CN110305401A - A kind of high fondant-strength PP resin and its preparation process - Google Patents
A kind of high fondant-strength PP resin and its preparation process Download PDFInfo
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- CN110305401A CN110305401A CN201910393474.XA CN201910393474A CN110305401A CN 110305401 A CN110305401 A CN 110305401A CN 201910393474 A CN201910393474 A CN 201910393474A CN 110305401 A CN110305401 A CN 110305401A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
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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
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
Abstract
The present invention provides a kind of high fondant-strength PP resin, and the content of graphene is 9.5-10.5%, melt strength 45-48cN；The present invention also provides the preparation process of above-mentioned high fondant-strength PP resin, the preparation process, including preparation single-layer graphene oxide, surface modification, copolymerization, cross-linked graft.The preparation method of high fondant-strength PP resin of the present invention, graphene are good with polyacrylic compatibility.Polymerization stage, graphene is dispersed in polypropylene matrix with nanoscale, melt stage, hydroxylating graphene is grafted on graphene/PP composite material, improve graphene and polyacrylic compatibility, the melt strength of high fondant-strength PP is 45-48cN, while improving the additive amount of graphene, improves tensile strength, bending modulus, notch impact strength.
Description
Technical field
The present invention relates to a kind of high fondant-strength PP resin and its preparation processes, belong to technical field of polymer materials.
Background technique
Presently commercially available PP resin mainly waits silicon to found structure polypropylene, and strand is line row chain structure, belongs to hypocrystalline
Polymer, isotactic polypropylene relative molecular mass distribution is narrow, and melt strength is low, in thermoforming production process, product side occurs
Edge curling, shrinkage phenomenon.
The method for improving PP melt strength mainly has direct polymerization method, radiation cross-linking process, chemical crosslinking modified, blending and modifying
Be Deng, blending modification method improve melt strength of polypropylene by adding high fondant-strength polymer or filler in PP, but
It is that blend is added in PP, it is usually bad with blend compatibility because of PP, cause PP mechanical property and transparent performance to decline.
CN109401058A discloses a kind of high melt strength, propylene and preparation method thereof, in grinding distribution and heated drying
In treatment process, the micro- wax powder body of polypropylene containing carboxyl functional group reacts under silane coupling agent effect with nano silica,
And during melt-processed, carboxyl functional group contained by the micro- wax powder body of polypropylene and hydroxyl contained by nano-silicon dioxide particle are anti-
It answers, to be prepared for polypropylene grafted nanometer silica composite, is mentioned by polypropylene grafted nanometer silica composite
High polyacrylic melt strength and mechanical property；But the additional amount of its nano silica is few, the addition of nano silica
Amount is only polyacrylic 0.2-1%；If additional amount is too big, silica still has the defect for being easy reunion.
Graphene has high elasticity modulus and bending strength, resistance to strong acid, highly basic are higher compared with conventional filler
Conductivity and excellent thermal conductivity.The preparation of graphene/composite polyolefine material is mostly to pass through modified graphite in the prior art
Prepared by alkene and polyolefin blend.Graphene large specific surface area, surface can be high, easily curl, bad with polypropylene compatible, hold
It is easy to reunite, it can not disperse in polypropylene well.
CN106810630A discloses a kind of preparation method of graphene/PP composite material, and graphene oxide is used
Organometallic reagent processing realizes that graphene is dispersed in polypropylene matrix with nanoscale.The patent there are it is following not
Foot:
Its polypropylene matrix prepared is linear chain structure, and high fondant-strength PP is the polypropylene with branched structure, it is seen then that should
Graphene, which is added, in patent can not effectively improve melt strength although tensile strength and bending modulus can be improved；And
When the additive amount of graphene is up to 9.33% or more, what declining occurred in the tensile strength and bending modulus of the composite material of preparation becomes
Gesture.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides the preparation methods of high fondant-strength PP a kind of, are issued with realizing
Improving eyesight:
(1) graphene and polyacrylic compatibility are improved, the melt strength of the high fondant-strength PP of preparation is improved；
(2) while improving the additive amount of graphene, tensile strength, bending modulus, notch impact strength are improved.
In order to reach the above goal of the invention, The technical solution adopted by the invention is as follows:
A kind of high fondant-strength PP resin, the content of graphene are 9.5-10.5%, melt strength 45-48cN.
It is further improvement to above-mentioned technical proposal below:
The high fondant-strength PP resin, tensile strength 65-70MPa, bending modulus 1850-1900MPa, notch shock are strong
Spend 30-35 kJ/m2。
A kind of preparation process of high fondant-strength PP resin, the preparation process, including preparation single-layer graphene oxide, table
Face is modified, is copolymerized, cross-linked graft.
The surface is modified, by single-layer graphene oxide, dodecyl trimethyl ammonium chloride is added, in n-hexane, carries out
It is ultrasonically treated 10-15min, supersonic frequency 15-18KHz obtains modified graphene oxide dispersion.
The mass volume ratio of the single-layer graphene oxide and dodecyl trimethyl ammonium chloride are as follows: 1g:3-3.6ml；Institute
State the volume ratio of dodecyl trimethyl ammonium chloride and n-hexane are as follows: 1:4.3-5.
Modified graphene oxide dispersion, propylene liquid are mixed, are stirred evenly, be added by the copolymerization
Ziegler-Natta catalyst, co-catalyst, dimethoxydiphenylsilane obtain stone in 60-65 DEG C of polymerization 40-50min
Black alkene/polyacrylic polymer.
The co-catalyst is cobalt acetate, graphene oxide and propylene in the modified graphene oxide dispersion
The mass ratio of liquid are as follows: 3.05-3.25:100；The catalyst accounts for the mass percent of propylene liquid are as follows: 0.004-
0.0045%；The mass percent that the co-catalyst accounts for propylene liquid is 0.002-0.003%；The diphenyl dimethoxy silicon
Alkane and the volume mass of propylene liquid ratio are as follows: 0.2-0.25ml:1kg.
The cross-linked graft, 100 parts of graphene/PP composite materials, 0.2 part of grafting catalysts, 6-7 parts of hydroxyl fossils
Black alkene, 1 part of coupling agent, 2 parts of antioxidant obtain high melt strength, propylene through screw extruder extruding pelletization.
The grafting catalysts are cobalt acetate, Dibutyltin oxide, mass ratio 1:1；
The coupling agent is vinyltriethoxysilane；
The antioxidant is one of antioxidant 1010, antioxidant 1076, antioxidant 264；
The hydroxylating graphene, single layer content 80%, thickness 0.6-1.2nm, lamella diameter are less than 300nm, and hydroxy radical content is
4wt%, black powder.
The temperature setting of the screw extruder be area's temperature be 180-185 DEG C, two area's temperature are 185-190 DEG C, three
190-195 DEG C of area's temperature, four area's temperature are 195-200 DEG C, five area's temperature are 195-200 DEG C, six area's temperature are 190-195 DEG C,
Screw speed is 300-400rpm, carries out melting extrusion, and high fondant-strength PP resin is prepared in cooling and dicing.
Above-mentioned preparation single-layer graphene oxide, method particularly includes:
Graphene oxide powder is added to the water, the suspension of 5-8mg/ml is obtained, adjusting temperature is 45-50 DEG C, in 1200-
It after being stirred 10-15 minutes under 1300r/min, is ultrasonically treated, the supersonic frequency is 100-120KHz, sonication treatment time
For 5-7min, oscillation removing is then carried out in an oscillator, and oscillator speed is 300-350rpm, and concussion splitting time is 3-
4h；Carry out it is high-pressure homogeneous, homogenizer pressure be 28-30MPa, carry out 2 homogenizations, obtain graphene oxide dispersion, take off
Water is dried to obtain single-layer graphene oxide.
The graphene oxide powder, partial size are 1-3 μm, and the number of plies is 1-5 layers, and with a thickness of 0.55-1.2nm, oxygen content is
30%；
Using ultrasonic treatment, in conjunction with oscillation, homogenization, may be implemented graphene oxide removing at single layer graphene oxide.
The present invention first makes propylene carry out polymerization reaction in the piece interlayer of graphene single layer, and graphene is uniformly divided with nanoscale
It is dispersed in polypropylene matrix, improves graphene and polyacrylic compatibility, graphene/PP composite material is prepared, so
Graphene/PP composite material is under action of coupling agents afterwards, carries out melting crosslinking in screw extruder, while graphene/
Graft reaction occurs for PP composite material and hydroxylating graphene, realizes that hydroxylating graphene is grafted to graphene/polypropylene
On composite material, the modified high fondant-strength PP of graphene is prepared, further increases graphene and polypropylene in melting rank
The compatibility of section, improves the additive amount of graphene, while improving the melt strength of composite material, tensile strength, bending modulus, lacking
Mouth impact strength.
Above-mentioned graft reaction is that esterification occurs for the carboxyl contained using graphene oxide and hydroxylating graphene, real
Now it is grafted.
By adopting the above-described technical solution, having the beneficial effect that of reaching of the present invention
(1) preparation method of high fondant-strength PP resin of the present invention, graphene are good with polyacrylic compatibility.It polymerize rank
Section, graphene is dispersed in polypropylene matrix with nanoscale, melt stage, hydroxylating graphene be grafted to graphene/
On PP composite material, graphene and polyacrylic compatibility are improved,
The melt strength of high fondant-strength PP is 45-48cN.
(2) while improving the additive amount of graphene, tensile strength, bending modulus, notch impact strength are improved.
The high fondant-strength PP that the present invention is prepared, tensile strength 65-70MPa, bending modulus 1850-
1900MPa, notch impact strength 30-35 kJ/m2, the content of graphene is 9.5-10.5%.
Specific embodiment
Below with reference to specific embodiment, the present invention is further explained.
A kind of high fondant-strength PP resin of embodiment 1 and its preparation process
The following steps are included:
(1) single-layer graphene oxide is prepared
Graphene oxide powder is added to the water, the suspension of 5mg/ml is obtained, adjusting temperature is 45 DEG C, at 1200r/min
Stirring after ten minutes, is ultrasonically treated, and the supersonic frequency is 100KHz, then sonication treatment time 5min is vibrating
Oscillation removing is carried out in device, oscillator speed is 300rpm, and concussion splitting time is 3h；Carry out high-pressure homogeneous, homogenizer pressure
For 28MPa, 2 homogenizations are carried out, obtain graphene oxide dispersion, dehydration and drying obtains single-layer graphene oxide.
The graphene oxide powder, partial size are 1-3 μm, and the number of plies is 1-5 layers, and with a thickness of 0.55-1.2nm, oxygen content is
30%；
Using ultrasonic treatment, in conjunction with oscillation, homogenization, may be implemented graphene oxide removing at single layer graphene oxide.
(2) surface is modified
By 30.5g single-layer graphene oxide, 100ml dodecyl trimethyl ammonium chloride is added, in 480ml n-hexane, is surpassed
Sonication 10min, supersonic frequency 15KHz；Obtain modified graphene oxide dispersion.
Graphene oxide, it is modified by surface, its lipophilicity can be enhanced, it is easier to be dissolved in n-hexane.
(3) it is copolymerized
Air and a small amount of water are displaced with high pure nitrogen in polymerization reaction kettle, above-mentioned modified graphene oxide point is added
Dispersion liquid, 1kg propylene liquid stir 3min at 2000r/min, and 40mgZiegler-Natta catalyst, 20mg co-catalysis is added
Agent, 0.2ml dimethoxydiphenylsilane obtain 700g graphene/polyacrylic polymer in 60 DEG C of polymerization 40min.
The Ziegler-Natta catalyst is bought, model ZN-114 for market,
The co-catalyst is cobalt acetate；
Propylene is polymerize under the action of catalyst, and polymerization reaction is carried out in the piece interlayer of graphene single layer, obtains stone after polymerization
Black alkene/PP composite material.
(4) cross-linked graft
100 parts of graphene/PP composite materials, 0.2 part of grafting catalysts, 6 parts of hydroxylating graphenes, 1 part of coupling agent, 2 parts
Antioxidant obtains high melt strength, propylene through screw extruder extruding pelletization；
The grafting catalysts are cobalt acetate, Dibutyltin oxide, mass ratio 1:1；
The coupling agent is vinyltriethoxysilane；
The antioxidant is one of antioxidant 1010, antioxidant 1076, antioxidant 264；
The hydroxylating graphene, buys, single layer content 80%, thickness 0.6-1.2nm to be originated from market, and lamella diameter is less than
300nm, hydroxy radical content 4wt%, black powder.
The temperature setting of the screw extruder be area's temperature be 180 DEG C, two area's temperature are 185 DEG C, three area's temperature 190
DEG C, four area's temperature be 195 DEG C, five area's temperature are 195 DEG C, six area's temperature are 190 DEG C, screw speed 300rpm is melted
It squeezes out, high fondant-strength PP resin is prepared in cooling and dicing.
Graphene/PP composite material carries out melting crosslinking, while stone under action of coupling agents in screw extruder
Graft reaction occurs for black alkene/PP composite material and hydroxylating graphene, realizes that hydroxylating graphene is grafted to graphene/poly-
On acrylic composite, the modified high fondant-strength PP of graphene is prepared；
Above-mentioned graft reaction is that esterification occurs for the carboxyl contained using graphene oxide and hydroxylating graphene, and realization connects
Branch.
The index for the high fondant-strength PP being prepared are as follows: melt strength 48cN；Tensile strength is 70MPa, bending die
Amount is 1900MPa, 35 kJ/m of notch impact strength2, the content of graphene is 9.5%.
A kind of high fondant-strength PP resin of embodiment 2 and its preparation process
The following steps are included:
(1) single-layer graphene oxide is prepared
Graphene oxide powder is added to the water, the suspension of 8mg/ml is obtained, adjusting temperature is 50 DEG C, at 1300r/min
It after stirring 15 minutes, is ultrasonically treated, the supersonic frequency is 120KHz, then sonication treatment time 7min is vibrating
Oscillation removing is carried out in device, oscillator speed is 350rpm, and concussion splitting time is 4h；Carry out high-pressure homogeneous, homogenizer pressure
For 30MPa, 2 homogenizations are carried out, obtain graphene oxide dispersion, dehydration and drying obtains single-layer graphene oxide.
The graphene oxide powder, partial size are 1-3 μm, and the number of plies is 1-5 layers, and with a thickness of 0.55-1.2nm, oxygen content is
30%；
Using ultrasonic treatment, in conjunction with oscillation, homogenization, may be implemented graphene oxide removing at single layer graphene oxide.
(2) surface is modified
By the 32.5g graphene oxide of single layer, 110ml dodecyl trimethyl ammonium chloride is added, in 500ml n-hexane, carries out
It is ultrasonically treated 15min, supersonic frequency 18KHz；Obtain modified graphene oxide dispersion.
Graphene oxide, it is modified by surface, its lipophilicity can be enhanced, it is easier to be dissolved in n-hexane.
(3) it is copolymerized
Air and a small amount of water are displaced with high pure nitrogen in polymerization reaction kettle, above-mentioned modified graphene oxide point is added
Dispersion liquid, 1kg propylene liquid stir 5min at 3000r/min, and 45mgZiegler-Natta catalyst, 30mg co-catalysis is added
Agent, 0.25ml dimethoxydiphenylsilane obtain 710g graphene/polyacrylic polymer in 65 DEG C of polymerization 50min.
The Ziegler-Natta catalyst is bought, model ZN-114 for market,
The co-catalyst is cobalt acetate.
Propylene is polymerize under the action of catalyst, and polymerization reaction is carried out in the piece interlayer of graphene single layer, after polymerization
To graphene/PP composite material.
(4) cross-linked graft
100 parts of graphene/PP composite materials, 0.2 part of grafting catalysts, 7 parts of hydroxylating graphenes, 1 part of coupling agent, 2 parts
Antioxidant obtains high melt strength, propylene through screw extruder extruding pelletization；
The grafting catalysts are cobalt acetate, Dibutyltin oxide, mass ratio 1:1；
The coupling agent is vinyltriethoxysilane；
The antioxidant is one of antioxidant 1010, antioxidant 1076, antioxidant 264；
The hydroxylating graphene, buys, single layer content 80%, thickness 0.6-1.2nm to be originated from market, and lamella diameter is less than
300nm, hydroxy radical content 4wt%, black powder.
The temperature setting of the screw extruder be area's temperature be 185 DEG C, two area's temperature are 190 DEG C, three area's temperature 195
DEG C, four area's temperature be 200 DEG C, five area's temperature are 200 DEG C, six area's temperature are 195 DEG C, screw speed 400rpm is melted
It squeezes out, high fondant-strength PP resin is prepared in cooling and dicing.
Graphene/PP composite material carries out melting crosslinking, while stone under action of coupling agents in screw extruder
Graft reaction occurs for black alkene/PP composite material and hydroxylating graphene, realizes that hydroxylating graphene is grafted to graphene/poly-
On acrylic composite, the modified high fondant-strength PP of graphene is prepared；
Above-mentioned graft reaction is that esterification occurs for the carboxyl contained using graphene oxide and hydroxylating graphene, and realization connects
Branch.
The index for the high fondant-strength PP being prepared are as follows: melt strength 45cN；Tensile strength is 65MPa, bending die
Amount is 1850MPa, notch impact strength 30kJ/m2, the content of graphene is 10.5%.
Comparative example 1: using the preparation method of embodiment 1, change place are as follows: be added without in step (4) hydroxylating graphene,
Grafting catalysts；The index of the high fondant-strength PP of preparation are as follows:
Melt strength is 35cN；Tensile strength is 50MPa, bending modulus 1700MPa, notch impact strength 22kJ/m2。
Comparative example 2: the polymerization of propylene is carried out only with above-mentioned steps (3), polypropylene is prepared, obtains 600g poly- third
Alkene.
Testing index are as follows: melt strength 3.5cN；Melt index is 3.5g/10min, tensile strength 31MPa, bending
Modulus is 900MPa, 7 kJ/m of notch impact strength2。
Unless specifically indicated, the ratio that the present invention uses is mass ratio, and the percentage of use is mass percent.
Finally, it should be noted that the foregoing is only a preferred embodiment of the present invention, it is not intended to restrict the invention,
Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features.
All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in of the invention
Within protection scope.
Claims (10)
1. a kind of high fondant-strength PP resin, feature are being: the content of graphene is 9.5-10.5%, melt strength 45-
48cN。
2. a kind of high fondant-strength PP resin according to claim 1, feature are being: the high fondant-strength PP tree
Rouge, tensile strength 65-70MPa, bending modulus 1850-1900MPa, notch impact strength 30-35 kJ/m2。
3. a kind of preparation process of high fondant-strength PP resin, it is characterised in that: the preparation process, including
Prepare single-layer graphene oxide, surface modification, copolymerization, cross-linked graft.
4. a kind of preparation process of high fondant-strength PP resin according to claim 3, it is characterised in that: the surface changes
Property, by single-layer graphene oxide, dodecyl trimethyl ammonium chloride is added, in n-hexane, carries out ultrasonic treatment 10-15min, surpass
Acoustic frequency is 15-18KHz, obtains modified graphene oxide dispersion.
5. a kind of preparation process of high fondant-strength PP resin according to claim 4, it is characterised in that:
The mass volume ratio of the single-layer graphene oxide and dodecyl trimethyl ammonium chloride are as follows: 1g:3-3.6ml；Described ten
The volume ratio of dialkyl group trimethyl ammonium chloride and n-hexane are as follows: 1:4.3-5.
6. a kind of preparation process of high fondant-strength PP resin according to claim 3, it is characterised in that: the copolymerization,
Modified graphene oxide dispersion, propylene liquid are mixed, stirred evenly, Ziegler-Natta catalyst is added, helps and urges
Agent, dimethoxydiphenylsilane obtain graphene/polyacrylic polymer in 60-65 DEG C of polymerization 40-50min.
7. a kind of preparation process of high fondant-strength PP resin according to claim 6, it is characterised in that:
The co-catalyst is cobalt acetate, graphene oxide and propylene liquid in the modified graphene oxide dispersion
Mass ratio are as follows: 3.05-3.25:100；The catalyst accounts for the mass percent of propylene liquid are as follows: 0.004-0.0045%；Institute
Stating co-catalyst and accounting for the mass percent of propylene liquid is 0.002-0.003%；The dimethoxydiphenylsilane and propylene liquid
The volume mass ratio of body are as follows: 0.2-0.25ml:1kg.
8. a kind of preparation process of high fondant-strength PP resin according to claim 3, it is characterised in that: the crosslinking connects
Branch, 100 parts of graphene/PP composite materials, 0.2 part of grafting catalysts, 6-7 parts of hydroxylating graphenes, 1 part of coupling agent, 2 parts
Antioxidant obtains high melt strength, propylene through screw extruder extruding pelletization.
9. a kind of preparation process of high fondant-strength PP resin according to claim 8, it is characterised in that:
The grafting catalysts are cobalt acetate, Dibutyltin oxide, mass ratio 1:1；
The coupling agent is vinyltriethoxysilane；
The antioxidant is one of antioxidant 1010, antioxidant 1076, antioxidant 264；
The hydroxylating graphene, single layer content 80%, thickness 0.6-1.2nm, lamella diameter are less than 300nm, and hydroxy radical content is
4wt%, black powder.
10. a kind of preparation process of high fondant-strength PP resin according to claim 8, it is characterised in that: the screw rod
The temperature setting of extruder be area's temperature be 180-185 DEG C, two area's temperature are 185-190 DEG C, three 190-195 DEG C of area's temperature,
Four area's temperature are 195-200 DEG C, five area's temperature are 195-200 DEG C, six area's temperature are 190-195 DEG C, screw speed 300-
400rpm, carries out melting extrusion, and high fondant-strength PP resin is prepared in cooling and dicing.
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| CN201910393474.XA CN110305401A (en) | 2019-05-13 | 2019-05-13 | A kind of high fondant-strength PP resin and its preparation process |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111423541A (en) * | 2020-04-15 | 2020-07-17 | 中化石化销售有限公司 | High-melt-strength polypropylene and preparation method thereof |
| CN113372653A (en) * | 2021-08-03 | 2021-09-10 | 苏州度辰新材料有限公司 | Stiffness-increasing master batch for BOPP film, preparation method of stiffness-increasing master batch and BOPP film |
-
2019
- 2019-05-13 CN CN201910393474.XA patent/CN110305401A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111423541A (en) * | 2020-04-15 | 2020-07-17 | 中化石化销售有限公司 | High-melt-strength polypropylene and preparation method thereof |
| CN113372653A (en) * | 2021-08-03 | 2021-09-10 | 苏州度辰新材料有限公司 | Stiffness-increasing master batch for BOPP film, preparation method of stiffness-increasing master batch and BOPP film |
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