CN107936458A - A kind of rubber impact hits enhancing composite plastic and preparation method thereof - Google Patents

A kind of rubber impact hits enhancing composite plastic and preparation method thereof Download PDF

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Publication number
CN107936458A
CN107936458A CN201711228379.1A CN201711228379A CN107936458A CN 107936458 A CN107936458 A CN 107936458A CN 201711228379 A CN201711228379 A CN 201711228379A CN 107936458 A CN107936458 A CN 107936458A
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parts
composite plastic
barium sulfate
abs resin
nano barium
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CN201711228379.1A
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舒春柳
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Sichuan Lizhi Jiuchuang Intellectual Property Operations Ltd
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Sichuan Lizhi Jiuchuang Intellectual Property Operations Ltd
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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
    • 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
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates
    • 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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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention discloses a kind of rubber impact to hit enhancing composite plastic and preparation method thereof, including following parts by weight raw material are prepared：55 75 parts of ABS resin, 5 10 parts of nano barium sulfate, 58 parts of modifying agent, 10 20 parts of poly- butyl rubber, 0.3 0.8 parts of coupling agent, 0.1 0.3 parts of crosslinking agent, 13 parts of trioctyl trimellitate (TOTM)；The present invention is for composite by the nano barium sulfate Jing Guo specific aim modification and ABS resin, and nano barium sulfate is dispersed in ABS resin system, and obtained modification composite plastic excellent shock resistance, is conducive to application of the ABS resin in more areas.

Description

A kind of rubber impact hits enhancing composite plastic and preparation method thereof
Technical field
The present invention relates to modified material field, and in particular to a kind of rubber impact hits enhancing composite plastic and its preparation side 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 shock resistance, the ABS resin without impact modification has been difficult to Meet demand, thus, impact modification is carried out to ABS resin and is necessitated.Now to the impact 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 impact resistance increase effect of ABS resin Fruit is notable, ABS resin is largely used in more areas, but there is also deficiency.Although nano material strengthens with shock resistance 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.During impact modification is carried out, receive Rice material, which disperses inequality, can influence its shock resistance effect, and obtained modified material impact resistance 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 impact resistance poor, there is provided a kind of rubber resists Impact enhancing composite plastic and preparation method thereof；The present invention is by the nano barium sulfate and ABS resin Jing Guo specific aim modification It is for composite, and nano barium sulfate is dispersed in ABS resin system, obtained modification composite plastic shock resistance is excellent It is different, be conducive to application of the ABS resin in more areas.
In order to realize foregoing invention purpose, the present invention provides a kind of rubber impact to hit enhancing composite plastic, including following Parts by weight raw material are prepared：55-75 parts of ABS resin, 5-10 parts of nano barium sulfate, 5-8 parts of modifying agent, 10-20 The poly- butyl rubber, 0.3-0.8 parts of coupling agent, 0.1-0.3 parts of crosslinking agent, 1-3 parts of trioctyl trimellitate (TOTM) of part.
A kind of above-mentioned rubber impact hits enhancing composite plastic, can increase resin material anti-impact according to nano barium sulfate and crosslinking The basic principle of hitting property, not only by targetedly screening modifying agent, coupling agent and the species of crosslinking agent, to improve a nanometer sulfuric acid Compatibility between barium and ABS resin, and make nano barium sulfate disperse evenly, to make nano barium sulfate to ABS in ABS resin The impact resistance humidification of resin is more preferable, also modified ABS resin material is existed by controlling the degree of polymerization of ABS resin Reach optimum balance relation between impact resistance and processability, so that the ABS resin material made is with excellent anti-impact Under conditions of hitting property, it may have excellent processability, allows it to be applied in more areas.
A kind of above-mentioned rubber impact hits enhancing composite plastic, wherein, the nano barium sulfate particle diameter is 10-80nm；Receive Nano-barium sulfate particle diameter is smaller, and dispersiveness is poorer, and nano barium sulfate particle diameter is bigger, and the shock resistance humidification to ABS resin is poorer； Preferably, the nano barium sulfate particle diameter is 30-50nm；Most preferably, the nano barium sulfate particle diameter is 40nm.
A kind of above-mentioned rubber impact hits enhancing composite plastic, wherein, the modifying agent for cetylpyridinium chloride with The mixture of isopropanol composition；The modifying agent can improve the compatibility of nano barium sulfate and ABS resin and in nanometer Barium sulfate surface forms polar group, beneficial to scattered；Preferably, cetylpyridinium chloride and isopropanol in the modifying agent The ratio between the amount of material be 1 ︰ 2.
A kind of above-mentioned rubber impact hits enhancing composite plastic, wherein, the degree of polymerization of poly- butyl rubber is bigger, then changes after being crosslinked Property composite plastic impact resistance it is poorer, processability is better, and the polymer of poly- butyl rubber is smaller, then be crosslinked post-modification composite plastic The impact resistance of material is better, and processability is poorer, therefore, selects the rational poly- butyl rubber degree of polymerization, be balance impact resistance and The important means of processability.The degree of polymerization of the poly- butyl rubber is 180-280；Preferably, the poly- butyl rubber The degree of polymerization is 200-250；Optimal, the degree of polymerization of the poly- butyl rubber is 230；By preferred, obtained modification is compound Plastics both have excellent impact resistance, it may have preferable processability, is adapted to.
Wherein, the ABS resin degree of polymerization is 900-1500；Preferably, the degree of polymerization of the ABS resin is 1000- 1400；Most preferably, the degree of polymerization of the ABS resin is 1200；By preferred, obtained modification composite plastic had both had excellent Different impact resistance, it may have preferable processability.
A kind of above-mentioned rubber impact hits enhancing composite plastic, wherein, the coupling agent is titanate coupling agent；Titanate esters The compatibility between nano barium sulfate and ABS resin material can be increased, improve the shock resistance of modified composite plastic.
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 impact resistance of ABS resin material.
A kind of above-mentioned rubber impact hits enhancing composite plastic, wherein, its raw material further includes dispersant, plasticizer, anti-quiet One or more auxiliary agents in electric agent, coloring agent, brightener；Above-mentioned auxiliary agent can improve the processability of modified composite plastic, increase Its feature etc. is added to act on, so as to increase its applicability.
In order to realize foregoing invention purpose, further, present invention also offers a kind of rubber impact to hit enhancing composite plastic The preparation method of material, comprises the following steps：
（1）Nano barium sulfate is handled with coupling agent；
（2）Nano barium sulfate Jing Guo coupling agent treatment is subjected to cladding processing with modifying agent；
（3）By the nano barium sulfate after cladding and ABS resin processing for composite in the electric field after mixing, mixed Material；
（4）By mixture and poly- butyl rubber, crosslinking agent, trioctyl trimellitate (TOTM) after mixing in processing for composite, obtain Enhancing composite plastic is hit to rubber impact.
A kind of rubber impact hits the preparation method of enhancing composite plastic, and first nano barium sulfate is carried out at coupling with coupling agent Reason, increase nano barium sulfate and modifying agent, the compatibility of ABS resin；Processing is modified to nano barium sulfate with modifying agent again, And form polar group on its surface；Finally make the polar group in nano barium sulfate surface and ABS resin chain using external electric field Polarization, it is powered,, also can be with ABS trees while making nano barium sulfate dispersed by repelling each other between electric charge or attracting principle Polar group in fat chain is bonded, so that the shock resistance enhancing effect of nano barium sulfate is farthest embodied so that To modified ABS resin impact resistance significantly improve；The preparation method is simple and reliable, be suitable for rubber impact hit enhancing it is compound Extensive, the industrialized production of plastics.
A kind of above-mentioned rubber impact hits the preparation method of enhancing composite plastic, wherein, it is preferred that step 1 is carried out at coupling Ultrasonic wave can be used to aid in during reason；Shaken by the high speed of ultrasonic wave, make nano barium sulfate dispersiveness more preferable, and to coupling Processing has facilitation.
A kind of above-mentioned rubber impact hits the preparation method of enhancing composite plastic, wherein, the electric field energy described in step 3 is to base Group produces polarization, makes group powered, so as to promote the scattered and bonded effect of nano barium sulfate, improves modified ABS tree The impact resistance of fat.
Preferably, the electric field strength is 0.5-2kv/m；Electric field strength is too small, and polarization effect is weak, to nano barium sulfate 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 shock resistance for having an impact, may be decreased modified composite plastic；Most preferably, the electricity Field intensity 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 barium sulfate Best results.
Compared with prior art, beneficial effects of the present invention：
1st, rubber impact of the present invention hits the species that enhancing composite plastic targetedly screens modifying agent, coupling agent and crosslinking agent, makes Compatibility between nano barium sulfate and ABS resin is more preferable, and the dispersiveness in ABS resin is more preferable, and nano barium sulfate is to ABS trees The impact resistance humidification of fat is more preferable.
2nd, rubber impact of the present invention hits enhancing composite plastic and is made by controlling the degree of polymerization of ABS resin and poly- butyl rubber Modified ABS resin material reaches optimum balance relation between impact resistance and processability, so as to get modification composite plastic Material is under conditions of with excellent impact resistance, it may have excellent processability.
3rd, rubber impact of the present invention hits the preparation method of enhancing composite plastic, using the polarization of external electric field, can promote Nano barium sulfate is scattered and bonded in ABS resin system, and the shock resistance enhancing effect of nano barium sulfate is more preferable, and what is obtained changes The impact resistance higher of property composite plastic.
4th, preparation method of the present invention is simple, reliable, and suitable rubber impact hits extensive, the industrial metaplasia of enhancing composite plastic Production.
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 barium sulfate is handled with 0.5 part of titanate esters；
（2）Nano barium sulfate Jing Guo coupling agent treatment is wrapped with 2 parts of cetylpyridinium chloride and 4 parts of isopropanol Cover processing；
（3）By ABS resin that the nano barium sulfate after cladding and 65 parts of the degree of polymerization are 1200 after mixing in electric field strength To be extruded in the constant parallel electric field of the direction of an electric field of 1.2kv/m, mixture is obtained；
（4）Poly- butyl rubber, the 0.2 part of peroxidating diisopropyl of the mixture that step 3 is obtained and 15 parts of the degree of polymerization for 230 Benzene, 2 parts of trioctyl trimellitate (TOTM) are extruded after mixing, are obtained rubber impact and are hit enhancing composite plastic.
Embodiment 2
（1）5 parts of nano barium sulfate is handled with 0.3 part of titanate esters；
（2）Nano barium sulfate Jing Guo coupling agent treatment is wrapped with 4 parts of cetylpyridinium chloride and 4 parts of isopropanol Cover processing；
（3）By ABS resin that the nano barium sulfate after cladding and 55 parts of the degree of polymerization are 900 after mixing in electric field strength To be extruded in the electric field of 2.0kv/m, mixture is obtained；
（4）Poly- butyl rubber, the 0.3 part of peroxidating diisopropyl of the mixture that step 3 is obtained and 10 parts of the degree of polymerization for 280 Benzene, 3 parts of trioctyl trimellitate (TOTM) are extruded after mixing, are obtained rubber impact and are hit enhancing composite plastic.
Embodiment 3
（1）10 parts of nano barium sulfate is handled with 0.8 part of titanate esters；
（2）Nano barium sulfate Jing Guo coupling agent treatment is wrapped with 2 parts of cetylpyridinium chloride and 3 parts of isopropanol Cover processing；
（3）By ABS resin that the nano barium sulfate after cladding and 75 parts of the degree of polymerization are 1500 after mixing in electric-field strength Spend to be extruded in the constant parallel electric field of the direction of an electric field of 0.5kv/m, obtain mixture；
（4）Poly- butyl rubber, the 0.1 part of peroxidating diisopropyl of the mixture that step 3 is obtained and 20 parts of the degree of polymerization for 180 Benzene, 1 part of trioctyl trimellitate (TOTM) are extruded after mixing, are obtained rubber impact and are hit enhancing composite plastic.
Comparative example 1
（1）8 parts of nano barium sulfate is handled with 0.5 part of titanate esters；
（2）By the nano barium sulfate Jing Guo coupling agent treatment and 5 parts of dispersant, the ABS resin that 65 parts of the degree of polymerization is 1200 Extruded after mixing in the constant parallel electric field of the direction of an electric field that electric field strength is 1.2kv/m, obtain mixture；
（3）Poly- butyl rubber, the 0.2 part of peroxidating diisopropyl of the mixture that step 2 is obtained and 15 parts of the degree of polymerization for 230 Benzene, 2 parts of trioctyl trimellitate (TOTM) are extruded after mixing, obtain modified composite plastic.
Comparative example 2
（1）8 parts of nano barium sulfate is handled with 0.5 part of titanate esters；
（2）Nano barium sulfate Jing Guo coupling agent treatment is wrapped with 2 parts of cetylpyridinium chloride and 4 parts of isopropanol Cover processing；
（3）By ABS resin that the nano barium sulfate after cladding and 65 parts of the degree of polymerization are 900,15 parts of the degree of polymerization be 120 it is poly- Butyl rubber, 0.2 part of cumyl peroxide, 2 parts of trioctyl trimellitate (TOTM) are extruded after mixing, are obtained modified multiple Close plastics.
Comparative example 3
（1）8 parts of nano barium sulfate is handled with 0.5 part of titanate esters；
（2）Nano barium sulfate Jing Guo coupling agent treatment is subjected to cladding processing with 2 parts of polystyrene and 4 parts of isopropanol；
（3）By ABS resin that the nano barium sulfate after cladding and 65 parts of the degree of polymerization are 1200 after mixing in electric field strength To be extruded in the constant parallel electric field of the direction of an electric field of 1.2kv/m, mixture is obtained；
（4）Poly- butyl rubber, the 0.2 part of peroxidating diisopropyl of the mixture that step 3 is obtained and 15 parts of the degree of polymerization for 230 Benzene, 2 parts of trioctyl trimellitate (TOTM) are extruded after mixing, obtain modified composite plastic.
Comparative example 4
（1）8 parts of nano barium sulfate is handled with 0.5 part of titanate esters；
（2）Nano barium sulfate Jing Guo coupling agent treatment is wrapped with 2 parts of cetylpyridinium chloride and 4 parts of isopropanol Cover processing；
（3）By the poly- butyl rubber of the nano barium sulfate after cladding and 15 parts of the degree of polymerization for 230,0.2 part of peroxidating diisopropyl The ABS resin that benzene, 2 parts of trioctyl trimellitate (TOTM), 65 parts of the degree of polymerization are 1200 is after mixing in electric field strength Extruded in the constant parallel electric field of the direction of an electric field of 1.2kv/m, obtain modified composite plastic.
Comparative example 5
（1）8 parts of nano barium sulfate is handled with 0.5 part of titanate esters；
（2）Nano barium sulfate Jing Guo coupling agent treatment is wrapped with 2 parts of cetylpyridinium chloride and 4 parts of isopropanol Cover processing；
（3）It is in electric field strength after mixing by the ABS resin that the nano barium sulfate after cladding is 800 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）The mixture that step 3 obtains and poly- butyl rubber that 15 parts of the degree of polymerization is 150,2 parts of tri trimellitate is pungent Ester, 0.2 part of cumyl peroxide are extruded after mixing, obtain modified composite plastic.
By the modification composite plastic in above-described embodiment 1-3 and comparative example 1-5, performance detection is carried out, record data are as follows：
Performance Notch impact strength（KJ/m2） Processability
Embodiment 1 21.5 ++++
Embodiment 2 20.7 ++++
Embodiment 3 21.3 ++++
Comparative example 1 15.8 ++++
Comparative example 2 16.5 ++++
Comparative example 3 18.4 ++++
Comparative example 4 19.2 ++++
Comparative example 5 21.6 ++
ABS resin 11.8 +++++
Note："+" is more, illustrates that performance is better.
Above-mentioned analysis of experimental data is understood, the modified composite plastic of the present invention being prepared in embodiment 1-3, nano-sulfur Sour barium is uniformly dispersed, good with the compatibility of ABS resin, modified composite plastic good impact resistance, and processability is good；And in comparative example 1, Modifying agent is not used processing is modified to nano barium sulfate, although adding dispersant, nano barium sulfate dispersion effect is poor, With the poor compatibility of ABS resin, the impact resistance of ABS resin material significantly reduces；It is not for composite in the electric field in comparative example 2 Processing, nano barium sulfate dispersion effect is poor, and the impact resistance of ABS resin material significantly reduces；Modifying agent is not this in comparative example 3 Apply for defined, nano barium sulfate dispersion effect is poor, and the impact resistance of ABS resin material significantly reduces；It is crosslinked in comparative example 4 Reaction equally carry out in the electric field, electric field has a negative impact cross-linking reaction, so as to get ABS resin material impact resistance Reduce；The ABS resin and the poly- butyl rubber degree of polymerization used in comparative example 5 is too small, although impact resistance increased after compound, But its processability significantly reduces, it is unfavorable for the application that rubber impact hits enhancing composite plastic.

Claims (10)

1. a kind of rubber impact hits enhancing composite plastic, it is characterised in that is prepared including following parts by weight raw material：55- 75 parts of ABS resin, 5-10 parts of nano barium sulfate, 5-8 parts of modifying agent, 10-20 parts of poly- butyl rubber, 0.3-0.8 parts Coupling agent, 0.1-0.3 parts of crosslinking agent, 1-3 parts of trioctyl trimellitate (TOTM)；The modifying agent is cetylpyridinium chloride With the mixture of isopropanol composition；The coupling agent is titanate coupling agent, and the crosslinking agent is cumyl peroxide；It is described The degree of polymerization of poly- butyl rubber is 180-280；The ABS resin degree of polymerization is 900-1500.
2. composite plastic according to claim 1, it is characterised in that in the modifying agent cetylpyridinium chloride with it is different The ratio between amount of material of propyl alcohol is 1 ︰ 2.
3. composite plastic according to claim 1, it is characterised in that the degree of polymerization of the poly- butyl rubber is 200-250.
4. composite plastic according to claim 3, it is characterised in that the degree of polymerization of the poly- butyl rubber is 230.
5. composite plastic according to claim 1, it is characterised in that the ABS resin degree of polymerization is 1000-1400.
6. composite plastic according to claim 5, it is characterised in that the ABS resin degree of polymerization is 1200.
7. a kind of rubber impact as described in claim 1-6 hit enhancing composite plastic preparation method, it is characterised in that including with Lower step：
（1）Nano barium sulfate is handled with coupling agent；
（2）Nano barium sulfate Jing Guo coupling agent treatment is subjected to cladding processing with modifying agent；
（3）By the nano barium sulfate after cladding and ABS resin processing for composite in the electric field after mixing, mixed Material；
（4）By mixture and poly- butyl rubber, crosslinking agent, trioctyl trimellitate (TOTM) after mixing in processing for composite, obtain Enhancing composite plastic is hit to rubber impact.
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.
CN201711228379.1A 2017-11-29 2017-11-29 A kind of rubber impact hits enhancing composite plastic and preparation method thereof Withdrawn CN107936458A (en)

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Application Number Priority Date Filing Date Title
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Publication Number Publication Date
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Country Status (1)

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