CN109553724A - A kind of high melt strength polypropylene material and preparation method thereof - Google Patents
A kind of high melt strength polypropylene material and preparation method thereof Download PDFInfo
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- CN109553724A CN109553724A CN201811434020.4A CN201811434020A CN109553724A CN 109553724 A CN109553724 A CN 109553724A CN 201811434020 A CN201811434020 A CN 201811434020A CN 109553724 A CN109553724 A CN 109553724A
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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
- C08F222/00—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 carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
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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
- C08F222/00—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 carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
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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
- C08F222/00—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 carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/104—Esters of polyhydric alcohols or polyhydric phenols of tetraalcohols, e.g. pentaerythritol tetra(meth)acrylate
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- Polymers & Plastics (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The present invention relates to field of high polymer material modification, a kind of high melt strength polypropylene material and preparation method thereof is particularly disclosed.Method includes the following steps: 100 parts of polypropylene powders, 2-30 parts of grafted monomers, 0.01-2 parts of initiators are uniformly mixed by (1)；(2) above-mentioned homogeneous material is reacted 1-2 hours at 110-140 DEG C, 0.5-1.5 parts of antioxidant is added after cooling and are granulated through extruder up to high melt strength, propylene.The present invention is by adjusting the ratio of polypropylene, grafted monomers, initiator, and prepared stable product quality, processing performance is excellent, is easy to industrialized production, can be applied to the fields such as blow molding, vacuum thermoforming, Extrusion Coating, foaming.
Description
(1) technical field
The present invention relates to field of high polymer material modification, in particular to a kind of high melt strength polypropylene material and its preparation
Method.
(2) background technique
Polypropylene has the characteristics that low-density, high-melting-point, source is wide, price is low and mechanical performance is superior, chemical stability is good,
It is widely used in packaging, light industry, building, electronics, electric appliance and automobile and other industries, is one of current fastest-rising resin.But often
Isotactic polypropylene is the semi-crystalline resins of linear structure, and molecular weight distribution relative narrower, softening point and fusing point are close, and melting range is shorter,
Thermoforming processing in show as when temperature be higher than fusing point after, melt viscosity sharply declines, under molten state stretching when there can be no
Strain hardening phenomenon, thermoformed articles wall unevenness poor so as to cause the sag resistant performance of polymer, Extrusion Coating, calendering when
The problems such as edge curl, contraction, abscess collapses when extrusion foaming.
To improve this problem, exploitation high melt strength, propylene seems particularly necessary.It is most that it is chain modified, which wherein to introduce branch,
One of common method, which can effectively reduce the growth of viscosity while improving melt strength, makes to polymerize
The processing performance of object still maintains good.
X ray irradiation x branched p 0 lypropylene technology is usually under conditions of inactive oxygen, using high-energy ray or the particle beams pair
Linear polypropylene radiates 2-30 minutes, and the auxiliary agents extruding pelletizations such as stabilizer are then added and obtain branched p 0 lypropylene, patent
US7019044, US5605936A, US6306970B1 etc. just belong to this kind of technology.But the implementation of this technology needs high set
Standby investment and stringent process regulation are restricted its application.
In the modified research for preparing high melt strength, propylene of extruding graft, generallys use organic peroxide and contain official
Compound (such as maleic acid anhydride, esters of acrylic acid, carboxylic acids) can be rolled into a ball to be modified polypropylene, it is therefore an objective to introduce long-chain branch
Structure, such as Chinese patent 200810050434.7, Chinese patent 200810061200.2.By type to initiator and its
The control of the conditions such as dosage, monomer dosage and technological parameter has obtained the long chain branching PP with higher melt intensity.Due to
Reactive extrursion is generally carried out in 175 DEG C or more of high temperature, thus easily causes polyacrylic serious and gelation problems of degrading, simultaneously
Since reaction time short polypropylene is often with decomposition of initiator object and monomer remnants problem.
(3) summary of the invention
That in order to compensate for the shortcomings of the prior art, the present invention provides a kind of monomer autohemagglutinations is few, grafting rate is high, stable product quality
High melt strength polypropylene material and preparation method thereof.
The present invention is achieved through the following technical solutions:
A kind of high melt strength polypropylene material, which is characterized in that be mixed by following parts by weight raw material: polypropylene powder
100 parts, 2-30 parts of grafted monomers, 0.01-2 parts of initiator, 0.5-1.5 parts of antioxidant.
The present invention occurs that free radical initiation grafting poly- third by adjusting the ratio of polypropylene, grafted monomers, initiator
In the surface of alkene powder and internal voids, reaction temperature is lower than extruding pelletization temperature, effectively prevents polypropylene at high temperature
It decomposes with side reactions such as crosslinkings, guarantees that polyacrylic weight average molecular weight is not present and be decreased obviously, while it is short to have evaded the reaction time
Initiator and monomer residue caused by and, this method is easy to implement, is easy to implement industrialization.
More excellent technical solution of the invention are as follows:
The polypropylene powder be linear homopolypropylene, copolymer polypropylene powder or with arbitrary proportion combine blending powder
Material, melt index 3-50g/10min.
The grafted monomers are one of the Monofunctional monomers containing carbon-carbon double bond and polyfunctional monomer or a variety of.
Wherein, the Monofunctional monomers include α-methylstyrene, styrene, methyl styrene, vinyl ethylo benzene etc., multifunctional
Single group body includes cyclopentadiene, divinylbenzene, multi-functional acrylate, such as pentaerythritol triacrylate, double methyl
Acrylic acid tetraethylene glycol ester or trimethylol-propane trimethacrylate etc..
The initiator is peroxide, mainly includes benzoyl peroxide, two tertiary amyl peroxide, 2,5- diformazan
Base -2,5- di-t-butyl peroxy -3- hexin, 2,5- dimethyl -2,5 di-t-butyl hexane peroxide, dilauroyl peroxide,
One of cumyl peroxide, peroxidized t-butyl perbenzoate, diacetyl peroxide, dioctanoyl peroxide are a variety of.
The antioxidant is Hinered phenols antioxidant or phosphite ester antioxidant, mainly includes 2,6- di-t-butyl -4-
Methylphenol, antioxidant 2246, antioxidant 1010, antioxidant 1076, bis- (2,6- di-t-butyl -4- aminomethyl phenyl) seasons penta
Tetrol bisphosphate, irgasfos 168 or antioxidant 626.
The preparation method of above-mentioned high melt strength polypropylene material, includes the following steps:
(1) it under nitrogen protection, after mixing by grafted monomers, initiator, is slowly added into polypropylene powder and stirs
20min；
(2) above-mentioned homogeneous material is reacted 1-2 hours at 110-140 DEG C, after being cooled to 50 DEG C once, with antioxidant through squeezing out
Machine is granulated, and obtains the polypropylene granules of high fondant-strength.
Present invention process step is simple, carries out at a lower temperature, reduces polyacrylic degradation and crosslinking, reduces simultaneously
The autohemagglutination of monomer improves grafting rate, and stable product quality, processing performance is excellent, while having excellent microwave adaptability, tool
There is the features such as good environmental effect and easy recyclability, has in fields such as thermoforming, Extrusion Coating, blow molding, foaming extensive
Using.
(4) specific embodiment
The invention will be further described combined with specific embodiments below, but application range of the invention is not only limited to these realities
Apply raw material involved in case and specific processing conditions.The polypropylene that following embodiment uses is by Shandong Yuhuang Chemical Industry Co., Ltd
It provides.
Embodiment 1:
A kind of high melt strength polypropylene material is obtained by following mass parts:
100 parts of polypropylene, 25 parts of styrene, 0.25 part of cumyl peroxide, 1 part of antioxidant 1010.
Uniformly mixed initiator, monomer are added in polypropylene under nitrogen protection, and stirred 20 minutes, monomer is made
It is sufficiently infiltrated into polypropylene with initiator.It is rapidly heated to reacting 2 hours at 125 DEG C, is cooled to mixed with antioxidant after room temperature
Close extruding pelletization.The polyacrylic melt strength of gained is 807PaS, melt index 3.5.
Embodiment 2:
A kind of high melt strength polypropylene material is obtained by following mass parts:
100 parts of polypropylene, 30 parts of styrene, 0.25 part of diacetyl peroxide, 1 part of antioxidant 1010.
The preparation method is the same as that of Example 1 for high melt strength polypropylene material, and the polyacrylic melt strength of gained is 951Pa
S, melt index 3.0.
Embodiment 3:
A kind of high melt strength polypropylene material is obtained by following mass parts:
100 parts of polypropylene, 5 parts of pentaerythritol triacrylate, 0.25 part of cumyl peroxide, resists 20 parts of styrene
1,010 1 parts of oxygen agent.
The preparation method is the same as that of Example 1 for high melt strength polypropylene material, and the polyacrylic melt strength of gained is
1172PaS, melt index 2.3.
Embodiment 4:
A kind of high melt strength polypropylene material is obtained by following mass parts:
100 parts of polypropylene, 20 parts of styrene, 5 parts of methacrylate tetraethylene glycol ester, 0.1 part of cumyl peroxide,
0.25 part of diacetyl peroxide, 1 part of antioxidant 1010.
The preparation method is the same as that of Example 1 for high melt strength polypropylene material, and the polyacrylic melt strength of gained is
1028PaS, melt index 2.5.
Embodiment 5:
A kind of high melt strength polypropylene material is obtained by following mass parts:
100 parts of polypropylene, 15 parts of styrene, 5 parts of pentaerythritol triacrylate, methacrylate tetraethylene glycol ester
2.5 parts, 0.15 part of peroxidized t-butyl perbenzoate, 0.1 part of diacetyl peroxide, 1 part of antioxidant 1010.
The preparation method is the same as that of Example 1 for high melt strength polypropylene material, and the polyacrylic melt strength of gained is
1406PaS, melt index 1.8.
Compare case 1:
A kind of high melt strength polypropylene material is obtained by following mass parts:
100 parts of polypropylene, 25 parts of styrene, 0.25 part of cumyl peroxide, 1 part of antioxidant 1010.
Initiator, monomer, polypropylene are uniformly mixed, through double-screw extruding pelletizing.Extruder temperature condition is 170 DEG C/175
DEG C/the polyacrylic melt strength of 180 DEG C/185 DEG C/185 DEG C/180 DEG C/170 DEG C/gained be 81PaS, melt index 5.3.
Compare case 2:
A kind of high melt strength polypropylene material is obtained by following mass parts:
100 parts of polypropylene, 25 parts of styrene, 0.25 part of cumyl peroxide, 1 part of antioxidant 1010.
Initiator, monomer, polypropylene are uniformly mixed, reacts in mixer and no longer changes to torque.Through squeezing after taking-up
It is granulated out, extruder temperature condition is that 165 DEG C/170 DEG C/175 DEG C/180 DEG C/180 DEG C/175 DEG C/170 DEG C/gained is polyacrylic molten
Body intensity is 174PaS, melt index 4.6.
Claims (10)
1. a kind of high melt strength polypropylene material, which is characterized in that be mixed by following parts by weight raw material: polypropylene powder
Expect 100 parts, 2-30 parts of grafted monomers, 0.01-2 parts of initiator, 0.5-1.5 parts of antioxidant.
2. high melt strength polypropylene material according to claim 1, it is characterised in that: the polypropylene powder is linear
Homopolypropylene, copolymer polypropylene powder or with arbitrary proportion combine blending powder, melt index 3-50g/
10min。
3. high melt strength polypropylene material according to claim 1, it is characterised in that: the grafted monomers are to contain carbon
One of the Monofunctional monomers of carbon double bond and polyfunctional monomer are a variety of.
4. high melt strength polypropylene material according to claim 1, it is characterised in that: the initiator is peroxidating
Object.
5. high melt strength polypropylene material according to claim 1, it is characterised in that: the antioxidant is Hinered phenols
Antioxidant or phosphite ester antioxidant.
6. high melt strength polypropylene material according to claim 3, it is characterised in that: the Monofunctional monomers are α-
Methyl styrene, styrene, methyl styrene or vinyl ethylo benzene, polyfunctional monomer are cyclopentadiene, divinylbenzene
Or multi-functional acrylate.
7. high melt strength polypropylene material according to claim 4, it is characterised in that: the initiator is benzoyl peroxide
Formyl, two tertiary amyl peroxide, 2,5- dimethyl -2,5- di-t-butyl peroxy -3- hexin, 2,5- dimethyl -2,5, two uncle
Butyl peroxy hexane, dilauroyl peroxide, cumyl peroxide, peroxidized t-butyl perbenzoate, diacetyl peroxide,
One of dioctanoyl peroxide is a variety of.
8. high melt strength polypropylene material according to claim 5, it is characterised in that: the antioxidant is 2,6-, bis- uncle
Butyl -4- methylphenol, antioxidant 2246, antioxidant 1010, antioxidant 1076, bis- (2,6- di-t-butyl -4- aminomethyl phenyls)
Pentaerythritol diphosphate, irgasfos 168 or antioxidant 626.
9. high melt strength polypropylene material according to claim 6, it is characterised in that: the multi-functional acrylic acid
Ester is pentaerythritol triacrylate, methacrylate tetraethylene glycol ester or trimethylol-propane trimethacrylate.
10. the preparation method of high melt strength polypropylene material according to claim 1, it is characterized in that, including walk as follows
It is rapid: (1) under nitrogen protection, after mixing by grafted monomers, initiator, to be slowly added into polypropylene powder and stir
20min；(2) above-mentioned homogeneous material is reacted 1-2 hours at 110-140 DEG C, after being cooled to 50 DEG C once, with antioxidant through squeezing
Machine is granulated out, obtains the polypropylene granules of high fondant-strength.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110092872A (en) * | 2019-05-31 | 2019-08-06 | 青岛海尔新材料研发有限公司 | The extrusion foaming of one-step method preparation damping PP composite material and preparation method thereof |
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| CN105504170A (en) * | 2014-09-22 | 2016-04-20 | 中国石化扬子石油化工有限公司 | High melt strength polypropylene preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110092872A (en) * | 2019-05-31 | 2019-08-06 | 青岛海尔新材料研发有限公司 | The extrusion foaming of one-step method preparation damping PP composite material and preparation method thereof |
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Application publication date: 20190402 |