CN108976599A - A kind of preparation method of PP/PLA composite degradable plastics bloom lubrication masterbatch - Google Patents
A kind of preparation method of PP/PLA composite degradable plastics bloom lubrication masterbatch Download PDFInfo
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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- C08J2323/12—Polypropene
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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Abstract
The present invention relates to a kind of preparation methods of PP/PLA composite degradable plastics bloom lubrication masterbatch, belong to masterbatch technique field.The present invention mixes dry polylactic acid and organo montmorillonite, obtains composite material；Stearic acid and atoleine are mixed, dispersing agent is obtained；According to parts by weight, calcium carbonate, titanate coupling agent, 4-4 '-methyl diphenylene diisocyanate, composite material dispersing agent are weighed respectively, calcium carbonate is added to the mixer mixing and is dried, obtain mixture, titanate coupling agent and 4-4 '-methyl diphenylene diisocyanate is added, continuess to mix, obtains material, composite material, dispersing agent are added in material and are mixed, filler is obtained；Filler, polypropylene, composite material are weighed respectively, by filler, polypropylene and composite material in mixed at high speed, it is squeezed out through double screw extruder, it obtains PP/PLA composite degradable plastics bloom and lubricates masterbatch, excellent in mechanical performance of the present invention, glossiness is high, and biodegradable properties are good, have wealthy market prospects.
Description
Technical field
The present invention relates to a kind of preparation methods of PP/PLA composite degradable plastics bloom lubrication masterbatch, belong to masterbatch technique
Field.
Background technique
Resource and environmental problem are most great two problems that human development faces.Nondegradable plastics are answered extensively
With promoting the civilization of the mankind, facilitate people's lives.But they are also a serious problem to the destruction of environment, are needed
It wants us conscientiously to examine closely, and researchs and solves method.Currently, best solution is exactly recycling and reusing, but in hardly possible recycling
Plastic applications field, can be used biodegradable plastic, to replace general-purpose plastics, avoid the non-degradable bring ring of general-purpose plastics
Border problem.Biodegradable plastic refers to the effect of a kind of such as bacterium, mould (fungi) and algae of the microorganism as existing for nature
And cause the plastics of degradation.Ideal biodegradable plastic be it is a kind of with excellent service performance, it is discarded after can be micro- by environment
The biological high molecular material for decomposing completely, finally being become a component part of Carbon cycle in nature by inorganization.One
As, main a few class fully biodegradable plastics are as follows: polylactic acid (PLA), poly butylene succinate (PBS), 3- hydroxyl
The copolyesters (PHBHHX) of butyric acid and 3- hydroxycaproic acid.Currently, having there is the general-purpose plastics processing of many patents and document report
At the formula and preparation method of absorbent masterbatch；But the formula of the masterbatch of fully biodegradable plastics has no phase with preparation method
Patent and document report are closed, this or a brand-new field.
Plastic raw materials all contain moisture, it is carried out there is a problem of in secondary operation application one it is universal: due to
The raising of temperature when processing, for rapid vaporization at steam, steam is melted the plastic molten mass package of state, nothing to moisture at high temperature
Method evolution leads to problems such as steam stay in plastics and forms more empty and bubble, moire, crackle, spots.It is asked to solve this
Topic, the prior art uses the gimmick of drying to be dried to plastic raw materials to remove moisture removal, but this method but has two
Defect: firstly, being takeed a long time using drying technology, long time drying not only needs expensive machine while also consuming
The a large amount of energy；Secondly, drying course can not thoroughly eliminate moisture, drying can only carry out the moisture on the surface of plastic raw materials
Removal, but the moisture for being hidden in plastics inner not can be removed but, as a result cause drying to be not thorough, residual moisture still affects
The appearance and performance of plastic products.Absorbent masterbatch main function is the moisture removed in plastics, which is otherwise known as: plastics remove
Jellyfish material, moisture absorption masterbatch, desiccant, defoaming agent etc..
Biodegradable plastic majority is that addition is added using the biodegradation materials such as starch or modified starch, poly- second lactone to help
Agent is made.Though biodegradable plastic is degradable, this kind of natural macromolecular material still has disadvantages that compared with synthetic resin, he
Mostly do not have heating, fusible thermoplasticity, it is difficult to common plastics processing method form, difficulty of processing is big, complex process,
Its physical and mechanical property is poor, and intensity has very big difference in dry and wet environment, and recoverable, not at high cost.
Plastics are most widely used high molecular materials, calculate occupied first place in the world by volume, since it is difficult to degrade, with
Dosage it is growing day by day, white pollution caused by waste plastic has become global public hazards.The current plastics in China are raw
It produces and using having leaped into the front ranks of the world, generates the nondegradable junk of millions of tons every year, seriously pollute environment and harm
Our health.Demand of the resident to plastics is increasing always, and a large amount of plastics cause serious pollution to environment.It can
See, exploitation degradable high polymer material finds new environment-friendly polymers to make plastics be the task of top priority.
Summary of the invention
The technical problems to be solved by the invention: being directed to conventional plastic non-degradable, though biodegradable plastic is degradable,
Complex process, the problem of physical and mechanical property difference provide a kind of PP/PLA composite degradable plastics bloom lubrication masterbatch
Preparation method.
In order to solve the above technical problems, the technical solution adopted by the present invention is that:
(1) dry to constant weight by polylactic acid in the baking oven that temperature is 60~80 DEG C, obtain dry polylactic acid, in mass ratio 2: 1
Dry polylactic acid and organo montmorillonite are mixed, fusion intercalation processing obtains composite material；
(2) according to parts by weight, 70~85 parts of calcium carbonate, 0.5~3 part of titanate coupling agent, 0.02~0.03 part are weighed respectively
4-4 '-methyl diphenylene diisocyanate, 10~30 parts of composite materials, 3~5 parts of dispersing agents, calcium carbonate is added to the mixer,
High-speed stirred and heating, drying obtain mixture, and titanate coupling agent and 4-4 '-methyl diphenylene diisocyanate is added, and continue
15~20min is mixed, material is obtained, composite material, dispersing agent is added in material, is mixed in the case where revolving speed is 200~300r/min
10~15min is closed, filler is obtained；
(3) according to parts by weight, filler, polypropylene, composite material are weighed respectively, by filler, polypropylene and composite material high-speed
It after mixing, is squeezed out through double screw extruder, obtains PP/PLA composite degradable plastics bloom lubrication masterbatch.
For the processing of fusion intercalation described in step (1) to be 800~1000r/min in revolving speed, temperature is high at 60~80 DEG C
20~30min of speed mixing.
The partial size of calcium carbonate described in step (2) is 6~15 μm.
Dispersing agent described in step (2) is that stearic acid and atoleine in mass ratio 1: 0.3 mix.
It is 800~1000r/min high-speed stirred that high-speed stirred described in step (2) and heating, drying, which are in revolving speed, and
Temperature is heating, drying 10min at 90~100 DEG C.
Mixed at high speed described in step (3) is 20~30min of mixed at high speed in the case where revolving speed is 800~1000r/min.
Extrusion condition described in step (3) are as follows: 170~190 DEG C of extrusion temperature, 60~80r/min of screw speed.
The present invention is compared with other methods, and advantageous effects are:
(1) present invention prepares a kind of composite material using organo montmorillonite and polylactic acid fusion intercalation, and polylactic acid has good
Biocompatibility, biological degradability and processability, organo montmorillonite is a kind of typical 2: 1 type phyllosilicate, by poly- cream
Acid and organo montmorillonite carry out intercalation, and the polylactic acid molecule chain that intercalation enters between montmorillonite layer will receive montmorillonite layer
Barrier action and restriction effect, so that the mechanical strength of composite material, heat resistance, tensile strength and elongation at break can be improved
Deng；
(2) for the present invention using calcium carbonate as filler core, titanate coupling agent and 4-4 '-methyl diphenylene diisocyanate are coupling
Layer, stearic acid and atoleine are that dispersion layer prepares a kind of PP/PLA composite degradable plastics bloom lubrication masterbatch, sodium carbonate valence
Lattice are cheap, abundance, nontoxic, tasteless and nonirritant, it is easily dry, be free of the crystallization water, can increase product whiteness, it is soft, from
Viscosity is good, can largely fill in the plastic, be easy to carry out dry state cladding in a high speed mixer, improve the melting rheological characteristic of plastics
Energy；4-4 '-methyl diphenylene diisocyanate is modified polylactic acid molecule chain end group, makes mechanics, the hot property of polylactic acid
All increase；The molecule category both sexes structure of titanate coupling agent, one end are close inorganic group, and one end is organic-philic group, even
When connection agent acts on calcium carbonate surface, since the calcium ion and carbanion on calcium carbonate granule surface connect with atmosphere moisture
It hydrolyzes after touch, generates the hydroxyl surface of there is alkalinity oleophobic, chemistry can occur without generator terminal with the parent of metatitanic acid vinegar coupling agent
In conjunction with, generate the modified calcium carbonate particle in surface, these particles and polylactic acid, it is polypropene blended after so that coupling agent molecule
Entanglement effect occurs for organic-philic end and molecular resin, improves the mechanical property of masterbatch.
Specific embodiment
It is dry to constant weight by polylactic acid in the baking oven that temperature is 60~80 DEG C, obtain dry polylactic acid, in mass ratio 2:
1 mixes dry polylactic acid and organo montmorillonite, is 800~1000r/min in revolving speed, temperature is to mix at a high speed at 60~80 DEG C
20~30min is closed, composite material is obtained；In mass ratio 1: 0.3 mixes stearic acid and atoleine, obtains dispersing agent；By weight
Number meter, weighs 70~85 parts of calcium carbonate, 0.5~3 part of titanate coupling agent, 0.02~0.03 part of 4-4 '-diphenyl methane respectively
The calcium carbonate that partial size is 6~15 μm is added to the mixer by diisocyanate, 10~30 parts of composite materials, 3~5 parts of dispersing agents,
Revolving speed be 800~1000r/min high-speed stirred, and temperature be 90~100 DEG C at heating, drying 10min, obtain mixture, add
Enter titanate coupling agent and 4-4 '-methyl diphenylene diisocyanate, 15~20min is continuesd to mix, material is obtained, by composite wood
Material, dispersing agent are added in material, are mixed 10~15min in the case where revolving speed is 200~300r/min, are obtained filler；In parts by weight
Meter, weigh filler, polypropylene, composite material respectively, by filler, polypropylene and composite material revolving speed be 800~1000r/min
It after 20~30min of lower mixed at high speed, is squeezed out through double screw extruder, obtains PP/PLA composite degradable plastics bloom lubrication masterbatch.
The extrusion condition are as follows: 170~190 DEG C of extrusion temperature, 60~80r/min of screw speed.
Example 1
It is dry to constant weight by polylactic acid in the baking oven that temperature is 60 DEG C, dry polylactic acid is obtained, in mass ratio 2: 1 will dry
Polylactic acid and organo montmorillonite mixing, revolving speed be 800r/min, temperature be 60 DEG C at mixed at high speed 20min, obtain composite wood
Material；In mass ratio 1: 0.3 mixes stearic acid and atoleine, obtains dispersing agent；According to parts by weight, 70 parts of carbonic acid are weighed respectively
Calcium, 0.5 part of titanate coupling agent, 0.02 part of 4-4 '-methyl diphenylene diisocyanate, 10 parts of composite materials, 3 parts of dispersing agents,
The calcium carbonate that partial size is 6 μm is added to the mixer, is 800r/min high-speed stirred in revolving speed, and is heated at being 90 DEG C in temperature
10min is dried, mixture is obtained, titanate coupling agent and 4-4 '-methyl diphenylene diisocyanate is added, continuess to mix 15min,
Material is obtained, composite material, dispersing agent are added in material, 10min is mixed in the case where revolving speed is 200r/min, obtains filler；By weight
Measure number meter, weigh filler, polypropylene, composite material respectively, by filler, polypropylene and composite material revolving speed be 800r/min
It after lower mixed at high speed 20min, is squeezed out through double screw extruder, obtains PP/PLA composite degradable plastics bloom lubrication masterbatch.It is described
Extrusion condition are as follows: 170 DEG C of extrusion temperature, screw speed 60r/min.
Example 2
It is dry to constant weight by polylactic acid in the baking oven that temperature is 70 DEG C, dry polylactic acid is obtained, in mass ratio 2: 1 will dry
Polylactic acid and organo montmorillonite mixing, revolving speed be 900r/min, temperature be 70 DEG C at mixed at high speed 25min, obtain composite wood
Material；In mass ratio 1: 0.3 mixes stearic acid and atoleine, obtains dispersing agent；According to parts by weight, 80 parts of carbonic acid are weighed respectively
Calcium, 1.7 parts of titanate coupling agents, 0.025 part of 4-4 '-methyl diphenylene diisocyanate, 20 parts of composite materials, 4 parts of dispersing agents,
The calcium carbonate that partial size is 10 μm is added to the mixer, is 900r/min high-speed stirred in revolving speed, and is added at being 95 DEG C in temperature
Heat drying 10min, obtains mixture, titanate coupling agent and 4-4 '-methyl diphenylene diisocyanate is added, continuess to mix
17min obtains material, and composite material, dispersing agent are added in material, mixes 13min in the case where revolving speed is 250r/min, must fill out
Material；According to parts by weight, filler, polypropylene, composite material are weighed respectively, are in revolving speed by filler, polypropylene and composite material
It under 900r/min after mixed at high speed 25min, is squeezed out through double screw extruder, it is female to obtain PP/PLA composite degradable plastics bloom lubrication
Material.The extrusion condition are as follows: 180 DEG C of extrusion temperature, screw speed 70r/min.
Example 3
It is dry to constant weight by polylactic acid in the baking oven that temperature is 80 DEG C, dry polylactic acid is obtained, in mass ratio 2: 1 will dry
Polylactic acid and organo montmorillonite mixing, revolving speed be 1000r/min, temperature be 80 DEG C at mixed at high speed 30min, obtain composite wood
Material；In mass ratio 1: 0.3 mixes stearic acid and atoleine, obtains dispersing agent；According to parts by weight, 85 parts of carbonic acid are weighed respectively
Calcium, 3 parts of titanate coupling agents, 0.03 part of 4-4 '-methyl diphenylene diisocyanate, 30 parts of composite materials, 5 parts of dispersing agents, will
Partial size is that 15 μm of calcium carbonate is added to the mixer, and is 1000r/min high-speed stirred in revolving speed, and is added at being 100 DEG C in temperature
Heat drying 10min, obtains mixture, titanate coupling agent and 4-4 '-methyl diphenylene diisocyanate is added, continuess to mix
20min obtains material, and composite material, dispersing agent are added in material, mixes 15min in the case where revolving speed is 300r/min, must fill out
Material；According to parts by weight, filler, polypropylene, composite material are weighed respectively, are in revolving speed by filler, polypropylene and composite material
It under 1000r/min after mixed at high speed 30min, is squeezed out through double screw extruder, obtains PP/PLA composite degradable plastics bloom lubrication
Masterbatch.The extrusion condition are as follows: 190 DEG C of extrusion temperature, screw speed 80r/min.
PP/PLA composite degradable plastics bloom prepared by the present invention lubrication masterbatch and Guangzhou company are produced common
Masterbatch is detected, specific testing result such as following table table 1:
Detection method:
By above embodiments be prepared can PP/PLA composite degradable plastics bloom lubrication masterbatch by be blow molded be made thickness
For the film of 20-30 μ m-thick, GB/T1843, GB/T1040 are tested for the property according to national standards.
Table 1PP/PLA composite degradable plastics bloom lubricates masterbatch performance characterization
PP/PLA composite degradable plastics bloom prepared by the present invention lubricates masterbatch, excellent in mechanical performance, glossiness as shown in Table 1
Height, biodegradability is good, has a vast market value and application prospect.
Claims (7)
1. a kind of preparation method of PP/PLA composite degradable plastics bloom lubrication masterbatch, it is characterised in that specific steps are as follows:
(1) dry to constant weight by polylactic acid in the baking oven that temperature is 60~80 DEG C, obtain dry polylactic acid, in mass ratio 2: 1
Dry polylactic acid and organo montmorillonite are mixed, fusion intercalation processing obtains composite material；
(2) according to parts by weight, 70~85 parts of calcium carbonate, 0.5~3 part of titanate coupling agent, 0.02~0.03 part are weighed respectively
4-4 '-methyl diphenylene diisocyanate, 10~30 parts of composite materials, 3~5 parts of dispersing agents, calcium carbonate is added to the mixer,
High-speed stirred and heating, drying obtain mixture, and titanate coupling agent and 4-4 '-methyl diphenylene diisocyanate is added, and continue
15~20min is mixed, material is obtained, composite material, dispersing agent is added in material, is mixed in the case where revolving speed is 200~300r/min
10~15min is closed, filler is obtained；
(3) according to parts by weight, filler, polypropylene, composite material are weighed respectively, by filler, polypropylene and composite material high-speed
It after mixing, is squeezed out through double screw extruder, obtains PP/PLA composite degradable plastics bloom lubrication masterbatch.
2. a kind of preparation method of PP/PLA composite degradable plastics bloom lubrication masterbatch according to claim 1, special
Sign is: for the processing of fusion intercalation described in step (1) to be 800~1000r/min in revolving speed, temperature is high speed at 60~80 DEG C
Mix 20~30min.
3. a kind of preparation method of PP/PLA composite degradable plastics bloom lubrication masterbatch according to claim 1, special
Sign is: the partial size of calcium carbonate described in step (2) is 6~15 μm.
4. a kind of preparation method of PP/PLA composite degradable plastics bloom lubrication masterbatch according to claim 1, special
Sign is: dispersing agent described in step (2) is that stearic acid and atoleine in mass ratio 1: 0.3 mix.
5. a kind of preparation method of PP/PLA composite degradable plastics bloom lubrication masterbatch according to claim 1, special
Sign is: it is 800~1000r/min high-speed stirred that high-speed stirred described in step (2) and heating, drying, which are in revolving speed, and in temperature
Degree is heating, drying 10min at 90~100 DEG C.
6. a kind of preparation method of PP/PLA composite degradable plastics bloom lubrication masterbatch according to claim 1, special
Sign is: mixed at high speed described in step (3) is 20~30min of mixed at high speed in the case where revolving speed is 800~1000r/min.
7. a kind of preparation method of PP/PLA composite degradable plastics bloom lubrication masterbatch according to claim 1, special
Sign is: extrusion condition described in step (3) are as follows: 170~190 DEG C of extrusion temperature, 60~80r/min of screw speed.
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Cited By (2)
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| CN110539971A (en) * | 2019-07-09 | 2019-12-06 | 中山市金群瑞科技有限公司 | Adopt packing carton of individual layer degradable carbon calcium board preparation |
| CN112341703A (en) * | 2020-06-22 | 2021-02-09 | 浙江翔光生物科技股份有限公司 | Manufacturing method of wear-resistant degradable PP hinge |
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