CN101717538B - Special compound additive for polyethylene film with high tranparency and low density - Google Patents

Special compound additive for polyethylene film with high tranparency and low density Download PDF

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CN101717538B
CN101717538B CN2009102326372A CN200910232637A CN101717538B CN 101717538 B CN101717538 B CN 101717538B CN 2009102326372 A CN2009102326372 A CN 2009102326372A CN 200910232637 A CN200910232637 A CN 200910232637A CN 101717538 B CN101717538 B CN 101717538B
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organosilicon
low density
integer
polyethylene film
compound additive
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CN101717538A (en
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彭令才
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NANJING CHUNDA SCIENCE TECHNOLOGY DEVELOPMENT Co Ltd
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Abstract

The invention relates to a special compound additive for a polyethylene film with high tranparency and low density, which is a particle prepared by the following steps of: stirring and mixing 25-30 percent of silicon dioxide anti-block agent, 5-15 percent of organic silicon glidant, 2-8 percent of organic silicon active crosslinking agent, 1-10 percent of organic silicon antioxidant and the balance of high pressure polyethylene resin by taking high-pressure polyethylene as a carrier; carrying out treatments including preheating, ball milling and dispersing at the temperature of 75-85 DEG C; and finally, extruding pelletization through a twin-screw granulator at the temperature of 140-170 DEG C. The low density polyethylene film prepared by adding the compound additive is tasteless, has high transparency, favorable physiological safety, high anti-blocking property, favorable smoothness and favorable transference resistance and can be particularly used for fields including food covering films, drug covering films, business card covering films, identification card covering films, advertisement packaging and the like which have the requirements of high transparency, high safety and high anti-blocking property.

Description

The special compound additive of polyethylene film with high tranparency and low density
Technical field
The present invention relates to a kind of special compound additive that polyethylene film with high tranparency and low density is produced that is used for.
Background technology
New LDPE (film grade) (LDPE), have another name called high-pressure polyethylene, it is the quality matetrial of packaging film, the packing that is widely used in food, medicine and daily necessities, it is ethylene free radical polymerization and the thermoplastics that obtains under the high pressure, the film that LDPE manufactures has showed good optical performance, intensity, bent rich property, stopping property, transparent, unreactiveness etc., is easy to forming process, and this has determined that LDPE is one of the most widely used material in the current polymer industry.No matter but the product that the employ Plastic Resin is produced, film article is very easily inter-adhesive, adds that conventional opening agent meeting produces flake, turbidity is too high, and transparency degradation detrimentally affect down directly influences its application and effect.Wherein some auxiliary agent adopts amine substance, aromatic series constituents etc., and there is physiological safety hidden danger in the film that is used for food and drug packaging.
Transparency is to weigh an important indicator of quality product quality, means that transparency is high more, product is high-grade more, added value is high more.Along with people's more and more higher to product requirement, also more and more higher to the transparency of LDPE.The turbidity of present domestic ldpe film product is substantially all more than 6%, and the turbidity of imported product best about 4%, therefore, high transparent ldpe film exploitation for dominate the market, substitute import, increasing economic efficiency has great significance.
Summary of the invention
The high density composite assistant that the purpose of this invention is to provide a kind of polyethylene film with high tranparency and low density, it is used for low-density polyethylene film production, makes high transparent, high physiological safety, weather resistance, dispersiveness, all splendid low-density polyethylene film of opening performance.
Auxiliary agent of the present invention is to be carrier with the high-pressure polyethylene; by the agent of silicon-dioxide opening, organosilicon glidant, organosilicon active crosslinker, organosilicon oxidation inhibitor and high pressure polyethylene resin by mix, 75～85 ℃ of following preheating Ball milling; at last under 140 ℃-170 ℃; by the particle that the dual-screw pelletizer extruding pelletization gets, the weight content of said each component is:
Silicon-dioxide opening agent 25%-30%,
Organosilicon glidant 5%-15%,
Organosilicon active crosslinker 2-8%,
Organosilicon oxidation inhibitor 1-10%,
The high pressure polyethylene resin surplus.
Said opening agent is by synthetic, and having specific surface area is 20-200m 2/ g, oil-absorption(number) 0.5～3.5ml/g, refractive index are 1.45-1.55, particle diameter 1500-5000 purpose silicon-dioxide.Preferred oil-absorption(number) 0.9-1.5ml/g, particle diameter 2000-3000 order, refractive index 1.46-1.48.
Said organosilicon glidant is the silicone elastomer material, and its chemical structural formula is:
Wherein:
N is 4040～20000 integer,
T1, T2 are independently selected from respectively-C 2H 5,-OH ,-CH 3,-C 2H 4Or-C 6H 5
The organosilicon glidant is microfluidic or immobilising transparent liquid, and the vinyl weight content that contains in the molecule is preferably 0.05-0.5%, more preferably 0.01-0.025% greater than 0.02% less than 3%.
Said organosilicon active crosslinker is the silicone oil of following chemical structural formula:
Figure DEST_PATH_GA20188070200910232637201D00012
Wherein:
N1 is 10～10000 integer,
T3 and T4 are independently selected from respectively-C 2H 5,-CH 3,-C 2H 4,-C 6H 5Or-OH;
Q1 and Q2 are-OH simultaneously, or one of them is-OH that another is selected from C mH 2m-1O, CH 2rO 2,-C sH 2sSH or-(CH 2) sCH 3
M is 2～5 integer, and r is 2～50 integer, and s is 3～50 integer;
In the molecule-the gross weight content of OH should be less than 12%.
This machine silicon active crosslinker is the oily mater with certain viscosity, and its boiling point is more than 180 ℃.
The chemical structural formula of said organosilicon antioxidant is as follows:
Wherein n2 is 10～1000 integer,
T5, T6 are independently selected from respectively-C 2H 5,-CH 3,-C 2H 4,-C 6H 5,-OH or-H,
T7, T8 are-H simultaneously, or one of them is-H that another is-C 2H 5,-CH 3,-C 2H 4,-C 6H 5,-OH or-(CH 2) sCH 3, s is 3～50 integer.
Be that the organosilicon antioxidant is at least a in Methyl Hydrogen Polysiloxane Fluid, phenyl hydrogen-containing silicon oil, ethyl containing hydrogen silicone oil, methylethyl containing hydrogen silicone oil, methyl and phenyl hydrogen-containing silicon oil, methylethyl phenyl containing hydrogen silicone oil or their modified silicon oil that contains above structural formula.
In this composite assistant, the opening agent is a silicon-dioxide, and other each activeconstituents is silicoorganic compound, does not contain non-silicon class additive.Having adopted the silicone oil of active moderate hydroxyl (or epoxy group(ing)) is linking agent, replace active at present too strong silane coupling agent, adopted the outstanding especially active silicone oil of smooth property as antioxidant, these organosilicon oils materials have splendid high temperature resistant, resistance to oxidation, UV resistant, insulativity, high photopermeability, and Extrusion Flow is fine.The transparent silicon dioxide that oil-absorption(number) is low, specific surface is little is selected in the agent of this composite assistant split shed for use, is synthesized into by the acid-base neutralisation method.Oil-absorption(number) is low, and the silicon-dioxide that specific surface is little can be avoided silicone oil to be sucked in a large number and reduce due function, so the dioxide-containing silica in the composite assistant of the present invention can be far up to 30%, thereby improves the opening performance of low-density polyethylene film.Adopt most liquid auxiliary agent and silicon-dioxide pre-mixing heating or low-grade fever to handle, fully moistening silicon-dioxide, become the material that paste or pressurization just can become paste, add the very environmental protection of getting up, material feeding speed is fast, and addition brings up to 30%.Simultaneously because organosilicon and silicon-dioxide have good avidity, silicone oil moistening to silica sphere in addition, greatly reduce the diffuse-reflectance of light, improve the transmitance of light, the mist degree of film reduces greatly, and the transparency is greatly improved, because to the moistening of silica sphere and better chemical bonding action, make the dispersiveness of silicon-dioxide in film improve greatly, brought into play good opening.Simultaneously at the silicon-dioxide of film surface owing to covered by organosilicon, its skin friction coefficient also decreases, and has improved the smooth property on surface.The organosilicon active crosslinker provides active group, can be to the silica sphere hydroxyl partially enclosed, its concavo-convex surface is modified and remedied, and these active crosslinker all have water white characteristic, refractive index is between 1.48-1.50, can improve the ray refraction transmitance, reduce casual radiation, thereby reduce the mist degree of film greatly.Active crosslinker has common organosilicon excellent electric performance, smooth property and high temperature resistant xanthochromia performance equally.Auxiliary agent of the present invention be with the form of master batch by interior mixing tank high shear force in specially designed twin screw extrusion equipment adds into polyethylene pellet, silica sphere is modified simultaneously, it and polyethylene have extraordinary intermiscibility, dispersing property improves greatly, prevent the reunion of silica dioxide granule, significantly reduce flake.
In sum, adopt the low-density polyethylene film of this composite assistant preparation, tasteless, high transparent, have good physiological safety, high opening, smooth property and fabulous resistance to migration.Can be applicable to food, medicine, business card, identity card overlay film and advertisement packing etc. especially and film is had the field of high transparent, high security and high opening requirement.
Embodiment
Embodiment 1
1. each auxiliary agent of the present invention is dropped into cantilever duplex conical agitator by following weight ratio and carries out the extensive dispersion of premix:
Efficient opening agent: 28
Organosilicon glidant: 12
Organosilicon active crosslinker: 5
Organosilicon oxidation inhibitor: 8
High-pressure polyethylene vector resin: 47
Cantilever duplex conical agitator technological operation rotating speed stirred 60 minutes for per minute 40-50 changes.
2, the raw material behind above-mentioned premix drops into horizontal ball mill, and rotating speed changes for per minute 45-50, and temperature is controlled at 80 ℃, and raw material is carried out preheating chemical bonding and refinement dispersion again.
3, the raw material after the above-mentioned refinement dispersion is dropped in the dual-screw pelletizer, under 140 ℃-170 ℃,, get composite assistant particle of the present invention with 200kg/ hour flow velocity extruding pelletization.
Embodiment 2:
Each components by weight is as follows:
Efficient opening agent: 30
Organosilicon glidant: 13
Organosilicon active crosslinker: 6
Organosilicon oxidation inhibitor: 8
High-pressure polyethylene vector resin: 43
With the processing condition operation that the mixture of above proportioning is pressed embodiment 1, last extruding pelletization gets builder granule of the present invention.
Embodiment 3:
Each component of the present invention is dropped into cantilever duplex conical agitator by following weight ratio carries out the extensive dispersion of premix:
Efficient opening agent: 20
Organosilicon glidant: 6
Organosilicon active crosslinker: 4
Organosilicon oxidation inhibitor: 8
High-pressure polyethylene vector resin: 62
Other operation production technique are with embodiment 1.
The relevant physical index of three routine composite assistants sees Table 1.
Table 1
Figure G2009102326372D00051
The composite assistant of above three examples is joined respectively in the ldpe resin by 2.5 ‰ (weight), test prepared high-pressure polyethylene product data such as table 2.
Table 2
Figure G2009102326372D00052
Figure G2009102326372D00061
Film is placed two weeks and is not found phenomenons such as oily, bloom.Product after film is preserved after half a year and new production was come out 7 days contrasts smooth degree indifference.

Claims (4)

1. the special compound additive of a polyethylene film with high tranparency and low density; it is characterized in that with the high-pressure polyethylene being carrier; by the agent of silicon-dioxide opening, organosilicon glidant, organosilicon active crosslinker, organosilicon oxidation inhibitor and high pressure polyethylene resin by mix, 75～85 ℃ of following preheating Ball milling; at last under 140 ℃-170 ℃; by the particle that the dual-screw pelletizer extruding pelletization gets, the weight content of said each component is:
Silicon-dioxide opening agent 25%-30%,
Organosilicon glidant 5%-15%,
Organosilicon active crosslinker 2-8%,
Organosilicon oxidation inhibitor 1-10%,
The high pressure polyethylene resin surplus;
Described opening agent silicon-dioxide is by synthetic, and having specific surface area is 20-200m 2/ g, oil-absorption(number) 0.5～3.5ml/g, refractive index are 1.45-1.55, particle diameter 1500-5000 order;
Said organosilicon glidant, its chemical structural formula is:
Figure FSB00000559191500011
Wherein:
N is 4040～20000 integer,
T1, T2 are independently selected from respectively-C 2H 5,-OH ,-CH 3,-C 2H 4Or-C 6H 5
Described organosilicon active crosslinker is the silicone oil of following chemical structural formula:
Figure FSB00000559191500012
Wherein:
N1 is 10～10000 integer,
T3 and T4 are independently selected from respectively-C 2H 5,-CH 3,-C 2H 4,-C 6H 5Or-OH;
Q1 and Q2 are-OH simultaneously, or one of them is-OH that another is selected from C mH 2m-1O, CH 2rO 2,-C sH 2sSH or-(CH 2) sCH 3
M is 2～5 integer, and r is 2～50 integer, and s is 3～50 integer;
The chemical structural formula of said organosilicon antioxidant is as follows:
Wherein n2 is 10～1000 integer,
T5, T6 are independently selected from respectively-C 2H 5,-CH 3,-C 2H 4,-C 6H 5,-OH or-H,
T7, T8 are-H simultaneously, or one of them is-H that another is-C 2H 5,-CH 3,-C 2H 4,-C 6H 5,-OH or-(CH 2) sCH 3
2. the special compound additive of polyethylene film with high tranparency and low density according to claim 1 is characterized in that the vinyl weight content in the organosilicon glidant molecule is 0.02%～3%.
3. the special compound additive of polyethylene film with high tranparency and low density according to claim 1 is characterized in that the vinyl weight content in the organosilicon glidant molecule is 0.05-0.5%.
4. according to the special compound additive of claim 1 or 2 or 3 described polyethylene film with high tranparency and low density, it is characterized in that in the said organosilicon active crosslinker molecule-the gross weight content of OH is less than 12%.
CN2009102326372A 2009-12-03 2009-12-03 Special compound additive for polyethylene film with high tranparency and low density Active CN101717538B (en)

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CN106188963A (en) * 2016-08-02 2016-12-07 扬州三星塑胶有限公司 PVC sheet and preparation technology thereof
CN110041817B (en) * 2019-04-01 2021-08-10 乐凯胶片股份有限公司 Smooth coating liquid, aluminum plastic film and lithium ion battery
CN113185770A (en) * 2021-05-14 2021-07-30 广东帝通新材料股份有限公司 Special functional material for modifying linear polyethylene 7042

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1358791A (en) * 2000-12-12 2002-07-17 海尔科化工程塑料国家工程研究中心有限公司 Polymer organic nano composite ocmposition for making agriculture greenhouse film and preparation process thereof
CN1718625A (en) * 2005-08-04 2006-01-11 沈阳华龙农地膜制造有限公司 Nano-silicon oxide modified polyolefin composite canopy film and its production technology

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1358791A (en) * 2000-12-12 2002-07-17 海尔科化工程塑料国家工程研究中心有限公司 Polymer organic nano composite ocmposition for making agriculture greenhouse film and preparation process thereof
CN1718625A (en) * 2005-08-04 2006-01-11 沈阳华龙农地膜制造有限公司 Nano-silicon oxide modified polyolefin composite canopy film and its production technology

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