CN106519123A - High-impact polypropylene grafted polymer and preparation method thereof - Google Patents
High-impact polypropylene grafted polymer and preparation method thereof Download PDFInfo
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- CN106519123A CN106519123A CN201610850445.8A CN201610850445A CN106519123A CN 106519123 A CN106519123 A CN 106519123A CN 201610850445 A CN201610850445 A CN 201610850445A CN 106519123 A CN106519123 A CN 106519123A
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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
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
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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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
Abstract
A high-impact polypropylene grafted polymer and a preparation method thereof belong to the technical field of high polymer materials. The invention is characterized in that the high-impact polypropylene grafted polymer contains a cross-linked rubber phase structure. The polypropylene grafted polymer with the structure has high impact strength, and tensile strength of raw material can be maintained. The polymer is prepared through a water-phase suspension grafting technology. In the grafting reaction, a cross-linking monomer and a grafting monomer undergo a crosslinking copolymerization reaction on a polypropylene matrix, and a formed crosslinked copolymer is used as a ''rubber phase'' to be dispersed in the polypropylene matrix. When external force is applied on the grafted polymer, the crosslinked copolymer absorbs energy, and impact resistance of the polypropylene grafted polymer is enhanced. The method is simple to operate; reaction temperature is low; the product is not easy to degrade; and no organic solvent is used (there is no pollution of volatile organic compounds). Impact resistance of the polypropylene grafted polymer prepared by the technology is remarkably enhanced, and tensile strength remains unchanged or decrease range is small.
Description
Technical field
The invention belongs to technical field of polymer materials, more particularly to a kind of high impact resistance polypropylene graft polymers and its system
Preparation Method.
Background technology
Polypropylene is by the hemicrystalline thermoplastic of propylene polymerization, because steady with good mechanical property, heat
Qualitative, chemical stability and electrical insulating property and be widely used in the fields such as automobile, fiber, packaging and the consumer goods.However, polypropylene
Poor with the compatibility of polar substances, cementability, shortcoming fragile under low temperature limits its application.Therefore, people often utilize
Various physics and chemical method are modified process to polypropylene so as to meet different applications.Wherein, modification by copolymerization is to adopt
Effective catalyst carries out random copolymerization or block copolymerization in polypropylene backbone in the propylene polymerization stage, can be to a certain extent
To polypropylene modification, polyacrylic impact strength, toughness etc. is improved.Patent CN104558339A discloses a kind of impact polypropylene
Production method, carry out the homopolymerization or ethene of propylene and the copolyreaction of propylene in the presence of catalyst, by with
The synergy of catalyst, expands the scope of polymerization temperature, and catalyst can keep higher activity.Blending and modifying is poly- third
Macromolecular material (rubber, thermoplastic elastomer (TPE) etc.) is mixed in thiazolinyl body, and the performance for having several macromolecular materials concurrently is obtained with this
Or the material of certain outstanding properties, blending and modifying can improve polyacrylic black brittleness, the transparency, antistatic behaviour and coloring
Property.Patent CN105566770A discloses a kind of shock resistance high-transparency polypropylene composition and preparation method thereof, using high-speed stirring
Mix machine and polypropylene, polyolefin elastomer, metallocene linear low density polyethylene etc. be well mixed into Jing double-screw extruding pelletizings again,
Shock resistance high-transparency polypropylene composition is obtained, but this method is difficult for elastomer polypropylene matrix to be dispersed in micro-meter scale
In, and rubber toughening polypropylene normally results in the tensile strength reduction of modified polypropene.
Graft modification is the conventional method of polypropylene modification, including solwution method, fusion method, solid phase method and suspension method etc..It is molten
Liquid graft reaction accessory substance is few, and percent grafting is of a relatively high, degradation of polypropylene low degree, but needs using a large amount of organic solvents, easily
Environmental pollution is caused, production cost is high, industrial seldom to adopt.Melting graft reaction is simple to operate, solvent-free recovery, produces into
This is low, is capable of achieving the continuous production of industrialization, but reaction temperature is high, and degradation of polypropylene degree is big, and course of reaction is difficult to control to, grafting
Rate is low, and the unreacted monomer of residual is difficult to remove.Solid state shear pulrerizing mild condition, post processing are simple, degradation of polypropylene degree
Low, using less solvent as interfacial agents, but it is intermittent reaction, and efficiency is low, and the reaction time is longer, is grafted uneven.Suspend
Graft reaction is simple to operate, and reaction temperature is low, and percent grafting is high, and degradation of polypropylene low degree, reaction are easily controlled, and product is easy
Separate, organic solvent-free is reclaimed, and is a kind of graft-modification method for having very much development potentiality.
Suspension Graft is increasingly subject to people's attention as a kind of simple gentle grafting method, patent
CN1884326A discloses a kind of porous polypropylene Suspension Graft method of modifying, using saline solution as suspension media, can
To improve percent grafting, depolymerization is reduced, while the compatilizer that graft product can be blended with other polymers as polypropylene,
Improve the compatibility of two-phase, improve composite materials property, but salt solution is corrosive to hardware.Patent
CN101492517A discloses a kind of preparation method of polypropylene graft polymer, does not use solvent, interface in implementation process
Agent or suspension media, grafted monomers conversion ratio is up to 95%, and at least 55% monomer has been grafted on polypropylene, and graft product can
Improve the dispersiveness and compatibility of polyolefin and inorganic filler.Li Zhuo etc. is in " A facile method to prepare
polypropylene/poly(butyl acrylate)alloy via water–solid phase suspension
Have studied in grafting polymerization " (Chin.Chem.Lett, 2015,26,1351-1354.) polypropylene grafted
The polymerisation of butyl acrylate, from triethylene glycol diacrylate as crosslinking agent, can significantly improve butyl acrylate
Percent grafting, but undeclared can improve polyacrylic toughness.
For reactor granules technology polypropylene, it is proposed by Basell companies, is passed through the polypropylene that the present invention is adopted
Control olefinic monomer is polymerized in porous spherical catalyst carrier growth, obtains the polymer beads of spherical, porous.This tool
The spherical PP GRANULES for having loose structure as microreactor, can carry out the copolyreaction of monomer.
The polypropylene graft polymer obtained by graft-modification method is essentially acted as polypropylene and polar polymer, nothing
The compatilizer of the composites such as machine filler.But the present invention adopts aqueous-phase suspending graft-modification method, on porous polypropylene surface and
Micropore internal graft crosslinking net copolymer improves polyacrylic toughness as " rubber phase ".
The content of the invention
The invention provides a kind of high impact resistance polypropylene graft polymers and preparation method thereof, the polypropylene graft polymer
Containing crosslinking " rubber phase " structure, impact strength is high.Yet another advantage of the present invention is that graft reaction is in polypropylene primary particle
Between restricted clearance in carry out, graft product Jing double screw extruder or torque rheometer mixing after, as the friendship of " rubber phase "
Ally the communists polymers can with micron or submicron-scale it is good be dispersed in (the mechanical blending of polypropylene and rubber in polypropylene matrix
It is extremely difficult to the rubber phase dispersion size of micro-meter scale), so as to realize the purpose of tenacity-increased profax.
Realize technical scheme：A kind of high impact resistance polypropylene graft polymers and preparation method thereof, mainly includes
Following steps：In terms of parts by weight, the initiator of 0.05-0.3 parts is dissolved in the grafted monomers of 5-30 parts and the friendship of 0.5-10 parts
Receipts or other documents in duplicate body is configured to mixed solution.100 parts of porous polypropylene raw materials are added, is shaken up, stand a period of time, it is ensured that monomer and initiation
The mixed solution of agent is to polyacrylic infiltration.Deionized water is added in reaction vessel as suspension, and is filled with inert gas.
60-70 DEG C of reaction 2-4h is first warming up to, the abundant swells polypropylene of grafted monomers is made, continues to be warmed up to 80-95 DEG C of reaction 2-8h.Instead
After the completion of answering, suction filtration is carried out with ethanol to graft product, remove unreacted monomer, obtain polypropylene graft polymer.Add
To in polypropylene graft polymer, Jing double screw extruders or torque rheometer mix antioxidant, make to be grafted on polypropylene matrix
On cross-linked copolymer be uniformly dispersed, so as to obtain the polypropylene graft polymer of high tenacity.
Further, the polypropylene is reactor granules technology polypropylene, and it is the direct growth globulate in reactor
, the PP GRANULES of porous can provide place for graft reaction, and its parts by weight is 100 parts.
Grafted monomers (monofunctional monomer) be methyl methacrylate, GMA, propylene
Acid butyl ester, hydroxyethyl methacrylate, butyl methacrylate, one or more in hydroxy propyl methacrylate, its weight
Number is 5-30 parts；Cross-linking monomer (polyfunctional monomer) be acroleic acid esterification castor oil, diethylene glycol diacrylate, poly- third
Diol dimethacrylate, diallyl maleate, one or more in trimethylolpropane trimethacrylate, its weight
Number is 0.5-10 parts.
The initiator be benzoyl peroxide, dilauroyl peroxide, peroxidized t-butyl perbenzoate, peroxidating trimethylacetic acid
One or more in the tert-butyl ester, its parts by weight are 0.05-0.3 parts.Benzoyl peroxide, benzoyl peroxide are preferably wherein
Formyl is preferentially captured the hydrogen atom on polypropylene macromolecular chain by the primary group of free radicals that thermal decomposition is produced, and generates macromolecular chain freedom
Base, can improve grafting efficiency.
The antioxidant be antioxidant 1010, antioxidant 1076, one or more in irgasfos 168.
Before water is not added as suspension media, a period of time is stood, it is ensured that the mixed liquor of monomer and initiator is to polypropylene
The infiltration (absorption of the reactant liquor inside polypropylene particles) of particulate.During reaction, first design temperature is 60-70 DEG C of reaction 2-4h,
Control decomposition of initiator produces the speed of primary group of free radicals, and then controls the speed that monomer occurs graft reaction on polypropylene,
Monomer is realized to polyacrylic fully swelling, so as to improve percent grafting；It is continuously heating to 80-95 DEG C of reaction 2-8h.Reaction is completed
Afterwards, unreacted monomer is eluted with ethanol or acetone, suction filtration, remove unreacted grafted monomers, obtain polypropylene grafted poly-
Compound.The polypropylene graft polymer that obtains of reaction is mixed in double screw extruder or torque rheometer, makes to be grafted on poly-
Cross-linked copolymer on propylene can be good be dispersed in polypropylene matrix.
The present invention relates to the preparating mechanism of Graft Polypropylene is initiator is decomposed into primary group of free radicals at a certain temperature,
Take hydrogen on polypropylene macromolecular chain by force, form macromolecular radical, so as to the grafting for causing single functionality, polyfunctional monomer gathers
Reaction is closed, grafted chain is formed in polypropylene backbone, due to the addition of polyfunctional monomer, grafted chain is cross-linked structure,
Therefore obtain the polypropylene graft polymer with cross-linked structure.Graft modification is connect with porous polypropylene particle as reacting environment
Branch reaction is carried out in the restricted clearance that polypropylene primary particle is formed, and the phase size of gained copolymer is micron or sub-micro meter ruler
Degree, therefore the size of dispersion phase (" rubber phase " in graft polymers) is micron or submicron-scale.It is common rubber toughened
Polyacrylic extrusion, Blending Processes do not reach so uniform degree of scatter.The present invention can pass through to adjust different monomers addition,
Different monomers ratio and different initiator amounts obtain the graft polymers of different crosslinking degrees the carrying out for controlling to react.
Beneficial effects of the present invention：Using aqueous-phase suspending graft-modification method, the graft crosslinking copolymer on polypropylene is fitted
The crosslinking of degree can make polypropylene graft polymer form space net structure.When polypropylene graft polymer is acted on by external force
When, network structure is conducive to energy absorption, shock resistance to be improved.Wherein, the impact strength of pp material is 2-
4kJ/m2, tensile strength is 37-44MPa, and the impact strength of obtained polypropylene graft polymer is 4-10kJ/m2, tensile strength
For 29-41MPa.The polypropylene graft polymer tensile strength prepared by the method is basically unchanged or reduction amplitude is less, and
Impact strength has significant raising.
Description of the drawings
Fig. 1 is polypropylene (PP) and polypropylene grafted butyl acrylate (BA)/acroleic acid esterification castor oil (ACO) polymer
Infrared spectrum.The infrared spectrum of contrast polypropylene and polypropylene graft polymer, it can be seen that graft polymers exists
There is the characteristic absorption peak of obvious ester carbonyl group at 1734cm-1, illustrate that monomer has successfully been grafted on polypropylene.
Wherein (a) GP=0% (pure PP)；(b) GP=9.1%；(c) GP=13.9%；(d) GP=18.4%
Wherein：The weight of GP (percent grafting)=(weight of the weight-virgin pp of graft product after extracting)/virgin pp
Amount.
Fig. 2 be different monomers addition to polypropylene grafted butyl acrylate/acroleic acid esterification castor oil polymers stretching,
The impact of impact strength.With butyl acrylate, the increase of acroleic acid esterification castor-oil plant oil content, the tensile strength of graft polymers
There is reduction slightly then to tend towards stability, impact strength is in rising trend, and ascensional range is larger, polypropylene prepared by this explanation
Graft polymers toughness while some strength is kept has significant raising.
Specific embodiment
Embodiment 1
0.2g benzoyl peroxides are dissolved in 16.0g butyl acrylates and 4.0g acroleic acid esterification castor oil, are added
100g polypropylene, shakes up, and stands 10h, monomer is fully adsorbed on polypropylene, adds deionized water as suspension media, fill
Enter the air that argon gas is excluded in reaction vessel, closed reaction vessel is positioned over into heating stirring in oil bath pan.Initial reaction stage temperature
Spend for 70 DEG C, react 2h, then be warming up to 90 DEG C, react 2h.Suction filtration is carried out to product with ethanol, unreacted list is washed away
Body, obtains 116.91g graft products.Take 3.1222g graft products and use acetone extraction 24h in Soxhlet extractor, then dry,
Product residuals weight 3.0980g.It is computed, product graft rate is 16.0%, grafting efficiency is 94.6%.At 230 DEG C, 2.16kg
Under the conditions of measure graft product melt index 3.24g/10min.Take 100g graft products add 0.2g antioxidant 1010 and
The irgasfos 168 of 0.1g, kneads 20min in torque rheometer, is well mixed graft product.By the graft product after mixing
Stretching, impact batten is molded into, and its stretching, impact strength is tested respectively according to the standard of ISO527, ISO178.Measure stretching strong
Spend for 34.42MPa, impact strength is 6.57kJ/m2。
Embodiment 2
0.3g benzoyl peroxides are dissolved in 14.0g butyl acrylates and 6.0g acroleic acid esterification castor oil, are added
100g polypropylene, shakes up, and stands 10h, monomer is fully adsorbed on polypropylene, adds deionized water as suspension media, fill
Enter the air that argon gas is excluded in reaction vessel, closed reaction vessel is positioned over into heating stirring in oil bath pan.Initial reaction stage temperature
Spend for 70 DEG C, react 2h, then be warming up to 90 DEG C, react 6h.Suction filtration is carried out to product with ethanol, unreacted list is washed away
Body, obtains 115.60g graft products.Take 3.1276g graft products and use acetone extraction 24h in Soxhlet extractor, then dry,
Product residuals weight 3.1144g.It is computed, product graft rate is 15.1%, grafting efficiency is 96.9%.At 230 DEG C, 2.16kg
Under the conditions of measure graft product melt index 1.83g/10min.Take 100g graft products add 0.2g antioxidant 1010 and
The irgasfos 168 of 0.1g, kneads 20min in torque rheometer, is well mixed graft product.By the graft product after mixing
Stretching, impact batten is molded into, and its stretching, impact strength is tested respectively according to the standard of ISO527, ISO178.Measure stretching strong
Spend for 33.15MPa, impact strength is 7.16kJ/m2。
Embodiment 3
0.2g benzoyl peroxides are dissolved in 10.0g butyl acrylates and 10.0g acroleic acid esterification castor oil, are added
100g polypropylene, shakes up, and stands 10h, monomer is fully adsorbed on polypropylene, adds deionized water as suspension media, fill
Enter the air that argon gas is excluded in reaction vessel, closed reaction vessel is positioned over into heating stirring in oil bath pan.Initial reaction stage temperature
Spend for 60 DEG C, react 4h, then be warming up to 80 DEG C, react 8h.Suction filtration is carried out to product with ethanol, unreacted list is washed away
Body, obtains 110.62g graft products.Take 3.1907g graft products and use acetone extraction 24h in Soxhlet extractor, then dry,
Product residuals weight 3.1701g.It is computed, product graft rate is 9.9%, grafting efficiency is 93.3%.At 230 DEG C, 2.16kg
Under the conditions of measure graft product melt index 0.75g/10min.Take 100g graft products add 0.2g antioxidant 1010 and
The irgasfos 168 of 0.1g, kneads 20min in torque rheometer, is well mixed graft product.By the graft product after mixing
Stretching, impact batten is molded into, and its stretching, impact strength is tested respectively according to the standard of ISO527, ISO178.Measure stretching strong
Spend for 31.87MPa, impact strength is 8.33kJ/m2。
Embodiment 4
0.3g benzoyl peroxides are dissolved in 30.0g butyl acrylates and 3.0g polypropylene glycol dimethacrylates,
100g polypropylene is added, is shaken up, stand 10h, monomer is fully adsorbed on polypropylene, add deionized water to be situated between as suspending
Matter, is filled with the air that argon gas is excluded in reaction vessel, closed reaction vessel is positioned over heating stirring in oil bath pan.Reaction is just
Phase temperature is 60 DEG C, reacts 4h, then is warming up to 80 DEG C, reacts 8h.Suction filtration is carried out to product with ethanol, is washed away unreacted
Monomer, obtains 128.99g graft products.Take 4.0866g graft products and use acetone extraction 24h in Soxhlet extractor, then dry
It is dry, product residuals weight 4.0619g.It is computed, product graft rate is 28.2%, grafting efficiency is 97.3%.At 230 DEG C,
Graft product melt index 1.95g/10min is measured under the conditions of 2.16kg.Take the antioxidant that 100g graft products add 0.3g
1010 and 0.1g irgasfos 168, kneads 20min in torque rheometer, is well mixed graft product.Connecing after by mixing
Branch product is molded into stretching, impact batten, tests its stretching, impact strength respectively according to the standard of ISO527, ISO178.Measure
Tensile strength is 32.51MPa, and impact strength is 4.33kJ/m2。
Embodiment 5
0.2g benzoyl peroxides are dissolved in 16.0g butyl acrylates and 4.0g polypropylene glycol dimethacrylates,
100g polypropylene is added, is shaken up, stand 10h, monomer is fully adsorbed on polypropylene, add deionized water to be situated between as suspending
Matter, is filled with the air that argon gas is excluded in reaction vessel, closed reaction vessel is positioned over heating stirring in oil bath pan.Reaction is just
Phase temperature is 65 DEG C, reacts 2h, then is warming up to 95 DEG C, reacts 4h.Suction filtration is carried out to product with ethanol, is washed away unreacted
Monomer, obtains 118.81g graft products.Take 4.0632g graft products and use acetone extraction 24h in Soxhlet extractor, then dry
It is dry, product residuals weight 4.0361g.It is computed, product graft rate is 18.0%, grafting efficiency is 95.8%.At 230 DEG C,
Graft product melt index 1.83g/10min is measured under the conditions of 2.16kg.Take the antioxidant that 100g graft products add 0.3g
1010 and 0.1g irgasfos 168, kneads 20min in torque rheometer, is well mixed graft product.Connecing after by mixing
Branch product is molded into stretching, impact batten, tests its stretching, impact strength respectively according to the standard of ISO527, ISO178.Measure
Tensile strength is 33.58MPa, and impact strength is 5.04kJ/m2。
Embodiment 6
0.3g benzoyl peroxides are dissolved in 20.0g butyl acrylates, 100g polypropylene are added, is shaken up, stand 10h,
Monomer is fully adsorbed on polypropylene, add deionized water as suspension media, be filled with argon gas and exclude the sky in reaction vessel
Closed reaction vessel is positioned over heating stirring in oil bath pan by gas.Reaction temperature is set to 95 DEG C, and the reaction time is 6h, uses
Ethanol carries out suction filtration to product, washes away unreacted monomer, obtains 118.78g graft products.Take 4.0894g graft products
Acetone extraction 24h is used in Soxhlet extractor, is then dried, product residuals weight 4.0588g.It is computed, product graft rate is
17.9%, grafting efficiency is 95.3%.At 230 DEG C, graft product melt index 2.47g/10min under the conditions of 2.16kg, is measured.
The irgasfos 168 that 100g graft products add the antioxidant 1010 and 0.2g of 0.2g is taken, 20min is kneaded in torque rheometer,
It is well mixed graft product.Graft product after mixing is molded into into stretching, impact batten, according to ISO527, ISO178
Standard tests its stretching, impact strength respectively.It is 30.85MPa to measure tensile strength, and impact strength is 4.76kJ/m2。
Embodiment 7
0.3g benzoyl peroxides are dissolved in 20.0g butyl acrylates, 100g polypropylene are added, is shaken up, stand 10h,
Monomer is fully adsorbed on polypropylene, add deionized water as suspension media, be filled with argon gas and exclude the sky in reaction vessel
Closed reaction vessel is positioned over heating stirring in oil bath pan by gas.Initial reaction stage temperature setting is 65 DEG C, reacts 2h, then rises
Temperature reacts 6h to 95 DEG C.Suction filtration is carried out to product with ethanol, unreacted monomer is washed away, 119.42g grafting is obtained and is produced
Thing.Take 4.1160g graft products and use acetone extraction 24h in Soxhlet extractor, then dry, product residuals weight 4.1031g.
It is computed, product graft rate is 19.0%, grafting efficiency is 98.1%.At 230 DEG C, graft product is measured under the conditions of 2.16kg and is melted
Melt index 2.29g/10min.The irgasfos 168 that 100g graft products add the antioxidant 1010 and 0.2g of 0.2g is taken, in torque
20min is kneaded in flow graph, is well mixed graft product.Graft product after mixing is molded into into stretching, impact batten, is pressed
Its stretching, impact strength is tested respectively according to the standard of ISO527, ISO178.Tensile strength is measured for 30.12MPa, impact strength
For 4.98kJ/m2。
Embodiment 8
0.05g benzoyl peroxides are dissolved in 4.50g butyl acrylates and 0.50g acroleic acid esterification castor oil, then plus
Enter 100g polypropylene, shake up, stand 10h, monomer is fully adsorbed on polypropylene matrix, add deionized water to be situated between as suspending
Matter, is filled with the air that argon gas is excluded in reaction vessel, closed reaction vessel is positioned over heating stirring in oil bath pan.Reaction is just
Phase temperature is 65 DEG C, reacts 4h, then is warming up to 90 DEG C, reacts 4h.Suction filtration is carried out to product with ethanol, is washed away unreacted
Monomer, obtains 104.24g graft products.Take 4.4271g graft products and use acetone extraction 24h in Soxhlet extractor, then dry
Dry, product residuals weight is 4.4215g.It is computed, the percent grafting of reaction is 4.1%, and grafting efficiency is 96.9%.At 230 DEG C,
Graft product melt index 7.86g/10min is measured under the conditions of 2.16kg.Take the antioxidant that 100g graft products add 0.2g
1010 and 0.1g irgasfos 168, kneads 20min in torque rheometer, is well mixed graft product.Connecing after by mixing
Branch product is molded into stretching, impact batten, tests its stretching, impact strength respectively according to the standard of ISO527, ISO178.Measure
Tensile strength is 35.00MPa, and impact strength is 3.81kJ/m2。
Embodiment 9
0.10g benzoyl peroxides are dissolved in 9.00g butyl acrylates and 1.00g acroleic acid esterification castor oil, then plus
Enter 100g polypropylene, shake up, stand 10h, monomer is fully adsorbed on polypropylene, deionized water is added as suspension media,
The air that argon gas is excluded in reaction vessel is filled with, closed reaction vessel is positioned over into heating stirring in oil bath pan.Initial reaction stage
Temperature is 65 DEG C, reacts 4h, then is warming up to 90 DEG C, reacts 4h.Suction filtration is carried out to product with ethanol, unreacted list is washed away
Body, obtains 109.38g graft products.Take 4.6968g graft products and use acetone extraction 24h in Soxhlet extractor, then dry,
Product residuals weight 4.6868g.It is computed, the percent grafting of reaction is 9.1%, and grafting efficiency is 97.5%.At 230 DEG C,
Graft product melt index 5.92g/10min is measured under the conditions of 2.16kg.Take the antioxidant that 100g graft products add 0.2g
1010 and 0.1g irgasfos 168, kneads 20min in torque rheometer, is well mixed graft product.Connecing after by mixing
Branch product is molded into stretching, impact batten, tests its stretching, impact strength respectively according to the standard of ISO527, ISO178.Measure
Tensile strength is 31.86MPa, and impact strength is 4.03kJ/m2。
Embodiment 10
0.15g benzoyl peroxides are dissolved in 13.50g butyl acrylates and 1.50g acroleic acid esterification castor oil, then plus
Enter 100g polypropylene, shake up, stand 10h, monomer is fully adsorbed on polypropylene, deionized water is added as suspension media,
The air that argon gas is excluded in reaction vessel is filled with, closed reaction vessel is positioned over into heating stirring in oil bath pan.Initial reaction stage
Temperature is 65 DEG C, reacts 4h, then is warming up to 90 DEG C, reacts 4h.Suction filtration is carried out to product with ethanol, unreacted list is washed away
Body, obtains 114.26g graft products.Take 4.4271g graft products and use acetone extraction 24h in Soxhlet extractor, then dry,
Product residuals weight 4.4215g.It is computed, the percent grafting of reaction is 13.9%, and grafting efficiency is 97.6%.At 230 DEG C,
Graft product melt index 4.69g/10min is measured under the conditions of 2.16kg.Take the antioxidant that 100g graft products add 0.2g
1010 and 0.1g irgasfos 168, kneads 20min in torque rheometer, is well mixed graft product.Connecing after by mixing
Branch product is molded into stretching, impact batten, tests its stretching, impact strength respectively according to the standard of ISO527, ISO178.Measure
Tensile strength is 30.08MPa, and impact strength is 6.41kJ/m2。
Embodiment 11
0.20g benzoyl peroxides are dissolved in 18.00g butyl acrylates and 2.00g acroleic acid esterification castor oil, then plus
Enter 100g polypropylene, shake up, stand 10h, monomer is fully adsorbed on polypropylene, deionized water is added as suspension media,
The air that argon gas is excluded in reaction vessel is filled with, closed reaction vessel is positioned over into heating stirring in oil bath pan.Initial reaction stage
Temperature is 65 DEG C, reacts 4h, then is warming up to 90 DEG C, reacts 4h.Suction filtration is carried out to product with ethanol, unreacted list is washed away
Body, obtains 118.83g graft products.Take 4.5252g graft products and use acetone extraction 24h in Soxhlet extractor, then dry,
Product residuals weight 4.5100g.It is computed, the percent grafting of reaction is 18.4%, and grafting efficiency is 97.9%.At 230 DEG C,
Graft product melt index 2.82g/10min is measured under the conditions of 2.16kg.Take the antioxidant that 100g graft products add 0.2g
1010 and 0.1g irgasfos 168, kneads 20min in torque rheometer, is well mixed graft product.Connecing after by mixing
Branch product is molded into stretching, impact batten, tests its stretching, impact strength respectively according to the standard of ISO527, ISO178.Measure
Tensile strength is 29.54MPa, and impact strength is 8.98kJ/m2。
Embodiment 12
0.25g benzoyl peroxides are dissolved in 22.50g butyl acrylates and 2.50g acroleic acid esterification castor oil, then plus
Enter 100g polypropylene, shake up, stand 10h, monomer is fully adsorbed on polypropylene, deionized water is added as suspension media,
The air that argon gas is excluded in reaction vessel is filled with, closed reaction vessel is positioned over into heating stirring in oil bath pan.Initial reaction stage
Temperature is 65 DEG C, reacts 4h, then is warming up to 90 DEG C, reacts 4h.Suction filtration is carried out to product with ethanol, unreacted list is washed away
Body, obtains 118.59g graft products.Take 4.5672g graft products and use acetone extraction 24h in Soxhlet extractor, then dry,
Product residuals weight 4.5481g.It is computed, the percent grafting of reaction is 18.2%, and grafting efficiency is 98.0%.At 230 DEG C,
Graft product melt index 1.75g/10min is measured under the conditions of 2.16kg.Take the antioxidant that 100g graft products add 0.2g
1010 and 0.1g irgasfos 168, kneads 20min in torque rheometer, is well mixed graft product.Connecing after by mixing
Branch product is molded into stretching, impact batten, tests its stretching, impact strength respectively according to the standard of ISO527, ISO178.Measure
Tensile strength is 29.37MPa, and impact strength is 8.27kJ/m2。
Embodiment 13
0.10g benzoyl peroxides are dissolved in into 8.75g butyl acrylates and 1.25g polypropylene glycol dimethacrylates
In, 200g polypropylene is added, is shaken up, stand 10h, monomer is fully adsorbed on polypropylene, deionized water is added as suspension
Medium, is filled with the air that argon gas is excluded in reaction vessel, closed reaction vessel is positioned over heating stirring in oil bath pan.Reaction
Initial stage temperature is 65 DEG C, reacts 4h, then is warming up to 90 DEG C, reacts 4h.Suction filtration is carried out to product with ethanol, unreacted is washed away
Monomer, obtain 207.67g graft products.Take 4.0649g graft products and use acetone extraction 24h in Soxhlet extractor, then
Drying, product residuals weight 4.0546g.It is computed, the percent grafting of reaction is 3.6%, and grafting efficiency is 93.1%.At 230 DEG C,
Graft product melt index 2.52g/10min is measured under the conditions of 2.16kg.Take the antioxidant that 200g graft products add 0.3g
1010 and 0.2g irgasfos 168, Jing double screw extruder extrusion mixings.Graft product after extrusion is molded into into stretching, punching
Batten is hit, and its stretching, impact strength is tested respectively according to the standard of ISO527, ISO178.It is 40.37MPa to measure tensile strength,
Impact strength is 4.21kJ/m2。
Embodiment 14
0.20g benzoyl peroxides are dissolved in into 17.50g butyl acrylates and 2.50g polypropylene glycol dimethacrylates
In, 200g polypropylene is added, is shaken up, stand 10h, monomer is fully adsorbed on polypropylene, deionized water is added as suspension
Medium, is filled with the air that argon gas is excluded in reaction vessel, closed reaction vessel is positioned over heating stirring in oil bath pan.Reaction
Initial stage temperature is 65 DEG C, reacts 4h, then is warming up to 90 DEG C, reacts 4h.Suction filtration is carried out to product with ethanol, unreacted is washed away
Monomer, obtain 218.99g graft products.Take 4.0759g graft products and use acetone extraction 24h in Soxhlet extractor, then
Drying, product residuals weight 4.0612g.It is computed, the percent grafting of reaction is 9.1%, and grafting efficiency is 95.8%.At 230 DEG C,
Graft product melt index 2.12g/10min is measured under the conditions of 2.16kg.Take the antioxidant that 200g graft products add 0.3g
1010 and 0.2g irgasfos 168, Jing double screw extruder extrusion mixings.Graft product after extrusion is molded into into stretching, punching
Batten is hit, and its stretching, impact strength is tested respectively according to the standard of ISO527, ISO178.It is 39.23MPa to measure tensile strength,
Impact strength is 6.73kJ/m2。
Embodiment 15
0.30g benzoyl peroxides are dissolved in into 26.25g butyl acrylates and 3.75g polypropylene glycol dimethacrylates
In, 200g polypropylene is added, is shaken up, stand 10h, monomer is fully adsorbed on polypropylene, deionized water is added as suspension
Medium, is filled with the air that argon gas is excluded in reaction vessel, closed reaction vessel is positioned over heating stirring in oil bath pan.Reaction
Initial stage temperature is 65 DEG C, reacts 4h, then is warming up to 90 DEG C, reacts 4h.Suction filtration is carried out to product with ethanol, unreacted is washed away
Monomer, obtain 229.16g graft products.Take 4.1391g graft products and use acetone extraction 24h in Soxhlet extractor, then
Drying, product residuals weight 4.1198g.It is computed, the percent grafting of reaction is 14.1%, and grafting efficiency is 96.3%.230
DEG C, graft product melt index 2.00g/10min is measured under the conditions of 2.16kg.Take the antioxidant that 200g graft products add 0.3g
1010 and 0.2g irgasfos 168, Jing double screw extruder extrusion mixings.Graft product after extrusion is molded into into stretching, punching
Batten is hit, and its stretching, impact strength is tested respectively according to the standard of ISO527, ISO178.It is 33.23MPa to measure tensile strength,
Impact strength is 6.22kJ/m2。
Embodiment 16
0.40g benzoyl peroxides are dissolved in into 35.00g butyl acrylates and 5.00g polypropylene glycol dimethacrylates
In, 200g polypropylene is added, is shaken up, stand 10h, monomer is fully adsorbed on polypropylene, deionized water is added as suspension
Medium, is filled with the air that argon gas is excluded in reaction vessel, closed reaction vessel is positioned over heating stirring in oil bath pan.Reaction
Initial stage temperature is 65 DEG C, reacts 4h, then is warming up to 90 DEG C, reacts 4h.Suction filtration is carried out to product with ethanol, unreacted is washed away
Monomer, obtain 238.40g graft products.Take 4.1037g graft products and use acetone extraction 24h in Soxhlet extractor, then
Drying, product residuals weight 4.0808g.It is computed, the percent grafting of reaction is 18.5%, and grafting efficiency is 96.5%.230
DEG C, graft product melt index 1.97g/10min is measured under the conditions of 2.16kg.Take the antioxidant that 200g graft products add 0.3g
1010 and 0.2g irgasfos 168, Jing double screw extruder extrusion mixings.Graft product after extrusion is molded into into stretching, punching
Batten is hit, and its stretching, impact strength is tested respectively according to the standard of ISO527, ISO178.It is 29.05MPa to measure tensile strength,
Impact strength is 4.84kJ/m2。
Embodiment 17
0.50g benzoyl peroxides are dissolved in into 43.75g butyl acrylates and 6.25g polypropylene glycol dimethacrylates
In, 200g polypropylene is added, is shaken up, stand 10h, monomer is fully adsorbed on polypropylene, deionized water is added as suspension
Medium, is filled with the air that argon gas is excluded in reaction vessel, closed reaction vessel is positioned over heating stirring in oil bath pan.Reaction
Initial stage temperature is 65 DEG C, reacts 4h, then is warming up to 90 DEG C, reacts 4h.Suction filtration is carried out to product with ethanol, unreacted is washed away
Monomer, obtain 246.95g graft products.Take 4.0920g graft products and use acetone extraction 24h in Soxhlet extractor, then
Drying, product residuals weight 4.0615g.It is computed, the percent grafting of reaction is 22.6%, and grafting efficiency is 96.1%.230
DEG C, graft product melt index 1.91g/10min is measured under the conditions of 2.16kg.Take the antioxidant that 200g graft products add 0.3g
1010 and 0.2g irgasfos 168, Jing double screw extruder extrusion mixings.Graft product after extrusion is molded into into stretching, punching
Batten is hit, and its stretching, impact strength is tested respectively according to the standard of ISO527, ISO178.It is 32.40MPa to measure tensile strength,
Impact strength is 4.27kJ/m2。
Claims (5)
1. a kind of preparation method of high impact resistance polypropylene graft polymers, it is characterised in that：The polymer is connect by aqueous-phase suspending
Branch method of modifying is obtained, and in graft reaction, polypropylene, initiator, grafted monomers and cross-linking monomer is added to reaction vessel
In；Under conditions of heating, grafted monomers crosslink copolyreaction, the crosslinking of formation on polypropylene matrix with cross-linking monomer
Copolymer is dispersed in polypropylene matrix as " rubber phase "；The graft reaction, is maintained at 60-70 in initial reaction stage temperature
DEG C, 2-4h continues to heat up, and reaction temperature is 80-95 DEG C, and the reaction time is 2-8h.
2. preparation method according to claim 1, it is characterised in that：The grafted monomers are monofunctional monomers, and which is heavy
Amount number is calculated as 5-30 parts for 100 parts with polypropylene；Cross-linking monomer is polyfunctional monomer, and its parts by weight is with 100 parts of polypropylene
It is calculated as 0.5-10 parts.
3. preparation method according to claim 2, it is characterised in that：The monofunctional monomer is methyl methacrylate
Ester, GMA, butyl acrylate, hydroxyethyl methacrylate, butyl methacrylate, methacrylic acid
One or more in hydroxypropyl acrylate.
4. preparation method according to claim 2, it is characterised in that：The polyfunctional monomer is acroleic acid esterification castor-oil plant
Oil, diethylene glycol diacrylate, polypropylene glycol dimethacrylate, diallyl maleate, trimethylolpropane tris third
One or more in olefin(e) acid ester.
5. preparation method according to claim 1, it is characterised in that：The graft reaction, the initiator of addition is peroxide
Change benzoyl, dilauroyl peroxide, peroxidized t-butyl perbenzoate, one or more in the peroxidating trimethylacetic acid tert-butyl ester, its
Parts by weight are calculated as 0.05-0.3 parts for 100 parts with polypropylene.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109251463A (en) * | 2018-08-01 | 2019-01-22 | 江苏益帆高分子材料有限公司 | A kind of HDPE grafting diethylene glycol list acrylic ester copolymer and preparation method thereof |
| CN113563527A (en) * | 2020-04-29 | 2021-10-29 | 中国石油化工股份有限公司 | Graft modified polypropylene material and preparation method and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5660224A (en) * | 1979-10-24 | 1981-05-25 | Mitsubishi Petrochem Co Ltd | Stretched film |
| US4303757A (en) * | 1977-10-15 | 1981-12-01 | Sekisui Kaseihin Kogyo Kabushiki Kaisha | Process for producing expandable thermoplastic resin beads using polypropylene as nucleus |
| CN1613887A (en) * | 2003-11-06 | 2005-05-11 | 浙江工业大学 | Preparation of water phase suspended swelling graft polypropylene |
| CN1884326A (en) * | 2005-06-21 | 2006-12-27 | 北京化工大学 | Porous polypropylene particle suspension solid phase graft-modification method |
| CN1948356A (en) * | 2005-10-11 | 2007-04-18 | 中国科学技术大学 | Method of preparing maleic anhydride copolymer by polypropylene suspension solid phase grafting |
| CN102060961A (en) * | 2010-12-09 | 2011-05-18 | 南京工业大学 | Method for preparing high-density polyethylene-maleic anhydride grafted copolymer by adopting suspension method |
| CN105504171A (en) * | 2014-10-20 | 2016-04-20 | 中国石化扬子石油化工有限公司 | Polypropylene graft and preparation method thereof |
| CN106543369A (en) * | 2015-09-18 | 2017-03-29 | 中国石油化工股份有限公司 | A kind of method of propylene polymer graft polar monomer |
-
2016
- 2016-09-26 CN CN201610850445.8A patent/CN106519123A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4303757A (en) * | 1977-10-15 | 1981-12-01 | Sekisui Kaseihin Kogyo Kabushiki Kaisha | Process for producing expandable thermoplastic resin beads using polypropylene as nucleus |
| JPS5660224A (en) * | 1979-10-24 | 1981-05-25 | Mitsubishi Petrochem Co Ltd | Stretched film |
| CN1613887A (en) * | 2003-11-06 | 2005-05-11 | 浙江工业大学 | Preparation of water phase suspended swelling graft polypropylene |
| CN1884326A (en) * | 2005-06-21 | 2006-12-27 | 北京化工大学 | Porous polypropylene particle suspension solid phase graft-modification method |
| CN1948356A (en) * | 2005-10-11 | 2007-04-18 | 中国科学技术大学 | Method of preparing maleic anhydride copolymer by polypropylene suspension solid phase grafting |
| CN102060961A (en) * | 2010-12-09 | 2011-05-18 | 南京工业大学 | Method for preparing high-density polyethylene-maleic anhydride grafted copolymer by adopting suspension method |
| CN105504171A (en) * | 2014-10-20 | 2016-04-20 | 中国石化扬子石油化工有限公司 | Polypropylene graft and preparation method thereof |
| CN106543369A (en) * | 2015-09-18 | 2017-03-29 | 中国石油化工股份有限公司 | A kind of method of propylene polymer graft polar monomer |
Non-Patent Citations (2)
| Title |
|---|
| LI ZHUO，等: "A facile method to prepare polypropylene/poly(butyl acrylate) alloy via water-solid phase suspension grafting polymerization", 《CHINESE CHEMICAL LETTERS》 * |
| 李卓: "反应器颗粒技术聚丙烯接枝物制备、性能及应用的研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109251463A (en) * | 2018-08-01 | 2019-01-22 | 江苏益帆高分子材料有限公司 | A kind of HDPE grafting diethylene glycol list acrylic ester copolymer and preparation method thereof |
| CN113563527A (en) * | 2020-04-29 | 2021-10-29 | 中国石油化工股份有限公司 | Graft modified polypropylene material and preparation method and application thereof |
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