Summary of the invention
Technical problem to be solved by this invention provides the short degradable master batch of a kind of thermooxidizing, and color is that white is extremely faint yellow, can not influence the color and the outward appearance of plastics, all can promote plastic degradation in visible light and invisible light system.It can effectively solve the problem that the photodegradable plastics underground part is not degraded, and can solve the problem that the biodegradable plastic over-ground part is difficult for degraded again, also can reach the effect of degraded to common plastics.The preparation method of the short degradable master batch of thermooxidizing who is used for plastics is simple, can finish in the universalization construction equipment, and the raw materials for production cost is low, and addition is few, can not increase production cost to plastics.
In order to address the above problem, the technical solution used in the present invention is: a kind of short degradable master batch of thermooxidizing that is used for plastics, (weight %) composed of the following components: modified filler 25~60%, polyolefin resin 30~50%, thermooxidizing degradation accelerating agent 1~15%, initiator 1~10%, the consisting of of described modified filler (parts by weight): 100 parts of fillers, 1~2 part of coupling agent, 1~3 part of lubricant.
Described filler is one or more mixtures in inorganic carbonate, grouan, talcum powder, magnesium hydroxide, aluminium hydroxide, diatomite, mica, the natural synthesizing organo-silicon, and packing material size is less than 150 orders.
When described filler was used for the blown film goods, packing material size was less than 1000 orders.
Described polyolefin resin is a kind of in high density polyethylene(HDPE) (HDPE), new LDPE (film grade) (LDPE), linear low density polyethylene (LLDPE), polypropylene (PP), the polyvinyl chloride (PVC).
Described coupling agent is a kind of in silicane, titanate ester or the aluminium esters of gallic acid.
In the stearate of described thermooxidizing degradation accelerating agent employing iron, zinc, tin, manganese, cobalt, cerium, nickel, copper, gallium, lithium, molybdenum, potassium, tungsten, vanadium, zirconium one or more.
Described initiator adopts a kind of in unsaturated olefin or the unsaturated lipid.
Described initiator is a kind of in the multipolymer (SBS), polyhutadiene, oxidic polyethylene, polyisoprene of polystyrene-divinyl.
Described lubricant adopts a kind of in stearic amide, polyethylene wax, stearic acid, the stearyl alcohol.
A kind of preparation method who is used for the short degradable master batch of thermooxidizing of plastics is characterized in that may further comprise the steps:
(1) filler is put into high-speed mixer, carry out high-speed stirring, when temperature rises to 80~120 ℃, add coupling agent and carry out coupling processing, stirred 15~30 minutes, add lubricant again after the modification and stir, stir, obtain modified filler;
(2) modified filler is put into cold mixer, after temperature is lower than 80 ℃, add polyolefin resin, thermooxidizing degradation accelerating agent, initiator, mechanical stirring 10~20 minutes mixes;
(3) with the extruding pelletization in twin screw extruder of the mixture in the above-mentioned operation; the barrel temperature scope of screw rod is 100~200 ℃; head temperature is 100~180 ℃; characteristic according to polyolefin resin; select air-cooled pelletizing or water-cooled pelletizing for use, obtaining color is that white is to the particle faint yellow, that outward appearance is regular.
It is applied widely that degradable master batch is urged in the thermooxidizing that is used for plastics provided by the invention, be easy to be processed into various degraded goods, the degraded controllability is good, mechanical property is superior, can require to add masterbatch according to the reality degraded, make corresponding product, and the short degradable master batch of thermooxidizing of the present invention has nontoxic, free from extraneous odour, non-corrosiveness, harmless characteristic, can not cause new pollution.Preparation process of the present invention is simple, adopts the universalization construction equipment, and cost is low.
Embodiment
Below in conjunction with specific embodiment short degradable master batch of thermooxidizing that is used for plastics of the present invention and preparation method thereof is described in further detail:
Embodiment 1:
To put into high-speed mixer less than 1000 purpose lime carbonate 200kg and carry out high-speed stirring, when temperature is 100 ℃, add titanate coupling agent 3kg, mixed 25 minutes, and added lubricant polyethylene wax 4kg again, high-speed stirring 10 minutes, dispose, be the modified calcium carbonate filler.
40kg puts into cold mixer modified calcium carbonate, when being cooled to 60~80 ℃, add new LDPE (film grade) (LDPE) 50kg, thermooxidizing degradation accelerating agent nickel stearate 5kg, initiator oxidic polyethylene 5kg thorough mixing, after mixing, use the twin screw extruder extruding pelletization.Adopt air-cooled pelletizing, make the short degradable master batch of the regular intact thermooxidizing that is used for plastics of particle shape.Processing temperature can by following temperature (℃) set:
Eight districts, seven districts, six districts, five districts, four districts, three districts, two districts, one district
110????115????120????125????130????130????125????125
Embodiment 2:
To put into high-speed mixer less than 1000 purpose talcum powder 200kg and carry out high-speed stirring, when temperature is 110 ℃, add silane coupling agent 3kg, mixed 20 minutes, and added lubricant stearic acid 5kg again, high-speed stirring 10 minutes, dispose, be the modified calcium carbonate filler.
50kg puts into cold mixer modified calcium carbonate, when being cooled to 60~80 ℃, after adding linear low density polyethylene (LLDPE) 30kg, cobalt stearate 5kg, cerium stearate 8kg, initiator polyhutadiene 7kg mix, uses the twin screw extruder extruding pelletization.Adopt air-cooled pelletizing, make the short degradable master batch of the regular intact thermooxidizing that is used for plastics of particle shape.Processing temperature can by following temperature (℃) set:
Eight districts, seven districts, six districts, five districts, four districts, three districts, two districts, one district
150????155???160???170???170???170???165???160
Embodiment 3:
To put into high-speed mixer less than 1000 purpose lime carbonate 200kg and carry out high-speed stirring, when temperature is 120 ℃, add silane coupling agent 3kg, mixed 20 minutes, and added lubricant stearic acid 4kg again, high-speed stirring 10 minutes, dispose, be the modified calcium carbonate filler.
30kg puts into cold mixer modified calcium carbonate, when being cooled to 60~80 ℃, adds the multipolymer 5kg of polypropylene (PP) 50kg, cobalt stearate 15kg, initiator polystyrene-divinyl, after mixing, uses the twin screw extruder extruding pelletization.Adopt the water-cooled pelletizing, make the short degradable master batch of the regular intact thermooxidizing that is used for plastics of particle shape.Processing temperature can by following temperature (℃) set:
Eight districts, seven districts, six districts, five districts, four districts, three districts, two districts, one district
140???145???150???155???160???160???156???150
Embodiment 4:
To put into high-speed mixer less than 150 purpose talcum powder and each 100kg of diatomite and carry out high-speed stirring, when temperature is 100 ℃, add titanate coupling agent 3kg, mixed 25 minutes, and adding stearic amide 4kg, high-speed stirring 10 minutes, dispose, be the modification mixed fillers.
Above-mentioned modification mixed fillers 200kg is put into the cold mixing machine, when being cooled to 60~80 ℃, after adding new LDPE (film grade) (LDPE) 120kg, cerium stearate 5kg, nickel stearate 5kg, polyisoprene 20kg mix, use the twin screw extruder extruding pelletization.Adopt air-cooled pelletizing, make the short degradable master batch of the rational intact thermooxidizing that is used for plastics.Processing temperature can by following temperature (℃) set:
Eight districts, seven districts, six districts, five districts, four districts, three districts, two districts, one district
110???115???120???125???130???130???125???125
Above example explanation, adopt different ratios and different types of raw material all can carry out normal granulation with mixed processes and extruding pelletization operation, the short degradable master batch particle shape made from twin screw extruder of the thermooxidizing that is used for plastics is regular intact, and color is that white is to light yellow.Degradable master batch is urged in these different types of thermooxidizings, can be when complete processing moulding such as blown film, extrusion molding, injection moulding, mold pressing and other raw material mechanical stirring mix the back and use, convenient and safe, and do not need processing temperature is adjusted.Can select the consumption of the short degradable master batch of suitable thermooxidizing according to different degradation times.
Above-mentioned filler is inorganic carbonate, grouan, talcum powder, Qing Yangization Magnesium, aluminium hydroxide, diatomite, mica, natural synthesizing organo-silicon etc., can use one or more mixtures as filler.Employed packing material size is less than 150 orders.If be used for the blown film goods, the particle diameter of used filler should be littler, and for example the particle diameter of lime carbonate is less than 1000 orders, otherwise, can produce flake or hole on the film article, cause the rerum natura of film to descend so that defective.
The surface of these fillers must be handled through modification, prevent to absorb moisture content, increases consistency and dispersiveness with polyolefin resin, otherwise can produce hole or reduce the physical and mechanical properties of plastics when blown film.Therefore, these fillers, for example lime carbonate after organic acid or ester coupling agent treatment, has improved its processing characteristics and water resistance.
The short degradable master batch of thermooxidizing that is used for plastics can discharge free radical at low temperatures lentamente, causes the fracture of polyolefine c h bond, the oxidising process of acceleration molecular chain; And at high temperature have certain stability, can under polyolefinic processing temperature, not decompose fast.The interpolation composition that the short degradable master batch of thermooxidizing that is used for plastics of the present invention can directly use at plastics forming as a profit.It and plastics have good consistency, moulding process such as be fit to blowing, injection moulding, mold pressing, extrude, and the material performance of goods had no adverse effects.Utilize the short degradable master batch of the thermooxidizing that is used for plastics of the present invention can be formed in plastic material and the goods that chemical degradation takes place behind the certain hour; As being used with photodegradable plastics and biodegradable plastic, can also improve the degradation rate of photodegradable plastics and biodegradable plastic, form the small shreds of environmental sound.Under heating or ultraviolet light conditions, can quicken to add the chemical degradation reaction that the present invention urgees the plastics of degradable master batch; Equally, under unglazed photograph or composting conditions, also can promote the degraded of plastics.Should short degradable master batch nontoxic, free from extraneous odour, non-corrosiveness, harmless not only can be used for ordinary packing, but also can be used for food product pack.
Can produce the characteristics of 55~70 ℃ of corruption temperature-rise periods during at garbage compost, the short degradable master batch of thermooxidizing that is used for plastics of the present invention, make the plastics that add this masterbatch can be under compost environment, accelerated degradation efficiently solves the degradation problem of plastics under compost environment.
Below the result of use that is used for the short degradable master batch of thermooxidizing of plastics of the present invention is described further, that uses in the prescription all is weight percentage:
The prescription of blown film experiment is as shown in table 1,
Table 1
Sequence number | Prescription | Ratio |
1# | BM1150∶HDPE∶LLDPE | ????50∶25∶25 |
2# | BM1150: HDPE: LLDPE: short degradable master batch | ????50∶23∶23∶4 |
3# | BM1150: HDPE: LLDPE: short degradable master batch | ????50∶21∶21∶8 |
4# | DM2150∶LDPE∶LLDPE | ????30∶35∶35 |
5# | DM215: LDPE: LLDPE: short degradable master batch | ????30∶33∶33∶4 |
6# | DM2150: LDPE: LLDPE: short degradable master batch | ????30∶31∶31∶8 |
BM1150, DM2150 are respectively packing film masterbatch and mulching film master batch, it is the amyloid biodegradable master batch that Danhai Co., Ltd., Tianjin produces, be suitable for blowing biodegradable mulch film and packing film, the masterbatch that the short degradable master batch of thermooxidizing is embodiment 1 preparation.Above the mechanical performance index of blowing degradable package film and mulch film see Table 2, table 3, table 4
Table 2
| ?1# | ???2# | ????3# | ????4# | ????5# | ???6# |
Short degradable master batch consumption % | | ???4 | ????8 | | ????4 | ???8 |
Thickness mm | ?0.018~0.020 | ???0.019~0.020 | ????0.019~0.020 | ????0.008~0.010 | ????0.008~0.010 | ???0.008~0.010 |
Tensile strength MPa indulges/horizontal stroke | ?31.2/18.6 | ????30.5/19.1 | ????30.1/18.3 | ????20.0/15.3 | ????21.1/14.5 | ???19.2/14.2 |
Elongation at break % indulges/horizontal stroke | ?270/350 | ????290/360 | ????280/340 | ????410/630 | ????420/620 | ???410/600 |
Grammes per square metre (g/m
2)
| ?19.4 | ????19.9 | ????20.3 | ????7.3 | ????7.5 | ???7.5 |
Table 3
Project | 400 hours degraded situations of simulation compost temperature experiment |
Tensile strength MPa | Elongation at break % |
Former film | After the degraded | Retention rate % | Former film | After the degraded | Retention rate % |
Vertically | Laterally | Vertically | Laterally | Vertically | Laterally | Vertically | Laterally | Vertically | Laterally | Vertically | Laterally |
1# | 31.2 | ??18.6 | ?31.4 | ??18.5 | ??100 | ?100 | ?270 | ??350 | ??275 | ?345 | ?100 | ?100 |
2# | 30.5 | ??19.1 | ?9.2 | ??6.9 | ??30 | ?36 | ?290 | ??360 | ??100 | ?110 | ?35 | ?30 |
3# | 30.1 | ??18.3 | ?3.6 | ??1.8 | ??11 | ?9.8 | ?280 | ??340 | ??10 | ?0 | ?3.6 | ?0 |
4# | 20.0 | ??15.3 | ??20.2 | ??15.2 | ??100 | ?100 | ?410 | ??630 | ??400 | ?630 | ?100 | ?100 |
5# | 21.1 | ??14.5 | ??5.3 | ??3.2 | ??25 | ?22 | ?420 | ??620 | ??115 | ?120 | ?28 | ?19. ?4 |
6# | 19.2 | ??14.2 | ??0.9 | ??0.8 | ??4.7 | ??5.6 | ?410 | ??600 | ??0 | ??0 | ?0 | ?0 |
The variation of the viscosity-average molecular weight of table 4 simulation compost temperature experiment after 400 hours
| ??1# | ??2# | ??3# | ??4# | ??5# | ??6# |
The initial molecule amount | ??157000 | ??173000 | ??166000 | ??94300 | ??86500 | ??87600 |
Degraded back molecular weight | ??159000 | ??71280 | ??38350 | ??93500 | ??29950 | ??12090 |
Retention rate % | ??100 | ??41.2 | ??23.1 | ??100 | ??34.6 | ??13.8 |
Table 5 experiment biological growth rank
| ????1# | ????2# | ????3# | ????4# | ????5# | ??6# |
Fungi | Level Four | Level Four | Level Four | Level Four | Level Four | Level Four |
Bacterium | Level Four | Level Four | Level Four | Level Four | Level Four | Level Four |
Rate of weight loss % | ????18.5 | ????19.7 | ????18.6 | ????10.5 | ????10.2 | ??11.1 |
The prescription of blown film experiment is as shown in table 6, and short degradable master batch is the masterbatch of embodiment 2 preparations.
Table 6
Sequence number | Prescription | Ratio |
????7# | ????HDPE∶LLDPE | ????80∶20 |
????8# | HDPE: LLDPE: short degradable master batch | ????76∶20∶4 |
????9# | HDPE: LLDPE: short degradable master batch | ????72∶20∶8 |
????10# | ????LLDPE∶LDPE | ????80∶20 |
????11# | LLDPE: LDPE: short degradable master batch | ????76∶20∶4 |
????12# | LLDPE: LDPE: short degradable master batch | ????72∶20∶8 |
The original rerum natura of 7~12# is a table 7, and the experimental physics performance sees Table 8,9.
Table 7
| ????7# | ??8# | ????9# | ?10# | ????11# | ????12# |
Short degradable master batch consumption % | | ??4 | ????8 | | ????4 | ????8 |
Thickness mm | ????0.012~0.019 | ??0.011~0.017 | ????0.012~0.018 | ?0.018~0.022 | ????0.019~0.022 | ????0.019~0.022 |
Tensile strength MPa indulges/horizontal stroke | ????46.3/38.8 | ??49.4/41.8 | ????48.0/34.9 | ?27.3/28.2 | ????24.6/23.8 | ????23.6/23.3 |
Elongation at break % indulges/horizontal stroke | ????295/435 | ??290/380 | ????275/395 | ?630/690 | ????600/730 | ????580/675 |
Grammes per square metre (g/m
2)
| ????12.67 | ??12.18 | ????12.26 | ?17.14 | ????16.87 | ????16.79 |
Table 8
Project | 400 hours degraded situations of simulation compost temperature experiment |
Tensile strength MPa | Elongation at break % |
Former film | After the degraded | Retention rate % | Former film | After the degraded | Retention rate % |
Vertically | Laterally | Vertically | Laterally | Vertically | Laterally | Vertically | Laterally | Vertically | Laterally | Vertically | Laterally |
7# | ??46.3 | 38.8 | ?46.1 | ????38.6 | ?100 | ??100 | ?295 | ??435 | ?290 | ??433 | ?100 | ??100 |
8# | ??49.4 | 41.8 | ?22.2 | ????13.6 | ?44.9 | ??32.5 | ?290 | ??380 | ?100 | ??130 | ?34.5 | ??34 |
9# | ??48.0 | 34.9 | ?10.2 | ????3.8 | ?21.3 | ??10.9 | ?275 | ??395 | ?35 | ??30 | ?12.7 | ??7.6 |
10# | ??27.3 | 28.2 | ?28.1 | ????28.6 | ?100 | ??100 | ?630 | ??690 | ?620 | ??680 | ?100 | ??100 |
11# | ??24.6 | 23.8 | ?1.1 | ????1.4 | ?4.5 | ??6 | ?600 | ??730 | ?12 | ??23 | ?2 | ??3.2 |
12# | ??23.6 | 23.3 | ?0 | ????0 | ?0 | ??0 | ?580 | ??675 | ?0 | ??0 | ?0 | ??0 |
The variation of the viscosity-average molecular weight of table 9 simulation compost temperature experiment after 400 hours
| ??7# | ??8# | ??9# | ??10# | ??11# | ??12# |
The initial molecule amount | ??213000 | ??180000 | ??207000 | ??129400 | ??113700 | ??115600 |
Degraded back molecular weight | ??214000 | ??81540 | ??54850 | ??129000 | ??28080 | ??17570 |
Retention rate % | ??100 | ??45.3 | ??26.5 | ??100 | ??24.7 | ??15.2 |
The molding experiment:
After using the short degradable master batch of plastic hot oxidation of embodiment 3 and polypropylene (PP) to stir, mixing on two roller mixing rolls evenly discharging refining in the rolling press goes out calendared sheet, and the temperature that calendared sheet uses is 170~180 ℃.Calendared sheet can be molded into the plastics of the different shape of actual needs, makes non-returnable containers such as mess-tin with the short degradation property of chemistry, medicine box, bowl, pastry case.
Prescription sees Table 10, and performance sees Table 11.
Table 10
Sequence number | Prescription | Ratio |
13# | ????PP | ????100 |
14# | PP: short degradable master batch | ????96∶4 |
15# | PP: short degradable master batch | ????92∶8 |
The variation of the viscosity-average molecular weight of table 11 simulation compost temperature experiment after 400 hours
| ??13# | ??14# | ??15# |
The initial molecule amount | ??136000 | ??134000 | ??128000 |
Degraded back molecular weight | ??135000 | ??43410 | ??18810 |
Retention rate % | ??100 | ??32.4 | ??14.7 |
Through experimental results demonstrate, the short degradable master batch of plastic hot oxidation has certain stability under hot conditions, can not decompose fast under the polyolefine processing temperature, but can discharge free radical lentamente under the compost temperature condition, bring out the fracture of polyolefine c h bond, quicken the degradation rate of plastics.
The short degradable master batch of plastic hot oxidation can directly use as a kind of additive in plastics forming.Its use range is very extensive, moulding process such as be fit to blowing, injection moulding, mold pressing, extrude, and physical properties of articles is had no adverse effects.After adding this masterbatch, degradative plastics products such as the short membrane product of degrading of chemistry, bag product, sheet material products, injecting products take place after can being formed in certain hour, can also promote simultaneously the degradation speed of photodegradation and biodegradable plastic, accelerate degradation rate, form the small shreds of environmental sound.So that the short degradable master batch of thermooxidizing of the present invention has more is nontoxic, free from extraneous odour, non-corrosiveness, harmless characteristic, can not cause new pollution.