CN107903568A - A kind of polyethylene ABS resin modified composite material and preparation method thereof - Google Patents
A kind of polyethylene ABS resin modified composite material and preparation method thereof Download PDFInfo
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- CN107903568A CN107903568A CN201711225605.0A CN201711225605A CN107903568A CN 107903568 A CN107903568 A CN 107903568A CN 201711225605 A CN201711225605 A CN 201711225605A CN 107903568 A CN107903568 A CN 107903568A
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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
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- 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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- 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
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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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
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Abstract
The invention discloses a kind of polyethylene ABS resin modified composite material and preparation method thereof, including following parts by weight raw material to be prepared：55 75 parts of ABS resin, 10 15 parts of polyethylene, 48 parts of nano-calcium carbonate, 1.5 3.8 parts of modifying agent, 0.3 0.8 parts of coupling agent, 0.1 0.3 parts of crosslinking agent, 13 parts of ultra-violet absorber, 13 parts of antioxidant；The present invention is for composite by the nano-calcium carbonate Jing Guo specific aim modification and ABS resin, and nano-calcium carbonate is set to be dispersed in ABS resin system, obtained polyethylene ABS resin modified composite material ageing-resistant performance is excellent, is conducive to application of the ABS resin in more areas.
Description
Technical field
The present invention relates to modified material field, and in particular to a kind of polyethylene-ABS resin modified composite material and its preparation
Method.
Background technology
The terpolymer that ABS resin is made of acrylonitrile, butadiene and styrene, because its impact resistance, heat-resisting
Property, lower temperature resistance, chemical proofing and excellent electrical properties, also with easy processing, product size is stable, lustrous surface is good
The features such as, easy application, coloring, can also carry out the secondary operation such as surface metallization, plating, welding, hot pressing and bonding, extensively
It is general to be applied to the industrial circles such as machinery, automobile, electronic apparatus, instrument and meter, weaving and building.
With the continuous improvement that people require material ageing-resistant performance, the ABS resin without ageing-resistant modification has been difficult to
Meet demand, thus, ageing-resistant modification is carried out to ABS resin and is necessitated.Now to the ageing-resistant modification processing method kind of ABS
Class is various, and modified effect is also fine, especially with the appearance and application of nano material, the resistance to ag(e)ing increase effect of ABS resin
Fruit is notable, ABS resin is largely used in more areas, but there is also deficiency.Although nano material has ageing-resistant enhancing
The advantages of effect is good, and additive amount is small, but there is also difficulties in dispersion, it is of high cost the defects of.In ageing-resistant modifying process is carried out, receive
Rice material, which disperses inequality, can influence its ageing-resistant effect, and obtained modified material resistance to ag(e)ing is relatively low, the production to modified material
Adversely affected with application.
The content of the invention
The defects of it is an object of the invention to overcome existing ABS resin material resistance to ag(e)ing poor, there is provided a kind of polyethylene-
ABS resin modified composite material and preparation method thereof；The present invention is by the nano-calcium carbonate Jing Guo specific aim modification and ABS trees
Fat is for composite, and nano-calcium carbonate is dispersed in ABS resin system, and obtained polyethylene-ABS resin is modified compound
Material ageing-resistant performance is excellent, is conducive to application of the ABS resin in more areas.
In order to realize foregoing invention purpose, the present invention provides a kind of polyethylene-ABS resin modified composite material, including
Following parts by weight raw material are prepared：4-8 parts of nano-calcium carbonate, 1.5-3.8 parts of modifying agent, 10-15 parts of polyethylene,
55-75 parts of ABS resin, 0.3-0.8 parts of coupling agent, 0.1-0.3 parts of crosslinking agent, 1-3 parts of ultra-violet absorber, 1-3
The antioxidant of part.
A kind of above-mentioned polyethylene-ABS resin modified composite material, can increase resin material according to nano-calcium carbonate and crosslinking
The basic principle of resistance to ag(e)ing, not only by targetedly screening modifying agent, coupling agent and the species of crosslinking agent, to improve nanometer
Compatibility between calcium carbonate and ABS resin, and make nano-calcium carbonate disperse evenly, to make nano-calcium carbonate in ABS resin
It is more preferable to the resistance to ag(e)ing humidification of ABS resin, the ABS resin also by controlling the degree of polymerization of ABS resin to make modified
Material reaches optimum balance relation between resistance to ag(e)ing and processability, so that the ABS resin material made is with excellent
Resistance to ag(e)ing under conditions of, it may have excellent processability, allows it to be applied in more areas.
A kind of above-mentioned polyethylene-ABS resin modified composite material, wherein, the nano-calcium carbonate particle diameter is 10-
80nm；Nano-calcium carbonate particle diameter is smaller, and dispersiveness is poorer, and nano-calcium carbonate particle diameter is bigger, and the ageing-resistant enhancing to ABS resin is made
With poorer；Preferably, the nano-calcium carbonate particle diameter is 30-50nm；Most preferably, the nano-calcium carbonate particle diameter is
40nm。
A kind of above-mentioned polyethylene-ABS resin modified composite material, wherein, the modifying agent is calcium stearate and phosphoric acid
The mixture of trimethyl composition；The modifying agent can improve the compatibility of nano-calcium carbonate and ABS resin and in nanometer
Calcium carbonate surface forms polar group, beneficial to scattered；Preferably, the thing of calcium stearate and trimethyl phosphate in the modifying agent
The ratio between amount of matter is 1 ︰ 1.
A kind of above-mentioned polyethylene-ABS resin modified composite material, wherein, the antioxidant is antioxidant 3314, antioxidant
One or both of 626.The ultra-violet absorber is UV-3813.
A kind of above-mentioned polyethylene-ABS resin modified composite material, wherein, the degree of polymerization of polyethylene is bigger, then gathers after being crosslinked
The resistance to ag(e)ing of ethene-ABS resin modified composite material is poorer, and processability is better, and the polymer of polyethylene is smaller, then after being crosslinked
The resistance to ag(e)ing of polyethylene-ABS resin modified composite material is better, and processability is poorer, therefore, selects rational polyethylene polymerization
Degree, is the important means for balancing resistance to ag(e)ing and processability.The degree of polymerization of the polyethylene is 80-180；Preferably, it is described
The degree of polymerization of polyethylene be 100-150；Optimal, the degree of polymerization of the polyethylene is 120；By preferred, what is obtained is poly-
Ethene-ABS resin modified composite material both has excellent resistance to ag(e)ing, it may have preferable processability, is adapted to ABS resin to exist
Promoted and applied in more areas.
Wherein, the ABS resin degree of polymerization is 600-1200；Preferably, the degree of polymerization of the ABS resin is 800-
1100；Most preferably, the degree of polymerization of the ABS resin is 1000；By preferred, obtained polyethylene-ABS resin is modified multiple
Condensation material both has excellent resistance to ag(e)ing, it may have preferable processability.
A kind of above-mentioned polyethylene-ABS resin modified composite material, wherein, the coupling agent is titanate coupling agent；Titanium
Acid esters can increase the compatibility between nano-calcium carbonate and ABS resin material, improve polyethylene-ABS resin modified composite material
Performance.
Wherein, the crosslinking agent is cumyl peroxide, which can be by the polymer of two kinds of different polymerization degrees
Raw material are suitably crosslinked, and improve the resistance to ag(e)ing of ABS resin material.
A kind of above-mentioned polyethylene-ABS resin modified composite material, wherein, its raw material further include dispersant, plasticizer,
One or more auxiliary agents in antistatic additive, coloring agent, brightener；Above-mentioned auxiliary agent can improve polyethylene-ABS resin and be modified again
The processability of condensation material, increases the effect such as its feature, so as to increase its applicability.
In order to realize foregoing invention purpose, further, it is modified present invention also offers a kind of polyethylene-ABS resin multiple
The preparation method of condensation material, comprises the following steps：
（1）Nano-calcium carbonate is handled with coupling agent；
（2）Nano-calcium carbonate Jing Guo coupling agent treatment is subjected to cladding processing with modifying agent；
（3）By the nano-calcium carbonate after cladding and ABS resin processing for composite in the electric field after mixing, mixed
Material；
（4）By mixture and polyethylene, crosslinking agent, antioxidant, ultra-violet absorber after mixing in processing for composite, obtain
To polyethylene-ABS resin modified composite material.
A kind of preparation method of polyethylene-ABS resin modified composite material, first carries out nano-calcium carbonate with coupling agent even
Connection processing, increase nano-calcium carbonate and modifying agent, the compatibility of ABS resin；Nano-calcium carbonate is modified with modifying agent again
Processing, and form polar group on its surface；Finally make the polarity in nano-calcium carbonate surface and ABS resin chain using external electric field
Group polarizes, powered,, also can be with while making nano-calcium carbonate dispersed by repelling each other between electric charge or attracting principle
Polar group on ABS resin chain is bonded, so that the ageing-resistant enhancing effect of nano-calcium carbonate is farthest embodied,
The modified ABS resin resistance to ag(e)ing made significantly improves；The preparation method is simple and reliable, is suitable for polyethylene-ABS resin
Extensive, the industrialized production of modified composite material.
A kind of preparation method of above-mentioned polyethylene-ABS resin modified composite material, wherein, it is preferred that step 1 carries out idol
Joining in processing procedure can use ultrasonic wave to aid in；Shaken by the high speed of ultrasonic wave, make nano-calcium carbonate dispersiveness more preferable and right
Coupling processing has facilitation.
A kind of preparation method of above-mentioned polyethylene-ABS resin modified composite material, wherein, the electric field energy described in step 3
Polarization is produced to group, makes group powered, so as to promote the scattered and bonded effect of nano-calcium carbonate, improves and is modified
The resistance to ag(e)ing of ABS resin.
Preferably, the electric field strength is 0.5-2kv/m；Electric field strength is too small, and polarization effect is weak, to nano-calcium carbonate
Dispersion effect it is poor；Electric field strength is excessive, and polarization effect is too strong, and intermolecular force is too big, and strand produces displacement, right
The arrangement of strand and the bonded performance for having an impact, may be decreased polyethylene-ABS resin modified composite material；Most preferably,
The electric field strength is 0.8-1.5kv/m.
Wherein, it is preferred that the electric field is the constant parallel electric field of direction of an electric field；The constant parallel electric field of direction of an electric field
Best to the polarization effect of polar group, group intermolecular forces are stablized, to the scattered and bonded facilitation of nano-calcium carbonate
Best results.
Compared with prior art, beneficial effects of the present invention：
1st, polyethylene of the present invention-ABS resin modified composite material targetedly screens the kind of modifying agent, coupling agent and crosslinking agent
Class, makes the compatibility between nano-calcium carbonate and ABS resin more preferable, and the dispersiveness in ABS resin is more preferable, nano-calcium carbonate pair
The resistance to ag(e)ing humidification of ABS resin is more preferable.
2nd, polyethylene of the present invention-ABS resin modified composite material is made by controlling the degree of polymerization of ABS resin and polyethylene
Modified ABS resin material reaches optimum balance relation between resistance to ag(e)ing and processability, so as to get polyethylene-ABS
Resin modified composite material is under conditions of with excellent resistance to ag(e)ing, it may have excellent processability.
3rd, the preparation method of polyethylene of the present invention-ABS resin modified composite material, utilizes the polarization of external electric field, energy
Promote nano-calcium carbonate scattered and bonded in ABS resin system, the ageing-resistant enhancing effect of nano-calcium carbonate is more preferable, obtains
Polyethylene-ABS resin modified composite material resistance to ag(e)ing higher.
4th, the preparation method of polyethylene of the present invention-ABS resin modified composite material is simple, reliable, is adapted to polyethylene-ABS
Extensive, the industrialized production of resin modified composite material.
Embodiment
With reference to test example and embodiment, the present invention is described in further detail.But this should not be understood
Following embodiment is only limitted to for the scope of the above-mentioned theme of the present invention, it is all that this is belonged to based on the technology that present invention is realized
The scope of invention.
Embodiment 1
（1）6 parts of nano-calcium carbonate is handled with 0.5 part of titanate esters；
（2）Nano-calcium carbonate Jing Guo coupling agent treatment is wrapped with 1.5 parts of calcium stearate and 1.5 parts of trimethyl phosphate
Cover processing；
（3）It is in electric field strength after mixing by the ABS resin that the nano-calcium carbonate after cladding is 900 with 65 parts of the degree of polymerization
Extruded in the constant parallel electric field of the direction of an electric field of 1.2kv/m, obtain mixture；
（4）Polyethylene that the mixture that step 3 is obtained and 12 parts of the degree of polymerization are 120,0.2 part of cumyl peroxide, 2 parts
Ultra-violet absorber, 2 parts of antioxidant extruded after mixing, obtain polyethylene-ABS resin modified composite material.
Embodiment 2
（1）4 parts of nano-calcium carbonate is handled with 0.3 part of titanate esters；
（2）Nano-calcium carbonate Jing Guo coupling agent treatment is coated with 1 part of calcium stearate and 0.5 part of trimethyl phosphate
Processing；
（3）By ABS resin that the nano-calcium carbonate after cladding and 55 parts of the degree of polymerization are 1200 after mixing in electric-field strength
Spend in the electric field for 2.0kv/m and extruded, obtain mixture；
（4）Polyethylene that the mixture that step 3 is obtained and 10 parts of the degree of polymerization are 180,0.3 part of cumyl peroxide, 1 part
Ultra-violet absorber, 3 parts of antioxidant extruded after mixing, obtain polyethylene-ABS resin modified composite material.
Embodiment 3
（1）8 parts of nano-calcium carbonate is handled with 0.8 part of titanate esters；
（2）Nano-calcium carbonate Jing Guo coupling agent treatment is wrapped with 1.5 parts of calcium stearate and 2.3 parts of trimethyl phosphate
Cover processing；
（3）By ABS resin that the nano-calcium carbonate after cladding and 75 parts of the degree of polymerization are 600 after mixing in electric field strength
To be extruded in the constant parallel electric field of the direction of an electric field of 0.5kv/m, mixture is obtained；
（4）Polyethylene that the mixture that step 3 is obtained and 15 parts of the degree of polymerization are 80,0.1 part of cumyl peroxide, 3 parts
Ultra-violet absorber, 1 part of antioxidant extruded after mixing, obtain polyethylene-ABS resin modified composite material.
Comparative example 1
（1）6 parts of nano-calcium carbonate is handled with 0.5 part of titanate esters；
（2）Nano-calcium carbonate Jing Guo coupling agent treatment and 3 parts of dispersant, the ABS resin that 65 parts of the degree of polymerization is 900 are mixed
Extruded after closing uniformly in the constant parallel electric field of the direction of an electric field that electric field strength is 1.2kv/m, obtain mixture；
（3）Polyethylene that the mixture that step 2 is obtained and 12 parts of the degree of polymerization are 120,0.2 part of cumyl peroxide, 2 parts
Ultra-violet absorber, 2 parts of antioxidant extruded after mixing, obtain polyethylene-ABS resin modified composite material.
Comparative example 2
（1）6 parts of nano-calcium carbonate is handled with 0.5 part of titanate esters；
（2）Nano-calcium carbonate Jing Guo coupling agent treatment is wrapped with 1.5 parts of calcium stearate and 1.5 parts of trimethyl phosphate
Cover processing；
（3）By ABS resin that the nano-calcium carbonate after cladding and 65 parts of the degree of polymerization are 900,12 parts of the degree of polymerization be 120 it is poly-
Ethene, 0.2 part of cumyl peroxide, 2 parts of ultra-violet absorber, 2 parts of antioxidant are extruded after mixing, are obtained
Polyethylene-ABS resin modified composite material.
Comparative example 3
（1）6 parts of nano-calcium carbonate is handled with 0.5 part of titanate esters；
（2）Nano-calcium carbonate Jing Guo coupling agent treatment is wrapped with 1.5 parts of polystyrene and 1.5 parts of trimethyl phosphate
Cover processing；
（3）It is in electric field strength after mixing by the ABS resin that the nano-calcium carbonate after cladding is 900 with 65 parts of the degree of polymerization
Extruded in the constant parallel electric field of the direction of an electric field of 1.2kv/m, obtain mixture；
（4）Polyethylene that the mixture that step 3 is obtained and 12 parts of the degree of polymerization are 120,0.2 part of cumyl peroxide, 2 parts
Ultra-violet absorber, 2 parts of antioxidant extruded after mixing, obtain polyethylene-ABS resin modified composite material.
Comparative example 4
（1）6 parts of nano-calcium carbonate is handled with 0.5 part of titanate esters；
（2）Nano-calcium carbonate Jing Guo coupling agent treatment is wrapped with 1.5 parts of calcium stearate and 1.5 parts of trimethyl phosphate
Cover processing；
（3）By the polyethylene of the nano-calcium carbonate after cladding and 12 parts of the degree of polymerization for 120,0.2 part of cumyl peroxide, 2
Part ultra-violet absorber, 2 parts of antioxidant, 65 parts of the degree of polymerization be 900 ABS resin be in electric field strength after mixing
Extruded in the constant parallel electric field of the direction of an electric field of 1.2kv/m, obtain polyethylene-ABS resin modified composite material.
Comparative example 5
（1）6 parts of nano-calcium carbonate is handled with 0.5 part of titanate esters；
（2）Nano-calcium carbonate Jing Guo coupling agent treatment is wrapped with 1.5 parts of calcium stearate and 1.5 parts of trimethyl phosphate
Cover processing；
（3）It is in electric field strength after mixing by the ABS resin that the nano-calcium carbonate after cladding is 500 with 65 parts of the degree of polymerization
Extruded in the constant parallel electric field of the direction of an electric field of 1.2kv/m, obtain mixture；
（4）Polyethylene that the mixture that step 3 is obtained and 12 parts of the degree of polymerization are 50,2 parts of ultra-violet absorber, 2 parts
Antioxidant, 0.2 part of cumyl peroxide are extruded after mixing, obtain polyethylene-ABS resin modified composite material.
By the polyethylene in above-described embodiment 1-3 and comparative example 1-5-ABS resin modified composite material, performance inspection is carried out
Survey, record data are as follows：
| Performance | Ageing resistance | Processability |
| Embodiment 1 | ++++++ | ++++ |
| Embodiment 2 | ++++++ | ++++ |
| Embodiment 3 | ++++++ | ++++ |
| Comparative example 1 | ++++ | ++++ |
| Comparative example 2 | ++++ | ++++ |
| Comparative example 3 | ++++ | ++++ |
| Comparative example 4 | ++++ | ++++ |
| Comparative example 5 | ++++++ | ++ |
| ABS resin | +++ | +++++ |
Note："+" is more, illustrates that performance is better.
Above-mentioned analysis of experimental data is understood, the polyethylene of the present invention being prepared in embodiment 1-3-ABS resin is modified
Composite material, nano-calcium carbonate are uniformly dispersed, good with the compatibility of ABS resin, and polyethylene-ABS resin modified composite material is resistance to
Aging is good, and processability is good；And in comparative example 1, modifying agent is not used processing is modified to nano-calcium carbonate, although adding
Dispersant, but nano-calcium carbonate dispersion effect is poor, and the poor compatibility with ABS resin, the resistance to ag(e)ing of ABS resin material significantly drops
It is low；Not processing for composite in the electric field in comparative example 2, nano-calcium carbonate dispersion effect is poor, the resistance to ag(e)ing of ABS resin material
Significantly reduce；Modifying agent is not the application defined in comparative example 3, and nano-calcium carbonate dispersion effect is poor, ABS resin material
Resistance to ag(e)ing significantly reduces；Cross-linking reaction equally carries out in the electric field in comparative example 4, and electric field produces unfavorable shadow to cross-linking reaction
Ring, so as to get ABS resin material resistance to ag(e)ing reduce；The ABS resin and polyethylene polymerization used in comparative example 5 is spent
Small, although resistance to ag(e)ing increased after compound, its processability significantly reduces, and it is compound to be unfavorable for polyethylene-ABS resin modification
The application of material.
Claims (10)
1. a kind of polyethylene-ABS resin modified composite material, it is characterised in that be prepared including following parts by weight raw material：
55-75 parts of ABS resin, 10-15 parts of polyethylene, 4-8 parts of nano-calcium carbonate, 1.5-3.8 parts of modifying agent, 0.3-0.8
The coupling agent, 0.1-0.3 parts of crosslinking agent, 1-3 parts of ultra-violet absorber, 1-3 parts of antioxidant of part；The modifying agent is hard
The mixture of resin acid calcium and trimethyl phosphate composition；The coupling agent is titanate coupling agent, and the crosslinking agent is peroxidating two
Isopropylbenzene；The degree of polymerization of the polyethylene is 80-180；The ABS resin degree of polymerization is 600-1200.
2. polyethylene according to claim 1-ABS resin modified composite material, it is characterised in that hard in the modifying agent
The ratio between amount of material of resin acid calcium and trimethyl phosphate is 1 ︰ 1.
3. polyethylene according to claim 1-ABS resin modified composite material, it is characterised in that the polyethylene gathers
Right is 100-150.
4. polyethylene according to claim 3-ABS resin modified composite material, it is characterised in that the polyethylene gathers
Right is 120.
5. polyethylene according to claim 1-ABS resin modified composite material, it is characterised in that the ABS resin gathers
Right is 800-1100.
6. polyethylene according to claim 5-ABS resin modified composite material, it is characterised in that the ABS resin gathers
Right is 1000.
A kind of 7. preparation method of the polyethylene as described in claim 1-6-ABS resin modified composite material, it is characterised in that bag
Include following steps：
（1）Nano-calcium carbonate is handled with coupling agent；
（2）Nano-calcium carbonate Jing Guo coupling agent treatment is subjected to cladding processing with modifying agent；
（3）By the nano-calcium carbonate after cladding and ABS resin processing for composite in the electric field after mixing, mixed
Material；
（4）By mixture and polyethylene, crosslinking agent, antioxidant, ultra-violet absorber after mixing in processing for composite, obtain
To polyethylene-ABS resin modified composite material.
8. preparation method according to claim 7, it is characterised in that step（3）Middle electric field strength is 0.5-2kv/m.
9. preparation method according to claim 8, it is characterised in that step（3）Middle electric field strength is 0.8-1.5kv/m.
10. preparation method according to claim 7, it is characterised in that step（3）Middle electric field is put down for direction of an electric field is constant
Row electric field.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711225605.0A CN107903568A (en) | 2017-11-29 | 2017-11-29 | A kind of polyethylene ABS resin modified composite material and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711225605.0A CN107903568A (en) | 2017-11-29 | 2017-11-29 | A kind of polyethylene ABS resin modified composite material and preparation method thereof |
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Application publication date: 20180413 |