CN104059197B - Polypropylene fusion graft vinyl ethers and preparation method thereof - Google Patents
Polypropylene fusion graft vinyl ethers and preparation method thereof Download PDFInfo
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- CN104059197B CN104059197B CN201310093616.3A CN201310093616A CN104059197B CN 104059197 B CN104059197 B CN 104059197B CN 201310093616 A CN201310093616 A CN 201310093616A CN 104059197 B CN104059197 B CN 104059197B
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- vinyl ethers
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Abstract
The present invention relates to a kind of polypropylene fusion graft vinyl ethers, it is characterized in that, comprise the raw material of following weight parts ratio: polypropylene 90-95 part, vinyl ethers 1-4 part, initator 0.3-1 part. The polypropylene grafted vinyl ethers of the present invention, as the compatilizer of inorganic filler RPP, can improve intensity and the toughness of composite simultaneously. When preferably hydroxy butyl vinyl ether is as grafted monomers, its boiling point is high, nontoxic, has no irritating odor, and does not damage health, not etching apparatus, environmental protection. Preparation method of the present invention is simple, and energy continued operation, is easy to industrialization, and without reclaiming solvent, product is without purifying.
Description
Technical field
The present invention relates to the modification of macromolecular material, relate in particular to a kind of polypropylene fusion graft secondAlkene ether.
Background technology
Polypropylene (PP) is a kind of cheap, wide material sources, the numerous plastics variety of application.Because PP has stronger impact strength, higher degree of crystallinity, good surperficial rigidity and anti-zonedTrace characteristic, stress crack resistant, resistance to chemical attack, good insulating properties and be easy to machine-shaping etc.Performance, has become one of plastics that have now development prospect. But, due to its thermal deformationTemperature is lower, and low temperature impact strength is low, and PP is non-polar polymer simultaneously, on strand, does not containHave polar group, thereby its compatibility, caking property, dyeability and antistatic behaviour are not good, specialBe PP and other most polymers and inorganic filler blend effectively, greatly limited PPTo engineering plastics and otherwise development.
In order to overcome above-mentioned shortcoming, by a large amount of research work, find grafted functional PPCan better address these problems, therefore the research of PP modification receives much concern always. Wherein graftingModification is comparatively effective a kind of means, and PP graft modification is introduced exactly on nonpolar PP chainPolar group or rigid radical, the PP after graft modification is because the end of the chain is with segment polarity groupBecome widely used compatilizer. At present, have about the conventional method of PP graft modification: meltingGraft Method, solution grafting, radiation graft process, light-initiated Graft Method, solid phase grafting method etc.Wherein, melt grafting becomes because it is easy and simple to handle, be applicable to the features such as suitability for industrialized production at presentTopmost method of modifying.
What research was many at present is polypropylene grafted maleic anhydride and acrylic acid. Maleic anhydride is easyDecompose, toxicity is large, acrylic acid toxicity is less, but they are strong acid, in preparation process, corrodeEquipment, easily forms volatility irritative gas, and skin, eyes and respiratory tract are had to intense stimulusProperty effect, infringement health, has the no free list of reaction in the post processing waste liquid of graftBody, serious environment pollution; As the compatilizer of inorganic filler, can cause interface in conjunction with mistake simultaneouslyBy force, significantly reduce the impact strength of composite, composite is changed into by ductile failureBrittle break.
Summary of the invention
For the above-mentioned defect of prior art, the invention provides a kind of high strength, high tenacity,Preparation method is simple, the polypropylene fusion graft vinyl ethers of environmental protection and preparation method thereof.
The present invention is achieved in that
A kind of polypropylene fusion graft vinyl ethers, comprises the raw material of following weight parts ratio: poly-Propylene 90-95 part, vinyl ethers 1-4 part, initator 0.3-1 part.
Preferably, described polypropylene fusion graft vinyl ethers, by following raw materials in parts by weightRatio composition: polypropylene 90-95 part, vinyl ethers 1-4 part, initator 0.3-1 part is anti-Oxidant 0.1-1 part.
Preferably, described polypropylene is HOPP or COPP.
More preferably, described polypropylene is HOPP powder.
Preferably, described vinyl ethers was hydroxy butyl vinyl ether.
Preferably, described initator is cumyl peroxide.
Preferably, described antioxidant is hindered phenol anti-oxidants.
More preferably, described antioxidant is antioxidant 1010.
Prepare the method for polypropylene fusion graft vinyl ethers of the present invention, comprise following stepRapid:
(1) cumyl peroxide is dissolved in hydroxy butyl vinyl ether, makes hydroxyl butyl secondAlkene ether solution;
(2) HOPP powder adds in high-speed mixer, under the condition of high-speed stirred,Add the hydroxy butyl vinyl ether solution making in step (1), the mixture after mixingPlace 24 hours, HOPP powder fully absorbs grafted monomers and initator, obtains onePlant polypropylene grafted vinyl ethers blend;
(3) by two the polypropylene fusion graft vinyl ethers blend use described in step (2)Screw extruder extruding pelletization, obtains polypropylene fusion graft vinyl ethers.
With respect to prior art, beneficial effect of the present invention is presented as:
1. the preferred hydroxy butyl vinyl ether of the present invention is as grafted monomers, and its boiling point is high, nontoxic,Have no irritating odor, do not damage health, not etching apparatus, environmental protection;
2. preparation method is simple, and energy continued operation, is easy to industrialization, without reclaiming solvent,Product is without purifying;
3. polypropylene grafted vinyl ethers, can be same as the compatilizer of inorganic filler RPPThe intensity of Shi Tigao composite and toughness.
Detailed description of the invention
Embodiment 1
According to the corresponding component of table 1 and addition, take each component. By load weighted initiationAgent cumyl peroxide is dissolved in hydroxy butyl vinyl ether, then by the polypropylene takingPowder adds in high mixer, then adds the antioxidant 1010 weighing up, in high-speed stirred,Add entrance at liquid and divide and add the hydroxy butyl vinyl ether solution that contains initator for three times, stir allAfter even, mixture sealing is preserved 24 hours, allow polypropylene powder fully absorb hydroxyl butylethyleneBase ether is then used double screw extruder extruding pelletization at 170-190 DEG C of temperature, must gather thirdAlkene fusion-grafting hydroxy butyl vinyl ether.
Embodiment 2
According to the corresponding component of table 1 and addition, take each component. All the other preparation processes are sameEmbodiment 1.
Embodiment 3
According to the corresponding component of table 1 and addition, take each component. All the other preparation processes are sameEmbodiment 1.
Table 1 is for the formula table unit of polypropylene fusion graft vinyl ethers: weight portion
| Material | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Polypropylene powder | 90 | 92.5 | 95 |
| Hydroxy butyl vinyl ether | 1 | 2.5 | 4 |
| Cumyl peroxide | 0.3 | 0.65 | 1 |
| Antioxidant 1010 | 0.1 | 0.55 | 1 |
Comparative example
Ratio by weight, by 0.8 part of maleic anhydride, 0.5 part of cumyl peroxide, anti-0.1 part, oxidant is added in 1.5 parts of styrene liquid, premix in the mixer of preparing burden at a high speedClose 3 minutes, then add 97.1 parts of PP that dried to preparing burden in mixer at a high speed, follow oneRise and stir 5 minutes, with for subsequent use, the mixture being stirred be placed in to dual-screw-stem machine and melt extrudeGranulation.
Its process conditions are: one section of temperature 140-150 of twin-screw DEG C, two sections of temperature 150-160DEG C, three sections of temperature 155-165 DEG C, turn/min of driving screw rotating speed 80-100, feed screw turnsTurn/min of speed 30-45.
Performance comparison:
Ratio by weight, polypropylene grafted vinethene (VPP) prepared by embodiment and rightPolypropylene grafted maleic anhydride (MPP) prepared by ratio takes respectively 5 parts, and respectively with 55After part polypropylene mixes, add the glass of 40 parts, be prepared into fiber glass reinforced polypropylene, testEvery mechanical property, in detail in table 2. Polypropylene grafted vinethene can be same as can be seen from Table 2Time play enhancing toughening effect, and that polypropylene grafted maleic anhydride has reduced in strengthening is multipleThe impact property of fit system.
The impact of table 2 compatilizer on fiber glass reinforced polypropylene mechanical property
Be appreciated that vinyl ethers of the present invention is preferably hydroxy butyl vinyl ether, stillBe not limited to hydroxy butyl vinyl ether, vinyl ethers of the present invention can be: methyl ethyleneEther, ethyl vinyl ether, isopropyl-ethylene base ether, IVE, normal-butyl etheneBase ether, Vinyl phenyl ether, ethylene vinyl base ether, ethoxy vinyl ethers or hydroxyl butyl secondAlkene ether; Preferably ethoxy vinyl ethers or hydroxy butyl vinyl ether; More preferably hydroxyl butylethyleneBase ether.
Be appreciated that initator of the present invention is preferably cumyl peroxide, but notBe limited to cumyl peroxide, initator of the present invention can be: cumyl peroxide,Tert-butyl peroxide benzoate, cyclohexanone peroxide, 2,5-dimethyl-2, the two (uncles of 5-Butyl peroxy) hexane, dual-tert-butyl peroxidating diisopropyl benzene, peroxidating-2-ethyl areTert-butyl acrylate or benzoyl peroxide; Preferably benzoyl peroxide or cumyl peroxide; MorePreferably cumyl peroxide.
Be appreciated that antioxidant of the present invention is preferably antioxidant 1010, stillBe not limited to antioxidant 1010, antioxidant of the present invention can be: Hinered phenolsAntioxidant, hindered amines antioxidant, phosphorous acid esters antioxidant, thiophenols are anti-oxidantAgent or monothioester class antioxidant, preferably hindered phenol anti-oxidants, more preferably antioxidant1010。
Be appreciated that in method of the present invention, melt process equipment can be general in prior artMelt blending equipment, continuously extrusion equipment. Wherein, melt blending equipment for example banbury,Intermittence mixing device, continuously extrusion equipment for example single screw extrusion machine, double screw extruder, Bu ShiBlender; Preferred reaction type double screw extruder.
The above, be only the specific embodiment of the present invention, and protection scope of the present invention is notBe confined to this, any be familiar with those skilled in the art the present invention disclose technical scopeIn, the variation that can expect easily or replacement, within all should being encompassed in protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain that claim was defined.
Claims (7)
1. a polypropylene fusion graft vinyl ethers, is characterized in that, is made up of following raw materials in parts by weight ratio: polypropylene 90-95 part, vinyl ethers 1-4 part, initator 0.3-1 part, antioxidant 0.1-1 part; Described vinyl ethers is hydroxy butyl vinyl ether.
2. polypropylene fusion graft vinyl ethers according to claim 1, is characterized in that, described polypropylene is HOPP or COPP.
3. polypropylene fusion graft vinyl ethers according to claim 2, is characterized in that, described polypropylene is HOPP powder.
4. polypropylene fusion graft vinyl ethers according to claim 1, is characterized in that, described initator is cumyl peroxide.
5. polypropylene fusion graft vinyl ethers according to claim 1, is characterized in that, described antioxidant is hindered phenol anti-oxidants.
6. polypropylene fusion graft vinyl ethers according to claim 5, is characterized in that, described antioxidant is antioxidant 1010.
7. the preparation method of polypropylene fusion graft vinyl ethers, is characterized in that, comprises the following steps:
(1) cumyl peroxide is dissolved in hydroxy butyl vinyl ether, makes hydroxy butyl vinyl ether solution;
(2) HOPP powder adds in high-speed mixer, under the condition of high-speed stirred, add the hydroxy butyl vinyl ether solution making in step (1), mixture after mixing is placed 24 hours, HOPP powder fully absorbs grafted monomers and initator, obtains a kind of polypropylene grafted vinyl ethers blend; Polypropylene grafted vinyl ethers blend prepares in melt blending equipment;
(3) by the polypropylene fusion graft vinyl ethers blend double screw extruder extruding pelletization described in step (2), obtain polypropylene fusion graft vinyl ethers;
Ratio meter by weight, described cumyl peroxide is 0.3-1 part, and described hydroxy butyl vinyl ether is 1-4 part, and described HOPP powder is 90-95 part.
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| CN201310093616.3A CN104059197B (en) | 2013-03-22 | 2013-03-22 | Polypropylene fusion graft vinyl ethers and preparation method thereof |
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| CN201310093616.3A CN104059197B (en) | 2013-03-22 | 2013-03-22 | Polypropylene fusion graft vinyl ethers and preparation method thereof |
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| CN104059197B true CN104059197B (en) | 2016-05-11 |
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| CN105061681A (en) * | 2015-09-01 | 2015-11-18 | 南通拜林新材料科技有限公司 | Polyethylene modified through vinyl ether melt grafting and preparing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1292397A (en) * | 1999-09-23 | 2001-04-25 | 华东理工大学 | New type polyolefin functionality special-purpose material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1292397A (en) * | 1999-09-23 | 2001-04-25 | 华东理工大学 | New type polyolefin functionality special-purpose material |
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