CN104513443A - Highly-conductive and high temperature resistant polymer - Google Patents

Highly-conductive and high temperature resistant polymer Download PDF

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Publication number
CN104513443A
CN104513443A CN201310447332.XA CN201310447332A CN104513443A CN 104513443 A CN104513443 A CN 104513443A CN 201310447332 A CN201310447332 A CN 201310447332A CN 104513443 A CN104513443 A CN 104513443A
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polymer
parts
temperature
high conductivity
temperature polymer
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CN201310447332.XA
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Chinese (zh)
Inventor
宋波
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Qingdao Lannonggu Agricultural Products Research and Development Co Ltd
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Qingdao Lannonggu Agricultural Products Research and Development Co Ltd
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Priority to CN201310447332.XA priority Critical patent/CN104513443A/en
Publication of CN104513443A publication Critical patent/CN104513443A/en
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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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/16—Homopolymers or copolymers or vinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • 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
    • 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
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/066—LDPE (radical process)

Abstract

The invention relates to a highly-conductive and high temperature resistant polymer. The polymer is characterized by being composed of the following components in parts by weight: 15 to 25 parts of polyamide resin, 10 to 15 parts of resole phenol-formaldehyde resin EPR, 20 to 30 parts of p-toluenesulfonic acid, 25 to 30 parts of fluorine-containing polymer, 10 to 15 parts of active polyol stearate, and 5 to 10 parts of a thermal stabilizer with a CuI/KI ratio of 1:8. The resole phenol-formaldehyde resin EPR is added, and thus the polymer can be used as an electrode or an electrode shielding material. The polymer can inhibit electromagnetic interference and prevent electrostatic discharge in a position, and is a carrier-free polymer with advantages of wide universality, good heatproof performance, and excellent conductive property.

Description

A kind of high conductivity high-temperature polymer
Technical field
The present invention relates to a kind of polymkeric substance and preparation method thereof, be specifically related to a kind of high conductivity high-temperature polymer.
Background technology
The source of polymkeric substance is divided into natural polymer (as Mierocrystalline cellulose, starch etc.), synthetic polymer (as phosphonium chloride nitrile rubber, various vinyl polymers etc.) and semi synthetic polymer (as cellulose acetate etc.).Addition polymer (i.e. addition polymer), condensation polymer (i.e. polycondensate) and ring-opening polymerization polymer etc. are divided into by the title of building-up reactions.Commodity polymer, special polymer, functional polymer, biomimetic polymer and medical polymer etc. are divided in addition by the application function of polymkeric substance.
In order to obtain lower production cost, wish with two-forty extruded polymer.Higher rate of extrusion can pass easily through raising extruder screw rotating speed and obtain.But because polymeric substrate has viscoelastic property, therefore this technology is restricted.Meanwhile, under very high rate of extrusion, unacceptable polymkeric substance thermolysis may be caused.Usually can obtain shaggy extrudate, this may cause forming undesirable pattern on the surface at extrudate, and these surface imperfection are also called melt fracture.Can avoid this problem although at high temperature extrude, can increase tooling cost, and the cooling of extrudate becomes problem, if polyene baby extrudes in the temperature close to its decomposition point, polymkeric substance will be degraded.
Therefore, those skilled in the art wish find high efficiency raising rate of extrusion and do not improve melt temperature, produce the method with the goods of smooth surface simultaneously.The change of forcing machine and die head structure can improve polymer melt flow, but these improve not always practicality or economically viable.Another kind of approach comprises and adds conventional wax-type processing aid, and it reduces bulk viscosity and improves processing characteristics in some cases, but its efficiency is limited.
Nylon66 fiber has very excellent physicals, high conductivity is high temperature resistant and plasticity-, has excellent intensity, suitable toughness and certain hot-air aging resistance after glass fiber reinforcement.But, there is the problem that thermotolerance is not enough and cause bad dimensional stability and physicals to decline due to water-absorbent in these general fatty polyamides, particularly be applied to long-term exposure in high temperature and/or the parts that contact with cooling fluid, it is still not fully up to expectations that performance separated by its thermotolerance and water-fast (alcohol).
Fluoropolymer additive " lubrication " function is strong, consumption low (200 ~ 1000ppm), and fluoropolymer particle diameter is less, and it is better to disperse, and processing characteristics is also better.For giving full play to its efficient " lubrication " function, the particle diameter of processing aid fluoropolymer is generally micron order, even nano level.But find aborning, directly added to by this analog assistant when using in resin, its extremely low consumption is difficult to dispersed, and particularly when using with pellet is blended, this problem is particularly outstanding, and also there is dust pollution question in producing.
But along with the raising of working temperature in industrial production, the thermotolerance of the polymkeric substance in industrial production that needs further improvement and electroconductibility, to meet the resistance to cooling fluid requirement of required excellence.By the molded article of this polymer formation and this polymkeric substance as electrode, as electrode screening material to suppress a purposes for electromagnetic interference or the static discharge of prevention in a position, more and more can adapt to the demand in market.How to provide a kind of and have that carrier free, versatility are wide, to have polymkeric substance that is well heat-resisting, conductivity be the technical problem to be solved in the present invention.
Summary of the invention
The object of the invention is to overcome deficiency of the prior art, provide a kind of high conductivity high-temperature polymer, it is characterized in that, its component comprises by weight: polyamide resin 15-25; Resole EPR 10-15; Tosic acid 20-30; Fluoropolymer 25-30; Reactive polyol stearate 10-15; Thermo-stabilizer CuI/KI(1:8) 5-10.
Above-mentioned a kind of high conductivity high-temperature polymer, is characterized in that, described polyamide resin is selected from based on one or more mixtures in PA46, PA6T/6I, PA6T/66, PA9T, PA10T.
Above-mentioned a kind of high conductivity high-temperature polymer, is characterized in that, described fluoropolymer is the multipolymer of tetrafluoroethylene and vinylidene fluoride.
Above-mentioned a kind of high conductivity high-temperature polymer, is characterized in that, described fluoropolymer particle diameter≤100 μm, vinylidene fluoride content >=45%, weight-average molecular weight 50 ~ 5,000,000.
Above-mentioned a kind of high conductivity high-temperature polymer, is characterized in that, described reactive polyol stearate selects the two stearate of tetramethylolmethane.
The preparation method of above-mentioned a kind of high conductivity high-temperature polymer, comprises the steps:
(1) by fluoropolymer, reactive polyol stearate, mix with high-speed mixer, rotating speed is 800 ~ 2000rpm, and airtight mixing time is 5 ~ 20 minutes, and temperature controls at 70-80 DEG C, then with singe screw or twin screw extruder, after drying, required binding material is namely obtained;
(2) binding material that step 1 mixes is mixed with resole IDP139, polyamide resin, thermo-stabilizer, add tosic acid and at room temperature solidify 7-8 days in an opening polyethylene mould.Normal temperature extruder grain, vibration screening, obtained high conductivity high-temperature polymer.
 
The beneficial effect of the invention: the invention provides a kind of high conductivity high-temperature polymer, with the addition of the compound of fluorinated copolymer, " lubrication " efficiency is high, can avoid directly adding brought mixing uneven, the shortcoming of affinity difference, adding of resole EPR makes this polymkeric substance as electrode, as electrode screening material, achieves the effect suppressing electromagnetic interference or the static discharge of prevention in a position.Be a kind of have carrier free, versatility wide, there is polymkeric substance that is well heat-resisting, conductivity.Preparation process is without the need to heating, and technological process is simple, and production unit is easy to get, and has stronger operability.
Embodiment
embodiment one
(1) just commercially available tetrafluoroethylene and vinylidene fluoride 20 parts of weight-average molecular weight 50 ~ 5,000,000, mix with high-speed mixer with the two stearate 15 parts of tetramethylolmethane, rotating speed is 1000rpm, airtight mixing time is 10 minutes, temperature controls at 70 DEG C, then with singe screw or twin screw extruder, after drying, required binding material is namely obtained;
(2) binding material step 1 mixed and resole IDP 15 parts, PA46 and PA6T/6I polyamide resin 15 parts, thermo-stabilizer CuI/KI(1:8) 5 parts mix, add tosic acid 20 parts; 7 days are at room temperature solidified in an opening polyethylene mould.Normal temperature extruder grain, vibration screening, obtained high conductivity high-temperature polymer.
embodiment two
(1) just commercially available tetrafluoroethylene and vinylidene fluoride 25 parts of weight-average molecular weight 50 ~ 5,000,000, mix with high-speed mixer with the two stearate 15 parts of tetramethylolmethane, rotating speed is 1000rpm, airtight mixing time is 15 minutes, temperature controls at 75 DEG C, then with singe screw or twin screw extruder, after drying, required binding material is namely obtained;
(2) binding material step 1 mixed and resole IDP 10 parts, PA46 and PA6T/6I polyamide resin 15 parts, thermo-stabilizer CuI/KI(1:8) 5 parts mix, add tosic acid 20 parts; 8 days are at room temperature solidified in an opening polyethylene mould.Normal temperature extruder grain, vibration screening, obtained high conductivity high-temperature polymer.
High conductivity high-temperature polymer of the present invention is white products, does not affect after adding resin on combinations color and lustre, also can add common Masterbatch and carry out painted to goods, as broad as long with common material.
The resole of solvation is weighed in a plastic cup, then adds acid.Use these two kinds of compositions of spatula hand mix 15 seconds.Liquid mixture is poured on a flat ceramic plate, to form thick film, and make it harden.By the resistivity of the volt ohm-milliammeter measure sample film used in embodiment 1 after 24 hours.The result obtained is shown in Table 1.
Graphite is weighed in a plastic cup by embodiment 3, then adds the resole of solvation.Before addition of the acid, by the resole pre-mixing 1 minute of graphite and solvation.After adding acid, the mixture of pasty state is mixed 30 seconds, then transfer in the mould of plastics of 2cm × 2cm × 1cm, and manually suppress.After 24 hours, measure the resistivity of the moulded specimens polymkeric substance of solidification with the volt ohm-milliammeter used in embodiment 1.The result obtained is shown in table 1.
Embodiment is numbered The resole of solvation The weight of acid The weight (based on resole) of graphite The weight of acid Resistivity
1 10g 1g 0 10 20*10 4
2 10g 2g 0 40 10000
3 10g 4g 15g 100 1.5
High conductivity high-temperature polymer made by the embodiment of the present invention one, embodiment two, the equivalent consumption being 800ppm according to effective concentration substitutes fluoropolymer (PPA 2800), be applied to LLDPE/LDPE(LLDPE/LDPE=60/40, weight ratio) plastic sheeting for farm use produce in, blown film unit model used is SJ-45B(Dalian Rubber Plastic Machinery Co), screw speed is 130rpm, to produce plastic sheeting for farm use fabric width be 1m, thickness is 0.08m.In the course of processing, the physical and mechanical properties of the machined parameters such as main frame electric current, extrusion capacity and plastic sheeting for farm use is as shown in table 2.
The contrast of table 2. LLDPE/LDPE plastic sheeting for farm use production application and physical and mechanical properties
Proved by above-mentioned simultaneous test, after adding the present embodiment polymkeric substance, processing and the physical and mechanical properties of LLDPE/LDPE plastic sheeting for farm use are improved.And with adds merely compared with fluoropolymer, high-content fluoropolymer processing master batch of the present invention add to plastic sheeting for farm use produce in after, die pressure, melt fracture, main frame electric current decline more, and production efficiency raising is larger; Transmittance and fracture productivity improve larger, and mist degree declines more.
Above-described embodiment is only be described the preferred embodiment of the present invention; not scope of the present invention is limited; do not departing under the present invention designs spiritual prerequisite; the various distortion that those skilled in the art make technical solution of the present invention and improvement, all should fall in protection domain that claims of the present invention determine.

Claims (6)

1. a high conductivity high-temperature polymer, is characterized in that, its component comprises by weight:
Polyamide resin 15-25;
Resole EPR 10-15;
Tosic acid 20-30;
Fluoropolymer 25-30;
Reactive polyol stearate 10-15;
Thermo-stabilizer CuI/KI(1:8) 5-10.
2. according to a kind of high conductivity high-temperature polymer described in claim 1, it is characterized in that, described polyamide resin is selected from based on one or more mixtures in PA46, PA6T/6I, PA6T/66, PA9T, PA10T.
3. a kind of high conductivity high-temperature polymer according to claim 1, is characterized in that, described fluoropolymer is the multipolymer of tetrafluoroethylene and vinylidene fluoride.
4. a kind of high conductivity high-temperature polymer according to claim 1 or 3, is characterized in that, described fluoropolymer particle diameter≤100 μm, vinylidene fluoride content >=45%, weight-average molecular weight 50 ~ 5,000,000.
5. a kind of high conductivity high-temperature polymer according to claim 1, is characterized in that, described reactive polyol stearate selects the two stearate of tetramethylolmethane.
6. in claim 1-5 described in, the preparation method of arbitrary described a kind of high conductivity high-temperature polymer, comprises the steps:
(1) by fluoropolymer, reactive polyol stearate, mix with high-speed mixer, rotating speed is 800 ~ 2000rpm, and airtight mixing time is 5 ~ 20 minutes, and temperature controls at 70-80 DEG C, then with singe screw or twin screw extruder, after drying, required binding material is namely obtained;
(2) binding material that step 1 mixes is mixed with resole IDP139, polyamide resin, thermo-stabilizer, adds tosic acid and at room temperature solidify 7-8 days in an opening polyethylene mould,
Normal temperature extruder grain, vibration screening, obtained high conductivity high-temperature polymer.
CN201310447332.XA 2013-09-27 2013-09-27 Highly-conductive and high temperature resistant polymer Pending CN104513443A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021224164A1 (en) * 2020-05-07 2021-11-11 Solvay Specialty Polymers Italy S.P.A. Polyamide/fluoroelastomer blends and corresponding articles and formation methods

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021224164A1 (en) * 2020-05-07 2021-11-11 Solvay Specialty Polymers Italy S.P.A. Polyamide/fluoroelastomer blends and corresponding articles and formation methods

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Application publication date: 20150415