CN101885806B - Preparation method for polypropylene resin graft - Google Patents
Preparation method for polypropylene resin graft Download PDFInfo
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- CN101885806B CN101885806B CN2009100839896A CN200910083989A CN101885806B CN 101885806 B CN101885806 B CN 101885806B CN 2009100839896 A CN2009100839896 A CN 2009100839896A CN 200910083989 A CN200910083989 A CN 200910083989A CN 101885806 B CN101885806 B CN 101885806B
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 96
- -1 polypropylene Polymers 0.000 title claims abstract description 85
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 76
- 239000011347 resin Substances 0.000 title claims abstract description 31
- 229920005989 resin Polymers 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000000178 monomer Substances 0.000 claims abstract description 91
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 239000000843 powder Substances 0.000 claims abstract description 39
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- 150000003254 radicals Chemical class 0.000 claims abstract description 29
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 13
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- 238000007254 oxidation reaction Methods 0.000 claims description 57
- 238000000034 method Methods 0.000 claims description 35
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
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- 150000008301 phosphite esters Chemical class 0.000 claims description 5
- GZBSIABKXVPBFY-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO GZBSIABKXVPBFY-UHFFFAOYSA-N 0.000 claims description 4
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 claims description 4
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 claims description 4
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- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical class OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 claims description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 2
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 239000004258 Ethoxyquin Substances 0.000 claims description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 2
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 2
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- DECIPOUIJURFOJ-UHFFFAOYSA-N ethoxyquin Chemical compound N1C(C)(C)C=C(C)C2=CC(OCC)=CC=C21 DECIPOUIJURFOJ-UHFFFAOYSA-N 0.000 claims description 2
- 229940093500 ethoxyquin Drugs 0.000 claims description 2
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- 239000000155 melt Substances 0.000 claims description 2
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical group CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 claims 1
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 abstract 1
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- 239000002245 particle Substances 0.000 description 7
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 5
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- 238000003756 stirring Methods 0.000 description 2
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Abstract
The invention provides a preparation method for a polypropylene resin graft, and relates to a maleic anhydride grafted polypropylene resin. The polypropylene resin is polypropylene powder which does not contain an antioxidant. Based on 100 weight parts of the polypropylene powder, 0.05 to 1 part of the antioxidant and the polypropylene powder are melted and blended; a molten free radical grafting reaction is performed on the polypropylene resin; the grafting reaction is initialized by using an oxide initiator; auxiliary monomers are introduced besides adding polar monomer maleic anhydride; the auxiliary monomers comprise a first auxiliary monomer and a second auxiliary monomer; the first auxiliary monomer is a styrene monomer; the dosage of the first auxiliary monomer is 0.5 to 3 parts based on 100 weight parts of the polypropylene resin; the second auxiliary monomer is an organic monomer of which the molecules comprise two or more carbon-carbon double bonds; and the dosage of the second auxiliary monomer is 2 to 8 parts based on 100 weight parts of the polypropylene resin. The grafted polypropylene resin which has high grafting rate, high molecular weight and high viscosity can be prepared by the preparation method of the polypropylene resin graft of the invention.
Description
Technical field
The present invention relates to a kind of preparation method of polypropylene resin graft, say further, relate to the method for maleic anhydride inoculated polypropylene resin.
Background technology
Vestolen PP 7052 is a kind of commodity polymer material of having many uses, and has good physical and mechanical property.But polyacrylic nonpolar and low surface energy makes the consistency of it and most polymers and filler poor, the poor performance that is difficult for wetting, bonding, printing and applies, can not obtained performance during with the polar material blend material preferably.Therefore need certain methods to improve polyacrylic polarity.Method of modifying commonly used is that the polar monomer with this type of maleic anhydride is grafted to the polarity that improves matrix on the polypropylene backbone.Especially fusion free radical grafting method because its economy simple to operate, is fit to suitability for industrialized production and becomes the main method of present employing.
For example U.S. Pat 5,955, and 547 have reported the continuous method for processing of employing, and the fused Vestolen PP 7052 is mixed in twin screw extruder with the fused maleic anhydride, add radical initiator, mixing granulation then.The maleic anhydride inoculated polypropylene of this method preparation has higher molecular weight and acid number, and number-average molecular weight is more than 20000, and acid number is more than 4.5.U.S. Pat 6; 228; 948 have reported in each section of twin screw extruder employing different parameter and condition, and Vestolen PP 7052, maleic anhydride are added in the forcing machine, treat to add initiator after the fusion; The maleic anhydride reactive grafting makes the Vestolen PP 7052 of percentage of grafting more than 2%, high comprehensive performance on polypropylene molecular chain.
The subject matter that radical fusion-grafting method is faced is the mechanical property that when obtaining enough maleic anhydride grafting ratios, will keep polypropylene matrix always; Promptly keep its due molecular weight, with the other materials blend time, just be unlikely to influence the whole mechanical property of final material like this.
Process according to the reaction of fusion free radical grafting can know that peroxide initiator at first produces elementary radical, attack polypropylene backbone then after decomposing; After peeling off the Wasserstoffatoms on the main chain, generate the Vestolen PP 7052 macromolecular radical, will obtain graft polypropylene (ReactiveModifiers for Polymers after this macromolecular radical and the grafted monomer reaction; Edited by S.Al-Malaika, Chapman&Hall press, London; UK, 1997, Chapter 1; Free-radical grafting of monomers onto polymers by reactiveextrusion:principles and applications, pp 1-77).Hydrogen on the tertiary carbon atom in the polypropylene molecule repeating unit has lower dissociation energy; Thereby obtained the tertiary carbon radical by elementary radical attack the most easily; The β chain-breaking reaction at high temperature can take place in this radical; This reaction can cause HOPP in the free radical grafting reaction, to produce severely degrade, thereby reduces the molecular weight of graft product greatly.
But can know that from the process of graft reaction will obtain graft product and just must obtain macromolecular radical earlier, polyacrylic thus β chain-breaking reaction is the unavoidable side reaction of following in the grafting process.If reduce the consumption of initiator, the macromolecular radical that generates in the reaction process is reduced, thereby can alleviate DeR, but also can cause polyacrylic percentage of grafting to descend simultaneously.
When bibliographical information Vestolen PP 7052 and maleic anhydride generation graft reaction were arranged, maleic anhydride monomer generally was grafted on (W.Heinen, C.H.Rosenmoller on the Vestolen PP 7052 with the form of individual molecule; C.B.Wenzel et al., Macromolecules, 1996; 29,1151-1157).Can know that according to different radicals and the monomeric relative reactivity data of differential responses the reactive behavior of styrene monomer and maleic anhydride radical is active 93 times of its homopolymerization; And the reactive behavior of maleic anhydride monomer and vinylbenzene radical (the J.Brandrup and E.H.Immergut that is its homopolymerization active 29 times; Polymer Handbook, 3
RdEdn, 1989, John Wiley, NewYork).Therefore; After in Vestolen PP 7052 maleic anhydride system, introducing other monomer such as vinylbenzene; Because the characteristic of copolyreaction takes place between maleic anhydride and the vinylbenzene more easily; A kind of maleic anhydride and cinnamic alternating copolymer can be formed, thereby more maleic anhydride monomer can be on a grafting site, introduced.So just can improve the conversion of monomer efficient of maleic anhydride, and then improve the percentage of grafting of whole system.
Compare with simple Vestolen PP 7052/maleic anhydride system, introduce styrene monomer and can improve grafting efficiency, make the Vestolen PP 7052 macromolecular radical participate in the graft reaction more simultaneously; Thereby can alleviate to a certain extent owing to disadvantageous effect (G.H.Hu, J.J.Flat and M.Lambla, the Makromol.Chem. of polypropylene beta chain-breaking reaction to molecular weight; Macromol.Symp.; 1993,75,137-157).
But the simple cinnamic method of adding that adopts still can't solve the degradation problem of Vestolen PP 7052 in fusion free radical grafting reaction process up hill and dale.
Summary of the invention:
The inventor is through discovering, polypropylene powder is added oxidation inhibitor and granulation after, again with the auxiliary monomer reaction, can prepare melting index and be lower than the raw material acrylic resin, have the more graft polypropylene of high fondant-strength.If directly the use polypropylene powder that do not contain oxidation inhibitor reacts with auxiliary monomer then can't reach above-mentioned effect.
Therefore, the purpose of this invention is to provide a kind of is the method that raw material prepares the polypropylene resin graft with high percentage of grafting and melt strength with the polypropylene powder that does not contain oxidation inhibitor.
The preparation method of a kind of polypropylene resin graft of the present invention reacts the polar monomer maleic anhydride graft to the molecular chain of acrylic resin through the fusion free radical grafting.The raw material acrylic resin that method of the present invention adopts is for not containing the polypropylene powder of oxidation inhibitor, like the HOPP powder that does not pass through granulation of small scale bulk method preparation.
Method of the present invention before carrying out fusion free radical grafting reaction, earlier with the above polypropylene powder and oxidation inhibitor melt blending, afterwards again with melt blending the acrylic resin of oxidation inhibitor carry out the fusion free radical grafting and react.
Above-described oxidation inhibitor can adopt any oxidation inhibitor general in the field of plastics processing.Preferentially be selected from a kind of or its combination in Hinered phenols antioxidant, phosphite ester kind antioxidant and the monothioester kind antioxidant.Wherein said Hinered phenols antioxidant is preferably from four [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester (being antioxidant 1010); Phosphite ester kind antioxidant is at least a in (2, the 4-di-tert-butyl-phenyl) tris phosphite (being oxidation inhibitor 168) and pair (2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphites preferably; The monothioester kind antioxidant is preferably from sulfo-dipropionic acid two lauryls.Its consumption is 0.05～1 part, is preferably 0.1～0.5 part in acrylic resin 100 parts by weight.
Polar monomer in the free radical grafting of fusion described in the inventive method reaction is a maleic anhydride, its consumption in above-mentioned melt blending acrylic resin 100 parts by weight of oxidation inhibitor, be 1～8 parts by weight, be preferably 2～5 parts by weight.
The reaction of the free radical grafting of fusion described in the inventive method is introduced auxiliary monomer except that adding the polar monomer maleic anhydride, said auxiliary monomer comprises first auxiliary monomer and second auxiliary monomer.First auxiliary monomer is a styrene monomer, and second auxiliary monomer is the organism monomer that contains two or more carbon-carbon double bonds on the molecule.The instance of the monomer that contains two carbon-carbon double bonds in second auxiliary monomer (two monomers) including, but not limited to: 1; 4～butylene glycol dimethacrylate, 1,6 hexanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, neopentylglycol diacrylate, Vinylstyrene; The instance that contains the monomer (trifunctional monomer) of three carbon-carbon double bonds includes, but are not limited to Viscoat 295, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, tri trimellitate propylene ester; The instance of monomer (four-functional group monomer) that contains four carbon-carbon double bonds is including, but not limited to tetramethylol methane tetraacrylate, ethoxyquin tetramethylol methane tetraacrylate; The instance of monomer (polyfunctional monomer) that contains four above carbon-carbon double bonds is including, but not limited to Dipentaerythritol five propenoate.And when using second auxiliary monomer, second auxiliary monomer can be selected at least a the use from above two monomers, trifunctional monomer, four-functional group monomer or polyfunctional monomer.
The first auxiliary monomer consumption in the above auxiliary monomer in melt blending the acrylic resin of oxidation inhibitor be 100 parts by weight, be 0.5～3 part.In the auxiliary monomer the second auxiliary monomer consumption in melt blending the acrylic resin of oxidation inhibitor be 100 parts by weight, be 2～8 parts, be preferably 3～5 parts.
Melting graft reaction described in the inventive method is caused by peroxide initiator.The peroxide initiator that is suitable for the reaction of fusion free radical grafting in the prior art all can use.Preferred dialkyl peroxide class initiator among the present invention.More preferably two (tert-butyl hydroperoxide sec.-propyl) benzene, 2,5-dimethyl--2, at least a in 5-di-t-butyl hexane peroxide, Di Cumyl Peroxide 99, t-tutyl cumyl peroxide and the ditertiary butyl peroxide.The consumption of said peroxide initiator in melt blending the acrylic resin of oxidation inhibitor be 100 parts by weight, be 0.05～1 part, be preferably 0.1～0.5 part.
Specifying further, the method for polar monomer graft polypropylene resin of the present invention may further comprise the steps:
After polypropylene powder and the said oxidation inhibitor that a. at first will not contain oxidation inhibitor mixes by said amount, melt blending and granulation;
B. said peroxide initiator is dissolved the auxiliary monomer mixing solutions that obtains containing peroxide initiator with said consumption in the mixing solutions of said auxiliary monomer;
C. with said melt blending the powder of maleic anhydride polar monomer of acrylic resin and said amount of oxidation inhibitor carry out solid phase and do and mix, evenly add the auxiliary monomer solution that contains peroxide initiator of step b gained in the mixing process; Wherein the powder of maleic anhydride monomer is preferably done mixed with said acrylic resin after grinding;
D. will send into melt process equipment through the reactant that above-mentioned steps mixes at last and carry out melting graft reaction;
E. add the oxidation inhibitor termination reaction in the melting graft reaction later stage, obtain the acrylic resin of polar monomer maleic anhydride graft.
The temperature of the temperature of polypropylene powder and oxidation inhibitor melt blending and fusion free radical grafting reaction is Vestolen PP 7052 processing temperature commonly used in the method for the present invention, and its scope is generally 180～220 ℃.
Among the method steps a of the present invention, preferably that the gained pellet is broken to increase its surface-area through suitably after said oxidation inhibitor and the granulation of polypropylene powder melt blending, be convenient to and the thorough mixing that contains the auxiliary monomer solution of peroxide initiator.Said disintegrating apparatus adopts common material fragmentation equipment, such as shredder, plant crusher in crushing etc.The ground grains particle diameter there is not particular requirement, generally can be at 0.5～2mm.
The termination reaction of the fusion free radical grafting of step e reaction is the conventional steps before common fusion free radical grafting reaction finishes in the method for the present invention.Generally according to reaction process, with reference to like parameters such as monomer, initiator amount, half-lives of initiators and reaction times, roughly when maleic anhydride monomer and initiator have reacted basically adding oxidation inhibitor in order to termination reaction, in case acrylic resin is degraded.Said oxidation inhibitor is with the above-mentioned and oxidation inhibitor polypropylene powder melt blending, for oxidation inhibitor commonly used in the plastic working, like Hinered phenols antioxidant, phosphite ester kind antioxidant etc.Can select a kind of oxidation inhibitor, also can be that several kinds of oxidation inhibitor mix use.The consumption of oxidation inhibitor is a conventional amount used also, is generally 0.1～1%wt of acrylic resin weight.
Melt process equipment can be a various melt blending equipment of the prior art in the method for the present invention, like Banbury mixer, intermittently milling device, extrusion equipment such as single screw extrusion machine, twin screw extruder, Bu Shi mixing tank etc. continuously.Preferred reaction type twin screw extruder.
In the method for polar monomer graft polypropylene resin of the present invention; Adopt two kinds of auxiliary monomers; First kind of vinylbenzene auxiliary monomer wherein; Can carry out alternating copolymerization with maleic anhydride monomer, improve the grafting transformation efficiency of macromolecular radical, thereby the consumption of reduction initiator reduces the generation of β chain-breaking reaction; Polyfunctional group in second auxiliary monomer of introducing simultaneously can be participated in reacting of macromolecular radical and offset the disadvantageous effect of β chain-breaking reaction to molecular weight; It is preceding with oxidation inhibitor and polypropylene powder blend to be employed in the reaction of fusion free radical grafting simultaneously; Can effectively alleviate the thermal-oxidative degradation degree of Vestolen PP 7052 in the course of processing; Thereby the melt elasticity of polypropylene grafted thing is significantly increased than the raw material Vestolen PP 7052; Be reflected in the storage modulus that obtains of rotation rheometer test and will be higher than the polyacrylic numerical value of raw material, and the melting index of graft product to be lower than the polyacrylic melting index of raw material at low frequency range; Also has very high percentage of grafting simultaneously.Can obtain having high percentage of grafting thus, HMW and full-bodied polypropylene grafted thing.
The polypropylene grafted thing of the high fondant-strength maleic anhydride graft that the inventive method obtains can be used as the compatilizer of acrylic resin, also can be used as to disperse the required polar resin matrix of polar nanoparticle to use.When using,, under the addition condition with higher, can not bring adverse influence to the mechanical property of blend because it has the melting index also low than the raw material Vestolen PP 7052 as blending compatilizer yet.When being used to prepare the masterbatch of nano material; Lower melting index and higher melt strength can guarantee in the melt-processed process, nanoparticle to be produced enough shearing forces; Thereby help the nanoparticle that flocks together is dispersed in the graft polypropylene matrix, obtain finely disseminated nanoparticle polypropylene masterbatch.
Description of drawings
Fig. 1 is the relation curve of the storage modulus that obtains of dynamic rheological property test with change of frequency.Wherein X-coordinate is frequency (Frequency), and unit is rad/s; Ordinate zou is storage modulus G ', and unit is Pa.Curve 1, curve 2, curve 3, curve 4 are respectively embodiment 1, embodiment 2, comparative example 1 and comparative example 2 gained among the figure.
Embodiment:
Below in conjunction with embodiment, further specify the present invention.
The dynamic rheological property testing method:
Use vulcanizing press to be pressed into the sheet of thickness testing sample, in the enterprising action attitude test of strain control type rotational rheometer (ARES-2KFRTN1-FCO-HR, U.S. science rheometer company) as 1.5mm.Adopt the parallel plate anchor clamps of diameter 2.5cm, distance between plates is set at 1mm.200 ℃ of probe temperatures, nitrogen atmosphere, strain 5%, range of frequency 0.017rad/s-100rad/s.
The infrared spectrum characterization method of maleic anhydride grafting ratio is following in the embodiment of the invention and the comparative example:
At first set up typical curve.Adopting the dodecenylsuccinic acid acid anhydride (DDSA) and the different ratios biased sample of virgin pp resin is standard specimen, and the C=O group among the mensuration DDSA is at 1818-1755cm
-1(point position, peak is about 1782cm
-1) ir absorption peak area and Vestolen PP 7052 in the mark peak at 484-435cm
-1(point position, peak is about 460cm
-1) the absorption peak area, to the mapping of the content of Succinic anhydried, can obtain the typical curve of maleic anhydride grafting ratio in the graft polypropylene by the two ratio.
The concrete test process of grafting sample is: take by weighing the graft polypropylene sample that the embodiment of about 1g obtains; Put into 20ml YLENE; After heating is dissolved fully; Pour into immediately in the 150ml acetone, unreacted small molecules and the monomer that does not graft on the polymer are dissolved in acetone, and the white floss of separating out is pure grafts.Its filtration, dry back are pressed into the transparent film about thickness 100um in (200 ℃ of temperature) on the vulcanizing press, use the determination of infrared spectroscopy charateristic avsorption band, calculate percentage of grafting through typical curve then.
The melting index testing standard of the acrylic resin of maleic anhydride graft is GB/T3682-2000 in the embodiment of the invention and the comparative example.
Embodiment 1:
With polypropylene powder (the Plant of Tianjin Petrochemical Company 3# of blue star group PP Pipe Compound; The powder that does not contain oxidation inhibitor; 3.0～5.9g/10min) 2 kilograms of melting index and the antioxidant 1010 of 8 grams and mixture (the mixed weight ratio 1: 1 of oxidation inhibitor 168; Switzerland Ciba-Geigy company produces) in impeller, mix after, granulation on WPZSK25 type twin screw extruder (melt temperature is 205 ℃).The pellet that obtains is carried out the small-particle that fragmentation obtains the about 1mm of diameter with the plant crusher, with the contact area of suitable increase itself and auxiliary monomer.Promptly as the raw material of graft reaction, code name is PP-1 (is 100 weight parts with polypropylene powder wherein, contains 0.4 part in oxidation inhibitor) to the acrylic resin small-particle that contains oxidation inhibitor after this fragmentation.
Initiator Di Cumyl Peroxide 99 (Beijing is sincerely believed in meticulous preparation factory and produced) 0.08 gram added in 2 gram tri trimellitate propylene esters (Baily medical material ltd) and the 0.4 gram vinylbenzene (Tianjin recovery fine chemistry industry institute produces) dissolve.Maleic anhydride powder after Vestolen PP 7052 PP-1 small-particle 40 gram and 1.2 grams are ground carries out solid phase with stirring rake in plastic beaker does and mixes, and in mixing process, evenly adds the above dissolving auxiliary monomer solution that contains said peroxide initiator well.At last the reactant that mixes is added in the HAAKE PolyLab OS Banbury mixer; Under 180 ℃ of temperature condition, with 30 rev/mins speed hybrid reactions 5 minutes, and then to add weight ratio be 1: 1 antioxidant 1010 (pentaerythritol tetrathioglycollate; Switzerland Ciba-Geigy company) and oxidation inhibitor 168 ((2; 4 di-tert-butyl-phenyls) mixture tris phosphite, Switzerland Ciba-Geigy company) is totally 0.2 gram, continues to mix the graft polypropylene of collecting preparation after 1 minute.The dependence test result of sample sees table 1.With polypropylene grafted thing sample preparation, carry out dependence test.The dependence test result of sample sees table 1 and Fig. 1.
Comparative example 1:
The PP-1 that obtains after the polypropylene powder granulation among the embodiment 1 is added in the HAAKE PolyLab OS Banbury mixer; Under 180 ℃ of temperature condition; Mixed 6 minutes with 30 rev/mins speed, carry out the test of melting index and dynamic rheological property again, the result lists among table 1 and Fig. 1.
Comparative example 2:
With the polypropylene powder that does not contain oxidation inhibitor used among the embodiment 1 is raw material, carries out melting graft reaction.Do not use auxiliary monomer used among the embodiment 1 in the melting graft reaction.Initiator Di Cumyl Peroxide 99 (with embodiment 1) 0.04 gram is dissolved in the 0.5 gram acetone (commercially available); Then with polypropylene powder (with embodiment 1) 40 grams; After maleic anhydride powder (with embodiment 1) 1.2 grams are done and are mixed; Vapor away acetone solvent, again by carrying out graft reaction with embodiment 1 identical processing conditions.The dependence test result who makes sample sees among table 1 and Fig. 1.
Comparative example 3:
The styrene monomer in not using embodiment 1, all the other conditions are all identical with embodiment 1, and identical among other condition of graft reaction and the embodiment 1, the test result of grafting sample is listed in table 1.
Comparative example 4:
With the polypropylene powder that does not contain oxidation inhibitor used among the embodiment 1 is raw material, carries out melting graft reaction; Identical among other condition of graft reaction and the embodiment 1, the test result of grafting sample is listed in table 1.
Embodiment 2:
With the PP-1 that obtains after the polypropylene powder granulation among the embodiment 1 is raw material; Auxiliary monomer adopts 1.8 gram tri trimellitate propylene esters (Baily medical material ltd) and 0.2 gram vinylbenzene (Tianjin recovery fine chemistry industry institute produces) to carry out melting graft reaction; Identical among other conditions of graft reaction and the embodiment 1, the test result of grafting sample is listed among table 1 and Fig. 1.
Comparative example 5:
With the polypropylene powder that does not contain oxidation inhibitor used among the embodiment 1 is raw material, carries out melting graft reaction; Identical among other condition of graft reaction and the embodiment 2, the test result of grafting sample is listed in table 1.
Comparative example 6:
The styrene monomer in not using embodiment 2, identical among other condition of graft reaction and the embodiment 2, the test result of grafting sample is listed in the table 1.
Embodiment 3:
With 2 kilograms of polypropylene powders (with embodiment 1) and the antioxidant 1010 of 3 grams and mixture (the mixed weight ratio 1: 1 of oxidation inhibitor 168; Switzerland Ciba-Geigy company produces) in impeller, mix after, granulation on WP ZSK25 type twin screw extruder (melt temperature is 205 ℃).The pellet that obtains is carried out the small-particle that fragmentation obtains the about 1mm of diameter with the plant crusher, with the contact area of suitable increase itself and auxiliary monomer.Promptly as the raw material of graft reaction, code name is PP-2 (is 100 weight parts with polypropylene powder wherein, contains 0.15 part in oxidation inhibitor) to the acrylic resin small-particle that contains oxidation inhibitor after this fragmentation.
Initiator Di Cumyl Peroxide 99 (Beijing is sincerely believed in meticulous preparation factory and produced) 0.16 gram added in 1.2 gram tri trimellitate propylene esters (Baily medical material ltd) and the 1.2 gram vinylbenzene (Tianjin recovery fine chemistry industry institute produces) dissolve.Maleic anhydride powder after Vestolen PP 7052 PP-2 small-particle 40 gram and 2 grams are ground carries out solid phase with stirring rake in plastic beaker does and mixes, and in mixing process, evenly adds the above dissolving auxiliary monomer solution that contains said peroxide initiator well.At last the reactant that mixes is added in the HAAKE PolyLab OS Banbury mixer; Under 180 ℃ of temperature condition, with 30 rev/mins speed hybrid reactions 5 minutes, and then to add weight ratio be 1: 1 antioxidant 1010 (pentaerythritol tetrathioglycollate; Switzerland Ciba-Geigy company) and oxidation inhibitor 168 ((2; 4 di-tert-butyl-phenyls) mixture tris phosphite, Switzerland Ciba-Geigy company) is totally 0.2 gram, continues to mix the graft polypropylene of collecting preparation after 1 minute.The dependence test result of sample sees table 1.With polypropylene grafted thing sample preparation, carry out dependence test.The dependence test result of sample sees table 1.
Comparative example 7:
The PP-2 that obtains after the polypropylene powder granulation among the embodiment 3 is added in the HAAKE PolyLab OS Banbury mixer, under 180 ℃ of temperature condition, mixed 6 minutes with 30 rev/mins speed, carry out the melting index test again, the result lists in the table 1.
Table 1
Data from table 1 can be found out; After the polypropylene powder interpolation oxidation inhibitor granulation that does not contain oxidation inhibitor; Adopt the graft product of compound auxiliary monomer preparation; Compare and only adopt a kind of polyfunctional group auxiliary monomer or high without the graft product percentage of grafting of auxiliary monomer preparation, melting index is also less than the raw material Vestolen PP 7052.Use third powder that gathers that does not add oxidation inhibitor to be raw material and since the grafting process in polypropylene powder be easy to degrade, so even the use auxiliary monomer can not make graft product melting index less than the raw material Vestolen PP 7052.Storage modulus G ' among Fig. 1 also demonstrates the sample that is higher than comparative example 1, comparative example 2 in the storage modulus of low frequency range embodiment 1 and embodiment 2 samples to the curve of frequency; Reflect the difference on the sample elasticity, thereby illustrative embodiment 1,2 samples has higher melt strength.
Claims (13)
1. the preparation method of a polypropylene resin graft is grafted to polar monomer on the molecular chain of acrylic resin through the reaction of fusion free radical grafting, it is characterized in that may further comprise the steps:
After polypropylene powder and the oxidation inhibitor that a. at first will not contain oxidation inhibitor mixes, melt blending and granulation; Be 100 parts by weight in polypropylene powder wherein, oxidation inhibitor is 0.05～1 part;
B. peroxide initiator is dissolved the auxiliary monomer mixing solutions that obtains containing peroxide initiator in the mixed solution of auxiliary monomer; Wherein auxiliary monomer comprises first auxiliary monomer and second auxiliary monomer, and said first auxiliary monomer is a styrene monomer, consumption in melt blending the acrylic resin of oxidation inhibitor be 100 parts by weight, be 0.5～3 part; Said second auxiliary monomer is the organism monomer that contains two above carbon-carbon double bonds on the molecule, consumption in melt blending the acrylic resin of oxidation inhibitor be 100 parts by weight, be 2～8 parts;
C. the melt blending that step a is obtained the powder of acrylic resin and maleic anhydride polar monomer of oxidation inhibitor carry out solid phase and do and mix, evenly add the auxiliary monomer mixing solutions that contains peroxide initiator of step b gained in the mixing process;
D. will send into melt process equipment through the reactant that above-mentioned steps mixes at last and carry out melting graft reaction;
E. add the oxidation inhibitor termination reaction in the melting graft reaction later stage, obtain the acrylic resin of polar monomer maleic anhydride graft.
2. according to the preparation method of the said polypropylene resin graft of claim 1, it is characterized in that said oxidation inhibitor is selected from a kind of or its combination in Hinered phenols antioxidant, phosphite ester kind antioxidant and the monothioester kind antioxidant.
3. according to the preparation method of the said polypropylene resin graft of claim 2, it is characterized in that said Hinered phenols antioxidant is selected from four [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester; Said phosphite ester kind antioxidant is selected from least a in (2, the 4-di-tert-butyl-phenyl) tris phosphite and two (2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphites; Said monothioester kind antioxidant is selected from Tyox B.
4. according to the preparation method of the said polypropylene resin graft of claim 1, it is characterized in that among the step a in polypropylene powder being 100 parts by weight, oxidation inhibitor is 0.1～0.5 part.
5. according to the preparation method of the said polypropylene resin graft of claim 1; It is characterized in that said second auxiliary monomer is selected from by 1; In 4-butylene glycol dimethacrylate, 1,6 hexanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, neopentylglycol diacrylate, Vinylstyrene, Viscoat 295, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, tri trimellitate propylene ester, tetramethylol methane tetraacrylate, ethoxyquin tetramethylol methane tetraacrylate and the Dipentaerythritol five propenoate institute composition group one or more.
6. according to the preparation method of the said polypropylene resin graft of claim 1, it is characterized in that the said second auxiliary monomer consumption in melt blending the acrylic resin of oxidation inhibitor be 100 parts by weight, be 3～5 parts.
7. according to the preparation method of the said polypropylene resin graft of claim 1, the consumption that it is characterized in that said peroxide initiator in melt blending the acrylic resin of oxidation inhibitor be 100 parts by weight, be 0.05～1 part.
8. according to the preparation method of the said polypropylene resin graft of claim 7, the consumption that it is characterized in that said peroxide initiator in melt blending the acrylic resin of oxidation inhibitor be 100 parts by weight, be 0.1～0.5 part.
9. according to the preparation method of the said polypropylene resin graft of claim 1, it is characterized in that said peroxide initiator is selected from dialkyl peroxide class initiator.
10. according to the preparation method of the said polypropylene resin graft of claim 9; It is characterized in that said dialkyl peroxide class initiator is selected from by two (tert-butyl hydroperoxide sec.-propyl) benzene, 2; 5-dimethyl--2, one or more in 5-di-t-butyl hexane peroxide, Di Cumyl Peroxide 99, t-tutyl cumyl peroxide and the ditertiary butyl peroxide institute composition group.
11. according to the preparation method of the said polypropylene resin graft of claim 1, it is characterized in that said polar monomer maleic anhydride consumption in melt blending the acrylic resin of oxidation inhibitor be 100 parts by weight, be 1～8 parts by weight.
12. according to the preparation method of the said polypropylene resin graft of claim 11, it is characterized in that said polar monomer maleic anhydride consumption in melt blending the acrylic resin of oxidation inhibitor be 100 parts by weight, be 2～5 parts by weight.
13. the preparation method according to each said polypropylene resin graft of claim 1～12 is characterized in that among the step a, after said oxidation inhibitor and the granulation of polypropylene powder melt blending, the gained pellet is ground fragmentation.
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