CN109294149A - A kind of preparation method of durable antibiotic polypropylene plastic cup - Google Patents
A kind of preparation method of durable antibiotic polypropylene plastic cup Download PDFInfo
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- CN109294149A CN109294149A CN201811077860.XA CN201811077860A CN109294149A CN 109294149 A CN109294149 A CN 109294149A CN 201811077860 A CN201811077860 A CN 201811077860A CN 109294149 A CN109294149 A CN 109294149A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/642—Component covered by group C08F4/64 with an organo-aluminium compound
- C08F4/6421—Titanium tetrahalides with organo-aluminium compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The present invention relates to plastic cup technical fields, disclose a kind of preparation method of durable antibiotic polypropylene plastic cup.The plastic cup preparation method is first to dry modified polypropylene resin particle, and control moisture content control is below 0.1%；Then mixing is uniformly mixing to obtain after mixing modified polypropylene resin particle, ethylene bis stearamide, dimethyl silicone polymer, thiopropionate kind antioxidant, modified sheeted nanometer aluminium oxide；Mixing will be finally fitted into melting mixing in injection molding machine, melt is sent into cavity forming, cooling and solidifying obtains durable antibiotic polypropylene plastic cup.Plastic cup of the present invention has preferable and lasting antibacterial effect, excellent in cushion effect.
Description
Technical field
The present invention relates to plastic cup technical fields, more particularly, to a kind of preparation side of durable antibiotic polypropylene plastic cup
Method.
Background technique
Polypropylene plastics is to form a kind of thermoplastic resin obtained by propylene polymerization.There are isotactic, random object and rule three
Kind configuration, industrial products are using isotactic as main component.Polypropylene is also including the copolymer of propylene and a small amount of ethylene.Usually
It is nontoxic odorless for translucent colorless solid.The highly crystallized due to compound with regular structure, Gu fusing point is up to 167 DEG C, heat-resisting, product
It can be its outstanding advantages with moise-heat sterilization.Density 0.9g/cm3, it is most light general-purpose plastics.It is corrosion-resistant, tensile strength
30MPa, intensity, rigidity and the transparency are all better than polyethylene.It is nontoxic to body since the fusing point of polypropylene plastics is up to 167 DEG C
It is harmless, it is usually used in preparing plastic cup.With the development of the social economy, polypropylene plastic cup has been difficult to meet the requirement of people, modeling
For material cup during routine use, internal bacterium easy to breed, bacterium influences health after entering human body.Chinese patent discloses
Number CN106750873 discloses a kind of plastic cup, and the plastic cup is by following parts by weight at being grouped as: polypropylene, enhancing be fine
Dimension, coupling agent, compatilizer, toughener, vanillic aldehyde, fire retardant, antioxidant and age resister.The plastic cup use polypropylene as
The main component of plastic cup assists the anti-aging of some other auxiliary agent reinforced plastics cup, flame retardant property and anti-microbial property.The technology
Use vanillic aldehyde as antimicrobial component and polypropylene congruent melting in scheme, so that plastic cup be made to have anti-microbial property, vanillic aldehyde is direct
With it is polypropene blended, since vanillic aldehyde and polyacrylic compatibility are bad, vanillic aldehyde is difficult to be uniformly dispersed in polypropylene, causes
The antibacterial effect of plastic cup is poor, also will cause vanillic aldehyde additionally, due to the bad problem of compatibility and dissolves out from plastic cup, makes
The anti-microbial property of plastic cup declines, and can not keep the anti-microbial property of plastic cup for a long time.
Summary of the invention
The present invention is to overcome the problems, such as that prior art plastic cup Durability of antimicrobial effect is poor, and providing one kind being capable of durable antibiotic
The preparation method of polypropylene plastic cup.
To achieve the goals above, the invention adopts the following technical scheme: a kind of system of durable antibiotic polypropylene plastic cup
Preparation Method, comprising the following steps:
(1) by modified polypropylene resin particle, heat dries 2~6h at 60~80 DEG C, and moisture content controls below 0.1%；
(2) by modified polypropylene resin particle, ethylene bis stearamide, dimethyl silicone polymer, thiopropionate kind antioxidant,
Mixing is uniformly mixing to obtain after the mixing of modified sheeted nanometer aluminium oxide；
(3) mixing is fitted into melting mixing in injection molding machine, melt is sent into cavity forming, cooling and solidifying obtains durable antibiotic poly- third
Alkene plastics cup.
The present invention first carries out hot baking to modified polypropylene resin particle, removes the moisture in modified polypropylene resin, reduces
The generation of bubble in plastic cup process, improves the quality of plastic cup.It the use of modified polypropylene resin particle is plastic cup
Main component, polypropylene have the advantages that high temperature resistant, high intensity；Process Technology of Polymer form when, there are molten polymer molecule it
Between friction and the friction between polymer melt and process equipment surface, rubbing action can reduce high molecular mobile performance, sternly
It will lead to the overheat and aging of material when weight, ethylene bis stearamide has preferable lubricating action, can reduce melt polymerization
Frictional force between friction and polymer melt between object molecule and process equipment surface；It the use of dimethyl silicone polymer is defoaming
Agent further removes the bubble that plastic cup generates in process；Polypropylene oxidation resistance is poor, holds after long-time use
Aging easily occurs, thiopropionate kind antioxidant, which is added, can be improved polyacrylic antioxidation, delay the aging of plastic cup；
Modified sheeted nanometer aluminium oxide plays the toughening effect to polypropylene plastic cup, improves the shock resistance of polypropylene plastic cup.
Each component is melted after mixing, solution is sent into die cavity and is formed, durable antibiotic polypropylene plastic cup, this hair are obtained
Bright plastic cup preparation method is simple, and cup body bubble generation rate is lower, is suitble to industrialized production.
Preferably, mixing includes following components by weight ratio in the step 2):
It is 60~70 parts of modified polypropylene resin particle, 1~3 part of ethylene bis stearamide, 1~3 part of dimethyl silicone polymer, thio
0.5~1 part of propionic acid ester antioxidant, 3~6 parts of modified sheeted nanometer aluminium oxide.
Preferably, the preparation method of the modified polypropylene resin particle the following steps are included:
A) feed purification: propylene is passed through in solid caustic soda tower and removes moisture, carbon monoxide and carbon dioxide, is then passed through propylene de-
In sulphur treating column, then the propylene after desulfurization is passed through deoxidation treating column, the propylene after deoxidation is finally passed through molecular sieve water separation tower
It carries out deep dehydration and obtains purification propylene；
B) it polymerize: purification propylene is passed through in the polymeric kettle containing n-hexane solvent, hydrogen, modification are then passed through into polymeric kettle
Brown algae polyphenols class extract and catalyst, control reaction temperature be 65~68 DEG C, kettle pressure be 2~2.2Mpa, the reaction time be 3~
3.5h；
C) it separates drying: after polymerization reaction then reaction solution being passed through centrifugal filtration in 0.8~1.3MPa by the voltage-controlled system of kettle
In machine, PP GRANULES is isolated, then PP GRANULES is sent into air-flow boiling drier and is dried to obtain polypropylene
Grain powder；
D) it is granulated: the PP GRANULES powder after drying being sent into Squeezinggranulator and carries out extruding agglomeration granulation, is modified
Acrylic resin particle.
The present invention first passes through prior art conventional method and cleans to propylene, removes water, oxygen, carbon monoxide, two in propylene
There is the polymerization reaction for not only influencing ethylene in the impurity such as carbonoxide, sulphur, impurity, can also generate larger shadow to polyacrylic quality
It rings；Then modification brown algae polyphenols class extract of the addition with anti-microbial property during propylene polymerization, is modified brown at this time
Algae Polyphenols extract is able to participate polyacrylic polymerization reaction, forms block in polypropylene macromolecular chain.The prior art
Used in method be that directly antibacterial material is blended with polypropylene fusion, to make plastic cup with anti-microbial property, the method
It has the drawback that antibacterial material and macromolecule polypropylene compatibility are poor, antibacterial material is caused to disperse in macromolecule polypropylene
Unevenness causes the anti-microbial property of plastic cup poor, with the aging action of plastic cup after long-time use, antibacterial material be easy from
It is precipitated in plastic cup, so that the antibiotic property of plastic cup is further deteriorated, i.e., Durability of antimicrobial effect is poor.Since the present invention will have antibacterial
In the modification brown algae polyphenols class extract insertion polypropylene molecular chain of effect, due to the effect of chemical bond, modified brown algae polyphenols class
Extract will not be precipitated from cup body, and Durability of antimicrobial effect can preferably be precipitated from cup body even if being modified brown algae polyphenols class extract,
Modified brown algae polyphenols class extract is natural component, will not be caused harm to the human body；In addition it is modified brown algae polyphenols class extract
It can be uniformly dispersed in cup body, there is stronger antibacterial action.
Preferably, the molar ratio of purification propylene and hydrogen is 1:3.3~3.6, the modified brown alga in the step b)
The mass ratio of Polyphenols extract and purification propylene is 1:4.2~4.5.
Preferably, the mass ratio of catalyst and purification propylene is 1:3~5 in the step b), the catalyst includes
Major catalyst titanium trichloride and cocatalyst chloro aluminum dialkyl, the mass ratio of the titanium trichloride and chloro aluminum dialkyl are
1:0.1~0.3.
Preferably, in the step b) modified brown algae polyphenols class extract preparation method the following steps are included:
By brown algae polyphenols class extract be added to mass fraction be 60~75% ethanol waters be configured to concentration be 20~
30wt% brown algae polyphenols class extract solution, is heated to 50~55 DEG C, then stirring and dissolving is added catalyst alchlor and continues
0.5~2min is stirred, 3,4- epoxy-1-butylene is slow added into, is warming up to 60~63 DEG C, be stirred to react 3~4h, stirring rate
Control is cooled to room temperature after completion of the reaction in 45~60r/min, is placed in Rotary Evaporators and is concentrated, finally by vacuum drying
Obtain modified brown algae polyphenols class extract.
Modified brown algae polyphenols class extract is to be modified brown algae polyphenols class extract, in brown algae polyphenols class extract
Ring-opening reaction occurs for hydroxyl and 3, the epoxy group in 4- epoxy-1-butylene, so that it is more that 4- epoxy-1-butylene introduces brown alga by 3
On phenols extract molecule, to make to be modified on brown algae polyphenols class extract in brown algae polyphenols class extract with olefin group
Olefin group can with propylene occur sudden reaction, so that antibacterial material is connected in polypropylene long-chain molecule；Brown alga is more
Phenols extract is the native compound extracted from seaweed, has phenolic hydroxyl group, phenolic hydroxyl group physiological activity with higher, to thin
Bacterium and virus have preferable inhibition killing effect.
Preferably, the catalyst alchlor and brown algae polyphenols class extract quality ratio are 1:4~6, described 3,4-
Epoxy-1-butylene and brown algae polyphenols class extract quality ratio are 1:2~3.
Preferably, the preparation method of the modified sheeted nanometer aluminium oxide the following steps are included:
Flake nano aluminium oxide, dimethyl sulfoxide and deionized water are mixed to form slurries, flake nano aluminium oxide, dimethyl are sub-
Sulfone, deionized water quality ratio are 1:0.5~0.8:1~1.5, are warming up to 80~85 DEG C, 4~6h are stirred, at 100~110 DEG C
It is dried to obtain flake nano alumina powder, flake nano alumina powder is added in ethyl alcohol and carries out 2~3h of sonic oscillation, piece
Shape nano alumina powder additive amount is 20~30wt% of ethyl alcohol, by centrifugation, is dried to obtain presoma, spare；By carboxylic
Methyl chitosan is added in 2- aminoheptylic acid, and the molar ratio of carboxymethyl chitosan and 2- aminoheptylic acid is 1:1~1.5, then plus
Enter catalyst sodium methoxide, catalyst sodium methoxide additive amount is 2~5wt% of carboxymethyl chitosan, is warming up to 85~90 DEG C, stirring
1~2h of isothermal reaction obtains modified carboxy methyl chitosan, and it is 60~80% second that mass fraction, which is added, in modified carboxy methyl chitosan
It is 15~20wt% modified carboxy methyl chitosan solution that concentration is configured in alcohol solution, presoma is then added, 65~80
It is stirred to react 15~20h at DEG C, by centrifugation, is dried to obtain modified sheeted nanometer aluminium oxide.
Dimethyl sulfoxide is the higher small molecule compound of polarity, is able to enter the interlayer of flake nano aluminium oxide, then
Ethyl alcohol is inserted into flake nano oxygen by the dimethyl sulfoxide that the interlayer of flake nano aluminium oxide is displaced using the method that intercalation replaces
Change the interlayer of aluminium, and long-chain molecule 2- aminoheptylic acid can displace ethyl alcohol, so that 2- aminoheptylic acid is inserted into flake nano oxygen
Change the interlayer of aluminium, increases the distance between flake nano alumina layer, to improve the dispersion performance of flake nano aluminium oxide, still
2- aminoheptylic acid can be detached from interlayer after team's research discovery a period of time of the present invention, cause the group of flake nano aluminium oxide
Poly-, dispersion performance is deteriorated, and the present invention is modified carboxymethyl chitosan, carboxyl and the 2- aminoheptylic acid of carboxymethyl chitosan
Amino reaction is received so that carboxymethyl chitosan be made to have into sheet to introduce 2- aminoheptylic acid on carboxymethyl chitosan
Ability between rice alumina layer, has more hydroxyl on carboxymethyl chitosan glycan molecule, can on flake nano aluminium oxide
Hydroxyl forms hydrogen bond action, so that 2- aminoheptylic acid be made to be not easy to be detached from from the interlayer of flake nano aluminium oxide, keeps for a long time
The dispersion performance of flake nano aluminium oxide.Great amount of hydroxy group on carboxymethyl chitosan is also respectively and in flake nano oxidation aluminium surface
Hydroxyl and modified brown algae polyphenols class extract in phenolic hydroxyl group form hydrogen bond action, so that flake nano aluminium oxide be made to be not easy
It is precipitated from plastic cup.In addition carboxymethyl chitosan has stronger antibacterial action, further increases the anti-microbial property of plastic cup.
Preferably, the mass ratio of the modified carboxy methyl chitosan and presoma is 1:3~6.
Preferably, at 160~162 DEG C, conveying section temperature controls the control of injection molding machine feeding section temperature in the step 4)
At 164~168 DEG C, at 170~172 DEG C, mold temperature is controlled at 75~80 DEG C the control of injection portion temperature.
Therefore, the invention has the following beneficial effects: (1) to have preferable and lasting anti-microbial property；(2) improve polypropylene
The toughness of plastic cup improves plastic cup and cheats impact property.
Specific embodiment
Below by specific embodiment, technical scheme is described further.
In the present invention, if not refering in particular to, used raw material and equipment etc. are commercially available or commonly used in the art,
Method in embodiment is unless otherwise instructed the conventional method of this field.
Embodiment 1
The preparation method of modified brown algae polyphenols class extract the following steps are included:
It is that be configured to concentration be that 25wt% brown alga is more to 65% ethanol water that brown algae polyphenols class extract, which is added to mass fraction,
Phenols extract solution, is heated to 53 DEG C, then stirring and dissolving is added catalyst alchlor and continues to stir 1min, catalyst
Alchlor and brown algae polyphenols class extract quality ratio are 1:5, are slow added into 3,4- epoxy-1-butylene, 3,4- epoxy -1- fourths
Alkene and brown algae polyphenols class extract quality ratio are 1:2.5, are warming up to 61 DEG C, are stirred to react 3.5h, and stirring rate is controlled in 55r/
Min is cooled to room temperature after completion of the reaction, is placed in Rotary Evaporators and is concentrated, and it is more finally to obtain modified brown alga by vacuum drying
Phenols extract.
The preparation method of modified polypropylene resin particle the following steps are included:
A) feed purification: propylene is passed through in solid caustic soda tower and removes moisture, carbon monoxide and carbon dioxide, is then passed through propylene de-
In sulphur treating column, then the propylene after desulfurization is passed through deoxidation treating column, the propylene after deoxidation is finally passed through molecular sieve water separation tower
It carries out deep dehydration and obtains purification propylene；
B) it polymerize: purification propylene is passed through in the polymeric kettle containing n-hexane solvent, hydrogen, modification are then passed through into polymeric kettle
Brown algae polyphenols class extract and catalyst, the molar ratio for refining propylene and hydrogen is 1:3.4, modified brown algae polyphenols class extract with
The mass ratio for refining propylene is 1:4.3, and catalyst and the mass ratio for refining propylene are 1:4, and catalyst includes major catalyst trichlorine
The mass ratio of change titanium and cocatalyst chloro aluminum dialkyl, the titanium trichloride and chloro aluminum dialkyl is 1:0.2, and control is anti-
Answering temperature is 66 DEG C, and kettle pressure is 2.1Mpa, reaction time 3h；
C) it separates drying: after polymerization reaction then reaction solution being passed through kettle voltage-controlled system in filter centrifugal in 1MPa, point
PP GRANULES is separated out, then PP GRANULES is sent into air-flow boiling drier and is dried to obtain PP GRANULES powder；
D) it is granulated: the PP GRANULES powder after drying being sent into Squeezinggranulator and carries out extruding agglomeration granulation, is modified
Acrylic resin particle.
The preparation method of the modified sheeted nanometer aluminium oxide the following steps are included:
Flake nano aluminium oxide, dimethyl sulfoxide and deionized water are mixed to form slurries, flake nano aluminium oxide, dimethyl are sub-
Sulfone, deionized water quality ratio are 1:0.6:1.3, are warming up to 83 DEG C, stir 5h, and flake nano oxidation is dried to obtain at 105 DEG C
Flake nano alumina powder is added in ethyl alcohol and carries out sonic oscillation 2.5h by aluminium powder, flake nano alumina powder additive amount
For the 25wt% of ethyl alcohol, by centrifugation, it is dried to obtain presoma, it is spare；2- aminoheptylic acid is added in carboxymethyl chitosan
In, the molar ratio of carboxymethyl chitosan and 2- aminoheptylic acid is 1:1.2, and catalyst sodium methoxide, catalyst sodium methoxide is then added
Additive amount is the 3.5wt% of carboxymethyl chitosan, is warming up to 88 DEG C, stirs isothermal reaction 1.5h, and it is poly- to obtain modified carboxy methyl shell
Modified carboxy methyl chitosan addition mass fraction is that concentration is configured in 70% ethanol water is the modified carboxylic first of 18wt% by sugar
Base chitosan solution, is then added presoma, and the mass ratio of modified carboxy methyl chitosan and presoma is 1:4.5, at 70 DEG C
It is stirred to react 18h, by centrifugation, is dried to obtain modified sheeted nanometer aluminium oxide.
The preparation method of durable antibiotic polypropylene plastic cup, comprising the following steps:
(1) by modified polypropylene resin particle, heat dries 4h at 70 DEG C, and moisture content is controlled 0.05%；
(2) following components is mixed by weight ratio: 65 parts of modified polypropylene resin particle, ethylene bis stearamide 2
Part, it 2 parts of dimethyl silicone polymer, 0.8 part of thiopropionate kind antioxidant, 4.5 parts of modified sheeted nanometer aluminium oxide, then stirs
Uniformly obtain mixing；
(3) mixing is fitted into melting mixing in injection molding machine, at 161 DEG C, conveying section temperature controls the control of injection molding machine feeding section temperature
At 166 DEG C, injection portion temperature is controlled at 171 DEG C, melt is sent into cavity forming, mold temperature is controlled at 77 DEG C, cooling and solidifying
Obtain durable antibiotic polypropylene plastic cup.
Embodiment 2
The preparation method of modified brown algae polyphenols class extract the following steps are included:
It is that be configured to concentration be that 22wt% brown alga is more to 65% ethanol water that brown algae polyphenols class extract, which is added to mass fraction,
Phenols extract solution, is heated to 54 DEG C, then stirring and dissolving is added catalyst alchlor and continues to stir 1.8min, catalysis
Agent alchlor and brown algae polyphenols class extract quality ratio are 1:4.5, are slow added into 3,4- epoxy-1-butylene, 3,4- epoxies-
1- butylene and brown algae polyphenols class extract quality ratio are 1:2.8, are warming up to 60.5 DEG C, are stirred to react 3.8h, stirring rate control
It in 55r/min, is cooled to room temperature after completion of the reaction, is placed in Rotary Evaporators and is concentrated, be finally modified by vacuum drying
Brown algae polyphenols class extract.
The preparation method of modified polypropylene resin particle the following steps are included:
A) feed purification: propylene is passed through in solid caustic soda tower and removes moisture, carbon monoxide and carbon dioxide, is then passed through propylene de-
In sulphur treating column, then the propylene after desulfurization is passed through deoxidation treating column, the propylene after deoxidation is finally passed through molecular sieve water separation tower
It carries out deep dehydration and obtains purification propylene；
B) it polymerize: purification propylene is passed through in the polymeric kettle containing n-hexane solvent, hydrogen, modification are then passed through into polymeric kettle
Brown algae polyphenols class extract and catalyst, the molar ratio for refining propylene and hydrogen is 1:3.4, modified brown algae polyphenols class extract with
The mass ratio for refining propylene is 1:4.3, and catalyst and the mass ratio for refining propylene are 1:4.5, and catalyst includes major catalyst three
The mass ratio of titanium chloride and cocatalyst chloro aluminum dialkyl, the titanium trichloride and chloro aluminum dialkyl is 1:0.15, control
Reaction temperature processed is 67 DEG C, and kettle pressure is 2Mpa, reaction time 3.4h；
C) it separates drying: after polymerization reaction then reaction solution being passed through kettle voltage-controlled system in filter centrifugal in 0.9MPa,
PP GRANULES is isolated, then PP GRANULES is sent into air-flow boiling drier and is dried to obtain PP GRANULES powder
Material；
D) it is granulated: the PP GRANULES powder after drying being sent into Squeezinggranulator and carries out extruding agglomeration granulation, is modified
Acrylic resin particle.
The preparation method of the modified sheeted nanometer aluminium oxide the following steps are included:
Flake nano aluminium oxide, dimethyl sulfoxide and deionized water are mixed to form slurries, flake nano aluminium oxide, dimethyl are sub-
Sulfone, deionized water quality ratio are 1:0.7:1.2, are warming up to 81 DEG C, stir 5.5h, flake nano oxygen is dried to obtain at 102 DEG C
Change aluminium powder, flake nano alumina powder is added in ethyl alcohol and carries out sonic oscillation 2.8h, the addition of flake nano alumina powder
Amount is the 22wt% of ethyl alcohol, by centrifugation, is dried to obtain presoma, spare；2- amino heptan is added in carboxymethyl chitosan
In acid, the molar ratio of carboxymethyl chitosan and 2- aminoheptylic acid is 1:1.4, and catalyst sodium methoxide, catalyst methanol is then added
Sodium additive amount is the 2.4wt% of carboxymethyl chitosan, is warming up to 88 DEG C, stirs isothermal reaction 1.2h, obtains modified carboxy methyl shell
Modified carboxy methyl chitosan addition mass fraction is that concentration is configured in 78% ethanol water is the modified carboxylic of 16wt% by glycan
Methyl chitosan solution, is then added presoma, and the mass ratio of modified carboxy methyl chitosan and presoma is 1:5.5, at 68 DEG C
Under be stirred to react 18h, by centrifugation, be dried to obtain modified sheeted nanometer aluminium oxide.
The preparation method of durable antibiotic polypropylene plastic cup, comprising the following steps:
(1) by modified polypropylene resin particle, heat dries 5h at 65 DEG C, and moisture content is controlled 0.08%；
(2) following components is mixed by weight ratio: 62 parts of modified polypropylene resin particle, ethylene bis stearamide 2
Part, it 2.5 parts of dimethyl silicone polymer, 0.6 part of thiopropionate kind antioxidant, 5.5 parts of modified sheeted nanometer aluminium oxide, then stirs
It mixes and uniformly obtains mixing；
(3) mixing is fitted into melting mixing in injection molding machine, at 161 DEG C, conveying section temperature controls the control of injection molding machine feeding section temperature
At 167 DEG C, injection portion temperature is controlled at 170 DEG C, melt is sent into cavity forming, mold temperature is controlled at 79 DEG C, cooling and solidifying
Obtain durable antibiotic polypropylene plastic cup.
Embodiment 3
The preparation method of modified brown algae polyphenols class extract the following steps are included:
It is that be configured to concentration be that 25wt% brown alga is more to 65% ethanol water that brown algae polyphenols class extract, which is added to mass fraction,
Phenols extract solution, is heated to 54 DEG C, then stirring and dissolving is added catalyst alchlor and continues to stir 1min, catalyst
Alchlor and brown algae polyphenols class extract quality ratio are 1:4.5, are slow added into 3,4- epoxy-1-butylene, 3,4- epoxy -1-
Butylene and brown algae polyphenols class extract quality ratio are 1:2.8, are warming up to 62 DEG C, are stirred to react 3.5h, and stirring rate control exists
55r/min is cooled to room temperature after completion of the reaction, is placed in Rotary Evaporators and is concentrated, and finally obtains being modified by vacuum drying brown
Algae Polyphenols extract.
The preparation method of modified polypropylene resin particle the following steps are included:
A) feed purification: propylene is passed through in solid caustic soda tower and removes moisture, carbon monoxide and carbon dioxide, is then passed through propylene de-
In sulphur treating column, then the propylene after desulfurization is passed through deoxidation treating column, the propylene after deoxidation is finally passed through molecular sieve water separation tower
It carries out deep dehydration and obtains purification propylene；
B) it polymerize: purification propylene is passed through in the polymeric kettle containing n-hexane solvent, hydrogen, modification are then passed through into polymeric kettle
Brown algae polyphenols class extract and catalyst, the molar ratio for refining propylene and hydrogen is 1:3.4, modified brown algae polyphenols class extract with
The mass ratio for refining propylene is 1:4.3, and catalyst and the mass ratio for refining propylene are 1:4, and catalyst includes major catalyst trichlorine
The mass ratio of change titanium and cocatalyst chloro aluminum dialkyl, the titanium trichloride and chloro aluminum dialkyl is 1:0.2, and control is anti-
Answering temperature is 67 DEG C, and kettle pressure is 2.1Mpa, reaction time 3.4h；
C) it separates drying: after polymerization reaction then reaction solution being passed through kettle voltage-controlled system in filter centrifugal in 1MPa, point
PP GRANULES is separated out, then PP GRANULES is sent into air-flow boiling drier and is dried to obtain PP GRANULES powder；
D) it is granulated: the PP GRANULES powder after drying being sent into Squeezinggranulator and carries out extruding agglomeration granulation, is modified
Acrylic resin particle.
The preparation method of the modified sheeted nanometer aluminium oxide the following steps are included:
Flake nano aluminium oxide, dimethyl sulfoxide and deionized water are mixed to form slurries, flake nano aluminium oxide, dimethyl are sub-
Sulfone, deionized water quality ratio are 1:0.6:1.2, are warming up to 81 DEG C, stir 5.5h, flake nano oxygen is dried to obtain at 105 DEG C
Change aluminium powder, flake nano alumina powder is added in ethyl alcohol and carries out sonic oscillation 2.2h, the addition of flake nano alumina powder
Amount is the 28wt% of ethyl alcohol, by centrifugation, is dried to obtain presoma, spare；2- amino heptan is added in carboxymethyl chitosan
In acid, the molar ratio of carboxymethyl chitosan and 2- aminoheptylic acid is 1:1.3, and catalyst sodium methoxide, catalyst methanol is then added
Sodium additive amount is the 3wt% of carboxymethyl chitosan, is warming up to 86 DEG C, stirs isothermal reaction 1.5h, and it is poly- to obtain modified carboxy methyl shell
Modified carboxy methyl chitosan addition mass fraction is that concentration is configured in 70% ethanol water is the modified carboxylic first of 16wt% by sugar
Base chitosan solution, is then added presoma, and the mass ratio of modified carboxy methyl chitosan and presoma is 1:5.5, at 66 DEG C
It is stirred to react 18h, by centrifugation, is dried to obtain modified sheeted nanometer aluminium oxide.
The preparation method of durable antibiotic polypropylene plastic cup, comprising the following steps:
(1) by modified polypropylene resin particle, heat dries 3h at 70 DEG C, and moisture content is controlled 0.1%；
(2) following components is mixed by weight ratio: 65 parts of modified polypropylene resin particle, ethylene bis stearamide
1.5 parts, 2.5 parts of dimethyl silicone polymer, 0.8 part of thiopropionate kind antioxidant, 4.5 parts of modified sheeted nanometer aluminium oxide, so
After be uniformly mixing to obtain mixing；
(3) mixing is fitted into melting mixing in injection molding machine, at 161 DEG C, conveying section temperature controls the control of injection molding machine feeding section temperature
At 165 DEG C, injection portion temperature is controlled at 172 DEG C, melt is sent into cavity forming, mold temperature is controlled at 78 DEG C, cooling and solidifying
Obtain durable antibiotic polypropylene plastic cup.
Embodiment 4
The preparation method of modified brown algae polyphenols class extract the following steps are included:
It is that be configured to concentration be that 22wt% brown alga is more to 65% ethanol water that brown algae polyphenols class extract, which is added to mass fraction,
Phenols extract solution, is heated to 51 DEG C, then stirring and dissolving is added catalyst alchlor and continues to stir 0.8min, catalysis
Agent alchlor and brown algae polyphenols class extract quality ratio are 1:4.5, are slow added into 3,4- epoxy-1-butylene, 3,4- epoxies-
1- butylene and brown algae polyphenols class extract quality ratio are 1:2.2, are warming up to 61 DEG C, are stirred to react 3h, and stirring rate control exists
45r/min is cooled to room temperature after completion of the reaction, is placed in Rotary Evaporators and is concentrated, and finally obtains being modified by vacuum drying brown
Algae Polyphenols extract.
The preparation method of modified polypropylene resin particle the following steps are included:
A) feed purification: propylene is passed through in solid caustic soda tower and removes moisture, carbon monoxide and carbon dioxide, is then passed through propylene de-
In sulphur treating column, then the propylene after desulfurization is passed through deoxidation treating column, the propylene after deoxidation is finally passed through molecular sieve water separation tower
It carries out deep dehydration and obtains purification propylene；
B) it polymerize: purification propylene is passed through in the polymeric kettle containing n-hexane solvent, hydrogen, modification are then passed through into polymeric kettle
Brown algae polyphenols class extract and catalyst, the molar ratio for refining propylene and hydrogen is 1:3.4, modified brown algae polyphenols class extract with
The mass ratio for refining propylene is 1:4.3, and catalyst and the mass ratio for refining propylene are 1:3.5, and catalyst includes major catalyst three
The mass ratio of titanium chloride and cocatalyst chloro aluminum dialkyl, the titanium trichloride and chloro aluminum dialkyl is 1:0.15, control
Reaction temperature processed is 66 DEG C, and kettle pressure is 2Mpa, reaction time 3.2h；
C) it separates drying: after polymerization reaction then reaction solution being passed through kettle voltage-controlled system in filter centrifugal in 0.9MPa,
PP GRANULES is isolated, then PP GRANULES is sent into air-flow boiling drier and is dried to obtain PP GRANULES powder
Material；
D) it is granulated: the PP GRANULES powder after drying being sent into Squeezinggranulator and carries out extruding agglomeration granulation, is modified
Acrylic resin particle.
The preparation method of the modified sheeted nanometer aluminium oxide the following steps are included:
Flake nano aluminium oxide, dimethyl sulfoxide and deionized water are mixed to form slurries, flake nano aluminium oxide, dimethyl are sub-
Sulfone, deionized water quality ratio are 1:0.6:1.2, are warming up to 81 DEG C, stir 4.5h, flake nano oxygen is dried to obtain at 102 DEG C
Change aluminium powder, flake nano alumina powder is added in ethyl alcohol and carries out sonic oscillation 2.2h, the addition of flake nano alumina powder
Amount is the 21wt% of ethyl alcohol, by centrifugation, is dried to obtain presoma, spare；2- amino heptan is added in carboxymethyl chitosan
In acid, the molar ratio of carboxymethyl chitosan and 2- aminoheptylic acid is 1:1.2, and catalyst sodium methoxide, catalyst methanol is then added
Sodium additive amount is the 2.5wt% of carboxymethyl chitosan, is warming up to 86 DEG C, stirs isothermal reaction 1.2h, obtains modified carboxy methyl shell
Modified carboxy methyl chitosan addition mass fraction is that concentration is configured in 65% ethanol water is the modified carboxylic of 16wt% by glycan
Methyl chitosan solution, is then added presoma, and the mass ratio of modified carboxy methyl chitosan and presoma is 1:3.5, at 66 DEG C
Under be stirred to react 16h, by centrifugation, be dried to obtain modified sheeted nanometer aluminium oxide.
The preparation method of durable antibiotic polypropylene plastic cup, comprising the following steps:
(1) by modified polypropylene resin particle, heat dries 3h at 65 DEG C, and moisture content is controlled 0.05%；
(2) following components is mixed by weight ratio: 62 parts of modified polypropylene resin particle, ethylene bis stearamide
1.5 parts, 1.5 parts of dimethyl silicone polymer, 0.5 part of thiopropionate kind antioxidant, 3.5 parts of modified sheeted nanometer aluminium oxide, so
After be uniformly mixing to obtain mixing；
(3) mixing is fitted into melting mixing in injection molding machine, at 160 DEG C, conveying section temperature controls the control of injection molding machine feeding section temperature
At 165 DEG C, injection portion temperature is controlled at 170 DEG C, melt is sent into cavity forming, mold temperature is controlled at 76 DEG C, cooling and solidifying
Obtain durable antibiotic polypropylene plastic cup.
Embodiment 5
The preparation method of modified brown algae polyphenols class extract the following steps are included:
It is that be configured to concentration be that 28wt% brown alga is more to 65% ethanol water that brown algae polyphenols class extract, which is added to mass fraction,
Phenols extract solution, is heated to 54 DEG C, then stirring and dissolving is added catalyst alchlor and continues to stir 1.8min, catalysis
Agent alchlor and brown algae polyphenols class extract quality ratio are 1:5.5, are slow added into 3,4- epoxy-1-butylene, 3,4- epoxies-
1- butylene and brown algae polyphenols class extract quality ratio are 1:2.8, are warming up to 62 DEG C, are stirred to react 3.8h, and stirring rate control exists
55r/min is cooled to room temperature after completion of the reaction, is placed in Rotary Evaporators and is concentrated, and finally obtains being modified by vacuum drying brown
Algae Polyphenols extract.
The preparation method of modified polypropylene resin particle the following steps are included:
A) feed purification: propylene is passed through in solid caustic soda tower and removes moisture, carbon monoxide and carbon dioxide, is then passed through propylene de-
In sulphur treating column, then the propylene after desulfurization is passed through deoxidation treating column, the propylene after deoxidation is finally passed through molecular sieve water separation tower
It carries out deep dehydration and obtains purification propylene；
B) it polymerize: purification propylene is passed through in the polymeric kettle containing n-hexane solvent, hydrogen, modification are then passed through into polymeric kettle
Brown algae polyphenols class extract and catalyst, the molar ratio for refining propylene and hydrogen is 1:3.5, modified brown algae polyphenols class extract with
The mass ratio for refining propylene is 1:4.4, and catalyst and the mass ratio for refining propylene are 1:4.5, and catalyst includes major catalyst three
The mass ratio of titanium chloride and cocatalyst chloro aluminum dialkyl, the titanium trichloride and chloro aluminum dialkyl is 1:0.25, control
Reaction temperature processed is 67 DEG C, and kettle pressure is 2.2Mpa, reaction time 3.5h；
C) it separates drying: after polymerization reaction then reaction solution being passed through kettle voltage-controlled system in filter centrifugal in 1.2MPa,
PP GRANULES is isolated, then PP GRANULES is sent into air-flow boiling drier and is dried to obtain PP GRANULES powder
Material；
D) it is granulated: the PP GRANULES powder after drying being sent into Squeezinggranulator and carries out extruding agglomeration granulation, is modified
Acrylic resin particle.
The preparation method of the modified sheeted nanometer aluminium oxide the following steps are included:
Flake nano aluminium oxide, dimethyl sulfoxide and deionized water are mixed to form slurries, flake nano aluminium oxide, dimethyl are sub-
Sulfone, deionized water quality ratio are 1:0.7:1.2, are warming up to 84 DEG C, stir 5.5h, flake nano oxygen is dried to obtain at 108 DEG C
Change aluminium powder, flake nano alumina powder is added in ethyl alcohol and carries out sonic oscillation 2.8h, the addition of flake nano alumina powder
Amount is the 28wt% of ethyl alcohol, by centrifugation, is dried to obtain presoma, spare；2- amino heptan is added in carboxymethyl chitosan
In acid, the molar ratio of carboxymethyl chitosan and 2- aminoheptylic acid is 1:1.4, and catalyst sodium methoxide, catalyst methanol is then added
Sodium additive amount is the 4.5wt% of carboxymethyl chitosan, is warming up to 88 DEG C, stirs isothermal reaction 1.5h, obtains modified carboxy methyl shell
Modified carboxy methyl chitosan addition mass fraction is that concentration is configured in 80% ethanol water is the modified carboxylic of 18wt% by glycan
Methyl chitosan solution, is then added presoma, and the mass ratio of modified carboxy methyl chitosan and presoma is 1:5.5, at 75 DEG C
Under be stirred to react 19h, by centrifugation, be dried to obtain modified sheeted nanometer aluminium oxide.
The preparation method of durable antibiotic polypropylene plastic cup, comprising the following steps:
(1) by modified polypropylene resin particle, heat dries 5h at 77 DEG C, and moisture content is controlled 0.1%；
(2) following components is mixed by weight ratio: 68 parts of modified polypropylene resin particle, ethylene bis stearamide
2.5 parts, 2.5 parts of dimethyl silicone polymer, 0.8 part of thiopropionate kind antioxidant, 5 parts of modified sheeted nanometer aluminium oxide, then
It is uniformly mixing to obtain mixing；
(3) mixing is fitted into melting mixing in injection molding machine, at 162 DEG C, conveying section temperature controls the control of injection molding machine feeding section temperature
At 167 DEG C, injection portion temperature is controlled at 172 DEG C, melt is sent into cavity forming, mold temperature is controlled at 77 DEG C, cooling and solidifying
Obtain durable antibiotic polypropylene plastic cup.
Embodiment 6
The preparation method of modified brown algae polyphenols class extract the following steps are included:
It is that be configured to concentration be that 30wt% brown alga is more to 75% ethanol water that brown algae polyphenols class extract, which is added to mass fraction,
Phenols extract solution, is heated to 55 DEG C, then stirring and dissolving is added catalyst alchlor and continues to stir 2min, catalyst
Alchlor and brown algae polyphenols class extract quality ratio are 1:6, are slow added into 3,4- epoxy-1-butylene, 3,4- epoxy -1- fourths
Alkene and brown algae polyphenols class extract quality ratio are 1:3, are warming up to 63 DEG C, are stirred to react 4h, and stirring rate is controlled in 60r/min,
It is cooled to room temperature after completion of the reaction, is placed in Rotary Evaporators and is concentrated, finally obtain modified brown algae polyphenols class by vacuum drying
Extract.
The preparation method of modified polypropylene resin particle the following steps are included:
A) feed purification: propylene is passed through in solid caustic soda tower and removes moisture, carbon monoxide and carbon dioxide, is then passed through propylene de-
In sulphur treating column, then the propylene after desulfurization is passed through deoxidation treating column, the propylene after deoxidation is finally passed through molecular sieve water separation tower
It carries out deep dehydration and obtains purification propylene；
B) it polymerize: purification propylene is passed through in the polymeric kettle containing n-hexane solvent, hydrogen, modification are then passed through into polymeric kettle
Brown algae polyphenols class extract and catalyst, the molar ratio for refining propylene and hydrogen is 1:3.6, modified brown algae polyphenols class extract with
The mass ratio for refining propylene is 1:4.5, and catalyst and the mass ratio for refining propylene are 1:5, and catalyst includes major catalyst trichlorine
The mass ratio of change titanium and cocatalyst chloro aluminum dialkyl, the titanium trichloride and chloro aluminum dialkyl is 1:0.3, and control is anti-
Answering temperature is 68 DEG C, and kettle pressure is 2.2Mpa, reaction time 3.5h；
C) it separates drying: after polymerization reaction then reaction solution being passed through kettle voltage-controlled system in filter centrifugal in 1.3MPa,
PP GRANULES is isolated, then PP GRANULES is sent into air-flow boiling drier and is dried to obtain PP GRANULES powder
Material；
D) it is granulated: the PP GRANULES powder after drying being sent into Squeezinggranulator and carries out extruding agglomeration granulation, is modified
Acrylic resin particle.
The preparation method of the modified sheeted nanometer aluminium oxide the following steps are included:
Flake nano aluminium oxide, dimethyl sulfoxide and deionized water are mixed to form slurries, flake nano aluminium oxide, dimethyl are sub-
Sulfone, deionized water quality ratio are 1:0.8:1.5, are warming up to 85 DEG C, stir 6h, and flake nano oxidation is dried to obtain at 110 DEG C
Aluminium powder, flake nano alumina powder is added in ethyl alcohol and carries out sonic oscillation 3h, and flake nano alumina powder additive amount is
The 30wt% of ethyl alcohol by centrifugation, is dried to obtain presoma, spare；Carboxymethyl chitosan is added in 2- aminoheptylic acid,
The molar ratio of carboxymethyl chitosan and 2- aminoheptylic acid is 1:1.5, and catalyst sodium methoxide, catalyst sodium methoxide addition is then added
Amount is the 5wt% of carboxymethyl chitosan, is warming up to 90 DEG C, stirs isothermal reaction 2h, obtains modified carboxy methyl chitosan, will be modified
It is that concentration is configured in 80% ethanol water is 20wt% modified carboxy methyl chitosan that mass fraction, which is added, in carboxymethyl chitosan
Solution, is then added presoma, and the mass ratio of modified carboxy methyl chitosan and presoma is 1:6, is stirred to react at 80 DEG C
20h by centrifugation, is dried to obtain modified sheeted nanometer aluminium oxide.
The preparation method of durable antibiotic polypropylene plastic cup, comprising the following steps:
(1) by modified polypropylene resin particle, heat dries 6h at 80 DEG C, and moisture content is controlled 0.1%；
(2) following components is mixed by weight ratio: 70 parts of modified polypropylene resin particle, ethylene bis stearamide 3
Part, it 3 parts of dimethyl silicone polymer, 1 part of thiopropionate kind antioxidant, 6 parts of modified sheeted nanometer aluminium oxide, then stirs evenly
Obtain mixing；
(3) mixing is fitted into melting mixing in injection molding machine, at 162 DEG C, conveying section temperature controls the control of injection molding machine feeding section temperature
At 168 DEG C, injection portion temperature is controlled at 172 DEG C, melt is sent into cavity forming, mold temperature is controlled at 80 DEG C, cooling and solidifying
Obtain durable antibiotic polypropylene plastic cup.
Embodiment 7
The preparation method of modified brown algae polyphenols class extract the following steps are included:
It is that be configured to concentration be that 20wt% brown alga is more to 60% ethanol water that brown algae polyphenols class extract, which is added to mass fraction,
Phenols extract solution, is heated to 50 DEG C, then stirring and dissolving is added catalyst alchlor and continues to stir 0.5min, catalysis
Agent alchlor and brown algae polyphenols class extract quality ratio are 1:4, are slow added into 3,4- epoxy-1-butylene, 3,4- epoxy -1-
Butylene and brown algae polyphenols class extract quality ratio are 1:2, are warming up to 60 DEG C, are stirred to react 3h, and stirring rate is controlled in 45r/
Min is cooled to room temperature after completion of the reaction, is placed in Rotary Evaporators and is concentrated, and it is more finally to obtain modified brown alga by vacuum drying
Phenols extract.
The preparation method of modified polypropylene resin particle the following steps are included:
A) feed purification: propylene is passed through in solid caustic soda tower and removes moisture, carbon monoxide and carbon dioxide, is then passed through propylene de-
In sulphur treating column, then the propylene after desulfurization is passed through deoxidation treating column, the propylene after deoxidation is finally passed through molecular sieve water separation tower
It carries out deep dehydration and obtains purification propylene；
B) it polymerize: purification propylene is passed through in the polymeric kettle containing n-hexane solvent, hydrogen, modification are then passed through into polymeric kettle
Brown algae polyphenols class extract and catalyst, the molar ratio for refining propylene and hydrogen is 1:3.3, modified brown algae polyphenols class extract with
The mass ratio for refining propylene is 1:4.2, and catalyst and the mass ratio for refining propylene are 1:3, and catalyst includes major catalyst trichlorine
The mass ratio of change titanium and cocatalyst chloro aluminum dialkyl, the titanium trichloride and chloro aluminum dialkyl is 1:0.1, and control is anti-
Answering temperature is 65 DEG C, and kettle pressure is 2Mpa, reaction time 3h；
C) it separates drying: after polymerization reaction then reaction solution being passed through kettle voltage-controlled system in filter centrifugal in 0.8MPa,
PP GRANULES is isolated, then PP GRANULES is sent into air-flow boiling drier and is dried to obtain PP GRANULES powder
Material；
D) it is granulated: the PP GRANULES powder after drying being sent into Squeezinggranulator and carries out extruding agglomeration granulation, is modified
Acrylic resin particle.
The preparation method of the modified sheeted nanometer aluminium oxide the following steps are included:
Flake nano aluminium oxide, dimethyl sulfoxide and deionized water are mixed to form slurries, flake nano aluminium oxide, dimethyl are sub-
Sulfone, deionized water quality ratio are 1:0.5:1, are warming up to 80 DEG C, stir 4h, flake nano aluminium oxide is dried to obtain at 100 DEG C
Flake nano alumina powder is added in ethyl alcohol and carries out sonic oscillation 2h by powder, and flake nano alumina powder additive amount is second
The 20wt% of alcohol by centrifugation, is dried to obtain presoma, spare；Carboxymethyl chitosan is added in 2- aminoheptylic acid, carboxylic
Methyl chitosan and the molar ratio of 2- aminoheptylic acid are 1:1, catalyst sodium methoxide are then added, catalyst sodium methoxide additive amount is
The 2wt% of carboxymethyl chitosan is warming up to 85 DEG C, stirs isothermal reaction 1h, obtains modified carboxy methyl chitosan, by modified carboxylic first
It is that concentration is configured in 60% ethanol water is 15wt% modified carboxy methyl chitosan solution that mass fraction, which is added, in base enclosure glycan,
Then it is added presoma, the mass ratio of modified carboxy methyl chitosan and presoma is 1:3, and 15h is stirred to react at 65 DEG C, is passed through
Centrifugation is dried to obtain modified sheeted nanometer aluminium oxide.
The preparation method of durable antibiotic polypropylene plastic cup, comprising the following steps:
(1) by modified polypropylene resin particle, heat dries 2h at 60 DEG C, and moisture content is controlled 0.1%；
(2) following components is mixed by weight ratio: 60 parts of modified polypropylene resin particle, ethylene bis stearamide 1
Part, 1 part of dimethyl silicone polymer, 0.5 part of thiopropionate kind antioxidant, 3 parts of modified sheeted nanometer aluminium oxide, then stirring is equal
It is even to obtain mixing；
(3) mixing is fitted into melting mixing in injection molding machine, at 160 DEG C, conveying section temperature controls the control of injection molding machine feeding section temperature
At 164 DEG C, injection portion temperature is controlled at 170 DEG C, melt is sent into cavity forming, mold temperature is controlled at 75 DEG C, cooling and solidifying
Obtain durable antibiotic polypropylene plastic cup.
Comparative example 1
Comparative example 1 is not that modified brown algae polyphenols class extract is changed to the system in antibiotic polypropylene plastic cup but with embodiment 1
Standby process steps 2) in addition.
Comparative example 2
It is more that not being but of comparative example 2 and embodiment 1 does not add modified brown alga in the preparation process of modified polypropylene resin particle
Phenols extract.
Comparative example 3
Comparative example 3 and embodiment 1 are not but not adding modified sheeted nanometer oxygen in the preparation process of antibiotic polypropylene plastic cup
Change aluminium.
Anti-microbial Performance Tests:
Anti-microbial property is tested by QB/T2591-2003A, and detection is Escherichia coli ATCC 25922, staphylococcus aureus with bacterium
ATCC6538.75% ethanol disinfection of antibiotic polypropylene plastic is handled and dried, strain is diluted to 1/500 nutrient broth suitable
When the bacteria suspension of concentration is spare.Take 0.2mL bacteria suspension drop in specimen surface, with the polyethylene film of 0.05~0.10mm thickness
(4.0cm × 4.0cm) is covered in specimen surface, and bacteria suspension is made to form uniform liquid film between sample and film.In (35 ± 1) DEG C
It is cultivated under conditions of relative humidity >=90% for 24 hours, cleans bacterium solution with 10mlSCDLP broth bouillon, and raw with phosphate-buffered
Reason salt water is diluted to the concentration gradient of debita spissitudo, by sample recovered liquid and 10 dilutions respectively take 1ml, be put in respectively sterile
In culture dish, 15ml plate count agar is injected in each culture dish, is gently mixed or shakes up with disperse bacterial, it is solidifying to culture medium
Gu culture dish is overturn after, in (35 ± 1) DEG C culture 48h, observes result.Respectively by antibiotic polypropylene plastic in 50 DEG C of hot water
Impregnate 30d and by antibiotic polypropylene plastic under ultraviolet lamp aging process 50h, then press QB/T2591-2003A test method
Test its anti-microbial property.
Antibiotic polypropylene plastic of the embodiment of the present invention is obtained with preferable antibacterial ability by antibacterial tests test result, is resisted
Bacterium performance reaches 95% or more, and embodiment is suitable with 1 plastics initial antibacterial effect of comparative example, impregnates when in the hot water by 50 DEG C
Or after ultraviolet lamp aging process, the antibacterial effect decline of comparative example 1 is very fast, illustrates the antibacterial material in comparative example 1 in plastics
It is precipitated from plastics, anti-microbial property is caused to decline, 2 plastics of comparative example do not add modified brown algae polyphenols class extract antibacterial
Matter but has certain anti-microbial property, is because there are carboxymethyl chitosan, carboxymethyl shells in modified sheeted nanometer aluminium oxide
Glycan has certain antibacterial effect.
Mechanical property test carries out impact test test according to national standard GB/T1843-2008, is tested and is surveyed using simply supported beam
Impact strength is tried, using 25J pendulum, energy needed for record is broken calculates impact strength according to formula.It is molded the batten of preparation
It is tested, rate of extension 50mm/min, is recorded aobvious on computer on testing machine in omnipotent draw high according to national standard GB1040-92
The tensile strength shown, elongation at break.
Polypropylene is improved to polypropylene plastics by Mechanical test results available addition modified sheeted nanometer aluminium oxide
The impact strength of plastics, this is because being easy to that all matrix resins is excited to generate crazing or crackle when by external impacts, being
The extension of crackle is prevented, modified sheeted nanometer aluminium oxide absorbs part energy, will not develop into destructive crackle, from
And improve matrix toughness.
The above described is only a preferred embodiment of the present invention, be not intended to limit the present invention in any form, though
So the present invention has been disclosed as a preferred embodiment, and however, it is not intended to limit the invention, any technology people for being familiar with this profession
Member, without departing from the scope of the present invention, when the technology contents using the disclosure above make a little change or modification
It is right according to the technical essence of the invention for the equivalent embodiment of equivalent variations, but without departing from the technical solutions of the present invention
Any simple modification, equivalent change and modification made by above embodiments, all of which are still within the scope of the technical scheme of the invention.
Claims (10)
1. a kind of preparation method of durable antibiotic polypropylene plastic cup, which comprises the following steps:
(1) by modified polypropylene resin particle, heat dries 2 ~ 6h at 60 ~ 80 DEG C, and moisture content controls below 0.1%；
(2) by modified polypropylene resin particle, ethylene bis stearamide, dimethyl silicone polymer, thiopropionate kind antioxidant,
Mixing is uniformly mixing to obtain after the mixing of modified sheeted nanometer aluminium oxide；
(3) mixing is fitted into melting mixing in injection molding machine, melt is sent into cavity forming, cooling and solidifying obtains durable antibiotic poly- third
Alkene plastics cup.
2. according to right want 1 described in a kind of preparation method of durable antibiotic polypropylene plastic cup, which is characterized in that the step
2) mixing includes following components by weight ratio in:
60 ~ 70 parts of modified polypropylene resin particle, 1 ~ 3 part of ethylene bis stearamide, 1 ~ 3 part of dimethyl silicone polymer, thio third
0.5 ~ 1 part of acid esters kind antioxidant, 3 ~ 6 parts of modified sheeted nanometer aluminium oxide.
3. a kind of preparation method of durable antibiotic polypropylene plastic cup according to claim 1 or 2, which is characterized in that institute
State the preparation method of modified polypropylene resin particle the following steps are included:
A) feed purification: propylene is passed through in solid caustic soda tower and removes moisture, carbon monoxide and carbon dioxide, is then passed through propylene de-
In sulphur treating column, then the propylene after desulfurization is passed through deoxidation treating column, the propylene after deoxidation is finally passed through molecular sieve water separation tower
It carries out deep dehydration and obtains purification propylene；
B) it polymerize: purification propylene is passed through in the polymeric kettle containing n-hexane solvent, hydrogen, modification are then passed through into polymeric kettle
Brown algae polyphenols class extract and catalyst, control reaction temperature be 65 ~ 68 DEG C, kettle pressure be 2 ~ 2.2Mpa, the reaction time be 3 ~
3.5h；
C) it separates drying: after polymerization reaction then reaction solution being passed through centrifugal filtration in 0.8 ~ 1.3MPa by the voltage-controlled system of kettle
In machine, PP GRANULES is isolated, then PP GRANULES is sent into air-flow boiling drier and is dried to obtain polypropylene
Grain powder；
D) it is granulated: the PP GRANULES powder after drying being sent into Squeezinggranulator and carries out extruding agglomeration granulation, is modified
Acrylic resin particle.
4. a kind of preparation method of durable antibiotic polypropylene plastic cup according to claim 3, which is characterized in that the step
The molar ratio of rapid b) middle purification propylene and hydrogen is 1:3.3 ~ 3.6, the modified brown algae polyphenols class extract and purification propylene
Mass ratio is 1:4.2 ~ 4.5.
5. a kind of preparation method of durable antibiotic polypropylene plastic cup according to claim 3, which is characterized in that the step
It is rapid b) in catalyst and purification propylene mass ratio be 1:3 ~ 5, the catalyst includes that major catalyst titanium trichloride and auxiliary are urged
The mass ratio of agent chloro aluminum dialkyl, the titanium trichloride and chloro aluminum dialkyl is 1:0.1 ~ 0.3.
6. a kind of preparation method of durable antibiotic polypropylene plastic cup according to claim 3, which is characterized in that the step
It is rapid b) in modified brown algae polyphenols class extract preparation method the following steps are included:
It is that be configured to concentration be that 20 ~ 30wt% is brown to 60 ~ 75% ethanol waters that brown algae polyphenols class extract, which is added to mass fraction,
Algae Polyphenols extract solution, is heated to 50 ~ 55 DEG C, stirring and dissolving, be then added catalyst alchlor continue stirring 0.5 ~
2min is slow added into 3,4- epoxy-1-butylene, is warming up to 60 ~ 63 DEG C, is stirred to react 3 ~ 4h, and stirring rate is controlled 45 ~ 60
R/min is cooled to room temperature after completion of the reaction, is placed in Rotary Evaporators and is concentrated, and finally obtains modified brown alga by vacuum drying
Polyphenols extract.
7. a kind of preparation method of durable antibiotic polypropylene plastic cup according to claim 6, which is characterized in that described to urge
Agent alchlor and brown algae polyphenols class extract quality ratio are 1:4 ~ 6, and 3, the 4- epoxy-1-butylene is mentioned with brown algae polyphenols class
Taking amount of substance ratio is 1:2 ~ 3.
8. a kind of preparation method of durable antibiotic polypropylene plastic cup according to claim 1 or 2, which is characterized in that institute
State the preparation method of modified sheeted nanometer aluminium oxide the following steps are included:
Flake nano aluminium oxide, dimethyl sulfoxide and deionized water are mixed to form slurries, flake nano aluminium oxide, dimethyl are sub-
Sulfone, deionized water quality ratio are 1:0.5 ~ 0.8:1 ~ 1.5, are warming up to 80 ~ 85 DEG C, stir 4 ~ 6h, dry at 100 ~ 110 DEG C
To flake nano alumina powder, flake nano alumina powder is added in ethyl alcohol and carries out 2 ~ 3h of sonic oscillation, flake nano
Alumina powder additive amount is 20 ~ 30wt% of ethyl alcohol, by centrifugation, is dried to obtain presoma, spare；By carboxymethyl chitosan
Sugar is added in 2- aminoheptylic acid, and the molar ratio of carboxymethyl chitosan and 2- aminoheptylic acid is 1:1 ~ 1.5, and catalyst first is then added
Sodium alkoxide, catalyst sodium methoxide additive amount are 2 ~ 5wt% of carboxymethyl chitosan, are warming up to 85 ~ 90 DEG C, stir 1 ~ 2h of isothermal reaction,
Modified carboxy methyl chitosan is obtained, it is to be configured in 60 ~ 80% ethanol waters that mass fraction, which is added, in modified carboxy methyl chitosan
Concentration is 15 ~ 20wt% modified carboxy methyl chitosan solution, and presoma is then added, is stirred to react 15 ~ 20h at 65 ~ 80 DEG C,
By centrifugation, it is dried to obtain modified sheeted nanometer aluminium oxide.
9. a kind of preparation method of durable antibiotic polypropylene plastic cup according to claim 8, which is characterized in that described to change
Property carboxymethyl chitosan and presoma mass ratio be 1:3 ~ 6.
10. a kind of preparation method of durable antibiotic polypropylene plastic cup according to claim 1, which is characterized in that described
The control of injection molding machine feeding section temperature is at 160 ~ 162 DEG C in step 4), and the control of conveying section temperature is at 164 ~ 168 DEG C, injection portion temperature
At 170 ~ 172 DEG C, mold temperature is controlled at 75 ~ 80 DEG C for control.
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| CN102124049A (en) * | 2008-06-25 | 2011-07-13 | 纳米生物物质有限责任公司 | Active nanocomposite materials and production method thereof |
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| CN102124049A (en) * | 2008-06-25 | 2011-07-13 | 纳米生物物质有限责任公司 | Active nanocomposite materials and production method thereof |
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| WO2021120864A1 (en) | 2019-12-17 | 2021-06-24 | 金发科技股份有限公司 | Polypropylene composition, preparation method therefor and use thereof |
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