CN117362894A - Ultrathin temperature-resistant bi-directional synchronous stretching special material and preparation method thereof - Google Patents
Ultrathin temperature-resistant bi-directional synchronous stretching special material and preparation method thereof Download PDFInfo
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- CN117362894A CN117362894A CN202311425463.8A CN202311425463A CN117362894A CN 117362894 A CN117362894 A CN 117362894A CN 202311425463 A CN202311425463 A CN 202311425463A CN 117362894 A CN117362894 A CN 117362894A
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- 239000000463 material Substances 0.000 title claims abstract description 47
- 230000001360 synchronised effect Effects 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000004743 Polypropylene Substances 0.000 claims abstract description 85
- -1 polypropylene Polymers 0.000 claims abstract description 85
- 229920001155 polypropylene Polymers 0.000 claims abstract description 85
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 29
- 239000011147 inorganic material Substances 0.000 claims abstract description 29
- 239000012779 reinforcing material Substances 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000012783 reinforcing fiber Substances 0.000 claims abstract description 25
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 24
- 230000004048 modification Effects 0.000 claims abstract description 11
- 238000012986 modification Methods 0.000 claims abstract description 11
- 230000005855 radiation Effects 0.000 claims abstract description 10
- 230000002457 bidirectional effect Effects 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 15
- XHGIFBQQEGRTPB-UHFFFAOYSA-N tris(prop-2-enyl) phosphate Chemical compound C=CCOP(=O)(OCC=C)OCC=C XHGIFBQQEGRTPB-UHFFFAOYSA-N 0.000 claims description 14
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 13
- 239000000835 fiber Substances 0.000 claims description 13
- 229910052726 zirconium Inorganic materials 0.000 claims description 13
- 239000004697 Polyetherimide Substances 0.000 claims description 11
- 229920001601 polyetherimide Polymers 0.000 claims description 11
- 238000001125 extrusion Methods 0.000 claims description 10
- 239000012530 fluid Substances 0.000 claims description 10
- 238000009998 heat setting Methods 0.000 claims description 10
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000010894 electron beam technology Methods 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000005266 casting Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 26
- 239000010408 film Substances 0.000 description 14
- 239000003990 capacitor Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
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- 230000001070 adhesive effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000011104 metalized film Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C08L2205/00—Polymer mixtures characterised by other features
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- C08L2205/16—Fibres; Fibrils
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Abstract
The application discloses an ultrathin temperature-resistant bidirectional synchronous stretching special material and a preparation method thereof, wherein the material comprises, by weight, 80-100 parts of modified polypropylene, 15-20 parts of reinforcing material and 1-4 parts of reaction auxiliary agent; the modified polypropylene is prepared by irradiation grafting modification, the reinforcing material comprises reinforcing fibers and nano inorganic materials, and the weight ratio of the reinforcing fibers to the nano inorganic materials is 1: (3-6). The polypropylene film has the advantages that the polypropylene film is ultrathin and high-temperature resistant, and the polypropylene film is excellent in performance by adopting the specific radiation modified polypropylene, the reinforcing material and the reaction auxiliary agent to realize synergistic effect.
Description
Technical Field
The application relates to an ultrathin temperature-resistant bi-directional synchronous stretching special material and a preparation method thereof, belonging to the technical field of high polymer films.
Background
The existing polypropylene film capacitor has wide application in electronic information industry and electric power industry, and is particularly used as a main dielectric material of the capacitor. The polypropylene film has small specific gravity and stable chemical property, and the biaxially stretched polypropylene film can keep smaller dielectric thickness and better electric resistance under the working voltage of the capacitor, so that the biaxially stretched polypropylene film becomes the main dielectric material of the film capacitor.
Along with the development of electronic information industry and electric power industry, higher requirements are put on the film capacitor, the existing polypropylene film has poorer temperature resistance, and the film is easy to soften and deform when the working temperature rises, so that the stability of the capacitor is influenced; meanwhile, the thermal shrinkage rate is high, shrinkage deformation is caused by temperature rise during use, the reliability of the capacitor is reduced, and the ultra-thin performance and the temperature resistance of the film are difficult to achieve at the same time. In the prior China patent CN 106024378A-an ultrathin high-temperature-resistant polypropylene capacitor metallized film and a preparation method thereof, a zinc coating is arranged on an aluminum coating, so that the heat dissipation performance of the capacitor is greatly enhanced, and a high-temperature-resistant layer with a plurality of convex thickening areas is arranged on the zinc coating, so that the firmness among the coatings is improved, and the temperature resistance of the capacitor is improved. However, on one hand, the actual processing difficulty is high, the production cost is high, and on the other hand, the actual heat preservation effect is not ideal, so that the existing requirement on high temperature resistance of the polypropylene film is difficult to meet.
Disclosure of Invention
In order to solve the problems, the special material for ultrathin temperature-resistant bidirectional synchronous stretching and the preparation method are provided, and the excellent performances of ultrathin and high temperature resistance of the polypropylene film are realized by adopting specific radiation modified polypropylene, reinforcing materials and reaction auxiliary agents to realize synergistic effect.
According to one aspect of the application, the special material for ultrathin temperature-resistant bidirectional synchronous stretching is provided, and comprises, by weight, 80-100 parts of modified polypropylene, 15-20 parts of reinforcing material and 1-4 parts of reaction auxiliary agent; the modified polypropylene is prepared by irradiation grafting modification, the reinforcing material comprises reinforcing fibers and nano inorganic materials, and the weight ratio of the reinforcing fibers to the nano inorganic materials is 1: (3-6).
Optionally, the modified polypropylene is prepared by grafting triallyl phosphate with polypropylene particles.
Alternatively, the polypropylene has a weight average molecular weight Mw of 30-50 ten thousand and a melt flow rate of 6-15g/10min; the particle size of the polypropylene particles is 0.5-1mm.
Optionally, the preparation method of the modified polypropylene comprises the steps of mixing and impregnating polypropylene particles with triallyl phosphate solution, then carrying out electron beam irradiation, heating to 50-70 ℃ after the irradiation, preserving heat for 1-2h, and washing and drying to obtain the modified polypropylene.
Alternatively, the radiation dose is 15-30kGy.
Specifically, the preparation method of the modified polypropylene comprises the steps of mixing polypropylene particles with triallyl phosphate solution, immersing for 2 hours at 30 ℃, then carrying out electron beam irradiation, wherein the radiation dose is 20kGy, heating to 60 ℃ after irradiation, preserving heat for 2 hours, and washing and drying to obtain the modified polypropylene.
According to the preparation method, the triallyl phosphate is used for irradiating and grafting polypropylene for modification, the triallyl phosphate is provided with a plurality of double bonds, the free radical polymerization reaction activity caused by radiation is high, each molecule can be grafted with a plurality of unsaturated side chains, the side chain structure of the polypropylene can be changed into an allyl structure containing branched chains and polar P=O bonds from simple methyl groups through grafting of the triallyl phosphate, the steric hindrance effect between chain segments is obviously increased, the chain segment movement is inhibited, the glass transition temperature of the polymer is improved, meanwhile, the interaction force between polymer chains and the rigidity of the chains are also enhanced by a novel grafting group, and the thermal stability and the mechanical strength of the material are improved. On the other hand, the grafting modification can improve the interface adhesion between the polypropylene and the subsequent reinforcing fiber and the nano inorganic material, is beneficial to dispersing and fixing the reinforcing material, and improves the overall performance.
Optionally, the reinforcing fiber is polyetherimide chopped fiber, the nano inorganic material is nano zirconium boride, and the weight ratio of the reinforcing fiber to the nano inorganic material is 1: (4-6).
Optionally, the particle size of the nano zirconium boride is 10-30nm.
Specifically, the polyetherimide chopped fiber had a length of 0.8mm and a diameter of 20. Mu.m.
Specifically, polyetherimide chopped fibers and nano zirconium boride are selected as reinforcing materials, the polyetherimide chopped fibers can be uniformly dispersed in a modified polypropylene matrix, an effective mechanical reinforcing framework can be formed, the tensile strength of the material is improved, meanwhile, the material has excellent thermal stability and is well matched with the modified polypropylene matrix, and the high-temperature resistance is improved; the addition of the nano zirconium boride ensures that the whole material has good thermal stability, the thermal expansion coefficient is matched with that of polypropylene, meanwhile, the nano zirconium boride has good flame retardant property, and finally, the three components have synergistic effect to realize excellent high temperature resistance of the whole material.
Optionally, the reaction auxiliary agent comprises gamma-aminopropyl triethoxysilane and polyvinyl alcohol, and the weight ratio is 1: (7-10).
Specifically, gamma-aminopropyl triethoxysilane and polyvinyl alcohol can react with the surfaces of nano inorganic materials on one hand, so that good dispersion between inorganic nano particles and a polymer matrix is realized, the dispersibility and interface binding force of filler are improved, on the other hand, the reinforced material is more uniformly dispersed in the modified polypropylene matrix, aggregation and dispersion non-uniformity among the reinforced materials are reduced, uniformity and performance of the composite material are improved, the composite reaction auxiliary agent can improve the interface binding force among the reinforced materials, effectively transfer stress, strengthen the interface strength, and improve the integral mechanical and high-temperature resistance performance of the material.
According to another aspect of the application, the preparation method of the ultrathin temperature-resistant bi-directional synchronous stretching special material comprises the following steps:
(1) Mixing and adding modified polypropylene, a reinforcing material and a reaction auxiliary agent into a screw extruder, and carrying out melt mixing extrusion to obtain a sheet-shaped fluid;
(2) Casting and molding the sheet-shaped fluid through a chilling roller and a high-pressure air knife to obtain a membrane;
(3) And (5) stretching longitudinally and transversely by adopting a mechanical stretcher, and cooling and solidifying after heat setting.
Optionally, the extrusion temperature in step (1) is 200-230 ℃; the temperature of the chilling roller in the step (2) is 85-95 ℃, and the gas temperature of the high-pressure air knife is 85-95 ℃;
in the step (3), the longitudinal and transverse stretching temperatures are 130-150 ℃ and the stretching ratio is 3:1; the heat setting temperature is 120-150 ℃ and the time is 20-40min.
Benefits of the present application include, but are not limited to:
1. according to the ultrathin temperature-resistant bi-directional synchronous stretching special material, the special modified polypropylene is adopted, the reinforcing material and the reaction auxiliary agent are matched, and the synergistic effect is achieved, so that the whole material is ultrathin and has excellent high temperature resistance.
2. According to the ultrathin temperature-resistant bidirectional synchronous stretching special material, the irradiation modified grafted modified polypropylene is adopted to enhance the rigidity of a polymer chain, the thermal stability and the mechanical strength of the material are improved, and meanwhile, the interface adhesion between the polypropylene and the subsequent reinforced fiber and the nano inorganic material can be improved by grafting modification, so that the overall performance is improved.
3. According to the ultrathin temperature-resistant bidirectional synchronous stretching special material, the compound reinforcing material is adopted as a reinforcing framework, so that a highly oriented molecular chain forms an effective mechanical support, the material has good mechanical properties, and meanwhile, the nano filler further improves the overall high temperature resistance of the material.
4. According to the ultrathin temperature-resistant bi-directional synchronous stretching special material, a compound reaction auxiliary agent is adopted to perform chemical reaction with the surfaces of the reinforcing material and the modified polypropylene to form stable chemical bonding, so that the adhesive force between the modified polypropylene and the reinforcing material is improved, and the interface bonding performance is enhanced; on the other hand, the compatibility of the reinforcing material and the modified polypropylene is improved, so that the modified polypropylene and the reinforcing material are more uniformly dispersed in a material system, the phase separation phenomenon is reduced, the uniformity of the composite material is improved, and the improvement of the integral temperature resistance of the material is facilitated.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. The reagents or materials used in the present invention may be purchased in conventional manners, and unless otherwise indicated, they may be used in conventional manners in the art or according to the product specifications. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention. The preferred methods and materials described in this patent are illustrative only. The thickness of the modified polypropylene film prepared in examples 1-3 was 2. Mu.m.
Example 1
The ultrathin temperature-resistant bidirectional synchronous stretching special material is prepared from 90 parts of modified polypropylene, 18 parts of reinforcing material and 3 parts of reaction auxiliary agent according to parts by weight; the modified polypropylene is prepared by irradiation grafting modification, the reinforcing material comprises reinforcing fibers and nano inorganic materials, and the weight ratio of the reinforcing fibers to the nano inorganic materials is 1:5.
the modified polypropylene is prepared by grafting triallyl phosphate with polypropylene particles. The weight average molecular weight Mw of the polypropylene was 40 ten thousand, and the melt flow rate was 10g/10min; the particle size of the polypropylene particles was 0.6mm. The preparation method of the modified polypropylene comprises the steps of mixing polypropylene particles with triallyl phosphate solution, soaking for 2 hours at 30 ℃, then carrying out electron beam irradiation, wherein the radiation dose is 20kGy, heating to 60 ℃ after irradiation, preserving heat for 2 hours, and washing and drying to obtain the modified polypropylene.
The reinforcing fiber is polyetherimide chopped fiber, the nano inorganic material is nano zirconium boride, and the weight ratio of the reinforcing fiber to the nano inorganic material is 1:5. the grain size of the nano zirconium boride is 20nm. The polyetherimide chopped fiber had a length of 0.8mm and a diameter of 20. Mu.m. The reaction auxiliary agent comprises gamma-aminopropyl triethoxysilane and polyvinyl alcohol, and the weight ratio is 1:8.
the preparation method of the ultrathin temperature-resistant bi-directional synchronous stretching special material comprises the following steps:
(1) Mixing and adding modified polypropylene, a reinforcing material and a reaction auxiliary agent into a screw extruder, and carrying out melt mixing extrusion to obtain a sheet-shaped fluid;
(2) Casting and molding the sheet-shaped fluid through a chilling roller and a high-pressure air knife to obtain a membrane;
(3) And (5) stretching longitudinally and transversely by adopting a mechanical stretcher, and cooling and solidifying after heat setting.
Wherein the extrusion temperature in the step (1) is 220 ℃; the temperature of the chilling roller in the step (2) is 90 ℃, and the gas temperature of the high-pressure air knife is 90 ℃; in the step (3), the longitudinal stretching temperature and the transverse stretching temperature are 140 ℃, and the stretching ratio is 3:1; the heat setting temperature is 130 ℃ and the time is 30min.
Example 2
The ultrathin temperature-resistant bidirectional synchronous stretching special material is prepared from 80 parts of modified polypropylene, 15 parts of reinforcing material and 2 parts of reaction auxiliary agent according to parts by weight; the modified polypropylene is prepared by irradiation grafting modification, the reinforcing material comprises reinforcing fibers and nano inorganic materials, and the weight ratio of the reinforcing fibers to the nano inorganic materials is 1:3.
the modified polypropylene is prepared by grafting triallyl phosphate with polypropylene particles. The weight average molecular weight Mw of the polypropylene was 30 ten thousand and the melt flow rate was 7g/10min; the particle size of the polypropylene particles was 0.5mm. The preparation method of the modified polypropylene comprises the steps of mixing polypropylene particles with triallyl phosphate solution, soaking for 2 hours at 30 ℃, then carrying out electron beam irradiation, wherein the radiation dose is 15kGy, heating to 70 ℃ after irradiation, preserving heat for 1 hour, and washing and drying to obtain the modified polypropylene.
The reinforcing fiber is polyetherimide chopped fiber, the nano inorganic material is nano zirconium boride, and the weight ratio of the reinforcing fiber to the nano inorganic material is 1:4. the grain size of the nano zirconium boride is 12nm. The polyetherimide chopped fiber had a length of 0.8mm and a diameter of 20. Mu.m. The reaction auxiliary agent comprises gamma-aminopropyl triethoxysilane and polyvinyl alcohol, and the weight ratio is 1:7.
the preparation method of the ultrathin temperature-resistant bi-directional synchronous stretching special material comprises the following steps:
(1) Mixing and adding modified polypropylene, a reinforcing material and a reaction auxiliary agent into a screw extruder, and carrying out melt mixing extrusion to obtain a sheet-shaped fluid;
(2) Casting and molding the sheet-shaped fluid through a chilling roller and a high-pressure air knife to obtain a membrane;
(3) And (5) stretching longitudinally and transversely by adopting a mechanical stretcher, and cooling and solidifying after heat setting.
Wherein the extrusion temperature in the step (1) is 200 ℃; the temperature of the chilling roller in the step (2) is 85 ℃, and the gas temperature of the high-pressure air knife is 85 ℃; in the step (3), the longitudinal stretching temperature and the transverse stretching temperature are 130 ℃, and the stretching ratio is 3:1; the heat setting temperature is 120 ℃ and the time is 40min.
Example 3
The ultrathin temperature-resistant bidirectional synchronous stretching special material is prepared from 100 parts of modified polypropylene, 20 parts of reinforcing material and 4 parts of reaction auxiliary agent according to parts by weight; the modified polypropylene is prepared by irradiation grafting modification, the reinforcing material comprises reinforcing fibers and nano inorganic materials, and the weight ratio of the reinforcing fibers to the nano inorganic materials is 1:6.
the modified polypropylene is prepared by grafting triallyl phosphate with polypropylene particles. The weight average molecular weight Mw of the polypropylene was 50 ten thousand and the melt flow rate was 15g/10min; the particle size of the polypropylene particles was 1mm. The preparation method of the modified polypropylene comprises the steps of mixing polypropylene particles with triallyl phosphate solution, soaking for 2 hours at 30 ℃, then carrying out electron beam irradiation, wherein the radiation dose is 30kGy, heating to 50 ℃, preserving heat for 1 hour, washing and drying to obtain the modified polypropylene.
The reinforcing fiber is polyetherimide chopped fiber, the nano inorganic material is nano zirconium boride, and the weight ratio of the reinforcing fiber to the nano inorganic material is 1:6. the grain size of the nano zirconium boride is 25nm. The polyetherimide chopped fiber had a length of 0.8mm and a diameter of 20. Mu.m. The reaction auxiliary agent comprises gamma-aminopropyl triethoxysilane and polyvinyl alcohol, and the weight ratio is 1:10.
the preparation method of the ultrathin temperature-resistant bi-directional synchronous stretching special material comprises the following steps:
(1) Mixing and adding modified polypropylene, a reinforcing material and a reaction auxiliary agent into a screw extruder, and carrying out melt mixing extrusion to obtain a sheet-shaped fluid;
(2) Casting and molding the sheet-shaped fluid through a chilling roller and a high-pressure air knife to obtain a membrane;
(3) And (5) stretching longitudinally and transversely by adopting a mechanical stretcher, and cooling and solidifying after heat setting.
Wherein the extrusion temperature in the step (1) is 230 ℃; the temperature of the chilling roller in the step (2) is 95 ℃, and the gas temperature of the high-pressure air knife is 95 ℃; in the step (3), the longitudinal stretching temperature and the transverse stretching temperature are 150 ℃ and the stretching ratio is 3:1; the heat setting temperature is 150 ℃ and the time is 20min.
Comparative example 1
Comparative example 1 differs from example 1 in that: only nano inorganic materials were used for the reinforcing material in comparative example 1.
Comparative example 2
Comparative example 2 is different from example 1 in that: in comparative example 2, no reaction auxiliary was used.
Comparative example 3
Comparative example 3 is different from example 1 in that: the polypropylene modification method in comparative example 3 was different, and the methyl methacrylate irradiation grafting was used in comparative example 3.
Comparative example 4
Comparative example 4 differs from example 1 in that: the weight ratio of the reinforcing fiber to the nano inorganic material in comparative example 4 is 1:10.
comparative example 5
Comparative example 5 is different from example 1 in that: in comparative example 5, only gamma-aminopropyl triethoxysilane was used as the reaction auxiliary.
Comparative example 6
Comparative example 6 differs from example 1 in that: the radiation dose in comparative example 6 was 50kGy.
Experimental example
The polypropylene capacitor films prepared in examples 1 to 3 and comparative examples 1 to 6 were tested according to GB/T13542.2-2009, and the experimental results are shown in Table 1.
TABLE 1
The results show that the capacitor film prepared by the materials and the method have excellent high temperature resistance, mechanical property and electrical property, high temperature resistance of more than 170 ℃, and high durability and reliability.
The comparative example 1, in which no reinforcing fiber was used, was inferior to example 1 in performance, because no fiber skeleton was synergistically enhanced, and the heat shrinkage was suppressed, and the high-temperature resistance was lowered; in comparative example 2, no reaction auxiliary agent is used, the performance is poor, the analysis reason is that the bonding force between the reinforcing material and the matrix interface is poor, the compatibility is poor, and the high-temperature resistance is reduced; in the comparative example 3, other substances are used for grafting, the performance is poor, and the high-temperature resistance is reduced; the amount of the nano inorganic material in the comparative example 4 exceeds the limit range of the application, the performance is poor, and the analysis is because the nano inorganic material is too much to generate aggregation; in the comparative example 5, the reaction auxiliary agent only uses a single auxiliary agent, the performance is poor, and the analysis is due to poor compatibility among the materials; the irradiation dose in comparative example 6 is outside the limits defined herein, and the performance is inferior because excessive irradiation causes breakage of part of the main chain, resulting in a decrease in thermal stability and a decrease in shrinkage.
The foregoing is merely exemplary of the present application, and the scope of the present application is not limited to the specific embodiments, but is defined by the claims of the present application. Various modifications and changes may be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the technical ideas and principles of the present application should be included in the protection scope of the present application.
Claims (10)
1. The ultrathin temperature-resistant bi-directional synchronous stretching special material is characterized by comprising, by weight, 80-100 parts of modified polypropylene, 15-20 parts of reinforcing materials and 1-4 parts of reaction auxiliary agents;
the modified polypropylene is prepared by irradiation grafting modification, the reinforcing material comprises reinforcing fibers and nano inorganic materials, and the weight ratio of the reinforcing fibers to the nano inorganic materials is 1: (3-6).
2. The ultrathin temperature-resistant bi-directional synchronous stretching special material according to claim 1, wherein the modified polypropylene is prepared by grafting triallyl phosphate with polypropylene particles.
3. The ultrathin temperature-resistant biaxially oriented synchronous drawing special material according to claim 2, wherein the polypropylene has a weight average molecular weight Mw of 30-50 ten thousand and a melt flow rate of 6-15g/10min; the particle size of the polypropylene particles is 0.5-1mm.
4. The ultrathin temperature-resistant bidirectional synchronous stretching special material according to claim 1, wherein the preparation method of the modified polypropylene is characterized in that polypropylene particles and triallyl phosphate solution are mixed and impregnated, then electron beam irradiation is carried out, the temperature is raised to 50-70 ℃ after the irradiation, the temperature is kept for 1-2h, and the modified polypropylene is obtained after washing and drying.
5. The ultrathin temperature-resistant biaxially oriented synchronous drawing special material according to claim 4, wherein the radiation dose is 15-30kGy.
6. The ultrathin temperature-resistant bi-directional synchronous stretching special material according to claim 1, wherein the reinforcing fiber is polyetherimide chopped fiber, the nano inorganic material is nano zirconium boride, and the weight ratio of the reinforcing fiber to the nano inorganic material is 1: (4-6).
7. The ultrathin temperature-resistant bi-directional synchronous stretching special material according to claim 6, wherein the particle size of the nano zirconium boride is 10-30nm.
8. The ultrathin temperature-resistant bi-directional synchronous stretching special material according to claim 1, wherein the reaction auxiliary agent comprises gamma-aminopropyl triethoxysilane and polyvinyl alcohol in a weight ratio of 1: (7-10).
9. A method for preparing the ultrathin temperature-resistant bi-directional synchronous stretching special material as set forth in any one of claims 1-8, which is characterized by comprising the following steps:
(1) Mixing and adding modified polypropylene, a reinforcing material and a reaction auxiliary agent into a screw extruder, and carrying out melt mixing extrusion to obtain a sheet-shaped fluid;
(2) Casting and molding the sheet-shaped fluid through a chilling roller and a high-pressure air knife to obtain a membrane;
(3) And (5) stretching longitudinally and transversely by adopting a mechanical stretcher, and cooling and solidifying after heat setting.
10. The method of manufacturing according to claim 9, wherein: the extrusion temperature in the step (1) is 200-230 ℃; the temperature of the chilling roller in the step (2) is 85-95 ℃, and the gas temperature of the high-pressure air knife is 85-95 ℃; in the step (3), the longitudinal and transverse stretching temperatures are 130-150 ℃ and the stretching ratio is 3:1; the heat setting temperature is 120-150 ℃ and the time is 20-40min.
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| GB844231A (en) * | 1957-03-01 | 1960-08-10 | Dow Chemical Co | Method for cross-linking polymers of hydrocarbon olefines |
| DE19721628A1 (en) * | 1997-05-23 | 1998-11-26 | Bayer Ag | Flame-retardant, highly heat-resistant polycarbonate molding compounds with high flow seam strength |
| CN101353863B (en) * | 2007-07-27 | 2011-02-16 | 中国石油化工股份有限公司 | Method for preparing flame-retardant anti-dripping fibre or fabric and flame-retardant anti-dripping fibre or fabric |
| WO2010017553A1 (en) * | 2008-08-08 | 2010-02-11 | Dow Global Technologies Inc. | Triallyl phosphate enabled grafting of compatible monomers to chain scissionable polyolefins |
| CN101838423B (en) * | 2010-06-10 | 2012-07-04 | 南京聚隆科技股份有限公司 | Modified polypropylene material for thin-wall bumper and preparation method thereof |
| US10441940B2 (en) * | 2012-08-20 | 2019-10-15 | University Of Maryland, College Park | Polymers grafted with organic phosphorous compounds for extracting uranium from solutions |
| CN105778297A (en) * | 2016-03-30 | 2016-07-20 | 上海俊尓新材料有限公司 | Polypropylene (PP) composite material used for thin-wall bumpers and preparation method thereof |
| CN107955683B (en) * | 2017-12-07 | 2020-10-13 | 山东一和润滑油有限公司 | Multifunctional lubricating oil |
| JP7209248B2 (en) * | 2018-09-28 | 2023-01-20 | 学校法人金沢工業大学 | Manufacturing method of fiber-reinforced polypropylene composite material and fiber-reinforced polypropylene composite material |
| CN109721829B (en) * | 2018-11-28 | 2021-06-25 | 金旸（厦门）新材料科技有限公司 | High-strength wear-resistant polypropylene compound and preparation method thereof |
| CN112175335B (en) * | 2020-10-29 | 2021-04-20 | 吉林化工学院 | Ablation-resistant aerospace material and preparation method thereof |
| CN113667311B (en) * | 2021-07-27 | 2022-09-16 | 杭州联和工具制造有限公司 | Polypropylene reinforced material for operation console |
| CN114106458A (en) * | 2021-11-17 | 2022-03-01 | 中核同辐（长春）辐射技术有限公司 | Irradiation modified PP melt-blown material and composite forming process thereof |
| CN114539707A (en) * | 2022-02-24 | 2022-05-27 | 浙江杭欧实业股份有限公司 | Reinforced MPP material, preparation method thereof and prepared cable protection tube |
| CN116606088B (en) * | 2023-05-23 | 2024-04-02 | 芜湖城瑞路桥建设有限公司 | Ultraviolet-resistant asphalt mastic macadam mixture and preparation method thereof |
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