CN113621109B - Preparation method of high-grafting-rate low-VOC polypropylene grafted maleic anhydride - Google Patents
Preparation method of high-grafting-rate low-VOC polypropylene grafted maleic anhydride Download PDFInfo
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- CN113621109B CN113621109B CN202110949419.1A CN202110949419A CN113621109B CN 113621109 B CN113621109 B CN 113621109B CN 202110949419 A CN202110949419 A CN 202110949419A CN 113621109 B CN113621109 B CN 113621109B
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 80
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 80
- -1 polypropylene Polymers 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000178 monomer Substances 0.000 claims abstract description 39
- 239000000463 material Substances 0.000 claims abstract description 35
- 239000011259 mixed solution Substances 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 30
- 239000003999 initiator Substances 0.000 claims abstract description 24
- 239000000243 solution Substances 0.000 claims abstract description 24
- 239000012298 atmosphere Substances 0.000 claims abstract description 18
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 17
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000004321 preservation Methods 0.000 claims abstract description 10
- 238000001125 extrusion Methods 0.000 claims abstract description 9
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical group C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 25
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 25
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 claims description 21
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 21
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 21
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 21
- 239000001307 helium Substances 0.000 claims description 10
- 229910052734 helium Inorganic materials 0.000 claims description 10
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical group [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims 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 group 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 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 abstract description 10
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 36
- 239000012855 volatile organic compound Substances 0.000 description 31
- 238000004519 manufacturing process Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 150000008064 anhydrides Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 230000005653 Brownian motion process Effects 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000002479 acid--base titration Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005537 brownian motion Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- OVYTZAASVAZITK-UHFFFAOYSA-M sodium;ethanol;hydroxide Chemical compound [OH-].[Na+].CCO OVYTZAASVAZITK-UHFFFAOYSA-M 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
-
- 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
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The application relates to the technical field of high polymer materials, and particularly discloses a preparation method of high-grafting-rate low-VOC polypropylene grafted maleic anhydride. The method comprises the following steps: dissolving an initiator and a grafting auxiliary monomer in an acetone solution, and placing the mixture in an inert atmosphere for heat preservation; putting polypropylene into a double-screw extruder, wherein the double-screw extruder is divided into 8 screw barrels, and the temperature of the screw barrels is sequentially increased; adding an antioxidant into the second screw barrel, adding maleic anhydride into the third screw barrel, and adding the prepared mixed solution into the fourth, fifth and sixth screw barrels in a divided manner, and carrying out melt blending extrusion to obtain a grafted coarse material; after the intermediate grafting coarse material is placed in a vacuum mixer for blending, ultraviolet irradiation is carried out, and blending is kept, so as to obtain grafting fine material; and (3) putting the grafting fine materials into an extruder at a temperature to obtain the grafting materials through extrusion. The method has the advantage of improving the problem of overlarge VOC emission in the process of grafting the polypropylene with the maleic anhydride.
Description
Technical Field
The application relates to the technical field of high polymer materials, in particular to a preparation method of high-grafting-rate low-VOC polypropylene grafted maleic anhydride.
Background
Polypropylene (PP) is a thermoplastic resin with regular structure, so that the polypropylene has excellent mechanical property, strength, rigidity and stress cracking resistance, good heat resistance, easy processing and forming and wide application value. Meanwhile, because of the non-polarity and low surface energy of polypropylene, the polypropylene has poor compatibility with most polymers and fillers, is not easy to wet, has poor bonding, printing and coating properties, and is difficult to obtain materials with good comprehensive properties when being blended with polar materials for preparation. In order to solve the above problems, a modification method of polypropylene is generally to graft a polar monomer such as maleic anhydride to a main chain of polypropylene to increase the polarity of a polypropylene matrix material.
When modifying polypropylene with maleic anhydride, the most common processes used at present are solution grafting, melt grafting, solid phase grafting or suspension grafting. However, in actual preparation, the grafting rate of the polypropylene grafted maleic anhydride is generally positively related to the addition amount of the maleic anhydride, the grafting rate is increased along with the increase of the addition amount of the maleic anhydride, however, the grafting material of the polypropylene grafted maleic anhydride has larger smell while the use amount of the maleic anhydride is increased, the VOC emission amount in the preparation process is too large, and a certain burden is caused to sewage and waste treatment.
Disclosure of Invention
In order to solve the above-mentioned problems, the present application provides a method for preparing high-grafting-rate low-VOC polypropylene grafted maleic anhydride.
The preparation method of the high-grafting-rate low-VOC polypropylene grafted maleic anhydride adopts the following technical scheme:
a preparation method of high-grafting-rate low-VOC polypropylene grafted maleic anhydride, which comprises the following steps:
s1, 1.3-2.8 parts of initiator and 3-5 parts of auxiliary grafting monomer are dissolved in an acetone solution according to parts by weight, and placed in an inert atmosphere for heat preservation; wherein the auxiliary grafting monomer is a composition of vinyl pyrrolidone and alpha-methyl styrene;
s2, 100 parts of polypropylene is put into a double-screw extruder according to parts by weight; wherein, the twin-screw extruder is divided into 8 screw barrels, and all are in high-pressure environment, 5-10 parts of maleic anhydride is put into a third screw barrel in sequence, and the volume ratio of the maleic anhydride to the fourth screw barrel to the fifth screw barrel is 1: (1-2): 1, adding the mixed solution prepared in the step S1 in batches, and carrying out melt blending extrusion to obtain a grafted coarse material;
s3, placing the grafted coarse material in a vacuum environment, blending for 0.5h, keeping blending, irradiating with ultraviolet rays for 100min, and extruding to obtain the grafted material.
According to the technical scheme, in S1, the initiator and the auxiliary grafting monomer are dissolved in an acetone solution, the initiator and the auxiliary grafting monomer are randomly diffused in the acetone solution due to the Brownian motion of molecules, so that the initiator and the auxiliary grafting monomer are mixed with each other, further, when the mixed solution is added into a double-screw extruder in S2, the initiator is heated and is broken by covalent bonds to generate free radicals, and the initiator and the auxiliary grafting monomer are mixed with each other, so that the contact between the initiator and the molecules is more intimate, the amount of the auxiliary grafting monomer grafted on polypropylene in unit time is increased, the auxiliary grafting monomer is used for auxiliary grafting of polypropylene, the use amount of maleic anhydride is relatively reduced, the VOC (volatile organic compound) generated when the maleic anhydride is grafted on the auxiliary grafting monomer is reduced, the grafting rate of the maleic anhydride is increased, and because the auxiliary grafting monomer is used by compounding vinyl pyrrolidone and alpha-methyl styrene, the vinyl pyrrolidone and the alpha-methyl styrene are copolymerized with each other in the acetone solution, the self molecular chain length of the self-grafting capacity of the polypropylene is increased; in S2, maleic anhydride is added into a third screw barrel, so that the maleic anhydride is mixed with polypropylene, the mixed solution prepared in S1 is added into a fourth screw barrel, a fifth screw barrel and a sixth screw barrel in batches, so that the polypropylene and the auxiliary grafting monomer and the maleic anhydride undergo a grafting reaction, and the adding volume ratio of the mixed solution in the fourth screw barrel, the fifth screw barrel and the sixth screw barrel is 1: (1-2): 1, adding a small amount of mixed solution into a fourth screw barrel, adding a mixed solution into a fifth screw barrel and a sixth screw barrel, and grafting and initiating maleic anhydride by using an initiator to enable the maleic anhydride to be grafted on the auxiliary grafting monomer and polypropylene, so that the grafting rate of the maleic anhydride on the polypropylene is improved; the 8 screw barrels of the double-screw extruder are in a high-pressure environment, so that the movement among molecules can be promoted, and the grafting rate in unit time is improved; in S3, the grafting coarse materials are vacuum blended, so that bubbles which are inevitably generated in the high-pressure environment in S2 can be eliminated, and the grafting rate of maleic anhydride and polypropylene can be further improved by ultraviolet irradiation.
Preferably, in the step S1, the initiator and the auxiliary grafting monomer are dissolved in an acetone solution and placed in an inert atmosphere at 45 ℃ for heat preservation for 1h.
By adopting the technical scheme, after the initiator and the auxiliary grafting monomer are dissolved in the solution, the temperature is kept in the environment of 45 ℃, so that the auxiliary grafting monomer is beneficial to copolymerization reaction, the grafting rate of maleic anhydride is relatively improved, and the auxiliary grafting monomer and air are prevented from undergoing oxidation reaction in inert atmosphere, so that the effective content of the auxiliary grafting monomer is reduced.
Preferably, the inert atmosphere is a helium atmosphere.
Preferably, the initiator in the S1 is a combination of cyclohexanone peroxide and benzoyl peroxide, and the mixing ratio of the cyclohexanone peroxide and the benzoyl peroxide is (0.5-1.3): (0.8-1.5).
By adopting the technical scheme, the mixing ratio of cyclohexanone peroxide and benzoyl peroxide is (0.5-1.3) by weight: (0.8-1.5) can generate remarkable coaction effect when being used in a compounding way, and further improves the grafting rate of maleic anhydride grafted on polypropylene in unit time.
Preferably, the weight mixing ratio of the vinyl pyrrolidone and the alpha-methylstyrene in the S1 is (1.8-2.6): (1.2-2.4).
By adopting the technical scheme, the weight mixing ratio of the vinyl pyrrolidone and the alpha-methyl styrene in the auxiliary grafting monomer is (1.8-2.6): (1.2-2.4) and can remarkably reduce the generation of VOC gas in the production process.
Preferably, the grafting material further comprises an antioxidant, and the antioxidant is antioxidant 1010; in the step S2, an antioxidant is added to the second screw cylinder before maleic anhydride is added.
By adopting the technical scheme, the antioxidant can improve the antioxidant capacity of the grafting material, and the antioxidant is added into the second screw barrel, so that the mixing uniformity of the antioxidant in the grafting material can be improved.
Preferably, the temperature of 8 barrels of the twin-screw extruder is 170-180 ℃,180-185 ℃, 185-195 ℃, 195-200 ℃, 200-205 ℃, 205-210 ℃, 200-205 ℃ and 190-200 ℃ in sequence, the twin-screw extruder is in a nitrogen environment with 1.5-2 standard atmospheres, and the length-diameter ratio of the twin-screw extruder is 48:1.
by adopting the technical scheme, the temperature of the first screw cylinder to the sixth screw cylinder of the double-screw extruder is gradually increased, the temperature increasing rate is gradually reduced, the polypropylene is prevented from being suddenly heated to cause molecular chain fracture, and the mixed solution prepared by S1 is added into the fourth screw cylinder, the fifth screw cylinder and the sixth screw cylinder at high temperature, so that the promotion effect of an initiator and a grafting assisting monomer on maleic anhydride grafting can be improved, the seventh screw cylinder and the eighth screw cylinder are slowly cooled, and the maleic anhydride is favorably grafted on the polypropylene stably.
Preferably, in the step S3, the grafting coarse material is placed in a nitrogen atmosphere with the temperature of 180-190 ℃ and the standard atmospheric pressure of 0.2-0.25 for 0.5h, and the mixture is kept to be irradiated by ultraviolet rays for 100min, extruded and kept warm for 1h, and then cooled to obtain the grafting material.
Preferably, in the step S3, the ultraviolet rays are irradiated for 10 minutes every 5 minutes, and the total irradiation time of the ultraviolet rays is 100 minutes.
Through adopting above-mentioned technical scheme, carry out ultraviolet irradiation to grafting coarse fodder, can improve the grafting of maleic anhydride, and ultraviolet ray is interrupted to be shone, can improve the operating time of ultraviolet ray, and then improve the grafting of maleic anhydride, and in the nitrogen atmosphere of 0.2-0.25 standard atmospheric pressure, avoid the oxidation of air in the high temperature environment to grafting coarse fodder, and do benefit to the bubble in the grafting coarse fodder and break, keep warm after the coarse fodder is extruded for 1h, cool off, do benefit to maleic anhydride and polypropylene, assist grafting monomer's mutual grafting, the VOC gas emission in the grafting material of being convenient for simultaneously, the VOC content of grafting material finished product has been reduced relatively.
Preferably, the wavelength of the ultraviolet rays is 250-350nm.
In summary, the present application has at least the following beneficial effects:
1. the auxiliary grafting monomer is adopted to assist in grafting the polypropylene, so that the use amount of maleic anhydride is relatively reduced, the VOC (volatile organic compound) production amount generated when the maleic anhydride is grafted with the polypropylene is reduced, and the maleic anhydride can be grafted on the auxiliary grafting monomer, so that the grafting rate of the maleic anhydride is improved.
2. According to the method, the initiator and the auxiliary grafting monomer are dissolved in an acetone solution in advance, the auxiliary grafting monomer is a composition of vinyl pyrrolidone and alpha-methyl styrene, and the mixed solution is placed in an environment of 45 ℃ for heat preservation, so that the mixing uniformity of the initiator and the auxiliary grafting monomer is improved, the auxiliary grafting monomer can undergo copolymerization reaction, the grafting reaction of the auxiliary grafting monomer and polypropylene is facilitated, and the grafting rate of maleic anhydride grafted on the polypropylene is indirectly improved.
3. The temperature of 8 screw barrels of the twin-screw extruder is 170-180 ℃,180-185 ℃, 185-195 ℃, 195-200 ℃, 200-205 ℃, 205-210 ℃, 200-205 ℃ and 190-200 ℃ respectively, the temperature of the first screw barrel to the sixth screw barrel is gradually increased, the temperature increasing rate is gradually reduced, the polypropylene is prevented from being suddenly heated to cause molecular chain breakage, the mixed solution prepared by S1 is added into the fourth, fifth and sixth screw barrels at high temperature, the promotion effect of an initiator and a grafting assisting monomer on maleic anhydride grafting can be improved, and the seventh screw barrel and the eighth screw barrel are slowly cooled, so that the maleic anhydride can be stably grafted on the polypropylene.
Detailed Description
The present application is described in further detail below in connection with examples 1-14 and comparative examples 1-7.
The experimental methods in the following examples are conventional methods unless otherwise specified. The raw materials used in the following examples are all commercially available and commercially available unless otherwise specified.
Examples
Examples 1 to 6
The weight parts of the respective raw materials in the grafts in this example 1-6 are shown in Table 1.
Table 1 weight parts of the graft materials in examples 1 to 6
In examples 1-6, the polypropylene was homo-polypropylene and the antioxidant was antioxidant 1010, wherein the polypropylene was in the form of powder or granules. In other embodiments, the polypropylene may also be a copolymerized polypropylene and the antioxidant is antioxidant 1010.
In examples 1-6, the method of grafting maleic anhydride to polypropylene comprises the steps of:
s1, preparing cyclohexanone peroxide, benzoyl peroxide, vinyl pyrrolidone and alpha-methyl styrene according to corresponding parts by weight; dissolving cyclohexanone peroxide, benzoyl peroxide, vinyl pyrrolidone and alpha-methyl styrene in an acetone solution, placing the mixture in a normal pressure helium atmosphere, and preserving the temperature for 1h at room temperature to obtain a mixed solution;
s2, preparing polypropylene, maleic anhydride and an antioxidant according to the corresponding parts by weight; feeding polypropylene into a twin screw extruder; wherein, the twin-screw extruder is divided into 8 screw barrels, and the length-diameter ratio is 48:1, and are all in an environment of 200-210 ℃ and 1.8 standard atmospheres, sequentially adding an antioxidant into a second screw cylinder, adding maleic anhydride into a third screw cylinder, and adding a third screw cylinder, a fourth screw cylinder, a fifth screw cylinder and a sixth screw cylinder according to a volume ratio of 1:1.5:1, adding the mixed solution prepared in the step S1 in batches, and carrying out melt blending extrusion to obtain a grafted coarse material;
s3, placing the grafted coarse material in a nitrogen environment with the temperature of 180 ℃ and the standard atmospheric pressure of 0.2, blending for 0.5h, keeping a blending state, continuously irradiating the blending material for 100min by using ultraviolet rays with the wavelength of 250-350nm, and extruding and cooling to obtain the grafted material.
Example 7
This example 7 is different from example 3 in that in the step S1 of grafting maleic anhydride onto polypropylene in example 7, cyclohexanone peroxide, benzoyl peroxide, vinylpyrrolidone and α -methylstyrene are dissolved in an acetone solution, and then placed in a helium atmosphere at 45℃for heat preservation for 1 hour to obtain a mixed solution.
Example 8
This example 8 is different from example 3 in that in the step S1 of grafting maleic anhydride onto polypropylene in example 8, cyclohexanone peroxide, benzoyl peroxide, vinylpyrrolidone and α -methylstyrene are dissolved in an acetone solution, and then placed in a helium atmosphere at 50℃for heat preservation for 1 hour to obtain a mixed solution.
Example 9
This example 9 differs from example 3 in that in the initiator of example 9, 1.7 parts by weight of cyclohexanone peroxide is singly selected, and in the step S1 of grafting maleic anhydride to polypropylene in example 9, cyclohexanone peroxide, vinylpyrrolidone and alpha-methylstyrene are prepared in corresponding parts by weight; dissolving cyclohexanone peroxide, vinyl pyrrolidone and alpha-methylstyrene in an acetone solution, placing the mixture in a normal pressure helium atmosphere, and preserving the temperature for 1h at room temperature to obtain a mixed solution.
Example 10
This example 10 differs from example 3 in that 1.7 parts by weight of benzoyl peroxide was singly used as the initiator in example 10, and in addition, in step S1 of grafting maleic anhydride to polypropylene in example 10, benzoyl peroxide, vinylpyrrolidone and α -methylstyrene were prepared in the corresponding parts by weight; benzoyl peroxide, vinyl pyrrolidone and alpha-methyl styrene are dissolved in an acetone solution, and the mixture is placed in a normal pressure helium atmosphere, and the mixture is kept at room temperature for 1 hour, so as to obtain a mixed solution.
Example 11
This example 11 is different from example 3 in that in step S2 of grafting maleic anhydride to polypropylene in example 11, the temperatures of 8 barrels of the twin-screw extruder are 170 to 180℃and 180 to 185℃and 185 to 195℃and 195 to 200℃and 200 to 205℃and 205 to 210℃and 200 to 205℃in this order.
Example 12
This example 12 is different from example 3 in that in step S3 of grafting maleic anhydride onto polypropylene in example 12, the graft was obtained by extruding and cooling after irradiation with ultraviolet rays for 10 minutes every 5 minutes and total irradiation with ultraviolet rays for 100 minutes.
Example 13
The difference between this example 13 and example 12 is that in step S3 of grafting maleic anhydride onto polypropylene in example 13, the irradiation of ultraviolet light is performed for 10 minutes every 5 minutes, and after the total irradiation of ultraviolet light is performed for 100 minutes, the graft is obtained by extrusion heat preservation for 1 hour and then cooling.
Example 14
This example 14 differs from example 3 in that the method of grafting maleic anhydride to polypropylene in example 14 comprises the steps of:
s1, preparing cyclohexanone peroxide, benzoyl peroxide, vinyl pyrrolidone and alpha-methyl styrene according to corresponding parts by weight; dissolving cyclohexanone peroxide, benzoyl peroxide, vinyl pyrrolidone and alpha-methyl styrene in an acetone solution, placing the mixture in a normal pressure helium atmosphere, and preserving the temperature at 45 ℃ for 1h to obtain a mixed solution;
s2, preparing polypropylene, maleic anhydride and an antioxidant according to the corresponding parts by weight; feeding polypropylene into a twin screw extruder; wherein, the twin-screw extruder is divided into 8 screw barrels, and the length-diameter ratio is 48:1, the temperatures of 8 barrels in a double screw extruder are 170-180 ℃,180-185 ℃, 185-195 ℃, 195-200 ℃, 200-205 ℃, 205-210 ℃, 200-205 ℃ and 190-200 ℃ in sequence, and all are 1.8 standard atmospheric pressures, an antioxidant is sequentially added into a second barrel, maleic anhydride is added into a third barrel, and the volume ratio of the fourth barrel, the fifth barrel and the sixth barrel is 1:1.5:1, adding the mixed solution prepared in the step S1 in batches, and carrying out melt blending extrusion to obtain a grafted coarse material;
s3, placing the grafted coarse material in a nitrogen environment with the temperature of 180 ℃ and the standard atmospheric pressure of 0.2, blending for 0.5h, keeping the blending state, using ultraviolet rays with the wavelength of 250-350nm, irradiating the blending material for 10min every 5min, and after the total irradiation of the ultraviolet rays for 100min, extruding, preserving heat for 1h, and cooling to obtain the grafted material.
Comparative example
Comparative example 1
The difference between the comparative example 1 and the example 3 is that 4.1 parts of vinyl pyrrolidone is singly selected as the auxiliary grafting monomer in the comparative example 1 in parts by weight, and then the step S1 of grafting maleic anhydride to polypropylene in the comparative example 1 is to prepare cyclohexanone peroxide, benzoyl peroxide and vinyl pyrrolidone according to the corresponding parts by weight; dissolving cyclohexanone peroxide, benzoyl peroxide and vinyl pyrrolidone in an acetone solution, placing the mixture in a normal pressure helium atmosphere, and preserving the temperature at room temperature for 1h to obtain a mixed solution.
Comparative example 2
The difference between the comparative example 2 and the example 3 is that 4.1 parts of alpha-methyl styrene is singly selected as the auxiliary grafting monomer in the comparative example 2 in parts by weight, and then the step S1 of grafting maleic anhydride to polypropylene in the comparative example 2 is to prepare cyclohexanone peroxide, benzoyl peroxide and alpha-methyl styrene according to the corresponding parts by weight; dissolving cyclohexanone peroxide, benzoyl peroxide and alpha-methylstyrene in an acetone solution, placing in a normal pressure helium atmosphere, and preserving the temperature for 1h at room temperature to obtain a mixed solution.
Comparative example 3
This comparative example 3 is different from example 3 in that in step S2 of grafting maleic anhydride to polypropylene in comparative example 3, 8 barrels of a twin screw extruder are all in an atmospheric environment.
Comparative example 4
This comparative example 4 is different from example 3 in that in step S2 of grafting maleic anhydride to polypropylene in comparative example 4, the mixed solution prepared in S1 is fed into a fourth screw cylinder.
Comparative example 5
This comparative example 5 is different from example 3 in that in step S2 of grafting maleic anhydride to polypropylene in comparative example 5, the mixed solution prepared in S1 is fed into a fifth screw cylinder.
Comparative example 6
This comparative example 6 is different from example 3 in that in step S2 of grafting maleic anhydride to polypropylene in comparative example 6, the mixed solution prepared in S1 is fed into a sixth screw cylinder.
Comparative example 7
This comparative example 7 is different from example 3 in that in step S3 of grafting maleic anhydride on polypropylene in comparative example 7, the grafted raw material was placed at 180 ℃ and 0.2 standard atmospheric pressure nitrogen atmosphere, and after blending for 0.5h, the grafted material was obtained by extrusion cooling.
Performance test
Detection method
The maleic anhydride grafted polypropylene in examples 1-14 and comparative examples 1-7 was subjected to grafting ratio detection using an acid-base titration method, and the main procedure was as follows: 0.5g of polypropylene grafted maleic anhydride is weighed and dissolved in 50ml of hot xylene, 10ml of 0.1mol/L NaOH-ethanol solution is added into the system after complete dissolution, reflux is carried out for 10min, so that anhydride groups in the maleic anhydride are fully reacted with alkali, then micro deionized water is added into the system while the maleic anhydride is hot, the anhydride is promoted to hydrolyze into carboxylic acid, and meanwhile, 3 drops of phenolphthalein indicator solution are added, and hydrochloric acid/isopropanol is used for titration to a terminal point. If the hydrochloric acid/isopropanol concentration is C (mol/L), the M (G) sample is titrated, the V1 (ml) solution is consumed, the blank titration consumes the V2 (ml) solution, and the grafting ratio G is calculated according to the following formula:
the EPA 8260C-2006 (GC-MS detection method for volatile organic compounds) was used to detect VOC emissions during the preparation of maleic anhydride grafted polypropylene in examples 1-14 and comparative examples 1-7.
The above test was repeated 10 times for each of examples 1 to 14 and comparative examples 1 to 7, and the test results were averaged to remove the highest and lowest values, as shown in Table 2.
TABLE 2 data for the detection of the grafting and VOC emissions in examples 1-14 and comparative examples 1-7
In combination with examples 1-3 and examples 4-6, and with Table 2, it can be seen that the mixing ratio by weight of cyclohexanone peroxide and benzoyl peroxide in example 4 is not in the range of (0.5-1.3): in the interval (0.8-1.5), the grafting rate is obviously reduced, and the influence on VOC emission is correspondingly reduced due to the reduced grafting rate; when the mixing ratio by weight of vinylpyrrolidone and α -methylstyrene is not (1.8 to 2.6) as in example 5: in the interval (1.2-2.4), the grafting rate of polypropylene is slightly influenced, the influence on the VOC discharge is large, and the VOC discharge is obviously improved.
By combining example 3 and example 7 and combining Table 2, it can be seen that the molecular activity of the initiator and the co-grafting monomer can be improved by placing the mixed solution in an environment of 45 ℃, the copolymerization reaction of vinyl pyrrolidone and alpha-methyl styrene can be promoted, the grafting rate of polypropylene to maleic anhydride can be improved, and the emission of VOC gas in the production process can be reduced.
In combination with examples 3 and 7-8 and in combination with Table 2, it can be seen that when the mixed solution is placed in an environment of 50 ℃, micro boiling phenomenon occurs in the acetone solution due to the fact that the ambient temperature is close to the boiling point of acetone, and the activity of acetone molecules is too strong, copolymerization reaction of vinyl pyrrolidone and alpha-methylstyrene can be inhibited, and further after the mixed solution is added into a twin-screw extruder, the grafting rate of maleic anhydride is reduced, and the VOC emission in the production process is remarkably improved.
In combination with examples 3 and 9-10, and with Table 2, it can be seen that when cyclohexanone peroxide or benzoyl peroxide is used alone as the initiator, the grafting rate is significantly reduced, and the VOC emission in the production process is increased, so that when cyclohexanone peroxide and benzoyl peroxide are used alone, the grafting rate of maleic anhydride and the grafting rate of the auxiliary grafting monomer are affected, and when both are compounded for use, the grafting rate is significantly improved.
It can be seen from the combination of example 3 and example 12, and the combination of table 2 that when intermittent irradiation is performed using ultraviolet rays, the grafting ratio of polypropylene to maleic anhydride can be improved, however, the amount of VOC discharged during the production process slightly increases due to the increase in the overall duration of the S3 step.
As can be seen from the combination of examples 12 and 13 and the combination of table 2, after the extrudate was incubated for 1h, the grafting rate of polypropylene to maleic anhydride was increased by cooling, however, the VOC emissions during the production process were slightly increased compared to example 12 due to the overall length of the S3 step.
In combination with examples 3, 7, 9-13 and 14, and with Table 2, it can be seen that the grafting ratio of the polypropylene grafted maleic anhydride of example 14 is significantly improved over the other examples, and the VOC emissions during production are at moderate levels.
In combination with example 3 and comparative examples 1 to 2, and with Table 2, it can be seen that only self-copolymerization can occur when one of vinyl pyrrolidone and alpha-methylstyrene is used alone as a co-grafting monomer, the grafting ratio of maleic anhydride is lowered, and the VOC emission is slightly increased during production.
In combination with example 3 and comparative example 3, and with Table 2, it can be seen that when all of the 8 barrels of the twin screw extruder were in an atmospheric environment, there was a significant drop in grafting, however, the impact on VOC emissions was insignificant.
As can be seen from the combination of example 3 and comparative examples 4 to 6 and the combination of table 2, the addition of the mixed solution prepared in S1 to the twin screw extruder at one time has a remarkable effect on the grafting ratio and VOC emission, as in comparative example 4, the total addition of the mixed solution to the fourth screw barrel, the grafting ratio of maleic anhydride is slightly decreased, but the VOC emission is remarkably increased due to the excessive addition amount; as in comparative examples 5-6, the mixed solution was added to the fifth screw barrel in total, and the addition of initiator and co-grafting monomer was too late, reducing the grafting ratio of maleic anhydride, and significantly increasing VOC emissions due to the excessively long time of maleic anhydride and polypropylene blending alone.
As can be seen from the combination of example 3 and comparative example 7 and the combination of table 2, comparative example 7 does not undergo ultraviolet irradiation, and has a significant decrease in the grafting ratio of polypropylene to maleic anhydride, however, the VOC emission is reduced due to the relatively small amount of time used for the whole production process.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (8)
1. The preparation method of the high-grafting-rate low-VOC polypropylene grafted maleic anhydride is characterized by comprising the following steps of:
s1, 1.3-2.8 parts of initiator and 3-5 parts of auxiliary grafting monomer are dissolved in an acetone solution according to parts by weight, and placed in an inert atmosphere for heat preservation; wherein the grafting auxiliary monomer is vinyl pyrrolidone and alpha-methyl styrene, and the weight mixing ratio of the vinyl pyrrolidone to the alpha-methyl styrene is (1.8-2.6): (1.2-2.4); the initiator is a combination of cyclohexanone peroxide and benzoyl peroxide, and the weight mixing ratio of the cyclohexanone peroxide and the benzoyl peroxide is (0.5-1.3): (0.8-1.5);
s2, 100 parts of polypropylene is put into a double-screw extruder according to parts by weight; wherein, the twin-screw extruder is divided into 8 screw barrels, and all are in high-pressure environment, 5-10 parts of maleic anhydride is put into a third screw barrel in sequence, and the volume ratio of the maleic anhydride to the fourth screw barrel to the fifth screw barrel is 1: (1-2): 1, adding the mixed solution prepared in the step S1 in batches, and carrying out melt blending extrusion to obtain a grafted coarse material;
s3, placing the grafted coarse material in a vacuum environment, blending for 0.5h, keeping blending, irradiating with ultraviolet rays for 100min, and extruding to obtain the grafted material.
2. The method for preparing the high-grafting-rate low-VOC polypropylene grafted maleic anhydride according to claim 1, which is characterized in that: in the step S1, an initiator and a grafting auxiliary monomer are dissolved in an acetone solution and placed in an inert atmosphere at 45 ℃ for heat preservation for 1h.
3. The method for preparing the high-grafting-rate low-VOC polypropylene grafted maleic anhydride according to claim 2, which is characterized in that: the inert atmosphere is helium atmosphere.
4. The method for preparing the high-grafting-rate low-VOC polypropylene grafted maleic anhydride according to claim 1, which is characterized in that: the grafting material also comprises an antioxidant, wherein the antioxidant is antioxidant 1010; in the step S2, an antioxidant is added to the second screw cylinder before maleic anhydride is added.
5. The method for preparing the high-grafting-rate low-VOC polypropylene grafted maleic anhydride according to claim 1, which is characterized in that: the temperature of 8 screw barrels of the double screw extruder is 170-180 ℃,180-185 ℃, 185-195 ℃, 195-200 ℃, 200-205 ℃, 205-210 ℃, 200-205 ℃ and 190-200 ℃ in sequence, the double screw extruder is in a nitrogen environment with 1.5-2 standard atmospheric pressures, and the length-diameter ratio of the double screw extruder is 48:1.
6. the method for preparing the high-grafting-rate low-VOC polypropylene grafted maleic anhydride according to claim 1, which is characterized in that: in the step S3, the grafting coarse material is placed in a nitrogen atmosphere with the temperature of 180-190 ℃ and the standard atmospheric pressure of 0.2-0.25 for 0.5h, and after the blending is carried out, the ultraviolet irradiation is carried out for 100min, the extrusion heat preservation is carried out for 1h, and then the grafting material is obtained after cooling.
7. The method for preparing the high-grafting-rate low-VOC polypropylene grafted maleic anhydride according to claim 1 or 6, which is characterized in that: in the step S3, the irradiation with ultraviolet rays is performed for 10 minutes every 5 minutes, and the total irradiation with ultraviolet rays is performed for 100 minutes.
8. The method for preparing the high-grafting-rate low-VOC polypropylene grafted maleic anhydride according to claim 7, which is characterized in that: the wavelength of the ultraviolet rays is 250-350nm.
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