CN106397987B - Polypropylene/the liquid crystal polymer composite and preparation method of high-beta crystal content - Google Patents
Polypropylene/the liquid crystal polymer composite and preparation method of high-beta crystal content Download PDFInfo
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 72
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 68
- -1 Polypropylene Polymers 0.000 title claims abstract description 61
- 239000013078 crystal Substances 0.000 title claims abstract description 57
- 229920000106 Liquid crystal polymer Polymers 0.000 title claims abstract description 51
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 title claims abstract description 51
- 239000002131 composite material Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 22
- 239000000654 additive Substances 0.000 claims abstract description 8
- 230000000996 additive effect Effects 0.000 claims abstract description 8
- 238000001125 extrusion Methods 0.000 claims abstract description 5
- 238000002844 melting Methods 0.000 claims abstract description 4
- 230000008018 melting Effects 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 45
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 24
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 15
- LVFFZQQWIZURIO-UHFFFAOYSA-N 2-phenylbutanedioic acid Chemical compound OC(=O)CC(C(O)=O)C1=CC=CC=C1 LVFFZQQWIZURIO-UHFFFAOYSA-N 0.000 claims description 12
- 241000790917 Dioxys <bee> Species 0.000 claims description 12
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 12
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 12
- 239000004305 biphenyl Substances 0.000 claims description 12
- 235000010290 biphenyl Nutrition 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000001746 injection moulding Methods 0.000 claims description 12
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical class [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 12
- 239000008188 pellet Substances 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 12
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical class [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 claims description 11
- 235000013904 zinc acetate Nutrition 0.000 claims description 11
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002667 nucleating agent Substances 0.000 abstract description 19
- 239000000463 material Substances 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- 239000003963 antioxidant agent Substances 0.000 description 10
- 230000003078 antioxidant effect Effects 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 10
- 230000006911 nucleation Effects 0.000 description 8
- 238000010899 nucleation Methods 0.000 description 8
- 239000004973 liquid crystal related substance Substances 0.000 description 5
- 229920002521 macromolecule Polymers 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000004990 Smectic liquid crystal Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 229920006126 semicrystalline polymer Polymers 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- JREYOWJEWZVAOR-UHFFFAOYSA-N triazanium;[3-methylbut-3-enoxy(oxido)phosphoryl] phosphate Chemical compound [NH4+].[NH4+].[NH4+].CC(=C)CCOP([O-])(=O)OP([O-])([O-])=O JREYOWJEWZVAOR-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000004736 wide-angle X-ray diffraction Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
- C08G63/86—Germanium, antimony, or compounds thereof
- C08G63/866—Antimony or compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- 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
- C08L2205/12—Polymer mixtures characterised by other features containing additives being liquid crystalline or anisotropic in the melt
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- 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
- C08L2205/24—Crystallisation aids
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Abstract
The invention discloses the polypropylene/liquid crystal polymer composites and preparation method of high-beta crystal content, belong to polypropylene toughness-increasing modified field.Isotactic polypropylene, liquid crystal polymer nucleating agent and function additive are uniformly mixed in high-speed mixer, and melting extrusion is granulated in double screw extruder, obtains the PP composite material of high-beta crystal content.For β crystalline substance relative amount 90% or more, resulting product has higher impact strength, elongation at break and better heat resistance compared with pure PP in preparation-obtained PP composite material.
Description
Technical field
The present invention relates to polypropylene/liquid crystal polymer composites of a kind of high-beta crystal content and preparation method thereof, further relate to
A kind of liquid crystal polymer polypropylene beta nucleating agent and preparation method, belong to polypropylene toughness-increasing modified field.
Background technique
Polypropylene (PP) is one of five big general-purpose plastics, is widely used in household electrical appliances, auto industry, packaging material, electronics
The industries such as product, construction material.Polypropylene have good mechanical performance and processing performance, but its still there is ageing-resistant
The disadvantages of property is poor, low temperature ductility is poor, the easy embrittlement of high-speed stretch, injection-molded item poor dimensional stability, limits its application.Isotactic
Polypropylene (iPP) is a kind of semicrystalline polymer, can form four kinds of crystal structures under certain conditions, is respectively as follows: α crystalline substance
Type, beta crystal, γ crystal form and smectic type.Wherein γ crystal form and smectic type are difficult to be formed under general processing conditions, study less, α
Crystal form is the most stable of crystal form of iPP thermodynamics, generates alpha-crystal form under general processing conditions.Compared with alpha-crystal form, beta crystal has more
Low crystal density, fusing point and higher heat distortion temperature is hit and will form crazing and micropore absorption energy, significantly promoted
The shock resistance of material.
The polypropylene of beta crystal needs some specific conditions that could be formed, such as: temperature gradient field, shearing force field, vibration
Caused crystallization and addition beta nucleater.Wherein, addition beta nucleater is efficiency highest and most easy industrialized method.β nucleation
Agent is divided into several classes of inorganic, small organic molecule, macromolecule.Inorganic is mainly inorganic salts, inorganic oxide and some low melting points gold
Belong to powder, it is characterized in that cheap but nucleation efficiencies are not high, additive amount is big, poor compatibility is not easy to be uniformly dispersed.It is organic
Small molecule class mainly includes condensed-nuclei aromatics class, certain salts of group iia metallic element and organic dibasic acid condensation product, fragrant acyl
Amine Crystalline Compound.Small organic molecule class beta nucleater nucleation efficiencies are high, but that there is also thermal stability is low, is not easy to disperse, poison
The limitations such as property.
It is compared with small molecule nucleating agent, polymer macromolecule has good processability, good with polymer matrix compatability
Well, the features such as safe and non-toxic.The polymer of commercialization such as polystyrene (PS), styrene-acrylonitrile copolymer (SAN) is to isotactic
Polypropylene has certain beta induced nucleation, but its β nucleation efficiencies is lower, beta crystal content about 16-23%.With these commercializations
Polymer phase ratio, certain liquid crystal polymers are higher to polyacrylic β nucleation efficiencies.It has been reported that using siloxanes as main chain
Side chain type liquid crystal macromolecule is blended with iPP, by adjusting side-chain liquid crystal primitive, reaches as high as to the nucleation induction of polypropylene beta crystalline substance
To 70%.However compared with small organic molecule nucleating agent, β nucleation efficiencies are still relatively low.The invention discloses a kind of new
Type backbone chain type liquid crystal macromolecule beta nucleater is compared with other liquid crystal polymers, and such liquid crystal polymer lures polyacrylic β crystalline substance
Lead outstanding selectivity, nucleation efficiencies are very high, in the case where controlling certain processing conditions beta crystal content can reach 95% with
On, β type polypropylene is formed completely, so that the impact strength of PP, elongation at break greatly reinforce, heat resistance is promoted.
Summary of the invention
The purpose of the present invention is to provide a kind of polypropylene of high-beta crystal content by the preparation of liquid crystal polymer type beta nucleater
Composite material and preparation method.By by polypropylene with special construction polymer macromolecule nucleating agent melt blending,
Liquid crystal polymer nucleating agent provides more nucleus, and special construction induces polypropylene to form beta crystal.The β-of this method preparation
IPP is higher compared to pure PP crystallization temperature, beta crystal content close to 100%, there is superior mechanical performance and heat resistance.
The technical solution of the present invention is as follows:
Polypropylene/liquid crystal polymer composite of high-beta crystal content, constituent and mass fraction are as follows:
100 parts of isotactic polypropylene
0.1~5 part of liquid crystal polymer beta nucleater
0.1~0.5 part of function additive.
β crystalline substance relative amount (k in the PP composite material of high-beta crystal content obtained by the present inventionβ) it is greater than 90%.
Wherein the isotactic polypropylene isotacticity is greater than 90%, and melt flow rate (MFR) range is 2~20g/10min, point
Son amount is 10~300,000.
Wherein the function additive is antioxidant 1010, and dosage is the 0.1~0.5% of polypropylene quality.
Wherein the liquid crystal polymer beta nucleater is LCP-NA, structural formula are as follows:
Wherein the liquid crystal polymer beta nucleater polymerization degree n is 10~150, and molecular weight is 5000~80000, dosage
It is the 0.1~5% of polypropylene quality.
The wherein preparation method of the liquid crystal polymer beta nucleater carries out as steps described below:
(1) biphenyl dioxy hexanol and phenylsuccinic acid that molar ratio is 1:1 are added in three-neck flask, 2 ‰ acetic acid is added
Mixture heating stirring is controlled reaction temperature and is 180 DEG C and is passed through nitrogen, instead by zinc and 3 ‰ antimony oxides as catalyst
It is 2~3h between seasonable；
(2) after reacting, nitrogen is disconnected, starts to vacuumize, control reaction temperature is warming up to 200 DEG C, and vacuum degree is less than
60Pa, reaction time are 1~4h, and finally cooling obtains liquid crystal polymer beta nucleater LCP-NA.
The PP composite material preparation method of above-mentioned high-beta crystal content carries out as steps described below:
(1) isotactic polypropylene, liquid crystal polymer beta nucleater and function additive are mixed 3~5 points in high-speed mixer
Clock, be uniformly mixed material；
(2) by above-mentioned mixture, melting extrusion is granulated in double screw extruder, and extrusion temperature is 180~260 DEG C, is obtained
The polypropylene granules of high-beta crystal content.Pellet is prepared into standard batten using injection molding machine.
The utility model has the advantages that
1. the PP prepared after a certain proportion of liquid crystal polymer beta nucleater and isotactic polypropylene melt blending, extruding pelletization
The beta crystal content of sample is improved significantly, and in the case where controlling certain processing conditions, beta crystal content is close to 100%.
2. liquid crystal polymer nucleating agent and PP compatibility are good, are easily dispersed, the β-iPP being prepared has higher punching
Hit intensity, elongation at break and excellent heat resistance.
Detailed description of the invention
Fig. 1 is the x-ray diffraction pattern of polypropylene and embodiment 4.Wherein (110), (040), be poly- third at (130) crystal face
Alkene α crystalline substance characteristic diffraction peak, (300) crystal face are β crystalline substance characteristic diffraction peak.Virgin pp only has the diffraction maximum of α crystalline substance, and liquid crystal high score is added
After sub- beta nucleater, occur apparent β crystalline substance characteristic diffraction peak at 16 ° of the angle of diffraction, and α crystalline substance characteristic diffraction peak almost disappears, and passes through
Turner-Jones formula is calculated β crystalline substance relative amount and is up to 97.6%.
Specific embodiment
The PP composite material of high-beta crystal content obtained by the present invention is made sample according to standard and carries out mechanical property survey
Examination.
(1) it the measurement of β crystalline substance relative amount: is measured using wide-angle X ray diffractor, with following Turner-Jones formula meter
Calculate β crystalline substance relative amount in sample:
In formula: KβFor β crystalline substance relative amount, K in sampleβ=0 shows in polypropylene specimen without β crystal, Kβ=100% table
All β crystal in bright polypropylene specimen.Hα(110)、Hα(040)、Hα(130) it is measured using Wide angle X-ray diffraction technology
Remove the correspondence peak height of α crystal face behind unformed peak, HβIt (300) is the correspondence peak height of β crystal face.
HαIt (110) is the peak height of (110) crystal face of alpha-crystal；
HαIt (040) is the peak height of (040) crystal face of alpha-crystal；
HαIt (130) is the peak height of (130) crystal face of alpha-crystal；
HβIt (300) is the peak height of (300) crystal face of β crystal.
(2) melt flow rate (MFR) measures: at 230 DEG C, carrying out under 2.16kg by GB/T3682-2000；
(3) it tensile strength and elongation at break measurement: is carried out by GB/T1040-92；
(4) Izod notched impact strength measures: carrying out by GB/T1843-96；
(5) heat distortion temperature measures: carrying out by GB/T1633-2000；
(6) it the molecular weight determination of liquid crystal polymer beta nucleater: is surveyed using 515 gel permeation chromatograph of U.S. WATERS
It is fixed.
Embodiment 1
Biphenyl dioxy hexanol and phenylsuccinic acid that molar ratio is 1:1 are added in three-neck flask, 2 ‰ zinc acetates of addition,
3 ‰ antimony oxides by mixture heating stirring, control reaction temperature and are 180 DEG C and are passed through nitrogen as catalyst, when reaction
Between be 3h.After reaction, nitrogen is disconnected, starts to vacuumize, control reaction temperature is warming up to 200 DEG C, and vacuum degree is less than 60Pa, instead
It is 3.5h between seasonable, finally cooling obtains liquid crystal polymer beta nucleater LCP-NA (degree of polymerization 90, molecular weight 50000).
Formula are as follows: isotactic polypropylene 400g (middle petrochemical industry PPH-T03, MFR=3.0g/10min), liquid crystal polymer β nucleation
Agent (LCP-NA) 0.4g, antioxidant 1010 (BASF Germany BASF) 0.4g.
By iPP, LCP-NA be put in vacuum drying oven dry 8 hours it is spare.Select suitable extruder temperature, revolving speed, major diameter
Than by dry isotactic polypropylene, beta nucleater and antioxidant, melt blending is squeezed out in double screw extruder, and then cooling is made
Grain.Gained pellet forms standard sample using injection molding machine, is pressed into thin slice using tablet press machine, passes through universal test tester, cantilever
Beam impact strength tester, heat distortion temperature tester, wide-angle X ray diffractor are respectively to the mechanical property of material, heat resistance
Can, the beta crystal content of sample characterized, test result such as table 1.
Embodiment 2
Biphenyl dioxy hexanol and phenylsuccinic acid that molar ratio is 1:1 are added in three-neck flask, 2 ‰ zinc acetates of addition,
3 ‰ antimony oxides by mixture heating stirring, control reaction temperature and are 180 DEG C and are passed through nitrogen as catalyst, when reaction
Between be 3h.After reaction, nitrogen is disconnected, starts to vacuumize, control reaction temperature is warming up to 200 DEG C, and vacuum degree is less than 60Pa, instead
It is 3.5h between seasonable, finally cooling obtains liquid crystal polymer beta nucleater LCP-NA (degree of polymerization 90, molecular weight 50000).
Formula are as follows: isotactic polypropylene 400g (middle petrochemical industry PPH-T03, MFR=3.0g/10min), liquid crystal polymer β nucleation
Agent (LCP-NA) 8g, antioxidant 1010 (BASF Germany BASF) 1.0g.
By iPP, LCP-NA be put in vacuum drying oven dry 8 hours it is spare.Select suitable extruder temperature, revolving speed, major diameter
Than by dry isotactic polypropylene, beta nucleater and antioxidant, melt blending is squeezed out in double screw extruder, and then cooling is made
Grain.Gained pellet forms standard sample using injection molding machine, is pressed into thin slice using tablet press machine, passes through universal test tester, cantilever
Beam impact strength tester, heat distortion temperature tester, wide-angle X ray diffractor are respectively to the mechanical property of material, heat resistance
Can, the beta crystal content of sample characterized, test result such as table 1.
Embodiment 3
Biphenyl dioxy hexanol and phenylsuccinic acid that molar ratio is 1:1 are added in three-neck flask, 2 ‰ zinc acetates of addition,
3 ‰ antimony oxides by mixture heating stirring, control reaction temperature and are 180 DEG C and are passed through nitrogen as catalyst, when reaction
Between be 3h.After reaction, nitrogen is disconnected, starts to vacuumize, control reaction temperature is warming up to 200 DEG C, and vacuum degree is less than 60Pa, instead
It is 3.5h between seasonable, finally cooling obtains liquid crystal polymer beta nucleater LCP-NA (degree of polymerization 90, molecular weight 50000).
Formula are as follows: isotactic polypropylene 400g (middle petrochemical industry PPH-T03, MFR=3.0g/10min), liquid crystal polymer β nucleation
Agent (LCP-NA) 16g, antioxidant 1010 (BASF Germany BASF) 1.2g.
By iPP, LCP-NA be put in vacuum drying oven dry 8 hours it is spare.Select suitable extruder temperature, revolving speed, major diameter
Than by dry isotactic polypropylene, beta nucleater and antioxidant, melt blending is squeezed out in double screw extruder, and then cooling is made
Grain.Gained pellet forms standard sample using injection molding machine, is pressed into thin slice using tablet press machine, passes through universal test tester, cantilever
Beam impact strength tester, heat distortion temperature tester, wide-angle X ray diffractor are respectively to the mechanical property of material, heat resistance
Can, the beta crystal content of sample characterized, test result such as table 1.
Embodiment 4
Biphenyl dioxy hexanol and phenylsuccinic acid that molar ratio is 1:1 are added in three-neck flask, 2 ‰ zinc acetates of addition,
3 ‰ antimony oxides by mixture heating stirring, control reaction temperature and are 180 DEG C and are passed through nitrogen as catalyst, when reaction
Between be 3h.After reaction, nitrogen is disconnected, starts to vacuumize, control reaction temperature is warming up to 200 DEG C, and vacuum degree is less than 60Pa, instead
It is 3.5h between seasonable, finally cooling obtains liquid crystal polymer beta nucleater LCP-NA (degree of polymerization 90, molecular weight 50000).
Formula are as follows: isotactic polypropylene 400g (middle petrochemical industry PPH-T03, MFR=3.0g/10min), liquid crystal polymer β nucleation
Agent (LCP-NA) 20g, antioxidant 1010 (BASF Germany BASF) 2.0g.
By iPP, LCP-NA be put in vacuum drying oven dry 8 hours it is spare.Select suitable extruder temperature, revolving speed, major diameter
Than by dry isotactic polypropylene, beta nucleater and antioxidant, melt blending is squeezed out in double screw extruder, and then cooling is made
Grain.Gained pellet forms standard sample using injection molding machine, is pressed into thin slice using tablet press machine, passes through universal test tester, cantilever
Beam impact strength tester, heat distortion temperature tester, wide-angle X ray diffractor are respectively to the mechanical property of material, heat resistance
Can, the beta crystal content of sample characterized, test result such as table 1.
Fig. 1 is the x-ray diffraction pattern of polypropylene and embodiment 4.Wherein (110), (040), be poly- third at (130) crystal face
Alkene α crystalline substance characteristic diffraction peak, (300) crystal face are β crystalline substance characteristic diffraction peak.Virgin pp only has the diffraction maximum of α crystalline substance, and liquid crystal high score is added
After sub- beta nucleater, occur apparent β crystalline substance characteristic diffraction peak at 16 ° of the angle of diffraction, and α crystalline substance characteristic diffraction peak almost disappears, and passes through
Turner-Jones formula is calculated β crystalline substance relative amount and is up to 97.6%.
Embodiment 5
Biphenyl dioxy hexanol and phenylsuccinic acid that molar ratio is 1:1 are added in three-neck flask, 2 ‰ zinc acetates of addition,
3 ‰ antimony oxides by mixture heating stirring, control reaction temperature and are 180 DEG C and are passed through nitrogen as catalyst, when reaction
Between be 2h.After reaction, nitrogen is disconnected, starts to vacuumize, control reaction temperature is warming up to 200 DEG C, and vacuum degree is less than 60Pa, instead
It is 1h between seasonable, finally cooling obtains liquid crystal polymer beta nucleater LCP-NA (degree of polymerization 9, molecular weight 5000).
Formula are as follows: isotactic polypropylene 400g (middle petrochemical industry PPH-T03, MFR=3.0g/10min), liquid crystal polymer β nucleation
Agent (LCP-NA) 8g, antioxidant 1010 (BASF Germany BASF) 0.4g.
By iPP, LCP-NA be put in vacuum drying oven dry 8 hours it is spare.Select suitable extruder temperature, revolving speed, major diameter
Than by dry isotactic polypropylene, beta nucleater and antioxidant, melt blending is squeezed out in double screw extruder, and then cooling is made
Grain.Gained pellet forms standard sample using injection molding machine, is pressed into thin slice using tablet press machine, passes through universal test tester, cantilever
Beam impact strength tester, heat distortion temperature tester, wide-angle X ray diffractor are respectively to the mechanical property of material, heat resistance
Can, the beta crystal content of sample characterized, test result such as table 1.
Embodiment 6
Biphenyl dioxy hexanol and phenylsuccinic acid that molar ratio is 1:1 are added in three-neck flask, 2 ‰ zinc acetates of addition,
3 ‰ antimony oxides by mixture heating stirring, control reaction temperature and are 180 DEG C and are passed through nitrogen as catalyst, when reaction
Between be 2h.After reaction, nitrogen is disconnected, starts to vacuumize, control reaction temperature is warming up to 200 DEG C, and vacuum degree is less than 60Pa, instead
It is 1.5h between seasonable, finally cooling obtains liquid crystal polymer beta nucleater LCP-NA (degree of polymerization 18, molecular weight 10000).
Formula are as follows: isotactic polypropylene 400g (middle petrochemical industry PPH-T03, MFR=3.0g/10min), liquid crystal polymer β nucleation
Agent (LCP-NA) 8g, antioxidant 1010 (BASF Germany BASF) 0.4g.
By iPP, LCP-NA be put in vacuum drying oven dry 8 hours it is spare.Select suitable extruder temperature, revolving speed, major diameter
Than by dry isotactic polypropylene, beta nucleater and antioxidant, melt blending is squeezed out in double screw extruder, and then cooling is made
Grain.Gained pellet forms standard sample using injection molding machine, is pressed into thin slice using tablet press machine, passes through universal test tester, cantilever
Beam impact strength tester, heat distortion temperature tester, wide-angle X ray diffractor are respectively to the mechanical property of material, heat resistance
Can, the beta crystal content of sample characterized, test result such as table 1.
Embodiment 7
Biphenyl dioxy hexanol and phenylsuccinic acid that molar ratio is 1:1 are added in three-neck flask, 2 ‰ zinc acetates of addition,
3 ‰ antimony oxides by mixture heating stirring, control reaction temperature and are 180 DEG C and are passed through nitrogen as catalyst, when reaction
Between be 2h.After reaction, nitrogen is disconnected, starts to vacuumize, control reaction temperature is warming up to 200 DEG C, and vacuum degree is less than 60Pa, instead
It is 2h between seasonable, finally cooling obtains liquid crystal polymer beta nucleater LCP-NA (degree of polymerization 36, molecular weight 20000).
Formula are as follows: isotactic polypropylene 400g (middle petrochemical industry PPH-T03, MFR=3.0g/10min), liquid crystal polymer β nucleation
Agent (LCP-NA) 8g, antioxidant 1010 (BASF Germany BASF) 1.0g.
By iPP, LCP-NA be put in vacuum drying oven dry 8 hours it is spare.Select suitable extruder temperature, revolving speed, major diameter
Than by dry isotactic polypropylene, beta nucleater and antioxidant, melt blending is squeezed out in double screw extruder, and then cooling is made
Grain.Gained pellet forms standard sample using injection molding machine, is pressed into thin slice using tablet press machine, passes through universal test tester, cantilever
Beam impact strength tester, heat distortion temperature tester, wide-angle X ray diffractor are respectively to the mechanical property of material, heat resistance
Can, the beta crystal content of sample characterized, test result such as table 1.
Embodiment 8
Biphenyl dioxy hexanol and phenylsuccinic acid that molar ratio is 1:1 are added in three-neck flask, 2 ‰ zinc acetates of addition,
3 ‰ antimony oxides by mixture heating stirring, control reaction temperature and are 180 DEG C and are passed through nitrogen as catalyst, when reaction
Between be 2h.After reaction, nitrogen is disconnected, starts to vacuumize, control reaction temperature is warming up to 200 DEG C, and vacuum degree is less than 60Pa, instead
It is 2.5h between seasonable, finally cooling obtains liquid crystal polymer beta nucleater LCP-NA (degree of polymerization 54, molecular weight 30000).
Formula are as follows: isotactic polypropylene 400g (middle petrochemical industry PPH-T03, MFR=3.0g/10min), liquid crystal polymer β nucleation
Agent (LCP-NA) 8g, antioxidant 1010 (BASF Germany BASF) 1.0g.
By iPP, LCP-NA be put in vacuum drying oven dry 8 hours it is spare.Select suitable extruder temperature, revolving speed, major diameter
Than by dry isotactic polypropylene, beta nucleater and antioxidant, melt blending is squeezed out in double screw extruder, and then cooling is made
Grain.Gained pellet forms standard sample using injection molding machine, is pressed into thin slice using tablet press machine, passes through universal test tester, cantilever
Beam impact strength tester, heat distortion temperature tester, wide-angle X ray diffractor are respectively to the mechanical property of material, heat resistance
Can, the beta crystal content of sample characterized, test result such as table 1.
Embodiment 9
Biphenyl dioxy hexanol and phenylsuccinic acid that molar ratio is 1:1 are added in three-neck flask, 2 ‰ zinc acetates of addition,
3 ‰ antimony oxides by mixture heating stirring, control reaction temperature and are 180 DEG C and are passed through nitrogen as catalyst, when reaction
Between be 3h.After reaction, nitrogen is disconnected, starts to vacuumize, control reaction temperature is warming up to 200 DEG C, and vacuum degree is less than 60Pa, instead
It is 3h between seasonable, finally cooling obtains liquid crystal polymer beta nucleater LCP-NA (degree of polymerization 72, molecular weight 40000).
Formula are as follows: isotactic polypropylene 400g (middle petrochemical industry PPH-T03, MFR=3.0g/10min), liquid crystal polymer β nucleation
Agent (LCP-NA) 8g, antioxidant 1010 (BASF Germany BASF) 2.0g.
By iPP, LCP-NA be put in vacuum drying oven dry 8 hours it is spare.Select suitable extruder temperature, revolving speed, major diameter
Than by dry isotactic polypropylene, beta nucleater and antioxidant, melt blending is squeezed out in double screw extruder, and then cooling is made
Grain.Gained pellet forms standard sample using injection molding machine, is pressed into thin slice using tablet press machine, passes through universal test tester, cantilever
Beam impact strength tester, heat distortion temperature tester, wide-angle X ray diffractor are respectively to the mechanical property of material, heat resistance
Can, the beta crystal content of sample characterized, test result such as table 1.
Embodiment 10
Biphenyl dioxy hexanol and phenylsuccinic acid that molar ratio is 1:1 are added in three-neck flask, 2 ‰ zinc acetates of addition,
3 ‰ antimony oxides by mixture heating stirring, control reaction temperature and are 180 DEG C and are passed through nitrogen as catalyst, when reaction
Between be 3h.After reaction, nitrogen is disconnected, starts to vacuumize, control reaction temperature is warming up to 200 DEG C, and vacuum degree is less than 60Pa, instead
It is 4h between seasonable, finally cooling obtains liquid crystal polymer beta nucleater LCP-NA (degree of polymerization 144, molecular weight 80000).
Formula are as follows: isotactic polypropylene 400g (middle petrochemical industry PPH-T03, MFR=3.0g/10min), liquid crystal polymer β nucleation
Agent (LCP-NA) 8g, antioxidant 1010 (BASF Germany BASF) 2.0g.
By iPP, LCP-NA be put in vacuum drying oven dry 8 hours it is spare.Select suitable extruder temperature, revolving speed, major diameter
Than by dry isotactic polypropylene, beta nucleater and antioxidant, melt blending is squeezed out in double screw extruder, and then cooling is made
Grain.Gained pellet forms standard sample using injection molding machine, is pressed into thin slice using tablet press machine, passes through universal test tester, cantilever
Beam impact strength tester, heat distortion temperature tester, wide-angle X ray diffractor are respectively to the mechanical property of material, heat resistance
Can, the beta crystal content of sample characterized, test result such as table 1.
It is compared from table 1 as can be seen that after the liquid crystal polymer beta nucleating agent modified polypropylene obtained using the present invention and pure
Polypropylene is compared, and the tensile strength of composite material is held essentially constant, and impact strength is 3~5 times of virgin pp, extension at break
Rate improves 68~344%, and heat distortion temperature improves 2~17 DEG C, and β crystalline substance relative amount reaches as high as 100% in composite material.
1 polypropylene of table/liquid crystal polymer composite mechanical property
Claims (2)
1. polypropylene/liquid crystal polymer composite of high-beta crystal content, it is characterised in that its constituent and mass fraction are such as
Under:
100 parts of isotactic polypropylene
0.1 ~ 5 part of liquid crystal polymer beta nucleater
0.1 ~ 0.5 part of function additive；
β crystalline substance relative amount (k in the PP composite material of high-beta crystal contentβ) it is greater than 90%；
Wherein the isotactic polypropylene isotacticity is greater than 90%, and melt flow rate (MFR) range is 2 ~ 20g/10min, and molecular weight is
10 ~ 300,000；
Wherein the function additive is antioxidant 1010, and dosage is the 0.1 ~ 0.5% of polypropylene quality；
Wherein the liquid crystal polymer beta nucleater is LCP-NA, structural formula are as follows:
；
Wherein the liquid crystal polymer beta nucleater polymerization degree n is 10 ~ 150, and molecular weight is 5000 ~ 80000, and dosage is poly- third
The 0.1 ~ 5% of alkene quality；
The wherein preparation method of the liquid crystal polymer beta nucleater carries out as steps described below:
(1) biphenyl dioxy hexanol and phenylsuccinic acid that molar ratio is 1:1 are added in three-neck flask, 2 ‰ zinc acetates of addition,
3 ‰ antimony oxides by mixture heating stirring, control reaction temperature and are 180 DEG C and are passed through nitrogen as catalyst, when reaction
Between be 2 ~ 3h；
(2) after reacting, nitrogen being disconnected, starts to vacuumize, control reaction temperature is warming up to 200 DEG C, and vacuum degree is less than 60Pa,
Reaction time is 1 ~ 4h, and finally cooling obtains liquid crystal polymer beta nucleater LCP-NA.
2. polypropylene/liquid crystal polymer composite preparation method of high-beta crystal content according to claim 1, special
Sign is, carries out as steps described below:
(1) isotactic polypropylene, liquid crystal polymer beta nucleater and function additive are mixed 3 ~ 5 minutes in high-speed mixer, is obtained
To uniform mixture；
(2) by above-mentioned mixture, melting extrusion is granulated in double screw extruder, and extrusion temperature is 180 ~ 260 DEG C, obtains high β
The polypropylene granules of brilliant content；Pellet is prepared into standard batten using injection molding machine.
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| CN101381491A (en) * | 2008-10-15 | 2009-03-11 | 南京工业大学 | Preparation method of high beta crystal content polypropelene composition |
| CN102199293A (en) * | 2011-03-25 | 2011-09-28 | 东北大学 | Liquid-crystalline polysiloxane type [beta]-crystalline polypropylene nucleating agent, and preparation method thereof |
| CN105566743A (en) * | 2014-10-15 | 2016-05-11 | 中国石油化工股份有限公司 | Beta-crystal-form polypropylene strip and preparation method thereof |
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| CN101381491A (en) * | 2008-10-15 | 2009-03-11 | 南京工业大学 | Preparation method of high beta crystal content polypropelene composition |
| CN102199293A (en) * | 2011-03-25 | 2011-09-28 | 东北大学 | Liquid-crystalline polysiloxane type [beta]-crystalline polypropylene nucleating agent, and preparation method thereof |
| CN105566743A (en) * | 2014-10-15 | 2016-05-11 | 中国石油化工股份有限公司 | Beta-crystal-form polypropylene strip and preparation method thereof |
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