CN107365482B - A kind of special reinforced toughened anti-reflection master batch of ultra-thin whole life cycle design - Google Patents

Abstract

The invention belongs to the field of biodegradable polymer materials, and in particular relates to a special reinforced, toughened and anti-permeable masterbatch for ultra-thin fully biodegradable mulch. The masterbatch is mainly composed of polyadipate/butylene terephthalate, polylactic acid It is prepared with strengthening, toughening, anti-permeability and stability additives. The preparation method is simple and easy to operate. The obtained special masterbatch can be completely degraded and has good dispersibility. Adding an appropriate amount of the masterbatch can blow the ultra-thin biological material below 6μm. Degradable mulch film, the film is easy to open during the ultra-thin mulch film blowing process, the processing stability and processing efficiency are improved, the mechanical properties of the processed mulch film are enhanced, the light transmittance of the mulch film is improved, the haze is reduced, and the weather resistance of the mulch film is significantly improved at the same time; The masterbatch combines multiple functions such as reinforcement, toughening, anti-reflection, and lubrication. It is easy to use, improves the processing performance of ultra-thin fully biodegradable mulch, and reduces the cost of using fully biodegradable mulch.

Description

A special reinforcement, toughening and anti-permeability masterbatch for ultra-thin fully biodegradable mulch

technical field

The invention belongs to the field of agricultural materials, and in particular relates to a plastic masterbatch, in particular to a special reinforcement, toughening and anti-permeability masterbatch for ultra-thin fully biodegradable plastic film.

Background technique

Plastic mulches play a huge role in agricultural production. However, most of the plastic mulches currently used are polyolefin mulches that are difficult to degrade in a short period of time or incompletely degradable polyolefin mulches that have been added with starch and photodegradants. The use of these mulch materials has caused "white pollution" of the environment and brought safety hazards to the sustainable development of human beings. Fully biodegradable mulch is made of completely biodegradable plastics through blow molding or tape casting. It can be completely decomposed by microorganisms. The final products of its degradation are carbon dioxide and water, which can be completely absorbed by nature. Therefore, it is replaced by fully biodegradable mulch. The current polyolefin products are an important means to solve the white pollution of farmland.

At present, the fully biodegradable mulch film is mainly composed of polylactic acid, polycaprolactone, aliphatic polyester, aliphatic polycarbonate, polyhydroxyester, starch, etc., but due to the characteristics and defects of the above-mentioned polymers, it is difficult for a single polymer to Used as mulch material. The current research is mainly through blending modification, copolymerization modification, plasticizing modification and composite modification to improve the comprehensive performance of the film. Patent CN 103589124B discloses a fully biodegradable PLA/PBAT composite mulch film and its preparation method; patent CN 104744898A discloses a fully biodegradable mulch film and its preparation method. Polyester (PPC), polybutylene adipate/terephthalate (PBAT) and heat stabilizer, but the thickness of these mulch films is generally high, 6um-50um, the cost of the mulch film remains high, and the light transmittance is poor. The strength is low, so it cannot be commercialized in the short term; different from the difficult-to-degrade polyolefin film, for the fully biodegradable film, as long as the processing is convenient and the performance is excellent, the thinner the film product, the better. We are also committed to solving the above problems. In 2013, we applied for a patent 201310749460.X for a fully biodegradable mulch masterbatch and its preparation method and application. However, we found that the masterbatch is used for blowing ultra-thin fully biodegradable film in practical applications. When using mulch, it is difficult to open the film bubble during the processing of the ultra-thin mulch film below 6 μm, the tensile strength and tear strength are greatly reduced, and the haze is large. Mulch film is easy to crack in advance, so this technology has certain defects, and how to overcome this defect and provide a more balanced performance of mulch masterbatch has become a problem that we need to solve.

Contents of the invention

Aiming at the many deficiencies in the prior art, the present invention provides a special reinforced, toughened and anti-permeable masterbatch for ultra-thin fully biodegradable mulch, which is mainly composed of poly(butylene adipate/terephthalate), It is prepared from polylactic acid, toughening, toughening, anti-permeability and stability additives. The preparation method is simple and easy to operate. The special masterbatch obtained can be completely degraded and has good dispersibility. Adding an appropriate amount of the masterbatch can blow the ultra- Thin biodegradable mulch film, the membrane is easy to open during the ultra-thin mulch film blowing process, the processing stability and processing efficiency are improved, the mechanical properties of the processed mulch film are enhanced, and the light transmittance of the mulch film is improved at the same time, and the haze is reduced; the masterbatch combination It has multiple functions such as reinforcement, toughening, anti-reflection, and lubrication, and is easy to use, which improves the processing performance of the ultra-thin fully biodegradable mulch film and reduces the cost of using the fully biodegradable mulch film.

Concrete technical scheme of the present invention is:

A special reinforcement, toughening and anti-reflection masterbatch for ultra-thin fully biodegradable mulch, the main components of which are calculated by weight:

65-85 parts of polyadipate/butylene terephthalate, 1-20 parts of polylactic acid, 10-20 parts of strengthening, toughening and anti-reflection agent, 5-30 parts of lubricant, 1-5 parts of dispersing agent, stable 1-5 parts of sexual aids;

Wherein said poly(butylene adipate/terephthalate) and poly(lactic acid) are used as the carrier resin, the melt flow rate of the two is 2-5g/10min, and the hydroxyl value is less than 15. The polybutylene adipate/terephthalate and polylactic acid used in the present invention are very important to the preparation and performance of the special masterbatch for ultra-thin fully degradable mulch film. Volatilization and decomposition, when preparing ultra-thin fully biodegradable mulch with the masterbatch of the present invention in the later stage, it must have better compatibility with other fully biodegradable resins, and will not induce the degradation of the mulch, so the inventors Among the many alternative resins, the above-mentioned resins are preferably used as the carrier resin of the masterbatch, and the specific dosage is limited as above, and the functions of the masterbatch are optimally balanced within this dosage range.

The described strengthening, toughening and anti-reflection agent is one or more of inorganic strengthening, toughening and anti-reflection agents, organic strengthening, toughening and anti-reflection agents: the inorganic strengthening, toughening and anti-reflection agents are selected from the group consisting of hydrophobic nano-dioxide Silicon, wherein the size of the hydrophobic nano-silica is 5-25nm; the organic reinforcement, toughening and anti-reflection agent is Akema AX-8900 or ADX-1200s resin compatibilizer or Hangzhou Aike CE-AZ01 enhancer One or several kinds of solvents;

The strengthening, toughening and anti-reflection agent does not exceed 20 parts, in order to ensure that the powder is less lost in the process of mixing with the resin, the distribution is uniform, and it is convenient for granulation; at the same time, it also improves the compatibility of various resins in the later film processing, and also The mechanical properties of the film will not be reduced due to the addition of too much compatibilizer.

Select the above-mentioned strengthening, toughening and anti-reflection agent, which has good blending compatibility with the carrier resin, and can produce high-concentration masterbatch; in the later film processing process, it can act as a nucleating agent and compatibilizer, which is beneficial to ultra-thin film processing stability, and at the same time, it is used to enhance the mechanical properties of ultra-thin fully biodegradable films.

The lubricant is one or both of polymer microspheres PMMA and silicon dioxide microspheres. The size of the polymer microspheres is 0.5-5 μm, and the size of the silica microspheres is 1-5 μm; both can be purchased directly from the market;

The above-mentioned lubricant mainly plays the role of lubricating the opening in the present invention, which is beneficial to the opening of the diaphragm when the ultra-thin fully biodegradable film is processed. sex;

The dispersant is selected from one or both of epoxidized soybean oil and silicone-based diffusing oil. After the above-mentioned dispersant is selected, it can better cooperate with the strengthening, toughening and anti-reflection agent, which is beneficial to the strengthening, toughening and anti-reflection agent. Dispersion in carrier resin;

Described stability assistant is one or both of ultraviolet absorber, ultraviolet stabilizer, and described ultraviolet absorber is low volatility benzotriazole ultraviolet absorber Tinuvin 234; Described ultraviolet stabilizer is Steric hindered amine stabilizer 5050H.

The above additives can avoid and improve the photodegradation problem during the processing of ultra-thin fully biodegradable mulch film and field use, and prolong its service life;

All the above-mentioned auxiliary agents used in the present invention are environmentally friendly reagents and materials, which can be completely degraded in nature.

Another feature of the present invention is to provide the preparation method of the special reinforcement, toughening and anti-reflection masterbatch for the ultra-thin fully biodegradable mulch film, comprising the following steps: (1) adding the strengthening, toughening and anti-reflection agent and the dispersing agent Dissolving and dispersing in carbon tetrachloride, after stirring evenly, distilling out carbon tetrachloride to obtain the mixture; (2) the mixture obtained in step (1), polyadipic acid/butylene terephthalate and polylactic acid, Stability aids and lubricants are put into a high-speed mixer in parts by weight in turn, stirred and kneaded at 700-1000r/min for 10-30 minutes; (3) put the homogeneously mixed mixture in step (2) into a twin-screw extruder, and grind at 135 Extruded at -160°C, air-cooled and granulated to obtain reinforced, toughened and anti-permeable masterbatches for ultra-thin fully biodegradable mulch films.

In the above preparation method, the inventor first selects carbon tetrachloride as a solvent to dissolve and disperse the reinforcing and toughening agent, and makes the dispersant evenly coat the surface of the reinforcing and toughening agent by volatilizing the solvent, which is beneficial to strengthening, toughening and anti-reflection agent Dispersion in carrier resin. Compared with the current conventional mixing method, the effect is better.

In summary, the use of the masterbatch provided by the present invention can not only maintain the smoothness of ultra-thin fully biodegradable mulch film processing, but also ensure the mechanical properties and use stability of ultra-thin fully biodegradable mulch products. Significantly reduce the cost of raw materials. The production process of the masterbatch is simple and easy to master. The masterbatch produced by this method is stable in nature, without any moisture, can be completely degraded, and has good dispersibility. Adding an appropriate amount of this masterbatch to a fully biodegradable resin can blow a 4-6μm ultra-thin biodegradable mulch film, and the ultra-thin mulch film blowing process film The sheet is easy to open, and the processing stability is improved. The special reinforcement, toughening and anti-reflection masterbatch for ultra-thin fully biodegradable mulch of the present invention combines multiple functions such as reinforcement, toughening, anti-reflection, lubrication, light stability, etc., the method of use is simple, and the processing performance of ultra-thin fully biodegradable mulch can be improved. , and at the same time solve the problems of poor mechanical strength of super mulch film, large haze and too fast degradation during field use.

Detailed ways

Example 1

Reinforcing, toughening and anti-reflection masterbatch for ultra-thin fully biodegradable mulch film, in parts by weight, includes the following components:

Prepared according to the following steps:

Dissolve and disperse hydrophobic nano-silica and epoxy soybean oil in carbon tetrachloride, stir evenly, distill off carbon tetrachloride to obtain mixture 1; then mix mixture 1, polyadipic acid/terephthalic acid Butylene glycol ester, polylactic acid, ultraviolet absorber Tinuvin 234, and polymer microspheres PMMA are sequentially put into a high-speed mixer for stirring at 700-1000 r/min, and mixed for 10-30 minutes to obtain a mixture 2; the mixture 2 is put into a twin-screw extruder, Extruded at 135-160°C, air-cooled and granulated to obtain reinforced, toughened, and anti-reflective masterbatches for ultra-thin fully biodegradable mulch films.

Example 2

Reinforcing, toughening and anti-reflection masterbatch for ultra-thin fully biodegradable mulch film, in parts by weight, includes the following components:

Prepared according to the following steps:

Dissolve and disperse hydrophobic nano-silica and silicone diffusion oil in carbon tetrachloride, stir evenly, distill off carbon tetrachloride to obtain mixture 1; then the mixture, polyadipate/butyl terephthalate Diester, polylactic acid, AICA CE-AZ01, UV absorber Tinuvin 234, UV stabilizer Put 5050H and silica microspheres into a high-speed mixer in turn at 700-1000r/min to stir and knead for 10-30 minutes to obtain mixture 2; put mixture 2 into a twin-screw extruder, extrude at 135-160°C, and air-cool granulate , to obtain a special reinforced, toughened and anti-permeable masterbatch for ultra-thin fully biodegradable mulch.

Example 3

Reinforcing, toughening and anti-reflection masterbatch for ultra-thin fully biodegradable mulch film, in terms of weight percentage, includes the following components:

Prepared according to the following steps:

Dissolve and disperse hydrophobic nano-silica and silicone diffusion oil in carbon tetrachloride, stir evenly, distill off carbon tetrachloride to obtain mixture 1; then the mixture, polyadipate/butyl terephthalate Diesters, UV Stabilizers 5050H, Akema AX-8900, and silica microspheres were sequentially put into a high-speed mixer at 700-1000r/min and stirred and mixed for 10-30 minutes to obtain mixture 2; mixture 2 was put into a twin-screw extruder, Extrusion and air-cooling granulation to obtain the reinforced, toughened and anti-permeable masterbatch for ultra-thin fully biodegradable mulch film.

Experimental example

The special reinforced, toughened and permeable masterbatch of the ultra-thin fully biodegradable mulch film of the present invention is applied to the blowing of the super mulch film. There are mainly two adding methods, one is to use the masterbatch according to the ratio of 1-5% of the super mulch film components It is directly mixed with the film blowing material, and then added to the blown film machine for extrusion blow molding; the other is to mix and granulate the masterbatch with other components according to 1-5% of the super mulch film component, and then add it to the blown film machine for extrusion. blow molding.

Application example 1

Components and dosage (number of parts)

90 copies of PBAT

PLA 5 parts

5 parts of the ultra-thin fully biodegradable mulch special reinforcement, toughening and anti-reflection masterbatch prepared in Example 1

Preparation process: weigh various raw materials according to the above formula, and place them in a high-speed mixer to stir for 5 minutes. After uniform mixing, extrude and granulate through twin-screws, put the mixture in the hopper of the extrusion film blowing machine, and extrude and blow it into a uniform cylindrical film (the thickness of the film is 4-5 μm, and the width of the film is 90- 200cm), cut and rolled to make ultra-thin fully biodegradable mulch.

Application example 2

PBAT 92 copies

PPC 5 copies

3 parts of the ultra-thin fully biodegradable mulch special reinforcement, toughening and anti-reflection masterbatch prepared in Example 1

Preparation process: weigh various raw materials according to the above formula, and place them in a high-speed mixer to stir for 5 minutes. After uniform mixing, the mixture is placed in the hopper of the extrusion blown film machine, extruded and blown into a uniform cylindrical film (the thickness of the film is 4-5μm, and the width of the film is 90-200cm). , Sub-rolls made of ultra-thin fully biodegradable mulch.

According to GB/T1040.3 Determination of tensile properties of plastics Part 3: Test conditions for films and sheets, the tensile rate is 200mm/min. The properties of the obtained film are shown in Table 1. The comparative example is a mulch film using the same resin without adding special reinforcement, toughening and anti-reflection masterbatch for ultra-thin fully biodegradable mulch film.

Application example 1 Comparative example 1 Application example 2 Comparative example 2 resin PBAT, PLA PBAT, PLA PBAT, PPC PBAT, PPC Thickness (μm) 5 8 5 8 Transmittance(%) 91 90 88 85 Tensile strength (MPa) 30 25 28 17 Elongation at break (%) 706 550 560 386 Right Angle Tear Strength (MPa) 117 108 93 85 Degradability Total degradation Total degradation Total degradation Total degradation blown film bubble opening + - + +-

+: The opening is smooth and the film is not continuous, +-: The opening is possible, but the film is easy to break, -: It is difficult to open, and the film is easy to break

It can be seen that the ultra-thin fully biodegradable mulch film prepared by the present invention is specially reinforced, toughened and anti-reflective masterbatch, and the ultra-thin fully biodegradable mulch film is blown, and its light transmittance, tensile strength and elongation at break are all better than those with a thinner thickness. Highly biodegradable mulch film with good processing performance.

Claims (1)

1. a kind of special reinforced toughened anti-reflection master batch of ultra-thin whole life cycle design, it is characterised in that: in parts by weight, including Following components:

67 parts of polyadipate/butylene terephthalate

1 part of polylactic acid

20 parts of hydrophobic nano silica

10 parts of polymer microballoon PMMA

2 parts of epoxidized soybean oil

234 1 parts of ultraviolet absorbing agent Tinuvin

It is prepared as steps described below:

It disperses hydrophobic nano silica, epoxidized soybean oil dissolution in carbon tetrachloride, stirs evenly, distill out four chlorinations Carbon obtains mixture 1；Again by the mixture 1, polyadipate/butylene terephthalate, polylactic acid, ultraviolet absorbing agent Tinuvin 234, polymer microballoon PMMA successively put into 700~1000r/min of high-speed mixer stirring, are kneaded 10-30 minutes, Obtain mixture 2；Mixture 2 is put into double screw extruder, is squeezed out in 135-160 DEG C, air-cooled granulation, and ultra-thin full biology drop is obtained Solve the special reinforced toughened anti-reflection master batch of mulch；

Wherein the hydrophobic nano silica partial size is 5-10nm, and the partial size of polymer microballoon PMMA is 2-3 μm.