CN102153838B - A kind of biodegradable polybutylene carbonate type composite material and preparation method thereof - Google Patents

Abstract

The invention relates to a biodegradable aliphatic polycarbonate butanediol ester type composite material and a preparation method thereof, which is characterized in that: the material comprises the following components in parts by weight: 30-70 parts of aliphatic polycarbonate butanediol ester, 10-40 parts of other biodegradable materials, 1.0-10 parts of filler, 0.5-1.5 parts of rare earth composite nucleating agent, 0.5-1.5 parts of dispersing agent, 4.0-15 parts of plasticizer, 1.5-4 parts of heat-resistant stabilizer, 0.05-1.5 parts of antioxidant, 0.5-1.0 part of lubricating agent, 0.1-1.0 part of opening agent and 0.05-0.5 part of biodegradation accelerator. The composite material has the advantages of high melt strength, good film forming property, high tensile strength, high tearing strength and good light conversion effect.

Description

A kind of biodegradable polybutylene carbonate type composite material and preparation method thereof

technical field

The invention relates to a biodegradable plastic material, in particular to a biodegradable polybutylene carbonate composite material and a preparation method thereof.

Background technique

While the development of the traditional plastics industry meets the needs of social development and people's lives, it also brings immeasurable negative impacts on the environment on which human beings depend. The waste of these traditional plastic products after use is as high as 50%-60%. According to incomplete statistics, the total amount of plastic waste in the world is as high as 50 million tons every year, and it takes 200-400 years for them to completely decompose in nature. The environmental pollution caused by these waste plastics is becoming more and more serious. In order to solve the problem of "white pollution" caused by plastic products, the use of environmentally friendly fully biodegradable polymers to replace traditional petroleum-based plastics has become a hot spot in current research and development.

At present, there are many biodegradable materials reported at home and abroad mainly include polyhydroxyalkanoate and polyhydroxyalkanoate (PHA) synthesized by microorganisms; chemically synthesized polylactic acid (PLA) and polycaprolactic acid (PCL) , polybutylene succinate (PBS), aliphatic/aromatic copolyester, aliphatic polycarbonate (APC), polyvinyl alcohol (PVA), etc., some of which have been commercialized. However, due to the stages of development, the existing biodegradable polymer materials have certain shortcomings. For example, polylactic acid is relatively cheap, but its melt strength is low, which makes it difficult to blow the film. low cracking strength; other films such as polyhydroxyalkanoate (PHA, PHB, PHBV), aliphatic polycarbonate (APC), polyvinyl alcohol (PVA), etc. have problems such as poor mechanical properties, and traditional Biodegradable films have poor UV resistance and no light conversion, which significantly affect the large-scale promotion and use of biodegradable plastics.

Contents of the invention

The purpose of the present invention is to overcome the above disadvantages, to provide a biodegradable aliphatic polybutylene carbonate type composite material with high melt strength, excellent mechanical properties and good UV resistance and a preparation method thereof.

The purpose of the present invention is achieved like this:

A kind of biodegradable aliphatic polybutylene carbonate type composite material, described material comprises following proportions by weight:

Aliphatic poly(butylene carbonate), PBC for short) 30-70 parts, other biodegradable materials 10-40 parts, filler 1.0-10 parts, rare earth composite nucleating agent 0.5-1.5 parts, 0.5-1.5 parts of dispersant, 4.0-15 parts of plasticizer, 1.5-4 parts of heat-resistant stabilizer, 0.05-1.5 parts of antioxidant, 0.5-1.0 parts of lubricant, 0.1-1.0 parts of anti-blocking agent, biodegradation accelerator 0.05-0.5 copies;

Wherein: the number average molecular weight of the aliphatic polybutylene carbonate is 60000～150000;

Other biodegradable materials mentioned: polylactic acid (PLA), polycaprolactone (PCL), polybutylene succinate (PBS), aliphatic/aromatic copolyesters, aliphatic polycarbonate (APC ), polyvinyl alcohol (PVA), polyhydroxyalkanoate (PHA, PHB, PHBV).

The rare earth composite nucleating agent is: main nucleating agent: nano cerium oxide; auxiliary nucleating agent: nano europium oxide, the ratio of the main nucleating agent to the auxiliary nucleating agent is 60:40～95:5;

The dispersant: cage octapaniline methyl silsesquioxane.

The particle diameters of the nano-cerium oxide and nano-europium oxide are all nano-materials in the order of 10 nm to 100 nm.

The plasticizer is: any epoxy resin plasticizer such as phthalate (such as: DBP, DOP, DIDP), polyethylene glycol, polypropylene glycol adipate, epoxy soybean oil, etc. A sort of.

The heat-resistant stabilizer is one of: maleic dibutyltin, calcium stearate, zinc oxide, and magnesium oxide.

The antioxidant is: any one of bisphenol A, ethyl phosphite, triphenyl phosphite or bisphenol A phosphite.

Described lubricant: stearic acid.

The anti-blocking agent: silicon dioxide with a particle diameter of 3-4 microns.

The biodegradation accelerator: one of oxalic acid, malonic acid, citric acid, malic acid and succinic anhydride.

The filler: one of calcium carbonate, talc, white carbon black, mica, and kaolin.

The preparation method of the aliphatic polybutylene carbonate comprises two steps of transesterification and polycondensation, and the specific steps are as follows:

step one:

Transesterification: In an inert gas atmosphere, the glycol and carbonate are heated up under the action of a transesterification catalyst to complete the transesterification reaction, and the by-products generated in the transesterification reaction are removed to obtain aliphatic polybutylene carbonate (polybutylene carbonate) (butylene carbonate)) prepolymer;

Step two:

Polycondensation: Add a polycondensation catalyst to the reaction system in the above step 1, and carry out polycondensation reaction in vacuum to obtain the aliphatic polybutylene carbonate (poly(butylene carbonate)) provided by the present invention.

In step 1 of the preparation method, the dihydric alcohol is: 1,4-butanediol; the carbonate is: dimethyl carbonate or diethyl carbonate; the transesterification catalyst is potassium hydroxide, sodium hydroxide, titanic acid Any one of tetraisopropyl esters; the polycondensation catalyst is any one of titanium dioxide, titanium trioxide and aluminum oxide.

A method for preparing a biodegradable aliphatic polybutylene carbonate composite material, characterized in that: the preparation steps and conditions are as follows: weigh the matrix resin in proportion, and dry it in an oven at 20-60°C for 5 ~ 10 hours, at the same time, mix the weighed nano-cerium oxide and nano-europium oxide in proportion, then put the baked matrix resin into the high-speed mixer, start stirring at a low speed, and add the weighed rare earth compound Nucleating agent, dispersant, plasticizer, heat-resistant stabilizer, antioxidant, lubricant, opening agent, biodegradation accelerator and filler, stir at low speed for 5-10 minutes, then add and stir at high speed for 5-10 minutes Finally, after stirring evenly, enter the co-rotating twin-screw extruder. The product is obtained by extruding and granulating at a temperature of 60-190°C.

Compared with prior art, the beneficial effect of the present invention is:

In the biodegradable aliphatic polybutylene carbonate type composite material of the present invention, a high molecular weight aliphatic polybutylene carbonate (poly(butylene carbonate), PBC for short) is selected, and the number average molecular weight is 60000-150000 , which has the advantages of low cost, high melt strength, and good heat resistance. It can be blown into a film after being blended with other biodegradable materials. The film has good flexibility and high tear strength.

Aiming at the problem of slow crystallization speed of PBC, the present invention adopts a complex type rare earth β nucleating agent, that is, a rare earth composite nucleating agent. The compound of europium is obtained. During the isothermal crystallization process of the melt, on the one hand, nano-cerium oxide plays the role of increasing the crystal nucleus; on the other hand, it reduces the interfacial free energy of macromolecular folding in the direction perpendicular to the molecular chain during crystal growth, making it easier for macromolecular chains to enter The crystal lattice, that is, plays a role in promoting crystal growth and increasing the crystallization rate. However, the β crystal form formed by it has poor thermodynamic stability, so nano europium oxide is compounded. Because the crystal plane lattice spacing of trivalent europium is small, its stability is improved after compounding, and at the same time, because europium element can absorb Ultraviolet light, thereby converting into red-orange light, makes the polybutylene carbonate biodegradable composite material have light conversion properties, and the prepared film can convert harmful ultraviolet light into beneficial red-orange light, which is beneficial The photosynthesis of plants promotes growth, reduces the use of chemical fertilizers, and plays an ecological and environmental role.

The nano-cerium oxide and nano-europium oxide selected in the present invention are all nano-materials of 10nm to 100nm level. Due to the small particle size and large specific surface area of the nano-components, they are easily aggregated to form larger aggregates, so that the nanoparticles are aggregated due to aggregation. However, it cannot be uniformly dispersed in the polymer matrix resin. In view of this problem, the present invention selects a cage-type octaaniline methyl silsesquioxane, which is a class of cage-type silsesquioxanes with both nanometer and fine structures. Special nanoparticles that can be functionalized. It has a cage-shaped core/shell structure, and its shell is usually 8 organic functional groups, of which 7 functional groups are inert organic groups and 1 is a reactive functional group. Its organic groups can achieve good compatibility with organic solvents and polymer matrix resins, thereby greatly reducing the agglomeration of nanoparticles and making them more uniformly dispersed.

The invention solves the problems of low melt strength of existing biodegradable polymer materials, difficulty in film blowing, high film brittleness, relatively poor light conversion property of the film, and the like. It has the characteristics of high melt strength, good film-forming property and good light conversion effect.

Detailed ways

Example 1:

Weigh each component according to the following parts by weight: PBC: 50.0, PLA: 36.0, compound type rare earth β nucleating agent, that is, rare earth composite nucleating agent (nano cerium oxide: nano europium oxide 65:35) 1.0, cage octamer Anilinomethylsilsesquioxane: 1.0, Polyethylene Glycol: 5.0, Butylene Dibutyltin: 2.5, Bisphenol A: 0.5, Stearic Acid: 0.7, Silicon Dioxide: 1.0, Malonic Acid: 0.05, Calcium Carbonate: 4.0.

Preparation steps and conditions are:

Weigh the matrix resin in proportion, dry it in an oven at 30°C for 6 hours in advance, and mix the weighed nano-cerium oxide and nano-europium oxide in proportion, then put the baked matrix resin into the high-speed mixer, and start to mix at a low speed. Stir, while stirring, add the weighed rare earth composite nucleating agent, dispersant, plasticizer, heat-resistant stabilizer, antioxidant, lubricant, anti-blocking agent, biodegradation accelerator and filler in turn, stir at low speed After 10 minutes, add and stir at high speed for 5 minutes, stir evenly, and then enter the co-rotating twin-screw extruder. The product is obtained by extruding and granulating at a temperature of 60-190°C. The composite material masterbatch prepared by the above process is blow-molded to obtain a film product.

The performance comparison of the obtained film products is shown in Table 1.

Table 1:

从表1可以看出，脂肪族聚碳酸丁二醇酯的加入大大提高了PLA断裂伸长率和撕裂强度，断裂伸长率是纯聚乳酸的大约50倍。撕裂强度是纯聚乳酸的大约4倍。

It can be seen from Table 1 that the addition of aliphatic polybutylene carbonate greatly improves the elongation at break and tear strength of PLA, and the elongation at break is about 50 times that of pure polylactic acid. Tear strength is about 4 times that of pure polylactic acid.

Example 2:

Weigh each component according to the following parts by weight: PBC: 55.0, polycaprolactic acid PCL: 30.0, complex rare earth β nucleating agent, that is, rare earth composite nucleating agent (nano cerium oxide: nano europium oxide 60:40): 1.5 , Cage octapolyaniline methyl silsesquioxane: 0.5, polypropylene glycol adipate: 5.0, zinc oxide: 2.5, ethyl phosphite: 0.5, stearic acid: 0.7, silicon dioxide: 1.0, propane Diacid: 0.05, calcium carbonate: 4.0;

See Example 1 for the preparation steps and conditions.

The performance comparison of the obtained film products is shown in Table 2.

Table 2:

实施例3：

Example 3:

Weigh each component according to the following parts by weight: PBC: 50.0, PBS: 35.0, compound type rare earth β nucleating agent, that is, rare earth composite nucleating agent (nano cerium oxide: nano europium oxide 70:30): 1.0, cage type eight Polyaniline methyl silsesquioxane: 0.5, epoxy soybean oil: 10.0, calcium stearate: 3.0, ethyl phosphite: 0.5, stearic acid: 1.0, silicon dioxide: 1.0, oxalic acid: 0.05, white Carbon black: 4.0;

See Example 1 for the preparation steps and conditions.

The performance comparison of the obtained film products is shown in Table 3.

table 3:

实施例4：

Example 4:

Weigh each component according to the following parts by weight: PBC: 60.0, PHB: 30.0, compound type rare earth β nucleating agent, that is, rare earth composite nucleating agent (nano cerium oxide: nano europium oxide 75:25): 1.0, cage type eight Polyanilinemethylsilsesquioxane: 1.0, Phthalate: 12.0, Magnesium Oxide: 3.5, Bisphenol A Phosphite: 1.0, Stearic Acid: 1.0, Silicon Dioxide: 1.0, Succinic Anhydride: 0.15, white carbon black: 4.0;

See Example 1 for the preparation steps and conditions.

The performance comparison of the obtained film products is shown in Table 4.

Table 4:

Example 5:

Weigh each component according to the following parts by weight: PBC: 70.0, PHBV: 25.0, compound type rare earth β nucleating agent, that is, rare earth composite nucleating agent (nano cerium oxide: nano europium oxide 80:20): 1.0, cage type eight Polyanilinemethylsilsesquioxane: 0.8, Polyethylene Glycol: 10.0, Butylene Dibutyltin: 3.0, Bisphenol A Phosphite: 1.0, Stearic Acid: 1.0, Silicon Dioxide: 1.0, Malonic Acid : 0.15, white carbon black: 4.0;

See Example 1 for the preparation steps and conditions.

The performance comparison of the obtained film products is shown in Table 5.

table 5:

实施例:6：

Embodiment: 6:

Weigh each component according to the following parts by weight: PBC: 65.0, PHA: 30.0, compound type rare earth β nucleating agent, that is, rare earth composite nucleating agent (nano cerium oxide: nano europium oxide 85:15): 1.0, cage type eight Polyanilinemethylsilsesquioxane: 1.0, Polyethylene Glycol: 10.0, Calcium Stearate: 3.0, Bisphenol A Phosphite: 1.0, Stearic Acid: 1.0, Silicon Dioxide: 1.0, Oxalic Acid: 0.2, Calcium carbonate: 4.0;

See Example 1 for the preparation steps and conditions.

The performance comparison of the obtained film products is shown in Table 6.

Table 6:

实施例:7：

Example: 7:

Weigh each component according to the following parts by weight: PBC: 65.0, PVA: 30.0, compound type rare earth β nucleating agent, that is, rare earth composite nucleating agent (nano cerium oxide: nano europium oxide 74:26): 0.8, cage type eight Polyanilinemethylsilsesquioxane: 1.1, Polyethylene Glycol: 10.0, Magnesium Oxide: 3.0, Bisphenol A: 1.0, Stearic Acid: 1.0, Silicon Dioxide: 1.0, Malonic Acid: 0.2, Calcium Carbonate :5.0;

See Example 1 for the preparation steps and conditions.

The performance comparison of the obtained film products is shown in Table 7.

Table 7:

The aliphatic polybutylene carbonate of the high molecular weight that the present invention uses, its general structural formula is as follows:

In the general structural formula above, n=345～875.

The preferred preparation method of the above-mentioned aliphatic poly(butylene carbonate) used in the present invention comprises two steps of transesterification and polycondensation, and the specific steps are as follows:

step one:

Transesterification: In an inert gas atmosphere, the glycol and carbonate are heated up under the action of a transesterification catalyst to complete the transesterification reaction, and the by-products generated in the transesterification reaction are removed to obtain aliphatic polybutylene carbonate (polybutylene carbonate) (butylene carbonate)) prepolymer;

Step two:

Polycondensation: Add a polycondensation catalyst to the reaction system in the above step 1, and carry out polycondensation reaction in vacuum to obtain the aliphatic polybutylene carbonate (poly(butylene carbonate)) provided by the present invention.

In step 1 of the above preparation method, the dihydric alcohol is: 1,4-butanediol; the carbonate is: dimethyl carbonate or diethyl carbonate; the transesterification catalyst is potassium hydroxide, sodium hydroxide, tetratitanate Any one of isopropyl esters; the polycondensation catalyst is any one of titanium dioxide, titanium trioxide and aluminum oxide.

Claims (5)

1. biodegradable aliphatics polytetramethylene carbonate diol type matrix material, it is characterized in that: said material comprises following parts by weight proportioning:

Aliphatics polytetramethylene carbonate diol 30-70 part, other Biodegradable materials 10-40 part, weighting agent 1.0-10 part, rare earth compound nucleating agent 0.5-1.5 part, dispersion agent 0.5-1.5 part, softening agent 4.0-15 part, heat-resisting stabilizing agent 1.5-4 part, oxidation inhibitor 0.05-1.5 part, lubricant 0.5-1.0 part, opening agent 0.1-1.0 part, biodegradation promotor 0.05-0.5 part;

Wherein: the number-average molecular weight 60000～150000 of said aliphatics polytetramethylene carbonate diol;

Said other Biodegradable materials are: a kind of in POLYACTIC ACID, polycaprolactone, poly butylene succinate, aliphatic/aromatic copolyesters, aliphatic polycarbonate, Z 150PH, the polyhydroxyalkanoate;

Said rare earth compound nucleating agent is: main nucleator: nano-cerium oxide; Auxiliary nucleator: nano europium oxide, the ratio of main nucleator and auxiliary nucleator are 60:40～95:5;

Said dispersion agent: cage anilino methyl sesquisiloxane octamer;

Said opening agent: particle diameter is 3～4 microns a silicon-dioxide;

Said biodegradation promotor: a kind of in oxalic acid, propanedioic acid, Hydrocerol A, oxysuccinic acid, the Succinic anhydried;

The method for preparing said aliphatics polytetramethylene carbonate diol comprises transesterify and two steps of polycondensation, and concrete steps are following:

Step 1:

Transesterify: in inert gas atmosphere, divalent alcohol and carbonic ether heated up under the effect of transesterification catalyst accomplish transesterification reaction, and remove the prepolymer that the by product that produces in the transesterification reaction obtains the aliphatics polytetramethylene carbonate diol;

Step 2:

Polycondensation: in the reaction system of above-mentioned step 1, add polycondensation catalyst, vacuum is carried out polycondensation, obtains said aliphatics polytetramethylene carbonate diol;

In said preparing method's the step 1, divalent alcohol is: 1, and the 4-butyleneglycol; Carbonic ether is: methylcarbonate or diethyl carbonate; Transesterification catalyst is any one in Pottasium Hydroxide, sodium hydroxide, the titanium isopropylate;

Said polycondensation catalyst is: a kind of in titanium oxide, titanium sesquioxide, the aluminum oxide.

2. a kind of biodegradable aliphatics polytetramethylene carbonate diol type matrix material according to claim 1, it is characterized in that: said nano-cerium oxide, nano europium oxide all are nano materials of 10nm～100nm level.

3. a kind of biodegradable aliphatics polytetramethylene carbonate diol type matrix material according to claim 1, it is characterized in that: said softening agent is: a kind of in phthalic ester, polyoxyethylene glycol, the epoxy soybean oil epoxy resin softening agent.

4. a kind of biodegradable aliphatics polytetramethylene carbonate diol type matrix material according to claim 1, it is characterized in that: said heat-resisting stabilizing agent is: a kind of in maleic dibutyl tin, calcium stearate, zinc oxide, the Natural manganese dioxide.

5. a kind of biodegradable aliphatics polytetramethylene carbonate diol type matrix material according to claim 1, it is characterized in that: said oxidation inhibitor is: a kind of in dihydroxyphenyl propane, phosphorous acid ethyl ester, triphenyl phosphite or the phosphorous acid dihydroxyphenyl propane.