CN117986749A - High-strength lasting fragrance-retaining polypropylene and preparation method thereof - Google Patents
High-strength lasting fragrance-retaining polypropylene and preparation method thereof Download PDFInfo
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- CN117986749A CN117986749A CN202211357786.3A CN202211357786A CN117986749A CN 117986749 A CN117986749 A CN 117986749A CN 202211357786 A CN202211357786 A CN 202211357786A CN 117986749 A CN117986749 A CN 117986749A
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- -1 polypropylene Polymers 0.000 title claims abstract description 65
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 62
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 230000002045 lasting effect Effects 0.000 title abstract description 17
- 229920000106 Liquid crystal polymer Polymers 0.000 claims abstract description 42
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 claims abstract description 42
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 39
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 31
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 24
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 20
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 16
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 14
- 239000000314 lubricant Substances 0.000 claims abstract description 12
- 229920001971 elastomer Polymers 0.000 claims abstract description 10
- 239000000806 elastomer Substances 0.000 claims abstract description 10
- 239000000945 filler Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- 235000010290 biphenyl Nutrition 0.000 claims description 13
- 239000004305 biphenyl Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000000796 flavoring agent Substances 0.000 claims description 11
- JNTPTNNCGDAGEJ-UHFFFAOYSA-N 6-chlorohexan-1-ol Chemical compound OCCCCCCCl JNTPTNNCGDAGEJ-UHFFFAOYSA-N 0.000 claims description 10
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- 235000019634 flavors Nutrition 0.000 claims description 7
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 5
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 claims description 4
- 229920006132 styrene block copolymer Polymers 0.000 claims description 4
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 244000269722 Thea sinensis Species 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 230000005923 long-lasting effect Effects 0.000 claims description 3
- VMGSQCIDWAUGLQ-UHFFFAOYSA-N n',n'-bis[2-(dimethylamino)ethyl]-n,n-dimethylethane-1,2-diamine Chemical compound CN(C)CCN(CCN(C)C)CCN(C)C VMGSQCIDWAUGLQ-UHFFFAOYSA-N 0.000 claims description 3
- UHKPXKGJFOKCGG-UHFFFAOYSA-N 2-methylprop-1-ene;styrene Chemical compound CC(C)=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 UHKPXKGJFOKCGG-UHFFFAOYSA-N 0.000 claims description 2
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- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
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- 235000008632 Santalum album Nutrition 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000005907 alkyl ester group Chemical group 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- 229920001400 block copolymer Polymers 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 229920005606 polypropylene copolymer Polymers 0.000 claims description 2
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 2
- 229920005604 random copolymer Polymers 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 229940037312 stearamide Drugs 0.000 claims description 2
- 235000019222 white chocolate Nutrition 0.000 claims description 2
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 claims 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims 1
- 244000290333 Vanilla fragrans Species 0.000 claims 1
- 235000009499 Vanilla fragrans Nutrition 0.000 claims 1
- 235000012036 Vanilla tahitensis Nutrition 0.000 claims 1
- 239000003205 fragrance Substances 0.000 abstract description 37
- 230000014759 maintenance of location Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 229920003023 plastic Polymers 0.000 description 12
- 239000004033 plastic Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000002667 nucleating agent Substances 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 125000003006 2-dimethylaminoethyl group Chemical group [H]C([H])([H])N(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 7
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000007792 addition Methods 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 150000001299 aldehydes Chemical class 0.000 description 4
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- 239000002585 base Substances 0.000 description 4
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
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- 238000005303 weighing Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 229910002808 Si–O–Si Inorganic materials 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 235000013355 food flavoring agent Nutrition 0.000 description 3
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- 150000001298 alcohols Chemical class 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
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- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
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- 125000000962 organic group Chemical group 0.000 description 1
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- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses high-strength lasting fragrance polypropylene and a preparation method thereof, wherein the lasting fragrance polypropylene is prepared from the following raw materials in parts by mass: 50-95 parts of polypropylene; 0-30 parts of an elastomer; 0-40 parts of filler; 0.1-10 parts of POSS-based polyacrylic acid side chain benzene ring liquid crystal polymer; 0.01-10 parts of essence master batch; 0.1-3 parts of antioxidant; 0.1-3 parts of lubricant. The effective length of the fragrance retention of the modified polypropylene can reach more than 2 years under the standard environment, and the modified polypropylene can be used at high temperature. On the other hand, the modified polypropylene prepared by the invention shows excellent mechanical properties. The material can be applied to the fields of household appliances, automobiles, toys and the like, and has wide application prospect and commercial value.
Description
Technical Field
The invention relates to a polypropylene material, in particular to high-strength lasting fragrance polypropylene and a preparation method thereof.
Background
Along with the development of market economy and the improvement of the living standard of people, people attach more importance to the quality of life and the safety and comfort of home and environment, and the plastic materials used for home, electronic appliances and automobiles are usually provided with peculiar smell, so that the use experience of consumers is reduced, and the physical health of people is endangered. Therefore, plastic products with fragrance are becoming increasingly popular. The aromatic plastic product is produced by adding flavoring agent during the molding process, and the migration and the volatilization of essence molecules in the material are utilized to make the product permanently emit special fragrance.
The current difficulty in studying scented plastics is how to improve the durability of the scent. The extrusion and injection molding temperatures of the modified PP are about 200 ℃, the essence is easy to volatilize at high temperature, and the lasting fragrance retaining effect is difficult to ensure. Meanwhile, modified PP generally requires the addition of various additives which, while improving the material properties, may affect the emission and durability of the fragrance. In addition, the components of the essence are generally polar small molecular compounds such as alcohols, esters, aldehydes, carboxylic acids and the like, and plastic matrixes such as polypropylene and the like are nonpolar, so that the compatibility of the polar small molecular compounds and the plastic matrixes is poor, and small molecules are easily separated out on the surface of the plastic, so that the slow release of the fragrance is difficult to control.
Research on fragrant plastics at home and abroad has been advanced, mainly focusing on four directions. Firstly, essence and resin are directly blended and extruded, for example, an engineering plastic capable of emitting fragrance and a preparation method thereof are disclosed in the application number 200610157754.3, and CN201480003989.0 uses aromatic oil as a flavoring agent and a plasticizer, but the essence has poor compatibility with the resin, is volatilized in a large amount, has poor dispersibility and is not durable in fragrance. Secondly, the fragrance plastic master batch and resin are subjected to composite extrusion or injection molding, and the adsorption performance of different adsorbents and carriers in the fragrance master batch on fragrance is mainly studied, for example, CN200410075857.6 uses kaolin and polyethylene wax, CN201110450573.0 uses calcium carbonate and talcum powder, and CN201710322981.5 uses active carbon as a fragrance adsorption additive to prepare the fragrance master batch. However, these fillers have poor adsorption properties and have a problem that the fragrance volatilization loss is not long-lasting. And thirdly, preparing essence microcapsules, wherein the patents CN201010579678.1 and CN201611173289.2 respectively invent a long-acting slow-release type high-concentration aromatic plastic, and the shell micropores of the microcapsules can ensure slow release of the fragrance, improve the dispersibility of the fragrance in a plastic matrix and reduce the volatilization loss in the high-temperature processing process. And fourthly, constructing a latent fragrance body of the essence, namely connecting a certain compound with the essence through a covalent bond, and then breaking the covalent bond under certain conditions to release the essence. The patent CN201711133279.0 utilizes the condensation reaction of POSS-based 1, 2-dihydroxyl compound and essence aldehyde and ketone to obtain a latent fragrance body, improves the slow release effect of the essence on fiber cloth, but the method has narrow universality on essence types, is only inapplicable to aldehyde and ketone essence, olefin, carboxylic acid, ester essence and the like, and only depends on the nano structure of POSS to enter a fiber cavity so as to achieve the effects of absorption and slow release of essence molecules, and has limited effect. Although various implementation methods have been developed, most of the methods have the defects of easy exudation and volatilization of essence and carrier resin, quicker fragrance loss and poor fragrance retaining effect, and meanwhile, the preparation process is complex, the cost is high, and the method is not beneficial to large-scale popularization. Therefore, improving the fragrance retention effect and durability of the fragrant plastic is still a problem to be solved.
Polyhedral oligomeric silsesquioxane (POSS) is an organic-inorganic intramolecular hybridization material on a molecular level, is a space cage type nano structure formed by inorganic kernel frameworks alternately connected with Si-O and peripherally connected organic groups, and has the toughness, hydrophobicity, compatibility of an organic polymer material and the stability and heat resistance of the inorganic material. The POSS is used as a plasticizer and a reinforcing agent to modify the polymer, so that the performances of heat resistance, modulus, compressive strength, hardness, wear resistance and the like of the polymer material can be improved. On one hand, POSS plays a role in chain extension and crosslinking, and improves the viscosity of a resin matrix, so that the strength of the material can be improved. The cage structure with nanometer size is favorable for the polymer chain to pass through, realizes the dispersion of molecular level, simultaneously generates physical entanglement effect on the passed polymer chain, and improves the glass transition temperature (T g) and the thermal decomposition temperature (T d) of the material. On the other hand, the rigid POSS nano particles are dispersed in the matrix, and when the material is impacted, silver grains can be induced to absorb impact energy at the periphery, so that the toughness of the material is improved.
The modification by adding a nucleating agent is a common method for improving the mechanical strength of polypropylene, and the nucleating agent can be divided into inorganic and organic micromolecules and macromolecule nucleating agents according to the main components of the nucleating agent. The inorganic nucleating agent has low nucleating efficiency, poor compatibility with a polymer matrix and uneven dispersion. The organic micromolecular nucleating agent has higher nucleating efficiency, but has the problems of high cost, easy agglomeration, difficult dispersion, migration, toxicity and the like. Based on this, the development of novel high molecular β nucleating agents has become a research hotspot. The liquid crystal polymer has the advantages of high strength, high modulus, chemical corrosion resistance, stable size and the like, can form microfibers in situ with thermoplastic plastics under certain processing conditions, and is dispersed in a base material at a molecular level to achieve the enhancement effect, and is widely focused. However, the liquid crystal polymer and the PP substrate are polymers, but the liquid crystal polymer and the PP substrate are non-compatible systems, and phase separation is easy to occur in the processing process. For example, CN201610941324.4 utilizes liquid crystal polymer beta nucleating agent to improve impact strength, elongation at break and heat resistance of PP, but the problem of compatibility is not solved yet.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of high-strength lasting fragrance-retaining polypropylene, which utilizes POSS-based polyacrylic acid side chain benzene ring liquid crystal polymers to improve the dispersibility and compatibility of essence in PP base materials, slow down the migration rate of essence molecules and effectively prolong the fragrance emission time. Meanwhile, the material is used as a nucleating agent to provide mechanical strength, and the compatibility of the material with PP is improved by modifying liquid crystal polymers.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
The modified polypropylene with lasting fragrance is prepared from the following raw materials in parts by mass:
50-95 parts of polypropylene;
0-30 parts, preferably 5-15 parts, of an elastomer;
0-40 parts, preferably 10-30 parts, of filler;
0.1 to 10 parts, preferably 0.5 to 5 parts, of POSS-based polyacrylic acid side chain benzene ring liquid crystal polymer;
0.01-10 parts, preferably 0.2-2 parts, of essence master batch;
0.1 to 3 parts of antioxidant, preferably 0.2 to 1 part;
0.1 to 3 parts, preferably 0.2 to 1.5 parts, of lubricant.
In the invention, the polypropylene is one or more than two of homo-polypropylene, random copolymer polypropylene and block copolymer polypropylene. Preferably, the melt flow index of the polypropylene is 10-100g/10min at 230℃and 2.16 KG.
In the present invention, the elastomer is one or a mixture of two or more of an ethylene-butene copolymer, a styrene-ethylene-isobutylene-styrene block copolymer and a styrene-isobutylene-styrene block copolymer.
In the invention, the filler is one or more of talcum powder, calcium carbonate, diatomite, kaolin and barium sulfate.
In the invention, the structure of the POSS-based polyacrylic acid side chain benzene ring liquid crystal polymer is shown in the following formula, the number average molecular weight Mn is 5-72 kg/mol, n=9-100, and the R group is one of phenyl, isobutyl, cyclopentyl and the like.
Further, the synthetic method of the POSS-based polyacrylic acid side chain benzene ring liquid crystal polymer comprises the following steps:
1) Adding 4,4 '-biphenol into DMF solution containing alkali compound, preferably anhydrous K 2CO3、Na2CO3 or NaOH, and adding 6-chloro-1-hexanol and KI or CuI, wherein the molar ratio of the 4,4' -biphenol, the 6-chloro-1-hexanol, the KI or CuI and the alkali compound is (1:3:0.03:9) - (1:5:0.05:12). Heating, condensing and refluxing for 10-24 h, reacting at 120-160 ℃, and filtering. Preferably, the filtered product is placed in a beaker, 100-200 mL of deionized water is added, the pH is regulated to 1-3 by concentrated hydrochloric acid after uniform stirring, the filtered product is repeatedly washed by distilled water for several times, and finally the white solid product biphenyl dioxyhexanol is obtained after vacuum drying.
2) Biphenyl dioxyhexanol is dissolved in a solvent, preferably DMF, methacrylic acid, substituted benzoic acid compound a is added, concentrated sulfuric acid is slowly added dropwise, preferably the four molar ratios (1:2:2: 0.1 (1:4:4): 0.4). Reacting for 10-20 h at 80-120 ℃, separating and purifying to obtain the methacrylate compound B.
3) Adding 3-hydroxypropyl heptaisobutyl POSS into a solvent, preferably DMF, stirring for 1-2 h, cooling to-20 ℃, adding triethylamine, slowly dropwise adding 2-chloroacetyl chloride in a stirring state, preferably, reacting for 20-40 h at room temperature, wherein the molar ratio of the three is (1:6:5) - (1:12:10). After the reaction is finished, cleaning the reactant by using 0.3-0.7 mol/L NaOH solution, 0.3-0.7 mol/L hydrochloric acid solution and a large amount of deionized water in sequence, adding the lower layer liquid into excessive methanol, benzene, acetone or acetonitrile after separation, and vacuum drying the precipitate at 80-120 ℃ for 5-10 hours to obtain the macromolecular initiator POSS-C1.
4) POSS-C1 is dissolved in a solvent, preferably DMF, then methacrylate compound B is added, stirring is carried out, ammonia gas is filled, cuC1 and tri (2-dimethylaminoethyl) amine are dissolved in the solvent, preferably DMF, then dropwise added into a reaction bottle, and the reaction is carried out for 1-6 h at 30-70 ℃. Preferably, the molar ratio of POSS-C1, compound B, cuC, tris (2-dimethylaminoethyl) amine is (1:50:10:10) - (1:100:20:20). Preferably, after the reaction is finished, separating and purifying, dialyzing for 1-3 days, and freeze-drying the dialyzed aqueous solution to obtain the POSS-based polyacrylic acid side chain benzene ring liquid crystal polymer C.
In the invention, the flavor type of the essence master batch mainly comprises floral, fruit and other types, and can resist the high temperature of 250 ℃, such as one or more of tea flavor type, white chocolate flavor type, violet flavor type, vanilla flavor type, basil flavor type and sandalwood flavor type. Preferably, the carrier of the essence master batch is EVA, and the EVA is of a linear branched structure, has high softness and cohesiveness, has a low melting point of about 100 ℃, has a low processing temperature, and is favorable for absorption and slow release of the flavoring agent. The VA content of the EVA is between 5 and 40.
In the invention, the antioxidant is one or a mixture of more of hindered phenol macromolecular antioxidants, phosphorous acid antioxidants and alkyl ester antioxidants. Preferably, the phosphorous acid antioxidant is 168, namely tris [ 2.4-di-tert-butylphenyl ] phosphite ester, and the adding amount is 0.1-1 part; the hindered phenol antioxidant is 1010, namely pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], and the adding amount is 0.1-1 part.
In the invention, the lubricant is one or more of polyolefin wax, stearate, stearamide lubricant or polyethylene glycol.
A preparation method of high-strength lasting fragrance-retaining polypropylene comprises the following steps:
(a) Preparing POSS-based polyacrylic acid side chain benzene ring liquid crystal polymers;
(b) Weighing the raw materials according to the mass percentage;
(c) The polypropylene, the elastomer, the filler, the antioxidant and the lubricant are evenly mixed and then put into a main feeding bin of a double-screw extruder, the POSS-based polyacrylic acid side chain benzene ring liquid crystal polymer and the essence master batch are put into a side feeding port, are melt extruded at the temperature of 140-240 ℃ and the rotating speed of 400-700 r/min, and are then granulated and dried, and finally the high-strength lasting fragrance-retaining polypropylene is obtained.
The invention provides high-strength lasting fragrance polypropylene and a preparation method thereof, and compared with the prior art, the invention has the advantages that:
1. The modified polypropylene can effectively release fragrance for a long time, so that people feel happy, and the requirements of consumers are met. The principle of the long-lasting fragrance retaining effect is as follows: 1) The POSS molecules are of a cage-shaped structure with nanometer size, and can effectively capture free essence small molecular compounds while generating physical entanglement effect on high molecular chains, so that the essence is dispersed more uniformly, and the migration speed to the surface of a product is reduced. Meanwhile, POSS as an organic-inorganic nano hybrid material can simultaneously act on nonpolar PP resin and polar EVA essence carrier, so that the compatibility of essence master batch and matrix resin is improved. And POSS is grafted on the liquid crystal polymer, so that the molecular weight of the liquid crystal polymer can be increased, and the risk of precipitation is reduced. 2) The POSS-based polyacrylic acid side chain benzene ring liquid crystal polymer has side chains containing phenyl groups and ester bonds, and essence molecules mainly comprise aromatic group-containing alcohols, esters, aldehydes and other small organic molecules, and have similar compatibility. And the side chain benzene rings of the liquid crystal polymers are orderly piled up, so that the liquid crystal polymer has larger steric hindrance, can increase the distance between molecular chains, and further adsorbs essence in gaps between the polymer chains, thereby playing a role in slow release. Under standard environment, the effective fragrance can be maintained for more than 2 years, and the product can be used at high temperature.
2. The modified polypropylene of the invention has excellent mechanical strength, can be applied to the fields of household appliances, automobiles, toys and the like, and can be popularized and applied in wider market environments. On one hand, the POSS framework is dispersed in the matrix, and when the POSS framework is impacted, silver grains can be triggered to absorb impact energy, so that the toughness of the material is improved. On the other hand, the side chain benzene rings of the liquid crystal polymer are staggered, parallel and orderly stacked to form strong pi-pi interaction, and the strong pi-pi interaction is used as crystal nucleus to induce polypropylene to form beta crystals, so that the rigidity of the material is improved. The terminal alkenyl structure on the side chain can be used for the compatibility of the POSS-based polyacrylic acid side chain benzene ring liquid crystal polymer and polypropylene.
Detailed Description
Specific embodiments within the scope of the present invention will be further described and illustrated by the following examples. The examples are merely illustrative and not limiting of the scope of the invention, as many variations of the invention are possible without departing from its spirit and scope.
All formulations and tests herein take place in an environment of 25 ℃, unless otherwise indicated.
The terms "comprising," "including," "containing," "having," or other variations thereof herein are intended to cover a non-closed inclusion, without distinguishing between them. The term "comprising" means that other steps and ingredients may be added that do not affect the end result. The term "comprising" also includes the terms "consisting of …" and "consisting essentially of …". The compositions and methods/processes of the present invention can comprise, consist of, and consist essentially of the essential elements and limitations described herein, as well as additional or optional ingredients, components, steps, or limitations of any of the embodiments described herein.
Unless otherwise specified, all materials and reagents involved in the experiments were purchased commercially.
TABLE 1 raw material information related thereto
The test methods used or possible to be used in the examples and comparative examples are described below.
Table 2 related test methods
Example 1
(A) Preparing the seven-isobutyl POSS-based polyacrylic acid side chain benzene ring liquid crystal polymer. 4,4' -biphenol was added to a DMF solution containing anhydrous K 2CO3 (molar ratio of 4,4' -biphenol to solution 1:50), followed by addition of 6-chloro-1-hexanol and KI, 4' -biphenol, 6-chloro-1-hexanol, KI, K 2CO3 in a molar ratio of 1:3:0.03:9. Heating, condensing and refluxing for 20 hours, reacting at 140 ℃, and filtering. And placing the filtered product in a beaker, adding 200mL of deionized water, uniformly stirring, regulating the pH to 2 by using concentrated hydrochloric acid, repeatedly washing the filtered product with distilled water for 3 times, and finally drying in vacuum to obtain the white solid product biphenyl dioxyhexanol. The biphenyl dioxyhexanol is dissolved in a solvent DMF (molar ratio 1:40), methacrylic acid and substituted benzoic acid compounds are added, concentrated sulfuric acid is slowly added dropwise, and the molar ratio of the biphenyl dioxyhexanol to the substituted benzoic acid compounds is 1:3:3:0.2. Reacting for 20h at 100 ℃, and separating and purifying to obtain the methacrylate compound. 3-hydroxypropyl heptaisobutyl POSS is added into DMF (molar ratio 1:20), stirred for 1h, cooled to 0 ℃, triethylamine is added, 2-chloroacetyl chloride is slowly added dropwise under stirring, the molar ratio of the three is 1:9:8, and the reaction is carried out for 24h at room temperature. After the reaction is finished, cleaning the reactant by using 0.5mol/L NaOH solution, 0.5mol/L hydrochloric acid solution and a large amount of deionized water in sequence, adding the lower layer solution into excessive methanol after separation, and vacuum drying the precipitate at 100 ℃ for 8 hours to obtain the macromolecular initiator heptaisobutyl POSS-C1. Seven isobutyl POSS-C1 is dissolved in DMF (molar ratio 1:30), then methacrylate compound is added, stirred and dissolved, and ammonia gas is filled. After CuC1 and tri (2-dimethylaminoethyl) amine are dissolved in DMF (molar ratio 1:20), the mixture is added into a reaction bottle in a dropwise manner, the mixture is reacted for 5 hours at 50 ℃, and the molar ratio of POSS-C1, methacrylate compounds, cuC1 and tri (2-dimethylaminoethyl) amine is 1:50:10:10. After the reaction is finished, separating and purifying by using column chromatography, dialyzing for 2 days, and freeze-drying the dialyzed aqueous solution at the temperature of minus 20 ℃ for 24 hours to obtain the heptaisobutyl POSS-based polyacrylic acid side chain benzene ring liquid crystal polymer, wherein the number average molecular weight Mn=51.8 kg/mol and n=71. Analyzing the chemical structure of the product by adopting an infrared spectrometer, wherein an telescopic vibration peak of olefin=CH appears at 3030cm -1, an telescopic vibration peak of-CH 2 -appears at 2930 and 2838cm -1, an telescopic vibration peak of ester group C=O appears at 1730cm -1, a deformation vibration peak of saturated-CH 3 appears at 1459 and 1377cm -1, an telescopic vibration peak of Si-O-Si appears at 1173cm -1, an telescopic vibration peak of benzene ring C=C appears at 1501cm -1, and an telescopic vibration peak of benzene ring-CH appears at 823cm -1;
(b) Weighing the raw materials according to the parts by mass;
(c) Evenly mixing the copolymer polypropylene, the elastomer, the talcum powder, the antioxidant and the lubricant, then putting the mixture into a main feeding bin of a double-screw extruder, putting 3 parts of POSS-based polyacrylic acid side chain benzene ring liquid crystal polymer and 0.5 part of tea charm essence master batch into a side feeding port, the screw temperature is set to 140 ℃, 180 ℃, 210 ℃, 200 ℃ and 600r/min of screw speed from a feed opening to a machine head section, and the high-strength lasting fragrance-retaining polypropylene is finally obtained after melt extrusion, pelleting and drying.
Example 2
(A) Preparing the heptacyclopentyl POSS-based polyacrylic acid side chain benzene ring liquid crystal polymer. 4,4 '-biphenol was added to a DMF (molar ratio 1:50) solution containing anhydrous Na 2CO3, and 6-chloro-1-hexanol and KI were added thereto, the molar ratio of 4,4' -biphenol, 6-chloro-1-hexanol, KI, na 2CO3 being 1:3:0.05:10. Heating, condensing and refluxing for 20 hours, reacting at 140 ℃, and filtering. And placing the filtered product in a beaker, adding 200mL of deionized water, uniformly stirring, regulating the pH to 2 by using concentrated hydrochloric acid, repeatedly washing the filtered product with distilled water for 3 times, and finally drying in vacuum to obtain the white solid product biphenyl dioxyhexanol. The biphenyl dioxyhexanol is dissolved in a solvent DMF (molar ratio 1:40), methacrylic acid and substituted benzoic acid compounds are added, concentrated sulfuric acid is slowly added dropwise, and the molar ratio of the biphenyl dioxyhexanol to the substituted benzoic acid compounds is 1:3:2:0.2. Reacting for 20h at 100 ℃, and separating and purifying to obtain the methacrylate compound. 3-hydroxypropyl heptacyclopentyl POSS is added into DMF (molar ratio 1:20), stirred for 1h, cooled to 0 ℃, triethylamine is added, 2-chloroacetyl chloride is slowly added dropwise under stirring, the molar ratio of the three is 1:12:10, and the reaction is carried out for 24h at room temperature. After the reaction is finished, cleaning the reactant by using 0.5mol/L NaOH solution, 0.5mol/L hydrochloric acid solution and a large amount of deionized water in sequence, adding the lower layer solution into excessive methanol after separation, and vacuum drying the precipitate at 100 ℃ for 8 hours to obtain the macromolecular initiator heptacyclopentyl POSS-C1. Seven-cyclopentyl POSS-C1 is dissolved in DMF (molar ratio 1:30), then methacrylate compounds are added, stirred and dissolved, and ammonia gas is filled. After CuC1 and tri (2-dimethylaminoethyl) amine are dissolved in DMF (molar ratio 1:20), the mixture is added into a reaction bottle in a dropwise manner, the mixture is reacted for 6 hours at 50 ℃, and the molar ratio of POSS-C1, methacrylate compounds, cuC1 and tri (2-dimethylaminoethyl) amine is 1:70:15:15. After the reaction is finished, separating and purifying by using column chromatography, dialyzing for 2 days, freeze-drying the dialyzed aqueous solution at the temperature of minus 20 ℃ for 24 hours to obtain the heptacyclopentyl POSS-based polyacrylic acid side chain benzene ring liquid crystal polymer, wherein the number average molecular weight Mn=67.2 kg/mol, and n=92. Analyzing the chemical structure of the product by adopting an infrared spectrometer, wherein an olefin=CH telescopic vibration peak appears at 3032cm -1, a-CH 2 -telescopic vibration peak appears at 2921 and 2837cm -1, an ester group C=O telescopic vibration peak appears at 1721cm -1, a saturated-CH 3 deformation vibration peak appears at 1460 and 1377cm -1, a Si-O-Si telescopic vibration peak appears at 1167cm -1, a benzene ring C=C telescopic vibration peak appears at 1549cm -1, a benzene ring-CH telescopic vibration peak appears at 822cm -1 and a (CH 2) n telescopic vibration peak appears at 720cm -1;
(b) Weighing the raw materials according to the weight percentage;
(c) Evenly mixing the copolymer polypropylene, the elastomer, the talcum powder, the antioxidant and the lubricant, then putting the mixture into a main feeding bin of a double-screw extruder, putting 0.5 part of POSS-based polyacrylic acid side chain benzene ring liquid crystal polymer and 2 parts of violet essence master batch into a side feeding port, the screw temperature is set to 140 ℃, 180 ℃, 210 ℃, 200 ℃ and 600r/min of screw speed from a feed opening to a machine head section, and the high-strength lasting fragrance-retaining polypropylene is finally obtained after melt extrusion, pelleting and drying.
Example 3
(A) Preparing the heptaphenyl POSS base polyacrylic acid side chain benzene ring liquid crystal polymer. 4,4 '-biphenol was added to a DMF (molar ratio 1:50) solution containing anhydrous K 2CO3, followed by addition of 6-chloro-1-hexanol and CuI, 4' -biphenol, 6-chloro-1-hexanol, KI, K 2CO3 in a molar ratio 1:4:0.04:12. Heating, condensing and refluxing for 15h, reacting at 140 ℃, and filtering. And placing the filtered product in a beaker, adding 200mL of deionized water, uniformly stirring, regulating the pH to 2 by using concentrated hydrochloric acid, repeatedly washing the filtered product with distilled water for 3 times, and finally drying in vacuum to obtain the white solid product biphenyl dioxyhexanol. The biphenyl dioxyhexanol is dissolved in a solvent DMF (molar ratio 1:40), methacrylic acid and substituted benzoic acid compounds are added, concentrated sulfuric acid is slowly added dropwise, and the molar ratio of the biphenyl dioxyhexanol to the substituted benzoic acid compounds is 1:4:4:0.4. Reacting for 20h at 100 ℃, and separating and purifying to obtain the methacrylate compound. 3-hydroxypropyl heptaphenyl POSS is added into DMF (molar ratio 1:20), stirred for 2 hours, cooled to-10 ℃, triethylamine is added, 2-chloroacetyl chloride is slowly added dropwise under stirring, the molar ratio of the three is 1:6:6, and the reaction is carried out for 30 hours at room temperature. After the reaction is finished, cleaning the reactant by using 0.5mol/L NaOH solution, 0.5mol/L hydrochloric acid solution and a large amount of deionized water in sequence, adding the lower layer solution into excessive methanol after separation, and vacuum drying the precipitate at 100 ℃ for 10 hours to obtain the macromolecular initiator heptaphenyl POSS-C1. Seven-phenyl POSS-C1 is dissolved in DMF (molar ratio 1:30), then methacrylate compounds are added, stirred and dissolved, and ammonia gas is filled. After CuC1 and tri (2-dimethylaminoethyl) amine are dissolved in DMF (molar ratio 1:20), the mixture is added into a reaction bottle in a dropwise manner, the mixture is reacted for 5 hours at 50 ℃, and the molar ratio of POSS-C1, methacrylate compounds, cuC1 and tri (2-dimethylaminoethyl) amine is 1:100:20:20. After the reaction is finished, separating and purifying by using column chromatography, dialyzing for 2 days, and freeze-drying the dialyzed aqueous solution at the temperature of minus 20 ℃ for 24 hours to obtain the heptaphenyl POSS-based polyacrylic acid side chain benzene ring liquid crystal polymer, wherein the number average molecular weight Mn=26.9 kg/mol and n=36. Analyzing the chemical structure of the product by adopting an infrared spectrometer, wherein an telescopic vibration peak of olefin=CH appears at 3025cm -1, an telescopic vibration peak of-CH 2 -appears at 2923 and 2837cm -1, an telescopic vibration peak of ester group C=O appears at 1715cm -1, a deformation vibration peak of saturated-CH 3 appears at 1459 and 1377cm -1, an telescopic vibration peak of Si-O-Si appears at 1162cm -1, an telescopic vibration peak of benzene ring C=C appears at 1504cm -1, and an telescopic vibration peak of benzene ring-CH appears at 820cm -1;
(b) Weighing the raw materials according to the weight percentage;
(c) Evenly mixing the copolymer polypropylene, the elastomer, the calcium carbonate, the antioxidant and the lubricant, then putting the mixture into a main feeding bin of a double-screw extruder, putting 5 parts of POSS-based polyacrylic acid side chain benzene ring liquid crystal polymer and 1 part of tea-flavor essence master batch into a side feeding port, the screw temperature is set to 140 ℃, 180 ℃, 210 ℃, 200 ℃ and 600r/min of screw speed from a feed opening to a machine head section, and the high-strength lasting fragrance-retaining polypropylene is finally obtained after melt extrusion, pelleting and drying.
Comparative example 1
The commercially available liquid crystal polymer E6008 is used as a raw material to replace the prepared POSS-based polyacrylic acid side chain benzene ring liquid crystal polymer, and modified polypropylene is prepared according to the method in example 1.
Comparative example 2
The commercially available 3-hydroxypropyl heptaisobutyl POSS was used as a raw material to replace the prepared POSS-based polyacrylic acid side chain benzene ring liquid crystal polymer, and polypropylene was prepared according to the method in example 1.
Comparative example 3
Polypropylene was prepared according to the method of example 1, except that the POSS-based polyacrylic acid side chain benzene ring liquid crystal polymer was not added.
Table 3 Material proportions of examples, comparative examples
Modified polypropylene pellets were prepared according to the above preparation method, and were injection-molded into bars, respectively, and subjected to performance test, and the results are shown in Table 4.
TABLE 4 results of Performance test of the products obtained in examples 1 to 3 and comparative examples 1 to 3
Note that: the molecular weight of the material was measured using a gel permeation chromatograph, and xylene was selected as the solvent after removal of the filler, since the filler would affect the molecular weight measurement.
Evaluation of fragrance duration: the bars of the above examples and comparative examples were left at 110℃for 200 hours, 600 hours and at normal temperature for 8 months, and then subjected to fragrance evaluation scoring. Please 5 panelists each rated the odor according to the PV3900 standard, with a score of each of 5 panelists as an average of the scores, and a total score of 6. The results are shown in Table 5.
Table 5 evaluation of odor of products obtained in examples 1 to 3 and comparative examples 1 to 3
As can be seen from Table 4, in examples 1 to 3, after the POSS-based polyacrylic acid side chain benzene ring liquid crystal polymer is added, the stretching, bending and impact properties of the material are all obviously improved, and the heat distortion temperature is improved from 99 to 116 ℃. The POSS base polyacrylic acid side chain benzene ring liquid crystal polymer plays a role in strengthening and toughening in a material, when the POSS end is impacted, silver grains are triggered to absorb impact energy to play a role in toughening, and the polyacrylic acid side chain benzene ring liquid crystal polymer end is used as a nucleating agent to play a role in strengthening, and has good compatibility with a PP matrix.
As can be seen from Table 5, the fragrance of examples 1 to 3 can be maintained for a longer time than that of comparative examples, fragrance can be maintained after the examples are placed for 1 year at normal temperature and for 600 hours at a high temperature of 110 ℃, and the fragrance of comparative examples is basically dissipated cleanly, which indicates that the POSS-based polyacrylic acid side chain benzene ring liquid crystal polymer has excellent compatibility and adsorption effect on essence molecules, so that better slow-release and lasting fragrance retaining effects are achieved.
The invention is suitable for various types and material systems, can obviously slow down the exudation and volatilization of essence in matrix resin, reduces the dispersion speed, has lasting fragrance, has excellent mechanical properties and high popularization value.
The high-strength lasting fragrance-retaining polypropylene and the preparation method thereof provided by the invention are described in detail, and the principle and the implementation mode of the invention are described by applying specific examples. Finally, it should be noted that the above description is only of a preferred embodiment of the invention, which is described in more detail and is not intended to limit the invention in any other way. Improvements, additions and modifications may be made by those skilled in the art without departing from the method of the present invention, and such improvements, additions and modifications are also considered to be within the scope of the present invention.
Claims (10)
1. A high strength, long lasting fragrance-retaining polypropylene, characterized in that: the material is prepared from the following raw materials in parts by mass:
50-95 parts of polypropylene;
0-30 parts, preferably 5-15 parts, of an elastomer;
0-40 parts, preferably 10-30 parts, of filler;
0.1 to 10 parts, preferably 0.5 to 5 parts, of POSS-based polyacrylic acid side chain benzene ring liquid crystal polymer;
0.01-10 parts, preferably 0.2-2 parts, of essence master batch;
0.1 to 3 parts of antioxidant, preferably 0.2 to 2 parts;
0.1 to 3 parts, preferably 0.2 to 1.5 parts, of lubricant.
2. The polypropylene according to claim 1, wherein: the polypropylene is one or more of homo-polypropylene, random copolymer polypropylene and block copolymer polypropylene, wherein the melt flow index is 10-100 g/10min at 230 ℃ and 2.16 KG.
3. The polypropylene of claim 1, wherein the elastomer is one or more of an ethylene-butene copolymer, a styrene-ethylene-isobutylene-styrene block copolymer, and a styrene-isobutylene-styrene block copolymer; and/or the filler is one or more of talcum powder, calcium carbonate, diatomite, kaolin and barium sulfate.
4. A polypropylene according to any one of claims 1 to 3, wherein the POSS-based polyacrylic acid side chain benzene ring liquid crystal polymer has a structure represented by the following formula, a number average molecular weight Mn of 5 to 72kg/mol, n=9 to 100, and an r group of one of phenyl, isobutyl, and cyclopentyl.
5. The polypropylene according to claim 4, wherein the preparation of the POSS-based polyacrylic acid side chain benzene ring liquid crystal polymer comprises the following steps:
1) Adding 4,4 '-biphenol into DMF solution containing alkali compounds, preferably anhydrous K 2CO3、Na2CO3 or NaOH, adding 6-chloro-1-hexanol and KI or CuI, heating, condensing and refluxing for 10-24 hours at a reaction temperature of 120-160 ℃, preferably, the molar ratio of 4,4' -biphenol, 6-chloro-1-hexanol, KI or CuI and alkali compounds (1:3:0.03:9) - (1:5:0.05:12); obtaining biphenyl dioxyhexanol;
2) Biphenyl dioxyhexanol is dissolved in a solvent, preferably DMF, methacrylic acid, substituted benzoic acid compound a is added, concentrated sulfuric acid is added, preferably in a molar ratio of four (1:2:2: 0.1 (1:4:4): 0.4 A) is provided; reacting for 10-20 h at 80-120 ℃, separating and purifying to obtain a methacrylate compound B;
3) Adding 3-hydroxypropyl heptaisobutyl POSS into DMF, preferably stirring for 1-2 h, cooling to-20 ℃, adding triethylamine, adding 2-chloroacetyl chloride in a stirring state, preferably reacting for 20-40 h at room temperature at the molar ratio of (1:6:5) - (1:12:10), and obtaining a macromolecular initiator POSS-C1;
4) And (2) dissolving POSS-C1 in a solvent, preferably DMF, adding the solvent to react, adding the methacrylate compound B to stir and dissolve, filling ammonia gas, dissolving CuC1 and tris (2-dimethylaminoethyl) amine in the solvent, preferably DMF, adding the solvent to a reaction bottle, and reacting for 1-6 h at 30-70 ℃ to obtain the POSS-based polyacrylic acid side chain benzene ring liquid crystal polymer C.
6. The polypropylene according to claim 5, wherein the molar ratio of POSS-C1, methacrylate-based compound B, cuC, tris (2-dimethylaminoethyl) amine in step 4) is from (1:50:10:10) to (1:100:20:20).
7. The polypropylene according to any one of claims 1 to 6, wherein the flavour master batch is one or more of a tea note type, a white chocolate note type, an violet note type, a vanilla note type, a basil note type, a sandalwood note type, preferably wherein the carrier of the flavour master batch is EVA.
8. The polypropylene according to any one of claims 1 to 7, wherein the antioxidant is a mixture of one or more of hindered phenol type macromolecular antioxidants, phosphorous acid type antioxidants and alkyl ester antioxidants; preferably, the phosphorous acid antioxidant is 168, namely tris [2, 4-di-tert-butylphenyl ] phosphite, the adding amount is 0.1-1 part, the hindered phenol antioxidant is 1010, namely tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, and the adding amount is 0.1-1 part.
9. The polypropylene according to any one of claims 1 to 8, wherein the lubricant is one or more of a polyolefin wax, a stearate, a stearamide lubricant or a polyethylene glycol.
10. A process for the preparation of polypropylene according to any one of claims 1 to 9, comprising the steps of:
Polypropylene, elastomer, filler, antioxidant and lubricant are mixed uniformly and then put into a main feeding bin of a double-screw extruder, liquid crystal polymer with POSS-group polyacrylic acid side chain benzene ring and essence master batch are put into a side feeding port, melt-extruded at 140-240 ℃ and with the rotating speed of 400-700 r/min, and then granulated and dried.
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