CN107892788A - A kind of low-shrinkage composite plastic and preparation method thereof - Google Patents
A kind of low-shrinkage composite plastic and preparation method thereof Download PDFInfo
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- CN107892788A CN107892788A CN201711228364.5A CN201711228364A CN107892788A CN 107892788 A CN107892788 A CN 107892788A CN 201711228364 A CN201711228364 A CN 201711228364A CN 107892788 A CN107892788 A CN 107892788A
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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
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
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Abstract
The invention discloses a kind of low-shrinkage composite plastic and preparation method thereof, including following parts by weight raw material to be prepared：5 10 parts of nano diatomite, 35 parts of modifying agent, 10 15 parts of polystyrene, 55 75 parts of ABS resin, 0.5 1.2 parts of coupling agent, 0.1 0.3 parts of crosslinking agent, 0.5 0.8 parts of calcium stearate；The present invention is compound by the nano diatomite Jing Guo specific aim modification and ABS resin progress, and nano diatomite is dispersed in ABS resin system, and obtained composite plastic shrinkage factor is low, is advantageous to application of the ABS resin in more areas.
Description
Technical field
The present invention relates to material modified field, and in particular to a kind of low-shrinkage composite plastic and preparation method thereof.
Background technology
The terpolymer that ABS resin is made up 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, the secondary operation such as surface metallization, plating, welding, hot pressing and bonding can also be carried out, extensively
It is general to be applied to the industrial circles such as machinery, automobile, electronic apparatus, instrument and meter, weaving and building.
As the continuous improvement that people are required plastic shaping shrinkage factor, the shrinkage factor of non-modified ABS resin are difficult
With meet demand, thus, carry out reducing shrinkage factor being modified necessitating to ABS resin.Now to ABS low-shrinkage modification at
Reason method species is various, and modified effect is also fine, especially with the appearance and application of nano material, the shrinkage factor of ABS resin
Reducing effect is notable, ABS resin is largely used in more areas, but there is also deficiency.Although nano material is moulded to reducing
Expect that shrinkage factor effect is good, the defects of addition is small, but there is also difficulties in dispersion, and cost is high.It was modified entering to be about to low-shrinkage
Cheng Zhong, nano material, which disperses inequality, can influence its shrinkage factor reducing effect, and obtained material modified shrinkage factor reduction is not notable, right
Material modified production and application adversely affects.
The content of the invention
A kind of the defects of it is an object of the invention to overcome existing ABS resin Material shrinkage rate larger, there is provided low-shrinkage
Composite plastic and preparation method thereof；The present invention is compound by the nano diatomite Jing Guo specific aim modification and ABS resin progress,
And nano diatomite is dispersed in ABS resin system, obtained composite plastic mechanical property is good, shrinkage factor is small, favorably
In application of the ABS resin in more areas.
In order to realize foregoing invention purpose, the invention provides a kind of low-shrinkage composite plastic, including following parts by weight
Raw material are prepared：The nano diatomite of 5-10 parts, the modifying agent of 3-5 parts, the polystyrene of 10-15 parts, 55-75 parts
ABS resin, the coupling agent of 0.5-1.2 parts, the crosslinking agent of 0.1-0.3 parts, the calcium stearate of 0.5-0.8 parts.
A kind of above-mentioned low-shrinkage composite plastic, the base of resin material shrinkage factor can be reduced according to nano diatomite and crosslinking
Present principles, not only by targetedly screening modifying agent, coupling agent and the species of crosslinking agent, to improve nano diatomite and ABS
Compatibility between resin, and make nano diatomite disperse evenly, to make nano diatomite to reducing ABS trees in ABS resin
The shrinkage factor effect of fat is more preferable, also made by controlling the degree of polymerization of ABS resin modified ABS resin material shrinkage factor with
Reach optimum balance relation between mechanical property, so as to which the ABS resin material that makes to obtain is in the condition with relatively low shrinkage factor
Under, it may have excellent mechanical property, it is applied in more areas.
A kind of above-mentioned low-shrinkage composite plastic, wherein, described nano diatomite particle diameter is 10-80nm；Nanometer diatom
Grogs footpath is smaller, and dispersiveness is poorer, and nano diatomite particle diameter is bigger, and the shrinkage factor reduction effect to ABS resin is poorer；It is preferred that
, described nano diatomite particle diameter is 30-50nm；Most preferably, described nano diatomite particle diameter is 40nm.
A kind of above-mentioned low-shrinkage composite plastic, wherein, described modifying agent is tetraethyl orthosilicate and trimethyl phosphate group
Into mixture；Described modifying agent can improve the compatibility of nano diatomite and ABS resin, and and can is in nano diatomite table
Face forms polar group, beneficial to scattered；Preferably, in described modifying agent the material of tetraethyl orthosilicate and trimethyl phosphate amount
The ratio between be 1 ︰ 1.
A kind of above-mentioned low-shrinkage composite plastic, wherein, the degree of polymerization of polystyrene is bigger, then composite plastic after being crosslinked
Shrinkage factor is smaller, and mechanical property is poorer, and the polymer of polystyrene is smaller, then the shrinkage factor of composite plastic is bigger after being crosslinked, power
It is better to learn performance, therefore, selects the rational polystyrene degree of polymerization, is the important means of balance contraction rate and mechanical property.Institute
The degree of polymerization for the polystyrene stated is 400-600；Preferably, the degree of polymerization of described polystyrene is 450-550；Optimal,
The degree of polymerization of described polystyrene is 500；By preferred, both shrinkage factor is small for obtained composite plastic, it may have preferable power
Performance is learned, is adapted to the application in more areas.
Wherein, the described ABS resin degree of polymerization is 1200-2000；Preferably, the degree of polymerization of the ABS resin is 1400-
1800；Most preferably, the degree of polymerization of described ABS resin is 1600；By preferred, both shrinkage factor is small for obtained composite plastic,
Also there is preferable mechanical property.
A kind of above-mentioned low-shrinkage composite plastic, wherein, described coupling agent is vinyl silicane coupling agent；Vinyl silicon
Alkane can increase the compatibility between nano diatomite and ABS resin material, improve the performance of composite plastic.
Wherein, described crosslinking agent is cumyl peroxide, and the crosslinking agent can be by the polymer of two kinds of different polymerization degrees
Raw material are suitably crosslinked, and reduce the shrinkage factor of ABS resin material.
A kind of above-mentioned low-shrinkage composite plastic, wherein, its raw material also includes dispersant, plasticizer, antistatic additive, dye
One or more auxiliary agents in toner, brightener；Above-mentioned auxiliary agent can improve the mechanical property of composite plastic, increase its feature
Deng effect, so as to increase its applicability.
In order to realize foregoing invention purpose, further, present invention also offers a kind of system of low-shrinkage composite plastic
Preparation Method, comprise the following steps：
（1）Nano diatomite is handled with coupling agent；
（2）Nano diatomite Jing Guo coupling agent treatment is subjected to cladding processing with modifying agent；
（3）Combined Processing is carried out after nano diatomite after cladding is well mixed with ABS resin in the electric field, is mixed
Material；
（4）By compound and polystyrene, crosslinking agent, calcium stearate, be well mixed after carrying out Combined Processing, obtain lower shrinkage
Rate composite plastic.
A kind of preparation method of low-shrinkage composite plastic, coupling processing first is carried out to nano diatomite with coupling agent, increased
Plus nano diatomite and modifying agent, the compatibility of ABS resin；Again processing is modified to nano diatomite with modifying agent, and
Its surface forms polar group；Finally the polar group in nano diatomite surface and ABS resin chain is set to polarize using external electric field,
It is powered,, also can be with ABS resin chain while making nano diatomite dispersed by repelling each other between electric charge or attracting principle
On polar group it is bonded so that the shrinkage factor reducing effect of nano diatomite is farthest embodied, so as to get
Modified ABS resin shrinkage factor is substantially reduced；The preparation method is simple and reliable, is suitable for the big rule of low-shrinkage composite plastic
Mould, industrialized production.
A kind of preparation method of above-mentioned low-shrinkage composite plastic, wherein, it is preferred that step 1 carries out coupling processing process
In can use ultrasonic assistant；Shaken by the high speed of ultrasonic wave, make nano diatomite dispersiveness more preferable, and have to coupling processing
There is facilitation.
A kind of preparation method of above-mentioned low-shrinkage composite plastic, wherein, the electric field energy described in step 3 produces to group
Polarization, make group powered, so as to promote the scattered and bonded effect of nano diatomite, reduce the receipts of modified ABS resin
Shrinkage.
Preferably, described electric-field intensity is 0.5-2kv/m；Electric-field intensity is too small, and polarization effect is weak, to nano diatomite
Dispersion effect it is poor；Electric-field intensity 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, composite plastic may being reduced；Most preferably, described electric-field intensity is
0.8-1.5kv/m。
Wherein, it is preferred that described 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 stable, to the scattered and bonded facilitation of nano diatomite
Best results.
Compared with prior art, beneficial effects of the present invention：
1st, composite plastic of the present invention targetedly screens the species of modifying agent, coupling agent and crosslinking agent, makes nano diatomite and ABS
Compatibility between resin is more preferable, and the dispersiveness in ABS resin is more preferable, and nano diatomite reduces to the shrinkage factor of ABS resin
Effect is more preferable.
2nd, composite plastic of the present invention passes through the ABS resin that controls the degree of polymerization of ABS resin and polystyrene to make modified
Material reaches optimum balance relation between shrinkage factor and mechanical property, so as to get composite plastic shrinkage factor it is small under conditions of,
Also there is excellent mechanical property.
3rd, the preparation method of composite plastic of the present invention, using the polarization of external electric field, nano diatomite can be promoted in ABS
Scattered and bonded in resin system, the shrinkage factor reducing effect of nano diatomite is more preferable, the shrinkage factor of obtained composite plastic
It is smaller.
4th, the preparation method of composite plastic of the present invention is simple, reliable, is adapted to the extensive, industrial of low-shrinkage composite plastic
Metaplasia is produced.
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）8 parts of nano diatomite is handled with 0.8 part of vinyl silanes；
（2）Nano diatomite Jing Guo coupling agent treatment is coated with 2 parts of tetraethyl orthosilicate and 2 parts of trimethyl phosphate
Processing；
（3）In electric-field intensity after nano diatomite after cladding is well mixed with the ABS resin that 65 parts of the degree of polymerization is 1600
To be extruded in the constant parallel electric field of 1.2kv/m direction of an electric field, compound is obtained；
（4）Polystyrene that the compound that step 3 is obtained and 12 parts of the degree of polymerization are 500,0.2 part of cumyl peroxide,
Extruded after 0.6 part of calcium stearate is well mixed, obtain low-shrinkage composite plastic.
Embodiment 2
（1）5 parts of nano diatomite is handled with 1.2 parts of vinyl silanes；
（2）Nano diatomite Jing Guo coupling agent treatment is carried out with 1.5 parts of tetraethyl orthosilicate and 1.5 parts of trimethyl phosphate
Cladding processing；
（3）In electric-field strength after nano diatomite after cladding is well mixed with the ABS resin that 55 parts of the degree of polymerization is 1200
Spend in the electric field for 2.0kv/m and extruded, obtain compound；
（4）Polystyrene that the compound that step 3 is obtained and 10 parts of the degree of polymerization are 400,0.3 part of cumyl peroxide,
Extruded after 0.5 part of calcium stearate is well mixed, obtain low-shrinkage composite plastic.
Embodiment 3
（1）10 parts of nano diatomite is handled with 0.5 part of vinyl silanes；
（2）Nano diatomite Jing Guo coupling agent treatment is carried out with 2.5 parts of tetraethyl orthosilicate and 2.5 parts of trimethyl phosphate
Cladding processing；
（3）In electric-field strength after nano diatomite after cladding is well mixed with the ABS resin that 75 parts of the degree of polymerization is 2000
Spend to be extruded in the constant parallel electric field of 0.5kv/m direction of an electric field, obtain compound；
（4）Polystyrene that the compound that step 3 is obtained and 15 parts of the degree of polymerization are 600,0.1 part of cumyl peroxide,
Extruded after 0.8 part of calcium stearate is well mixed, obtain low-shrinkage composite plastic.
Comparative example 1
（1）8 parts of nano diatomite is handled with 0.8 part of vinyl silanes；
（2）By the nano diatomite Jing Guo coupling agent treatment and 5 parts of dispersant, the ABS resin that 65 parts of the degree of polymerization is 1600
Extruded after well mixed in the constant parallel electric field of the direction of an electric field that electric-field intensity is 1.2kv/m, obtain compound；
（3）Polystyrene that the compound that step 2 is obtained and 12 parts of the degree of polymerization are 500,0.2 part of cumyl peroxide,
Extruded after 0.6 part of calcium stearate is well mixed, obtain composite plastic.
Comparative example 2
（1）8 parts of nano diatomite is handled with 0.8 part of vinyl silanes；
（2）Nano diatomite Jing Guo coupling agent treatment is coated with 2 parts of tetraethyl orthosilicate and 2 parts of trimethyl phosphate
Processing；
（3）It is 500 by ABS resin that the nano diatomite after cladding and 65 parts of the degree of polymerization are 1600,12 parts of the degree of polymerization
Extruded after polystyrene, 0.2 part of cumyl peroxide, 0.6 part of calcium stearate are well mixed, obtain composite plastic.
Comparative example 3
（1）8 parts of nano diatomite is handled with 0.8 part of vinyl silanes；
（2）Nano diatomite Jing Guo coupling agent treatment is carried out at cladding with 2 parts of polystyrene and 2 parts of trimethyl phosphate
Reason；
（3）In electric-field intensity after nano diatomite after cladding is well mixed with the ABS resin that 65 parts of the degree of polymerization is 1600
To be extruded in the constant parallel electric field of 1.2kv/m direction of an electric field, compound is obtained；
（4）Polystyrene that the compound that step 3 is obtained and 12 parts of the degree of polymerization are 400,0.2 part of cumyl peroxide,
Extruded after 0.6 part of calcium stearate is well mixed, obtain composite plastic.
Comparative example 4
（1）8 parts of nano diatomite is handled with 0.8 part of vinyl silanes；
（2）Nano diatomite Jing Guo coupling agent treatment is coated with 2 parts of tetraethyl orthosilicate and 2 parts of trimethyl phosphate
Processing；
（3）By polystyrene that the nano diatomite after cladding and 12 parts of the degree of polymerization are 500,0.2 part of cumyl peroxide,
The electricity for being 1.2kv/m in electric-field intensity after ABS resin that 0.6 part of calcium stearate, 65 parts of the degree of polymerization are 1600 is well mixed
Extruded in the constant parallel electric field of field direction, obtain composite plastic.
Comparative example 5
（1）8 parts of nano diatomite is handled with 0.8 part of vinyl silanes；
（2）Nano diatomite Jing Guo coupling agent treatment is coated with 2 parts of tetraethyl orthosilicate and 2 parts of trimethyl phosphate
Processing；
（3）In electric-field intensity after nano diatomite after cladding is well mixed with the ABS resin that 65 parts of the degree of polymerization is 2500
To be extruded in the constant parallel electric field of 1.2kv/m direction of an electric field, compound is obtained；
（4）Polystyrene that the compound that step 3 is obtained and 12 parts of the degree of polymerization are 600,0.6 part of calcium stearate, 0.2 part
Extruded after cumyl peroxide is well mixed, obtain composite plastic.
By the composite plastic in above-described embodiment 1-3 and comparative example 1-5, performance detection is carried out, record data is as follows：
| Performance | Molding shrinkage（%） | Mechanical property |
| Embodiment 1 | 0.18 | +++++ |
| Embodiment 2 | 0.20 | +++++ |
| Embodiment 3 | 0.19 | +++++ |
| Comparative example 1 | 0.38 | ++++ |
| Comparative example 2 | 0.41 | ++++ |
| Comparative example 3 | 0.35 | ++++ |
| Comparative example 4 | 0.32 | ++++ |
| Comparative example 5 | 0.17 | +++ |
| Pure ABS resin | 0.53 | +++ |
Note："+" is more, illustrates that performance is better.
Above-mentioned analysis of experimental data is understood, the low-shrinkage composite plastic of the present invention being prepared in embodiment 1-3, received
Rice diatomite is uniformly dispersed, and good with the compatibility of ABS resin, composite plastic shrinkage factor is small, and mechanical property is good；And in comparative example 1,
Modifying agent is not used processing is modified to nano diatomite, although adding dispersant, nano diatomite dispersion effect is poor,
With the poor compatibility of ABS resin, the shrinkage factor of ABS resin material significantly increases；Do not carry out compound place in comparative example 2 in the electric field
Reason, nano diatomite dispersion effect is poor, and the shrinkage factor of ABS resin material significantly increases；Modifying agent is not the application in comparative example 3
Defined, nano diatomite dispersion effect is poor, and the shrinkage factor of ABS resin material significantly increases；Cross-linking reaction is same in comparative example 4
Sample is carried out in the electric field, and electric field has a negative impact to cross-linking reaction, so as to get ABS resin material shrinkage factor increase；It is right
The ABS resin and the polystyrene degree of polymerization used in ratio 5 is excessive, although shrinkage factor is small after compound, its mechanical property is notable
Reduce, be unfavorable for the application of composite plastic.
Claims (10)
1. a kind of low-shrinkage composite plastic, it is characterised in that be prepared including following parts by weight raw material：5-10 parts are received
Rice diatomite, the modifying agent of 3-5 parts, the polystyrene of 10-15 parts, the ABS resin of 55-75 parts, 0.5-1.2 parts coupling agent,
The crosslinking agent, the calcium stearate of 0.5-0.8 parts of 0.1-0.3 parts；The modifying agent is that tetraethyl orthosilicate forms with trimethyl phosphate
Mixture；The coupling agent is vinyl silicane coupling agent, and the crosslinking agent is cumyl peroxide；The polystyrene
The degree of polymerization be 400-600；The ABS resin degree of polymerization is 1200-2000.
2. composite plastic according to claim 1, it is characterised in that tetraethyl orthosilicate and tripotassium phosphate in the modifying agent
The ratio between amount of material of ester is 1 ︰ 1.
3. composite plastic according to claim 1, it is characterised in that the degree of polymerization of the polystyrene is 450-550.
4. composite plastic according to claim 3, it is characterised in that the degree of polymerization of the polystyrene is 5000.
5. composite plastic according to claim 1, it is characterised in that the ABS resin degree of polymerization is 1400-1800.
6. composite plastic according to claim 5, it is characterised in that the ABS resin degree of polymerization is 1600.
7. a kind of preparation method of the composite plastic as described in claim 1-6, it is characterised in that comprise the following steps：
（1）Nano diatomite is handled with coupling agent；
（2）Nano diatomite Jing Guo coupling agent treatment is subjected to cladding processing with modifying agent；
（3）Combined Processing is carried out after nano diatomite after cladding is well mixed with ABS resin in the electric field, is mixed
Material；（4）By compound and polystyrene, crosslinking agent, calcium stearate, be well mixed after carrying out Combined Processing, obtain lower shrinkage
Rate composite plastic.
8. preparation method according to claim 7, it is characterised in that step（3）Middle electric-field intensity is 0.5-2kv/m.
9. preparation method according to claim 8, it is characterised in that step（3）Middle electric-field intensity is 0.8-1.5kv/m.
10. preparation method according to claim 7, it is characterised in that step（3）Middle electric field, which is that direction of an electric field is constant, puts down
Row electric field.
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| CN201711228364.5A CN107892788A (en) | 2017-11-29 | 2017-11-29 | A kind of low-shrinkage composite plastic and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711228364.5A CN107892788A (en) | 2017-11-29 | 2017-11-29 | A kind of low-shrinkage composite plastic and preparation method thereof |
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