CN117106237A - Composite modifier and polypropylene composition thereof - Google Patents
Composite modifier and polypropylene composition thereof Download PDFInfo
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- CN117106237A CN117106237A CN202310817332.8A CN202310817332A CN117106237A CN 117106237 A CN117106237 A CN 117106237A CN 202310817332 A CN202310817332 A CN 202310817332A CN 117106237 A CN117106237 A CN 117106237A
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- polypropylene
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- phenyldihydrazide
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 99
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 99
- -1 polypropylene Polymers 0.000 title claims abstract description 82
- 239000002131 composite material Substances 0.000 title claims abstract description 60
- 239000003607 modifier Substances 0.000 title claims abstract description 29
- 239000000203 mixture Substances 0.000 title claims abstract description 24
- 239000000835 fiber Substances 0.000 claims abstract description 72
- 150000001875 compounds Chemical class 0.000 claims abstract description 38
- 241000196324 Embryophyta Species 0.000 claims description 28
- 240000000491 Corchorus aestuans Species 0.000 claims description 10
- 235000011777 Corchorus aestuans Nutrition 0.000 claims description 10
- 235000010862 Corchorus capsularis Nutrition 0.000 claims description 10
- 235000004431 Linum usitatissimum Nutrition 0.000 claims description 10
- 229920013822 aminosilicone Polymers 0.000 claims description 9
- 239000000839 emulsion Substances 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 244000280244 Luffa acutangula Species 0.000 claims description 4
- 235000009814 Luffa aegyptiaca Nutrition 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- PNWFFTWFSDDZTE-UHFFFAOYSA-N 2-aminoethanol;copper Chemical compound [Cu].NCCO PNWFFTWFSDDZTE-UHFFFAOYSA-N 0.000 claims description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 2
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 240000006240 Linum usitatissimum Species 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 12
- 238000012986 modification Methods 0.000 abstract description 9
- 230000004048 modification Effects 0.000 abstract description 9
- 238000010899 nucleation Methods 0.000 abstract description 6
- 230000006911 nucleation Effects 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 230000021615 conjugation Effects 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract description 2
- 125000004430 oxygen atom Chemical group O* 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 15
- 239000003963 antioxidant agent Substances 0.000 description 12
- 230000003078 antioxidant effect Effects 0.000 description 12
- 239000002667 nucleating agent Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 241000208202 Linaceae Species 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 238000001125 extrusion Methods 0.000 description 7
- 238000005469 granulation Methods 0.000 description 7
- 230000003179 granulation Effects 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 238000007873 sieving Methods 0.000 description 7
- 238000002791 soaking Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 239000000155 melt Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 238000010298 pulverizing process Methods 0.000 description 6
- 239000004927 clay Substances 0.000 description 4
- 229920001903 high density polyethylene Polymers 0.000 description 4
- 239000004700 high-density polyethylene Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000000600 sorbitol Substances 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920001432 poly(L-lactide) Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- QUUCYKKMFLJLFS-UHFFFAOYSA-N Dehydroabietan Chemical class CC1(C)CCCC2(C)C3=CC=C(C(C)C)C=C3CCC21 QUUCYKKMFLJLFS-UHFFFAOYSA-N 0.000 description 1
- NFWKVWVWBFBAOV-UHFFFAOYSA-N Dehydroabietic acid Chemical class OC(=O)C1(C)CCCC2(C)C3=CC=C(C(C)C)C=C3CCC21 NFWKVWVWBFBAOV-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- WARCRYXKINZHGQ-UHFFFAOYSA-N benzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1 WARCRYXKINZHGQ-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000007707 calorimetry Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- NFWKVWVWBFBAOV-MISYRCLQSA-N dehydroabietic acid Chemical class OC(=O)[C@]1(C)CCC[C@]2(C)C3=CC=C(C(C)C)C=C3CC[C@H]21 NFWKVWVWBFBAOV-MISYRCLQSA-N 0.000 description 1
- 229940118781 dehydroabietic acid Drugs 0.000 description 1
- 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 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052751 metal Chemical class 0.000 description 1
- 239000002184 metal Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L99/00—Compositions of natural macromolecular compounds or of derivatives thereof not provided for in groups C08L89/00 - C08L97/00
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/6436—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing amino groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to the technical field of high polymer material modification, and particularly relates to a composite modifier and a polypropylene composition thereof. The composite modifier consists of a phenyldihydrazide compound with a specific structure and chemically modified plant composite fibers, and is used as a modifier of the polypropylene material, wherein the phenyldihydrazide compound has high electronegativity, and oxygen atoms of carbonyl groups expand an electronic conjugation range, so that the composite modifier is beneficial to promoting polypropylene nucleation, the plant composite fibers are beneficial to improving the adhesion connection among polypropylene molecules, the modification of the phenyldihydrazide compound on the polypropylene is further promoted, the performance of the polypropylene material is cooperatively promoted, and the industrial application value of the polypropylene material is greatly promoted.
Description
Technical Field
The invention belongs to the technical field of high polymer material modification. More particularly, to a composite modifier and a polypropylene composition thereof.
Background
As a thermoplastic general plastic with abundant sources, wide application and high cost performance, the polypropylene (PP) has excellent comprehensive properties of easy processing and molding, good mechanical property, good electrical insulation property and the like. However, the use of the alloy is extremely limited in industrial applications due to the disadvantages of poor rigidity, weak impact strength, and the like.
Improving PP performance by adding Nucleating Agents (NAs) is an effective way to expand its range of applications. NAs of PP are various, and can be classified into alpha-NAs and beta-NAs according to the induced PP crystal forms, wherein the alpha-NAs is the most widely used nucleating agent in PP and can be classified into inorganic, organic and high polymer nucleating agents. The inorganic nucleating agent is mainly metal oxide or metal salt, such as talcum powder, calcium carbonate and silicon dioxide, which are low in price, but have the defects of poor transparency nucleation effect and weak mechanical property improvement effect; organic nucleating agents can be subdivided into sorbitol, aromatic carboxylates, substituted aromatic heterocyclic phosphates, dehydroabietic acid and its salts and branched amides, with sorbitol nucleating agents being the most studied. Unfortunately, sorbitol releases toxic and unpleasant aldehyde materials during processing, which limits their use. Other nucleating agents also have the disadvantages of high cost, poor dispersibility, low nucleation efficiency, and the like. Therefore, finding a highly efficient and good α -NA for PP remains a scientific challenge, and has great significance for industrial applications.
In recent years, some hydrazide compounds have received attention because of their high nucleation in poly-L-lactic acid (PLA). Research shows that the hydrazide compound is an efficient PP alpha-NAs, which can obviously shorten the semi-crystallization time of nucleated PP, for example, chinese patent applications CN108424545A and CN109942887A respectively adopt diphenyl dihydrazide sebacate and trimesoyl tris (benzoyl hydrazine) as nucleating agents of polypropylene materials, so that the crystallization peak temperature of the polypropylene materials is improved, but the improvement effect of the mechanical properties of the obtained materials is still limited.
Disclosure of Invention
The invention aims to overcome the defect and the defect that the prior phenyldihydrazide compound has limited effect on improving the performance of a polypropylene material, and provides a composite modifier.
It is another object of the present invention to provide the use of said composite modifier in modified polypropylene.
It is another object of the present invention to provide a high modulus, low shrinkage polypropylene composition.
The above object of the present invention is achieved by the following technical scheme:
the invention protects a composite modifier, which consists of a phenyldihydrazide compound and plant composite fibers;
the phenyldihydrazide compound has the following structure:
wherein R is monosubstituted or polysubstituted, and the structure of the R group is as follows:
preferably, the phenyldihydrazide compound has any one of the following structures:
preferably, the plant composite fiber is mainly prepared from jute, flax and loofah sponge fibers.
Preferably, the mass ratio of the jute, the flax and the loofah sponge fibers is 0.1-1.5: 0.1 to 1.5:0.1 to 1.5.
Preferably, the mass ratio of the phenyldihydrazide compound to the plant composite fiber is 1-2: 5 to 20.
Further, the plant composite fiber is obtained by soaking a fiber raw material in a fiber treating agent and fully contacting and modifying. The natural fiber surface contains a large amount of hydroxyl and alcoholic hydroxyl, has larger polarity difference with the PP resin surface, and can microscopically present a heterogeneous system when the two are compounded, so that the adhesiveness is poor, and the compatibility of the two can be enhanced after the two are modified.
Preferably, the fiber treatment agent is amino silicone oil emulsion, sodium hydroxide, benzoyl chloride, acrylic acid, ethanolamine copper or KH-570.
Preferably, the drying temperature is 75-95 DEG C
Preferably, the fibrous material is further pretreated, including crushing, sieving, washing and drying.
Preferably, the time for the sufficient contact modification is 2.5 to 3 hours.
Preferably, the cooling is at room temperature.
The invention also protects the application of the composite modifier in modified polypropylene.
The invention also provides a polypropylene composition comprising polypropylene and the composite modifier. The unshared electrons of nitrogen atoms in the phenyldihydrazide compound are relatively active to each other, and can accept free electrons generated by propylene polymerization, so that free radicals can be formed, and therefore, the polymerization of polypropylene is initiated through the free radical reaction, and meanwhile, the free radicals at the tail ends of a polymerization chain are transferred to a hydrazide molecule, so that the initiation of the polymerization reaction and the chain transfer reaction are realized, and the polymerization rate is increased. The phenyl has high electron cloud density due to the electron conjugation effect of large pi bond, and the electronegativity of nitrogen atoms and hydrogen atoms in the hydrazide groups is equal, the charge distribution is uniform, and a certain electron enrichment force is shown, so that the phenyldihydrazide compound plays an important role in polymerization, modification and regulation of high polymer materials; in addition, the natural fiber surface contains a large number of hydroxyl groups and alcohol hydroxyl groups, the polarity difference with the polypropylene surface is large, a heterogeneous system is microscopically presented when the two are compounded, so that the adhesiveness is poor, the compatibility of the two can be enhanced after modification, when the phenyldihydrazide compound and the plant composite fiber are simultaneously added into the polypropylene as a composite modifier, the nucleation effect of the polypropylene can be synergistically enhanced, the physical and mechanical properties of the formed polypropylene pipe can be enhanced, and the polypropylene pipe can be further utilized to be applied to preparation of other composite pipes, for example, the ribbed pipe as a Kramer can effectively enhance the integral mechanical strength of the pipe.
Further, the components in the composite modifier are added into polypropylene independently or after being mixed.
Preferably, the mass ratio of the composite modifier to the polypropylene is 6-22: 100.
further, the polypropylene composition further comprises an antioxidant.
Preferably, the antioxidant is an AT-215 antioxidant.
Preferably, the mass ratio of the antioxidant to the polypropylene is 0.1-1: 100.
the invention has the following beneficial effects: the invention provides a composite modifier, which consists of a phenyldihydrazide compound with a specific structure and chemically modified plant composite fibers, and is used as a modifier of a polypropylene material, wherein the phenyldihydrazide compound has high electronegativity, and oxygen atoms of carbonyl groups expand an electronic conjugation range, so that the nucleation of polypropylene is promoted, the plant composite fibers are beneficial to improving the bonding connection among polypropylene molecules, the modification of the phenyldihydrazide compound on the polypropylene is further promoted, the phenyldihydrazide compound and the plant composite fibers cooperatively promote the performance of the polypropylene material, and the industrial application value of the polypropylene material is greatly improved.
Detailed Description
The present invention is further illustrated below with reference to specific examples, which are not intended to limit the invention in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
Reagents and materials used in the following examples are commercially available unless otherwise specified.
The hydrazide compounds of the formulae (1) to (5) are derived from the customization of enokie, wherein the hydrazide compounds of the formulae (1) to (3) are disclosed in the literature [ Zhou H, zhang Y f.effect of aromatic dihydrazide compounds on crystallization behavior and mechanical properties of isotactic polypropylene [ J ]. Journal of Thermal Analysis and Calorimetry,2021 (5): 1-9.doi:10.1007/s10973-021-10961-6 ], CAS No. 35658-27-6 of the formula (4), CAS No. 6645-65-4 of the formula (5);
the amino silicone oil emulsion is derived from the aratin;
AT-215 antioxidant is derived from Kayinjia chemical industry.
The preparation method of the Kela pipe comprises the following steps: and (3) coating the prepared polypropylene pipe by using HDPE (high-density polyethylene) on a preheated integral steel roller die by adopting a hot winding forming process, synchronously winding the HDPE on a steel die heated to a preset temperature (230 ℃), demolding, and finally cutting to a standard size.
Example 1 preparation of Polypropylene pipe
A method for preparing a polypropylene composition comprising the steps of:
s1, preparing plant composite fibers: respectively pulverizing, sieving and cleaning three natural fibers of jute, flax and retinervus Luffae fructus without mildew, caking and impurities, and heating at 90deg.C to constant weight. The dried natural fibers were prepared in a 1:1:1, soaking the natural fiber in amino silicone oil emulsion in a mass ratio, performing ultrasonic vibration for 3 hours to enable the natural fiber to fully contact and react, and drying the natural fiber to constant weight at 90 ℃.
S2, a polypropylene composition: adding 0.2g of a phenyldihydrazide compound (with a structure shown as a formula (1)) and 10g of plant composite fiber into 100g of PP, adding 0.1g of AT-215 antioxidant, stirring for 5min in a mixer, fully and uniformly mixing, introducing the mixture into a double-screw extruder for extrusion granulation, and cooling AT room temperature to obtain the polypropylene pipe. Discharge conditions of the extruder: the temperature of the melt is 190 ℃, and the rotating speeds of the main motor and the feeder are 15 r.s -1 。
Example 2 preparation of Polypropylene pipe
Example 2 differs from example 1 in that the phenyldihydrazide compound used is different, and the other steps and parameters are the same as example 1.
The preparation method of the polypropylene composition specifically comprises the following steps:
s1, preparing plant composite fibers: respectively pulverizing, sieving and cleaning three natural fibers of jute, flax and retinervus Luffae fructus without mildew, caking and impurities, and heating at 90deg.C to constant weight. The dried natural fibers were prepared in a 1:1:1, soaking the natural fiber in amino silicone oil emulsion in a mass ratio, performing ultrasonic vibration for 3 hours to enable the natural fiber to fully contact and react, and drying the natural fiber to constant weight at 90 ℃.
S2, polypropylene (PP) composite material: adding 0.2g of a phenyldihydrazide compound (with a structure shown as a formula (2)) and 10g of plant composite fiber into 100g of PP, adding 0.1g of AT-215 antioxidant, stirring for 5min in a mixer, fully and uniformly mixing, introducing the mixture into a double-screw extruder for extrusion granulation, and cooling AT room temperature to obtain the polypropylene pipe. Discharge conditions of the extruder: the temperature of the melt is 190 ℃, and the rotating speeds of the main motor and the feeder are 15 r.s -1 。
Example 3 preparation of Polypropylene pipe
Example 3 differs from example 1 in that the phenyldihydrazide compound used is different, and the other steps and parameters are the same as example 1.
The preparation method of the polypropylene composition specifically comprises the following steps:
s1, preparing plant composite fibers: respectively pulverizing, sieving and cleaning three natural fibers of jute, flax and retinervus Luffae fructus without mildew, caking and impurities, and heating at 90deg.C to constant weight. The dried natural fibers were prepared in a 1:1:1, soaking the natural fiber in amino silicone oil emulsion in a mass ratio, performing ultrasonic vibration for 3 hours to enable the natural fiber to fully contact and react, and drying the natural fiber to constant weight at 90 ℃.
S2, polypropylene (PP) composite material: adding 0.2g of a phenyldihydrazide compound (with a structure shown as a formula (3)) and 10g of plant composite fiber into 100g of PP, adding 0.1g of AT-215 antioxidant, stirring for 5min in a mixer, fully and uniformly mixing, introducing the mixture into a double-screw extruder for extrusion granulation, and cooling AT room temperature to obtain the polypropylene pipe. Discharge conditions of the extruder: melt temperature 190 ℃, main motor and feeder rotationThe speeds are all 15 r.s -1 。
Comparative example 1 preparation of Polypropylene pipe
Comparative example 1 differs from example 1 in that the phenyldihydrazide compound used was different, and the other steps and parameters were the same as those of example 1.
The preparation method of the polypropylene composition specifically comprises the following steps:
s1, preparing plant composite fibers: respectively pulverizing, sieving and cleaning three natural fibers of jute, flax and retinervus Luffae fructus without mildew, caking and impurities, and heating at 90deg.C to constant weight. The dried natural fibers were prepared in a 1:1:1, soaking the natural fiber in amino silicone oil emulsion in a mass ratio, performing ultrasonic vibration for 3 hours to enable the natural fiber to fully contact and react, and drying the natural fiber to constant weight at 90 ℃.
S2, polypropylene (PP) composite material: adding 0.2g of a phenyldihydrazide compound (with a structure shown as a formula (4)) and 10g of plant composite fiber into 100g of PP, adding 0.1g of AT-215 antioxidant, stirring for 5min in a mixer, fully and uniformly mixing, introducing the mixture into a double-screw extruder for extrusion granulation, and cooling AT room temperature to obtain the polypropylene pipe. Discharge conditions of the extruder: the temperature of the melt is 190 ℃, and the rotating speeds of the main motor and the feeder are 15 r.s -1 。
Comparative example 2 preparation of Polypropylene pipe
Comparative example 2 differs from example 1 in that the phenyldihydrazide compound used was different, and the other steps and parameters were the same as those of example 1.
The preparation method of the polypropylene composition specifically comprises the following steps:
s1, preparing plant composite fibers: respectively pulverizing, sieving and cleaning three natural fibers of jute, flax and retinervus Luffae fructus without mildew, caking and impurities, and heating at 90deg.C to constant weight. The dried natural fibers were prepared in a 1:1:1, soaking the natural fiber in amino silicone oil emulsion in a mass ratio, performing ultrasonic vibration for 3 hours to enable the natural fiber to fully contact and react, and drying the natural fiber to constant weight at 90 ℃.
S2, polypropylene (PP) composite material: adding 0.2g of a phenyldihydrazide compound (with a structure shown as a formula (5)) and 10g of plant composite fiber into 100g of PP, adding 0.1g of AT-215 antioxidant, stirring for 5min in a mixer, fully and uniformly mixing, introducing the mixture into a double-screw extruder for extrusion granulation, and cooling AT room temperature to obtain the polypropylene pipe. Discharge conditions of the extruder: the temperature of the melt is 190 ℃, and the rotating speeds of the main motor and the feeder are 15 r.s -1 。
Comparative example 3 preparation of Polypropylene pipe
Comparative example 3 differs from example 1 in that no plant fiber was added, and other steps and parameters were the same as example 1.
The preparation method of the polypropylene composition specifically comprises the following steps:
adding 0.2g of a benzene dihydrazide compound (with a structure shown as a formula (1)) into 100g of PP, adding 0.1g of AT-215 antioxidant, stirring for 5min in a mixer, fully and uniformly mixing, introducing the mixture into a double-screw extruder for extrusion granulation, and cooling AT room temperature to obtain the polypropylene pipe. Discharge conditions of the extruder: the temperature of the melt is 190 ℃, and the rotating speeds of the main motor and the feeder are 15 r.s -1 。
Comparative example 4 preparation of Polypropylene pipe
Comparative example 4 was different from example 1 in that no phenyldihydrazide compound was added, and the other steps and parameters were the same as example 1.
The preparation method of the polypropylene composition specifically comprises the following steps:
s1, preparing plant composite fibers: respectively pulverizing, sieving and cleaning three natural fibers of jute, flax and retinervus Luffae fructus without mildew, caking and impurities, and heating at 90deg.C to constant weight. The dried natural fibers were prepared in a 1:1:1, soaking the natural fiber in amino silicone oil emulsion in a mass ratio, performing ultrasonic vibration for 3 hours to enable the natural fiber to fully contact and react, and drying the natural fiber to constant weight at 90 ℃.
S2, polypropylene (PP) composite material: adding 10g of plant composite fiber into 100g of PP, adding 0.1g of AT-215 antioxidant, stirring for 5min in a mixer, fully and uniformly mixing, introducing the mixture into a double-screw extruder for extrusion granulation, and cooling AT room temperature to obtain the polypropylene pipe. Discharge conditions of the extruder: the temperature of the melt is 190 ℃, and the rotating speeds of the main motor and the feeder are 15 r.s -1 。
Performance testing
The polypropylene tubing obtained in examples 1 to 3 and comparative examples 1 to 4 was further prepared into a Clay pipe (i.e., a high density polyethylene structured wall hot wound pipe), and the Clay pipe obtained was subjected to performance test according to GB/T19472.2-2017 Polyethylene (PE) structured wall tubing for buried use 2 nd section: polyethylene wound structured wall tubing), and the properties of the prepared Clay pipe were greatly affected by the different tubing as a ribbed pipe, and the Clay pipe prepared with pure polypropylene as a ribbed pipe was used as a control, and the results are shown in Table 1.
TABLE 1 Performance test results
As is clear from Table 1, polypropylene pipes prepared by adding plant composite fibers and specific phenyldihydrazide compounds as modifiers in examples 1 to 3 can be further prepared into a ribbed pipe with high modulus (ring stiffness > 12kN/m 2 ) Low shrinkage (longitudinal shrinkage less than or equal to 1.2%).
Compared with the clara pipe taking pure polypropylene as the ribbed pipe, the ring stiffness of the clara pipe taking the polypropylene pipe modified by the specific modifier is improved by more than 50%, the maximum can be improved to 70%, the tensile force at the welding part is improved by more than 7%, the reduction of the longitudinal retraction rate is more than or equal to 40%, the maximum can be reduced to 50%, and the mechanical property of the clara pipe are greatly improved.
When plant composite fiber or phenyldihydrazide compound is adopted to independently modify polypropylene, the improvement performance effect of the Clara pipe further prepared by using the obtained polypropylene pipe as a ribbed pipe is limited, and the ring stiffness of the Clara pipe is lower than 11kN/m 2 The tensile force of the welding part is lower than 400N, and the longitudinal retraction rate is higher than 1.5%; when other hydrazide compounds and plant composite fibers are compounded for polypropylene modification, the improvement performance effect of the Clara pipe further prepared by using the obtained polypropylene pipe as a ribbed pipe is also not ideal, and the ring stiffness of the Clara pipe is lower than 11kN/m 2 The tensile force of the welding part is lower than 400N, and the longitudinal retraction rate is higher than 1.5%.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. The composite modifier is characterized by comprising a phenyldihydrazide compound and plant composite fibers;
the phenyldihydrazide compound has the following structure:
wherein R is monosubstituted or polysubstituted, and the structure of the R group is as follows:
2. the composite modifier according to claim 1, wherein the phenyldihydrazide compound has any one of the following structures:
3. the composite modifier of claim 1, wherein the plant composite fiber is prepared mainly from jute, flax and loofah sponge fibers.
4. The composite modifier according to claim 3, wherein the mass ratio of the jute, the flax and the loofah sponge fibers is 0.1-1.5: 0.1 to 1.5:0.1 to 1.5.
5. The composite modifier according to claim 1, wherein the mass ratio of the phenyldihydrazide compound to the plant composite fiber is 1-2: 5 to 20.
6. The composite modifier according to claim 1, wherein the plant composite fiber is obtained by immersing a fiber raw material in a fiber treating agent, and sufficiently contacting and modifying.
7. The composite modifier of claim 6, wherein the fiber treating agent is an aminosilicone emulsion, sodium hydroxide, benzoyl chloride, acrylic acid, ethanolamine copper, or KH-570.
8. Use of the composite modifier according to any one of claims 1 to 7 for modifying polypropylene.
9. A polypropylene composition comprising polypropylene and the composite modifier of any one of claims 1 to 7.
10. The polypropylene composition according to claim 9, wherein the mass ratio of the composite modifier to the polypropylene is 6 to 22:100.
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