CN108276624A - A kind of preparation that graphene adulterates anti-impact modifier and the application in PVC matrix - Google Patents

A kind of preparation that graphene adulterates anti-impact modifier and the application in PVC matrix Download PDF

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Publication number
CN108276624A
CN108276624A CN201810153296.9A CN201810153296A CN108276624A CN 108276624 A CN108276624 A CN 108276624A CN 201810153296 A CN201810153296 A CN 201810153296A CN 108276624 A CN108276624 A CN 108276624A
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China
Prior art keywords
impact modifier
graphene oxide
micelle
polymethyl methacrylate
graphene
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CN201810153296.9A
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Chinese (zh)
Inventor
马超
邱桂学
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Gaomi Vast Wood Mstar Technology Ltd
Qingdao University of Science and Technology
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Gaomi Vast Wood Mstar Technology Ltd
Qingdao University of Science and Technology
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Priority to CN201810153296.9A priority Critical patent/CN108276624A/en
Publication of CN108276624A publication Critical patent/CN108276624A/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02Copolymers with acrylonitrile
    • C08L9/04Latex
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06Homopolymers or copolymers of vinyl chloride
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/02Flame or fire retardant/resistant
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/08Stabilised against heat, light or radiation or oxydation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/14Gas barrier composition
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/04Polymer mixtures characterised by other features containing interpenetrating networks

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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)
  • Graft Or Block Polymers (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The preparation and the application in PVC matrix for adulterating anti-impact modifier the present invention relates to a kind of graphene, a kind of anti-impact modifier, graphene oxide is adulterated in rubber latex, then by methyl methacrylate addition system, in-situ polymerization obtains the composite material of polymethyl methacrylate cladding or polymethyl methacrylate inierpeneirating network structure.It is an advantage of the invention that:New type functional anti-impact modifier can not only make PVC Type of Collective object materials have good shock resistance, and the anti-impact modifier has the special attribute of nano-particle, as high intensity, high-modulus, high tenacity, high-fire resistance, high conductivity, anti-flammability and to oil and gas high barrier the advantages that.The anti-impact modifier is expected to be used for more demanding packaging material for food, part etc. in outdoor building materials such as window frame, shutter and electronic instrument shell, aircraft storehouse.

Description

A kind of preparation that graphene adulterates anti-impact modifier and the application in PVC matrix
Technical field
The preparation and the application in PVC matrix for adulterating anti-impact modifier the present invention relates to a kind of graphene, belong to PVC Processing technique field.
Background technology
PVC is that a kind of yield is big, resins for universal use of high comprehensive performance, and product has good mechanics and electrical property Can, there is anti-flammability, the transparency, chemical resistance.But PVC cannot be extensively using structural material be made, mainly as hard product It is poor by its erosion-resisting characteristics, being easy that thermal deformation and thermal stability are low, processing performance is bad etc., factors are limited.In order to improve PVC These the shortcomings of, usually require that a small amount of processing aid (l-3phr) is added in process of production, be especially used in plasticizer and contain It measures in less hard PVC article formulations.Most common processing aid is esters of acrylic acid (ACR), is methyl methacrylate With the copolymer of the monomers such as ethyl acrylate, butyl acrylate, butyl methacrylate.The 1950s is by U.S. Rohm& Haas companies develop, and are more and more widely used as the PVC good auxiliary agents being modified.It is big it to be roughly divided into two according to its effect Class:Modifier and impact modifier.Wherein, impact modifier (ACR) is a kind of with butyl polyacrylate (PBA) crosslinking Body is core, outer layer grafting polymethyl methacrylate (PMMA) and the copolymer with nucleocapsid.Shock resistance type ACR has excellent Different increasing tougheness, good heat resistance, molding processibility and the product transparency are good and can be in very wide use temperature range The advantages that keeping best shock resistance, is paid close attention to by people.
However the shortcomings that tradition impact resistance ACR, is:First, ignition-proof element and ingredient have been typically free of inside component; The addition of second, usual anti-impact modifier ACR can reduce its tensile strength, hardness while improving material impact intensity Etc. performances.
Invention content
In order to overcome the shortcomings of ACR does not have anti-flammability, reduces tensile strength of material, hardness in the prior art, the present invention A kind of anti-impact modifier is provided, the manufacture field of PVC is can be used for.The advantages of material is:The anti-impact modifier is filled PVC material not only there is good shock resistance, but also have special functionality, be mainly manifested in have and receive The special attribute of some of rice corpuscles, such as fire-retardant, high intensity, high-modulus, high tenacity, high-fire resistance, high conductivity and to oil and The advantages that high barrier of gas.
The modifying agent of the present invention is by the graphite alkenes material with fire retardation, soft crosslinking micelle nucleome, vitrifying The high shell three parts composition of transition temperature.This three parts plays the role of the improvement of PVC performances vital.Graphene portion Point, itself excellent flame retardant property can optimize the fire safety evaluating performance of PVC nanocomposites, in addition can be to the height of material Remarkable effect is played in the promotion of intensity, high-modulus, anti-flammability etc.;Soft crosslinking micelle shell can absorb impact energy, The shock resistance of PVC material can be increased;The high shell of glass transition temperature has connection PVC matrix and micelle particle, increasing The effects that appearance.
It is an advantage of the invention that:It is good that new type functional anti-impact modifier can not only be such that PVC Type of Collective object materials have Good shock resistance, and the anti-impact modifier has the special attribute of nano-particle, such as high intensity, high-modulus, height Toughness, high-fire resistance, high conductivity, anti-flammability and to oil and gas high barrier the advantages that.The anti-impact modifier has It hopes and is used for more demanding packaging material for food, outdoor building materials such as window frame, shutter etc. and electronic instrument shell, aircraft Part etc. in storehouse.
The technical scheme is that:
A kind of graphene doping anti-impact modifier, adulterates graphene oxide, then by metering system in rubber latex In sour methyl esters addition system, in-situ polymerization obtains polymethyl methacrylate cladding or polymethyl methacrylate interpenetrating networks knot The composite material of structure.
The method for preparing above-mentioned anti-impact modifier, includes the following steps:
1) after mixing NBR latex, peroxide DCP or Sulfur and graphene oxide aqueous dispersion, in room temperature condition Under, mixing time 5-300min, rotating speed of agitator 500-2000rpm obtain the complex emulsions of graphene oxide/latex; Then, by complex emulsions heating stirring, temperature is 70 DEG C, mixing time 20-30min, rotating speed of agitator 500- 2000rpm, the graphene oxide with intercalation configuration vulcanized/micelle Aqueous dispersions material;
2) MMA monomers, peroxide BPO are added in the compound water phase dispersion of graphene oxide/micelle and are mixed It closes, mixing time 5-300min;The mixed liquor is stirred evenly at a temperature of 40 DEG C, mixing time 5-300min;Filtering Obtain polymethyl methacrylate cladding or polymethyl methacrylate interpenetrating micelle network structure particle.
Preferably:The mass fraction of each component is in step 1):
Acrylonitrile-butadiene rubber latex in terms of dry rubber content 100;
Graphene oxide aqueous dispersion, with graphene oxide content meter 0.1-30;
Peroxide DCP or Sulfur 0.5-2.
Preferably:The mass fraction of each component is in step 2):
MMA 10-80;
The compound aqueous phase system of graphene oxide/micelle, in terms of dry rubber content 100;
Peroxide BPO amount of monomer 0.1%-0.5%.
The present invention also provides application of the above-mentioned modifying agent in PVC matrix.
Specific implementation mode
Embodiment 1
100 parts of nitrile rubber latex (dry glue)
1 part of graphene oxide
1 part of antioxidant 4010NA
1.5 parts of Sulfur
MMA 30
Peroxide BPO amount of monomer 0.08
NBR latex, Sulfur and graphene dispersion aqueous solution are placed into being carried out in agitating paddle and thermometer reaction kettle Mixing, first, at ambient temperature, mixing time 5-300min, rotating speed of agitator 500-2000rpm obtain oxidation stone The complex emulsions of black alkene/latex;Then, complex liquid is placed into microwave equipment heating stirring, mixing time 20-30min is stirred It is 500-2000rpm, the graphene oxide with the intercalation configuration/micelle water phase vulcanized by this process to mix paddle rotating speed Dispersion.MMA monomers, peroxide BPO are added to containing being carried out in the compound aqueous phase system kettle of graphene oxide/micelle again Mixing, mixing time 5-300min;Secondly, which is put into 40 degree of water-bath or baking oven, is stirred evenly, when stirring Between be 5-300min;Finally, polymethyl methacrylate cladding or polymethyl methacrylate interpenetrating micelle network is obtained by filtration The formation of structure particles.Mechanical property in PVC material is shown in Table 1.
Embodiment 2
100 parts of nitrile rubber latex (dry glue)
2 parts of graphene oxide
1 part of antioxidant 4010NA
1.5 parts of Sulfur
MMA 30
Peroxide BPO amount of monomer 0.08
NBR latex, Sulfur and graphene dispersion aqueous solution are placed into being carried out in agitating paddle and thermometer reaction kettle Mixing, first, at ambient temperature, mixing time 5-300min, rotating speed of agitator 500-2000rpm obtain oxidation stone The complex emulsions of black alkene/latex;Then, complex liquid is placed into microwave equipment heating stirring, mixing time 20-30min is stirred It is 500-2000rpm, the graphene oxide with the intercalation configuration/micelle water phase vulcanized by this process to mix paddle rotating speed Dispersion.MMA monomers, peroxide BPO are added to containing being carried out in the compound aqueous phase system kettle of graphene oxide/micelle again Mixing, mixing time 5-300min;Secondly, which is put into 40 degree of water-bath or baking oven, is stirred evenly, when stirring Between be 5-300min;Finally, polymethyl methacrylate cladding or polymethyl methacrylate interpenetrating micelle network is obtained by filtration The formation of structure particles.
By functional 3 parts of anti-impact modifier obtained, 100 parts of PVC, 5 parts of plasticizer DOP, calcium-zinc composite stabilizing agent 3 Part, the mill in two-roll mill, bottom sheet, the then tabletting on hot press carry out the test of performance.Functional impact modification And the mechanical property in PVC material is shown in Table 1.
Embodiment 3
100 parts of nitrile rubber latex (dry glue)
2 parts of graphene oxide
1 part of antioxidant 4010NA
1.5 parts of Sulfur
MMA 70
Peroxide BPO amount of monomer 0.08
NBR latex, Sulfur and graphene dispersion aqueous solution are placed into being carried out in agitating paddle and thermometer reaction kettle Mixing, first, at ambient temperature, mixing time 5-300min, rotating speed of agitator 500-2000rpm obtain oxidation stone The complex emulsions of black alkene/latex;Then, complex liquid is placed into microwave equipment heating stirring, mixing time 20-30min is stirred It is 500-2000rpm, the graphene oxide with the intercalation configuration/micelle water phase vulcanized by this process to mix paddle rotating speed Dispersion.MMA monomers, peroxide BPO are added to containing being carried out in the compound aqueous phase system kettle of graphene oxide/micelle again Mixing, mixing time 5-300min;Secondly, which is put into 40 degree of water-bath or baking oven, is stirred evenly, when stirring Between be 5-300min;Finally, polymethyl methacrylate cladding or polymethyl methacrylate interpenetrating micelle network is obtained by filtration The formation of structure particles.
By functional 3 parts of anti-impact modifier obtained, 100 parts of PVC, 5 parts of plasticizer DOP, calcium-zinc composite stabilizing agent 3 Part, the mill in two-roll mill, bottom sheet, the then tabletting on hot press carry out the test of performance.Functional impact modification And the mechanical property in PVC material is shown in Table 1.
Comparative example 1
In the material that commercially available ACR is equally formulated for PVC, 100 parts of 3 parts of ACR, PVC, 5 parts of plasticizer DOP, calcium zinc 3 parts of compound stabilizer, the mill in two-roll mill, bottom sheet, the then tabletting on hot press carry out the test of performance.Function Property impact modification and the mechanical property in PVC material are shown in Table 1.Its mechanical property is shown in Table 1.
The properties tables of data of 1 several samples of table
Data explanation:
Hardness reflects the rigidity of material, illustrates the anti-impact modifier of our preparations compared with commercially available ACR, rigid difference Less.
The variation of tensile strength illustrates the anti-impact modifier of our preparations compared with commercially available ACR, and tensile strength improves 2-3MPa, this is because the addition of graphene keeps composite materials property more preferable.
The variation of impact strength illustrates the anti-impact modifier of our preparations compared with commercially available ACR, and shock resistance carries High about 6KJ/m2, this is because the contribution of micelle, makes the toughness of material become more preferably.
The variation of oxygen index (OI) reflects the anti-flammability of material, the anti-impact modifier and commercially available ACR phases that we prepare Than oxygen index (OI) higher improves about 4 units, illustrates that Flame Retardancy can be more excellent.

Claims (5)

1. a kind of graphene adulterates anti-impact modifier, it is characterised in that:Graphene oxide is adulterated in rubber latex, then will In methyl methacrylate addition system, in-situ polymerization obtains polymethyl methacrylate cladding or polymethyl methacrylate is mutual Wear the composite material of network structure.
2. the method for preparing anti-impact modifier as described in claim 1, it is characterised in that:Include the following steps:
1) after NBR latex, peroxide DCP or Sulfur and graphene oxide aqueous dispersion being mixed, at ambient temperature, Mixing time is 5-300min, and rotating speed of agitator 500-2000rpm obtains the complex emulsions of graphene oxide/latex;So Afterwards, by complex emulsions heating stirring, temperature is 70 DEG C, mixing time 20-30min, rotating speed of agitator 500-2000rpm, The graphene oxide with intercalation configuration vulcanized/micelle Aqueous dispersions material;
2) MMA monomers, peroxide BPO are added in the compound water phase dispersion of graphene oxide/micelle and are mixed, stirred It is 5-300min to mix the time;The mixed liquor is stirred evenly at a temperature of 40 DEG C, mixing time 5-300min;It is obtained by filtration poly- Methyl methacrylate coats or polymethyl methacrylate interpenetrating micelle network structure particle.
3. method as claimed in claim 2, it is characterised in that:
The mass fraction of each component is in step 1):
Acrylonitrile-butadiene rubber latex in terms of dry rubber content 100;
Graphene oxide aqueous dispersion, with graphene oxide content meter 0.1-30;
Peroxide DCP or Sulfur 0.5-2.
4. method as claimed in claim 2, it is characterised in that:
The mass fraction of each component is in step 2):
MMA 10-80;
The compound aqueous phase system of graphene oxide/micelle, in terms of dry rubber content 100;
Peroxide BPO amount of monomer 0.1%-0.5%.
5. application of the modifying agent as described in claim 1 in PVC matrix.
CN201810153296.9A 2018-02-22 2018-02-22 A kind of preparation that graphene adulterates anti-impact modifier and the application in PVC matrix Pending CN108276624A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112175509A (en) * 2020-09-25 2021-01-05 深圳市嘉卓成科技发展有限公司 Graphene-reinforced acrylic polyurethane water-based paint and preparation method thereof
CN116376296A (en) * 2023-06-06 2023-07-04 山东宏福化学有限公司 Preparation method of PVC processing aid

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CN1488657A (en) * 2003-08-22 2004-04-14 中国科学院长春应用化学研究所 Nucleocapside structure PVC impact resistance modifier, and preparing method and use thereof
JP2005112907A (en) * 2003-10-03 2005-04-28 Mitsubishi Rayon Co Ltd Graft copolymer, impact resistance modifier and thermoplastic resin composition
CN106905569A (en) * 2017-03-27 2017-06-30 北京化工大学 The preparation method of High-performance graphite oxide alkene/black rubber nano composite material

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
CN1418898A (en) * 2002-11-14 2003-05-21 河北工业大学 Process for preparing high shock-resistance polyacrylic ester composite particle grafted vinyl chloride emulsion resin
CN1488657A (en) * 2003-08-22 2004-04-14 中国科学院长春应用化学研究所 Nucleocapside structure PVC impact resistance modifier, and preparing method and use thereof
JP2005112907A (en) * 2003-10-03 2005-04-28 Mitsubishi Rayon Co Ltd Graft copolymer, impact resistance modifier and thermoplastic resin composition
CN106905569A (en) * 2017-03-27 2017-06-30 北京化工大学 The preparation method of High-performance graphite oxide alkene/black rubber nano composite material

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112175509A (en) * 2020-09-25 2021-01-05 深圳市嘉卓成科技发展有限公司 Graphene-reinforced acrylic polyurethane water-based paint and preparation method thereof
CN116376296A (en) * 2023-06-06 2023-07-04 山东宏福化学有限公司 Preparation method of PVC processing aid
CN116376296B (en) * 2023-06-06 2023-08-11 山东宏福化学有限公司 Preparation method of PVC processing aid

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