table ware, various household supplies articles for use, agricultural materials, biological medical polymer material, also can be used as material toy, household electrical appliances, daily use chemicals, food, pharmaceutical packing material.
At first the preparation of graphene oxide is to prepare graphite oxide, first Graphite Powder 99 is dispersed in strong oxidizing property mixing acid, for example concentrated nitric acid and the vitriol oil, then add potassium permanganate or Potcrate to wait by force oxygenant to obtain graphite oxide, then obtain graphene oxide through supersound process.The graphene oxide surface has many hydroxyls, epoxy group(ing), carbonyl, carboxyl, the existence of oxy radical makes Graphene be easy to be dispersed in solvent, and make graphene functionalized, be easy to and a lot of substance reactions, the basis that graphene oxide is become prepare the Graphene functional composite material.The simultaneous oxidation Graphene also has excellent mechanical property and heat conductivility, adds mechanics and the heat conductivility that can significantly improve matrix material in material to.
Therefore, want to improve mechanical property and the thermotolerance of poly butylene succinate, to enlarge its range of application.
Summary of the invention
The present invention to solve first technical problem be to provide a kind of poly butylene succinate/graphene oxide composite material.
The present invention to solve second technical problem be to provide a kind of preparation method of poly butylene succinate/graphene oxide composite material.
For solving the problems of the technologies described above, the invention provides a kind of poly butylene succinate/graphene oxide composite material, comprise poly butylene succinate and graphene oxide, described graphene oxide disperse phase yardstick is 5 ~ 50nm, and ratio of weight and number is poly butylene succinate: graphene oxide=100:0.1 ~ 10.
For solving the problems of the technologies described above, the invention provides a kind of preparation method of poly butylene succinate/graphene oxide composite material, comprise the following steps:
(1) graphene oxide is scattered in water, obtains the graphene oxide dispersion liquid;
(2) graphene oxide dispersion liquid and succinic acid, butyleneglycol are mixed, stir, carry out esterification;
(3) after esterification completes, mixed solution is used to Titanium series catalyst, carry out polycondensation, obtain poly butylene succinate/graphene oxide composite material.
The concentration of described graphene oxide dispersion liquid is 0.1mg/mL ~ 10mg/mL.
The temperature of reaction of described esterification is 150 ~ 200 ℃.
The reaction times of described esterification is 1 ~ 5h.
The temperature of reaction of described polycondensation is 200 ~ 300 ℃.
The reaction times of described polycondensation is 2 ~ 5h.
Described mixed solution is not more than under the 100Pa condition and carries out polycondensation in vacuum tightness.
The invention has the advantages that:
Compared with prior art, at first the present invention is scattered in graphene oxide in water, with succinic acid, butyleneglycol direct polymerization, react, at Graphene in situ Polymerization poly butylene succinate, graphene oxide is scattered in the poly butylene succinate matrix uniformly, because graphene oxide has good mechanical property and thermal conductivity, poly butylene succinate/the graphene oxide composite material obtained also has good resistance toheat, toughness, mechanical property, and its tensile strength, heat decomposition temperature, heat-drawn wire have all improved.
The accompanying drawing explanation
The synthetic route chart that Fig. 1 is preparation method of the present invention.
The atomic force microscopy that Fig. 2 is the graphene oxide that uses of the present invention.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is further described.
The synthetic route chart that Fig. 1 is preparation method of the present invention.The atomic force microscopy that Fig. 2 is the graphene oxide that uses of the present invention.
Embodiment 1
A kind of preparation method of poly butylene succinate/graphene oxide composite material comprises the following steps:
At first be scattered in deionized water graphene oxide is ultrasonic, be mixed with the graphene oxide colloidal dispersion of 0.5mg/mL;
Succinic acid, butyleneglycol, graphene oxide dispersion liquid are joined in four-hole boiling flask simultaneously, carry out prepolymerization reaction, temperature of reaction is 200 ℃, reacts 3 hours;
Then carry out polycondensation, add Titanium series catalyst, vacuum tightness is 40Pa, and temperature of reaction is 250 ℃, reacts 3 hours, obtains poly butylene succinate/graphene oxide composite material, and the Graphene massfraction is 0.5%.
Poly butylene succinate/the graphene oxide composite material obtained is carried out to performance test, the results are shown in Table one.As can be seen from the table, the melting index of poly butylene succinate/graphene oxide composite material, tensile strength, elongation at break, heat-drawn wire are all higher than simple poly butylene succinate.
Embodiment 2
A kind of preparation method of poly butylene succinate/graphene oxide composite material comprises the following steps:
At first be scattered in deionized water graphene oxide is ultrasonic, be mixed with the graphene oxide colloidal dispersion of 1mg/mL;
Succinic acid, butyleneglycol, graphene oxide dispersion liquid are joined in four-hole boiling flask simultaneously, carry out prepolymerization reaction, temperature of reaction is 200 ℃, reacts 3 hours;
Then carry out polycondensation, add Titanium series catalyst, vacuum tightness is 40Pa, and temperature of reaction is 250 ℃, reacts 3 hours, obtains poly butylene succinate/graphene oxide composite material, and the Graphene massfraction is 1%.
Poly butylene succinate/the graphene oxide composite material obtained is carried out to performance test, the results are shown in Table one.As can be seen from the table, the melting index of poly butylene succinate/graphene oxide composite material, tensile strength, elongation at break, heat-drawn wire are all higher than simple poly butylene succinate.
Embodiment 3
A kind of preparation method of poly butylene succinate/graphene oxide composite material comprises the following steps:
At first be scattered in deionized water graphene oxide is ultrasonic, be mixed with the graphene oxide colloidal dispersion of 2mg/mL;
Succinic acid, butyleneglycol, graphene oxide dispersion liquid are joined in four-hole boiling flask simultaneously, carry out prepolymerization reaction, temperature of reaction is 200 ℃, reacts 4 hours;
Then carry out polycondensation, add Titanium series catalyst, vacuum tightness is 40Pa, and temperature of reaction is 250 ℃, reacts 5 hours, obtains poly butylene succinate/graphene oxide composite material, and the Graphene massfraction is 3%.
Poly butylene succinate/the graphene oxide composite material obtained is carried out to performance test, the results are shown in Table one.As can be seen from the table, the melting index of poly butylene succinate/graphene oxide composite material, tensile strength, elongation at break, heat-drawn wire are all higher than simple poly butylene succinate.
The performance perameter of the poly butylene succinate/graphene oxide composite material of table one preparation
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Poly butylene succinate | Testing standard |
| Melting index g/10min | 11 | 12.5 | 14 | 10 | GB/T3682-2000 |
| Tensile strength (MPa) | 44 | 47 | 49 | 36 | GB/T1040.2-2006 |
| Elongation at break (%) | 350 | 110 | 40 | 10 | GB/T1040.2-2006 |
| Heat-drawn wire ℃ | 109 | 112 | 116 | 105 | GB/T1633-2000 |
Embodiment 4
A kind of preparation method of poly butylene succinate/graphene oxide composite material comprises the following steps:
(1) graphene oxide is scattered in water, obtains the graphene oxide dispersion liquid, the concentration of described graphene oxide dispersion liquid is 0.1mg/mL;
(2) graphene oxide dispersion liquid and succinic acid, butyleneglycol are mixed, 150 ℃ of stirrings, carry out esterification 1h;
(3) after esterification completes, mixed solution is used to Titanium series catalyst under vacuum tightness 0.0000001Pa condition, 200 ℃ are carried out polycondensation 2h, obtain poly butylene succinate/graphene oxide composite material.
Embodiment 5
A kind of preparation method of poly butylene succinate/graphene oxide composite material comprises the following steps:
(1) graphene oxide is scattered in water, obtains the graphene oxide dispersion liquid, the concentration of described graphene oxide dispersion liquid is 10mg/mL;
(2) graphene oxide dispersion liquid and succinic acid, butyleneglycol are mixed, 200 ℃ of stirrings, carry out esterification 5h;
(3) after esterification completes, mixed solution is used to Titanium series catalyst under vacuum tightness 100Pa condition, 300 ℃ are carried out polycondensation 5h, obtain poly butylene succinate/graphene oxide composite material.
Obviously, the above embodiment of the present invention is only for example of the present invention clearly is described, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here can't give all embodiments exhaustive.Every still row in protection scope of the present invention of apparent variation that technical scheme of the present invention extends out or change that belong to.
Claims (8)
1. a poly butylene succinate/graphene oxide composite material, comprise poly butylene succinate and graphene oxide, it is characterized in that, described graphene oxide disperse phase yardstick is 5 ~ 50nm, and ratio of weight and number is poly butylene succinate: graphene oxide=100:0.1 ~ 10.
2. the preparation method of poly butylene succinate/graphene oxide composite material as claimed in claim 1, is characterized in that, comprises the following steps:
(1) graphene oxide is scattered in water, obtains the graphene oxide dispersion liquid;
(2) graphene oxide dispersion liquid and succinic acid, butyleneglycol are mixed, stir, carry out esterification;
(3) after esterification completes, mixed solution is used to Titanium series catalyst, carry out polycondensation, obtain poly butylene succinate/graphene oxide composite material.
3. the preparation method of poly butylene succinate/graphene oxide composite material according to claim 2, is characterized in that, the concentration of described graphene oxide dispersion liquid is 0.1mg/mL ~ 10mg/mL.
4. the preparation method of poly butylene succinate/graphene oxide composite material according to claim 2, is characterized in that, the temperature of reaction of described esterification is 150 ~ 200 ℃.
5. the preparation method of poly butylene succinate/graphene oxide composite material according to claim 2, is characterized in that, the reaction times of described esterification is 1 ~ 5h.
6. the preparation method of poly butylene succinate/graphene oxide composite material according to claim 2, is characterized in that, the temperature of reaction of described polycondensation is 200 ~ 300 ℃.
7. the preparation method of poly butylene succinate/graphene oxide composite material according to claim 2, is characterized in that, the reaction times of described polycondensation is 2 ~ 5h.
8. the preparation method of poly butylene succinate/graphene oxide composite material according to claim 2, is characterized in that, described mixed solution is not more than under the 100Pa condition and carries out polycondensation in vacuum tightness.
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Cited By (10)
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| CN105017511A (en) * | 2015-08-20 | 2015-11-04 | 浙江万凯新材料有限公司 | Preparation method of oxidized graphene modified PET (polyethylene terephthalate) material |
| CN105199087A (en) * | 2015-10-21 | 2015-12-30 | 张东海 | Water-based graphene conductive polyester resin and preparation method thereof |
| CN105331058A (en) * | 2015-11-17 | 2016-02-17 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for preparing conductive polyester master batch with in-situ polymerization method |
| CN106317388A (en) * | 2016-08-23 | 2017-01-11 | 杭州鑫富科技有限公司 | Heat-resistant poly(butylene succinate) and preparation method thereof |
| CN106744826A (en) * | 2016-11-22 | 2017-05-31 | 长春工业大学 | A kind of method that the few layer graphene oxide film of large area is prepared based on esterification |
| CN107266889A (en) * | 2017-07-31 | 2017-10-20 | 陕西理工大学 | A kind of conductive antibacterial 3D printing PLA silk materials and preparation method thereof of low melting point |
| CN107722246A (en) * | 2017-10-29 | 2018-02-23 | 兰州城市学院 | A kind of preparation method of poly butylene succinate/class graphene molybdenum disulfide nano-composite material |
| CN108690262A (en) * | 2017-04-12 | 2018-10-23 | 合肥杰事杰新材料股份有限公司 | A kind of antistatic polypropylene composite material and preparation method thereof that modified graphene is modified |
| CN112409763A (en) * | 2020-11-05 | 2021-02-26 | 彤程化学（中国）有限公司 | Degradable conductive phosphorus-alkene composite material with gradient functional structure and preparation method and application thereof |
| CN114163784A (en) * | 2021-08-19 | 2022-03-11 | 山西盛景康科技有限公司 | Graphene oxide/poly (butylene succinate) composite material and preparation method thereof |
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2012
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| CN105017511A (en) * | 2015-08-20 | 2015-11-04 | 浙江万凯新材料有限公司 | Preparation method of oxidized graphene modified PET (polyethylene terephthalate) material |
| CN105199087A (en) * | 2015-10-21 | 2015-12-30 | 张东海 | Water-based graphene conductive polyester resin and preparation method thereof |
| CN105331058A (en) * | 2015-11-17 | 2016-02-17 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for preparing conductive polyester master batch with in-situ polymerization method |
| CN106317388A (en) * | 2016-08-23 | 2017-01-11 | 杭州鑫富科技有限公司 | Heat-resistant poly(butylene succinate) and preparation method thereof |
| CN106744826A (en) * | 2016-11-22 | 2017-05-31 | 长春工业大学 | A kind of method that the few layer graphene oxide film of large area is prepared based on esterification |
| CN108690262A (en) * | 2017-04-12 | 2018-10-23 | 合肥杰事杰新材料股份有限公司 | A kind of antistatic polypropylene composite material and preparation method thereof that modified graphene is modified |
| CN107266889A (en) * | 2017-07-31 | 2017-10-20 | 陕西理工大学 | A kind of conductive antibacterial 3D printing PLA silk materials and preparation method thereof of low melting point |
| CN107266889B (en) * | 2017-07-31 | 2018-08-07 | 陕西理工大学 | A kind of conductive antibacterial 3D printing PLA silk materials and preparation method thereof of low melting point |
| CN107722246A (en) * | 2017-10-29 | 2018-02-23 | 兰州城市学院 | A kind of preparation method of poly butylene succinate/class graphene molybdenum disulfide nano-composite material |
| CN112409763A (en) * | 2020-11-05 | 2021-02-26 | 彤程化学（中国）有限公司 | Degradable conductive phosphorus-alkene composite material with gradient functional structure and preparation method and application thereof |
| CN114163784A (en) * | 2021-08-19 | 2022-03-11 | 山西盛景康科技有限公司 | Graphene oxide/poly (butylene succinate) composite material and preparation method thereof |
| CN114163784B (en) * | 2021-08-19 | 2024-01-19 | 青岛同心振茂塑染有限公司 | Graphene oxide/polybutylene succinate composite material and preparation method thereof |
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